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THESIS 


THE FISCHER'-TROPSCH SYNTHESIS 

The Development of Methods and Apparatus, 
and Preliminary Studies on Catalyst 


by 

J* Harry Donald, B.Sc, 
an f 

Donald Q,uon, B.Sc. 


University of Alberta, 
Edmonton, Alberta. 


September, 


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UNIVERSITY OF ALBERTA 


Faculty of Arts and Science 


This is to certify that the undersigned have 
read and recommended to the Committee of Graduate 
Studies for acceptance, a thesis submitted jointly by 
J. H. A. Donald, B.Sc. in Chemical Engineering, and 
D. Quon, B.Sc. in Chemical Engineering, entitled: 

THE FISCHER-TROPSCIi SYNTHESIS 


The development of methods and apparatus, and pre¬ 
liminary studies on catalysts. 



Professor 

Professor 


Professor 


















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THE FISCHER-TROPSCH SYNTHESIS 


The development of methods and apparatus, 
and preliminary studies on catalysts. 


Submitt ed in Partial Fulfullment 
of the 

Requirements for the Degree of 
MASTER of SCIENCE 


by 


J. Harry Donald, B.Sc. 
and 

Donald Quon, B.Sc. 


Under the Direction of 
Dr. E. H. Boomer. 


University of Alberta, 

Department of Chemistry, 

Edmonton, Alberta. September, 1945. 







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Acknowledgement 


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The authors wish to take this opportunity 
to extend sincere thanks to all those who have 
assisted in this investigation: 

To Dr. E. H. Boomer, director of the project, 
whose assistance and advice were invaluable. 

To J. G. Knudsen, for assistance in and 
supervision of this research. 

To the Research Council of Alberta, who 
financed the project. 

To the Board of Governors of the University 
of Alberta, for the Research Scholarships which 
enabled the writers to carry on this investigation. 

To the Department of Chemistry for services 
and supplies. 





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Table of Contents 


Page 

I Introduction ..* 1 

II Literature Review ...« . 9 

III Experimental Equipment ................ 34 

IV Catalysts and their Preparation . 63 

V Analytical Methods and Operational Tech¬ 
niques 67 

VI Experimental Results .. 76 

VII Summary and Conclusions .. 103 

Appendix 

A Preparation of Synthesis Gas . 105 

B Design and Calibration of Flowmeters 111 

C Short-Time Catalyst Testing in a 

Static System .. 123 

Bibliography . 132 















List of Figures 


Page 

Figure I . . . . ^ 2cf 

Figure II . 20 

Figure III . 23 

Figure IV .... . 31 

Figure V . 37 

Figure VI .. 38 

Figure VII . 39 

Figure VIII . 45 

Figure IX . 50 

Figure X .. 53 

Figure XI . 54 

Figure XII . 56 

Figure XIII.!. 57 

Figure XIV .. 91 

Figure XV . 96 

Figure XVI . 107 

Figure XVII . 112 

Figure XVIII . 118 

Figure XIX . 119 

Figure XX . 122 

Figure XXI . 125 

Figure XXII . 128 

Figure XXIII 


129 



































I INTRODUCTION 


The discovery of petroleum and its applica¬ 
tions have been largely responsible for the great 
industrial development of this century. So large has 
been the consumption (and no decrease in the future 
can be expected) that some oil authorities have pre¬ 
dicted a definite shortage within a period of forty 
years. Extensive exploration is under way to discover 
new oil fields but it is felt that the real solution 
lies in the development of synthetic fuels and 
supplementary reserves. 

Even a preliminary examination of supplemen¬ 
tary reserves of liquid fuels in the form of oil shales 
and sands, and coal, discloses quantities of products 
that in principle remove for generations to come any 
possibility of a shortage. The problem is not one of 
scarce raw materials but one of economics, to provide 
liquid fuels from coal, for example, at a cost not 
substantially different from present costs based on 
petroleum. 





















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In the past few years, there has been a 
growing interest in this problem. This is particularly 
true of those countries with limited or no oil resources. 
Spurred on by an endeavor to become economically self- 
sufficient, Germany has been leading the field in 
research, and commercial development. Japan, Britain, 
and the United States, however, are now taking an 
increasingly active interest in the possible production 
of synthetic petroleum. 

At the present time, two important processes 
are receiving considerable attention. 

1} Berguis Process - a catalytic hydrogena¬ 
tion of coal under high pressures and temperatures. 

2) Fischer-Tropsch Process - an indirect 
catalytic hydrogenation of coal and other carbonaceous 
materials. 

Both processes present excellent possibilities 
and both have reached the commercial stage of develop¬ 
ment. However, only the latter process will be con¬ 
sidered in this report. 

The Fischer-Tropsch synthesis consists of the 
catalytic hydrogenation of carbon monoxide at medium 
pressures (5-15 atm.) into a mixture of gaseous and 
liquid hydrocarbons, suitable for the manufacture of 
fuels. Comparatively low temperatures are employed 


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(190° to 250°C)- depending upon the catalyst. The 
synthesis gas, a mixture of CO and H 2 often known as 
water gas, is produced by the incomplete oxidation of 
coal, coke, and other carbonaceous materials, such as 
natural gas. 

The production of synthetic hydrocarbons 
from water gas was first carried out by P. Fischer 
and H. Tropsch in 1925 - 26 (17). Working at atmos¬ 
pheric pressure and at temperatures of 2500 „ 300°G, 
they obtained a product which was principally aliphatic 
hydrocarbons, containing little or no oxygenated 
compounds. Their research was so fruitful in the next 
few years that in 1933 the Ruhrchemie A - G undertook 
the construction of a plant at Holten, Germany, with 
a capacity of 1000 tons per year. Much progress was 
made in the years following. By the end of 1936, five 
plants were completed or under construction, boosting 
the production of primary oils to 145,000 metric tons 
per annum (30). Germany continued to increase its 
production of synthetic fuels until, in 1940, an 
annual production of 1,000,000 tons of Fischer-Tropsch 
liquids was reported (31). Undoubtedly this figure 
was increased substantially during the war years. 

In Japan, by 1938, two plants had been 
reported giving an annual output of 150,000 tons. 


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Later information revealed that the erection of three 
new plants had increased the annual production by 
260,000 tons. Small scale plants have been built in 
both France and Britain. 

The extensive development of the Fischer- 
Tropsch synthesis has been promoted in Germany, not 
particularly by economic, but by nationalistic motives. 
An investigation by the U.S. Senate (27) into the 
economics of this process indicates the relative costs 
of gasoline produced by two methods. 

1) Fischer-Tropsch synthesis 

a. from coal - 19.2//gal. with the 
present European design. 

b. from natural gas - 8.8//gal. with 
the present design. However a cost of only 4.8//gal. 
is possible if large scale production were carried 
out using American technology and natural gas at less 
than 5/ per 1000 cu. ft. 

2) Petroleum Refining 

- 5.3 - 5.5//gal. with present day methods. 

While the production of synthetic fuels from 
natural gas could, under the most favorable circum¬ 
stances, compete economically with that from petroleum, 
it cannot be considered as a long time solution to the 
problem. Any real solution lies in the use of coal as 
the primary raw material. The resources of natural gas 


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are of the same order of magnitude as petroleum and 
further the economic and social value of natural gas 
as an industrial and domestic fuel may rule out its 
extensive use as a chemical raw material. 

The Fischer-Tropsch process has attracted 
the interest of several research organizations in the 
United States. At present the Bureau of Mines, U.S. 
Department of the Interior, is vitally interested in ' 
its development and is planning the construction of 
several pilot plants. Research work is also being 
carried out in a number of oil companies (the most 
important of which are probably the Standard Oil of 
Hew Jersey and the Gulf Oil Co.) but information 
about their progress is unavailable. 

Canada, up to the present time, has shown 
little interest in the Fischer-Tropsch synthesis. 
However, in 1944 the Research Council of Alberta 
initiated a program of research in this connection. 
This question is of particular interest to Alberta 
which is enormously rich in reserves of coal and 
natural gas, the basic raw materials for the manu¬ 
facture of synthetic fuels. Important industrial 
development of this process would be of immense 
economic value to this province. 


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In the research and development of the 
Pischer-Tropsch process, the following general 
problems must be solved: 

1) Industrial development of laboratory 
operations. This is a problem common to all new 
processes. Economic design and operation depend 
upon the availability of fundamental data on the 
process. Much work remains to be done in this field. 

2) Heat exchange. Since the reaction is 
highly exothermic, and since the catalysts are very 
sensitive to temperature, means must be devised to 
dissipate the heat. At the present time, the allow¬ 
able space velocities (and hence gas velocities) are 
low, resulting in poor heat transfer. Consequently 
thin layers of catalyst must be used to properly dis¬ 
sipate the heat. All this means comparatively large 
amounts of steel per unit of catalyst i.e. unit of 
production. 

3) Development of catalysts. This involves 
the preparation, conditioning, maintenance, and 
evaluation of new and more effective catalysts. Improve¬ 
ment of catalysts can lead to elimination of the heat 
exchange problem. It is with the development of 
catalysts that the present investigation is primarily 


concerned 


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The theory of catalysis is as yet poorly 
developed and the problem can be attacked only upon 
an empirical basis. Long term tests under conditions 
approximating commercial production are necessary to 
properly evaluate a catalyst. This testing is an 
integral part of any long range program of fundamental 
research on the whole question of catalyst development. 

Research on Fischer-Tropsch catalysts at the 
University of Alberta was begun in the summer and fall 
of 1944 and only the preliminary work has been done on 

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the problem. This involved the construction and 
assembly of the experimental equipment, the solution 
of the operational difficulties, and the initial tests 
upon a few catalysts. 

In the course of this investigation, several 
problems were encountered, which are related, but which 
have no direct bearing upon the catalyst testing. Two 
in particular, might be mentioned: 

1) Preparation of the synthesis gas 

2) Design and calibration of capillary flow- 
meters. They are of such general interest that it was 
felt that they should be included in an Appendix of 
this report. 

Preliminary experiments were also carried out 
on the short-time testing of Fischer-Tropsch catalysts 




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in a static system at atmospheric pressure. A brief 
discussion of this phase of the project is included 
in the Appendix. 



II LITERATURE REVIEW 


Since its original discovery in 1926, the 
Fischer-Tropsch synthesis has received wide-spread 
attention throughout the world, with extensive investi¬ 
gations being carried out largely in Germany but with 
important contributions from Japan, Russia, England 
and the United States. As a result, the literature 
on this process is extensive. Most of the original 
papers have been published in foreign journals and, 
except for their abstracts, have not been consulted. 

In view of the importance of the process, however, 
many of these papers have been translated and 
reprinted in available journals. In addition, the 
information has been brought up to date by several 
comprehensive reviews (18, 23, 30). While the follow¬ 
ing literature review does not profess to be complete, 
it is believed that the major contributions have been 


included. 




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The production of hydrocarbons from water 
gas was pioneered in 1913 by Sabatier (28). He found 
that finely divided nickel catalyzed the reduction of 
carbon monoxide to methane according to the following 
reaction: 

CO + 3H 2 CH 4 + H 2 0 

However, no higher hydrocarbons were obtained. 

In the same year the Badische Anilin and 
Sodafrabrik organization patented a process (4) in 
which saturated and unsaturated gaseous and liquid 
hydrocarbons, alcohols, aldehydes, acids and ketones 
were produced from water gas. The reaction took 
place at elevated temperatures and pressures (300° 

- 400° C, 100 - 200 atmospheres) over a methansl 
catalyst impregnated with alkali and oxides of cobalt, 
osmium or zinc.. 

In 1913 Franz Fischer and Hans Tropsch (16), 
on passing water gas over an alkali iron catalyst at 
400 - 450°C and 100 - 150 atmospheres, obtained a 
mixture of aliphatic alcohols, aldehydes, ketones, 
acids and esters. This product was called n Synthol !5 . 
It was not until three years later, however, that 
these two workers reported (17) the famous synthesis 
which bears their name. By operating at lower 
pressures and temperatures, and by using alkali-free 






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iron and cobalt catalysts, they obtained a product 
(given the name "Kogasin") which consisted almost 
entirely of hydrocarbons ranging from ethane to solid 
paraffin. 

Since the original announcement, research 
workers in many countries have studies this synthesis 
and its implications. Attention has been devoted 
chiefly to the following phases of the process - the 
development of new and more active catalysts; the 
determination of the optimum operating conditions for 
existing catalysts; and the study of the mechanism of 
the reactions involved. These will be dealt with in 
turn. 

Catalysts and their Properties . 

Many catalysts have been suggested for the 
Fischer-Tropsch synthesis. On the whole, however, the 
main constituent of these catalysts is one or more 
metals from the Eighth Group of the Periodic Table 
(i.e. Hi, Co, and Fe) usually in the metallic form. 

Before any fundamental research on Fischer- 
Tropsch catalysts is possible, it is first necessary 
to know the distinguishing characteristics of these 
catalysts - their desired properties and their faults. 
Eomarewsky and Riesz (23) state that Fischer-Tropsch 
catalysts must comply with the following requirements: 



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1) Ability to form a carbide from carbon- 
monoxide 

2) Hydrogenating ability 

3) Polymerizing ability 

All metals in the Eighth Group satisfy the 
first two, and, to a certain extent, the third con¬ 
dition. These investigators further suggest that 
multi-component or ”complex-action” catalysts are 
the most suitable. 

Although Fischer and Tropsch employed an 
iron catalyst in the original synthesis, most of their 
later work was carried out on cobalt and nickel 
catalysts. The following table shows the yield and 
life of some of the catalysts which they had studied 
up to 1936 (9). 


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Table I 


Yield and Life of Some Fischer- 



Catalyst 


Ip on: 

Fe Cu Mn Silicagel 0.4 % KgCQ^ 
Fe Cu on Kieselguhr 

Nickel: 

Ni Th on Kieselguhr 
Ni Mn A1 on Kieselguhr 

Cobalt: 

Co Th on Kieselguhr 
Co Th Kieselguhr decomposed 
Co Mn on Kieselguhr 
Co Ni alloyed (Si) 

Co Th Cu on Kieselguhr 


Yield Life till de¬ 

crease to 80$ 
g/meter of of original 


synthesis gas 

activity 

30-35 

8 days 

28 

8 days 

100 

30 days 

105 

45 days 

110 

60 days 

105 

25 days 

105 

Min. 30 days 

85 

12 days 

105 

60 days 


It is seen that the Co-Th-Kieselguhr catalyst 
appeared to be the best at that time. However, in 1943, 
Fischer and co-workers (13) report that further studies 
have shown that a nickel-manganese-alumina catalyst was 
clearly superior. 

Other investigators have been actively engaged 
in the development of new catalysts. Although attempts 
have been made and are being made to develop short time, 
positive test methods, there has been no success, and 

















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to date this problem can be attacked only empirically. 
The value of a catalyst can be assessed only after 
long continuous tests under conditions approximating 
commercial operation. Cobalt and nickel catalysts have 
received the most attention and are consequently more 
developed than the iron catalysts. However, the 
relatively high cost of cobalt and nickel has prompted 
many research workers to study and develop the latter. 

I. G. Farbenindustrie A.-G. has patented 
the so-called '’Iso” process, using a robust iron 
catalyst, operating at 200 psi. and 300°C. This is 
probably a fused iron oxide catalyst which has been 
reduced at 850°C. Little is known about this process 
but development in Germany had apparently reached the 
commercial stage. Recent information (private) suggests, 
however, that this process is not yet successful. 

The action of promoters on Fischer-Tropsch 
catalysts is obscure and the only guide being followed 
is that of trial and error. Foster (18) has reviev/ed 
some of the catalysts which have been suggested. The 
promoters used include alkali and alkaline earth metal 
oxides, copper, thoria, and the oxides or sulphides of 
uranium, chromium, tungsten, aluminium, and manganese. 
Other proposed promoters are found in the patent litera¬ 
ture but the latter contains little information of value. 


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Napthall (26) has offered explanations for 
the action of some of these promoters. Copper facili¬ 
tates the action of the catalyst by lowering the 
temperature necessary for the reduction of carbon 
monoxide. It is effective with iron and cobalt but 
not with nickel. Small quantities of alkali in iron 
catalysts favor wax formation. Thorium, manganese, 
and similar metals, when precipitated together with 
the contact mass, appear to function by distorting 
the metal surface enhancing the activity. Space 
lattice distortion changes the inter-atomic distance 
to permit cross linkages, thus affecting the chain 
length and the iso-normal paraffin ratio. 

In general, cobalt catalysts are promoted 
by thorium or by rare earths while iron catalysts 
are promoted by copper. The best carrier or support 
for cobalt catalysts is kieselguhr. Iron catalysts 
are not supported since all known carriers to date 
exert only a detrimental effect. 

In line with the general theory of solid 
catalysts, there is evidence to indicate that the 
synthesis takes place only at a comparatively few 
active centres on the surface of the catalyst. Even 
in the best Fischer-Tropsch catalysts, these few 
active centres become deactivated rather rapidly. 

The following possibilities have been suggested for 





- 16 - 


the loss of activity of cobalt catalysts: 

1) Wax formation on the surface of the 
catalyst - reversed by hydrogen treatment at 200°C. 

2) Oxidation of the active centres by 
water - reversed by hydrogen treatment at 400°C. 

3) Carbiding - irreversible. 

Underwood (31) has reported that, under 

optimum operating conditions, the catalyst life is 
from four to six months. This is only approximate 
since life depends upon manner of operation, period 
and manner of reactivation, minimum yield allowed and 
economics. For instance, Fischer (15) states that a 
nickel-manganese-alumina will remain active one to 
two years provided that it is regenerated periodically. 
In general, hov/ever, the life of Fischer-Tropsch 
catalysts is relatively short and it is desirable to 
lengthen it. 

It might be mentioned that while cobalt 
catalysts can be regenerated by a hydrogen treatment 
(at either 200°C or 400°C depending upon the circum¬ 
stances) this is not possible for iron catalysts. If 
for any reason, the latter loses its activity, it can¬ 
not be reactivated. Permanent loss of activity for 
both cobalt and iron catalysts has been attributed to 
the loss of active centres through volatilization as 
carbonyls. 


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Closely allied with the problem of deactiva¬ 
tion is the question of poisoning. Fischer-Tropsch 
catalysts are characterized by their high susceptibility 
to poisoning, particularly by minute quantities of 
sulphur. Herington and Woodward (21) have investigated 
the effect of small quantities of hydrogen sulphide on 
a Co-Th-kieselguhr catalyst. The first addition of 
hydrogen sulphide caused a marked increase in the yield 
of liquid hydrocarbons. This continued until more 
than 8 milligrams of sulphur had been added per gram of 
catalyst. Further addition caused a drop in total 
hydrocarbon yield but this could be offset by raising 
the reaction temperature. The addition of hydrogen 
sulphide in quantities over 34 milligrams of sulphur 
per gram of catalyst resulted in a continuous decrease 
in activity until complete poisoning was reached. How¬ 
ever, even as little as 10 milligrams of sulphur per 
gram of catalyst is sufficient to prevent the periodic 
regeneration of the catalyst. Sulphur poisoning is 
irreversible. In commercial operation the maximum 
tolerance for sulphur content is 0.1 grain per 100 cubic 
feet. Myddleton (24) has reported on efforts to develop 
sulphur resistant catalysts but the results have not 
been conclusive. 

Fischer-Tropsch catalysts are also poisoned 
by minute quantities of oxygen gas. The latter appears 


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- 13 - 


to attack the active catalyst centers preferentially. 
However, cobalt catalysts which have been poisoned in 
this way can be reactivated by a hydrogen treatment 
at 400°C• 


Operating Conditions for Fischer-Tropsch Catalysts 

The various operating conditions-temperature, 
pressure, space velocity, and composition of synthesis 
gas - all have a marked effect on the behavior of 
Fischer-Tropsch catalysts. Fischer and co-workers 
have done considerable work on this phase of the 
problem in an effort to determine the optimum operating 
conditions for commercial plants. 

Fischer-Tropsch catalysts are very sensitive 
to temperature - the maximum range of variation being 
15 centigrade degrees. Storch (30) reports that, even 
for the most active cobalt catalysts, the reaction 
rate is very slow below 175°C and above 225°C and the 
production of liquid falls off sharply, with methane 
formation predominating. The best cobalt catalysts 
operate at a temperature of 195 - 200°C. Nickel- 
manganese- alumina catalysts, as developed by Fischer 
(14), operate between 190° - 210°C. As the catalyst 
slowly loses its activity during operation, the temp¬ 
erature has to be raised slightly. Higher temperatures 
favor methane formation with a corresponding loss in 



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- 19 - 


yield of liquid hydrocarbons and furthermore causes 
the catalyst to become irreversibly poisoned, possibly 
due to carbon formation. In this connection, Hofer’s 
observation (22) that the upper temperature limits of 
the Fiseher-Tropsch synthesis and the lower temperature 
limits of carbon formation (i.e. from the metallic 
carbide) very nearly coincide, may be of significance. 

For iron catalysts, the optimum temperature is around 
250°C but with higher temperatures, carbiding and 
carbonyl formation deactivate the catalyst irreversibly. 

The synthesis pressure affects both the yield 
and type of product, and the life of the catalyst. 

Earlier work by Fischer and Tropsch (16) has shown that 
high pressures (100 - 150 atmospheres) favored the forma¬ 
tion of ’’syntho!’ 1 or oxygenated compounds. On reducing 
the pressure to 20 atmospheres or less, the reaction 
produced hydrocarbons almost exclusively. Fischer and 
Pichler ! s curves (13) showing the effect of pressure 
on total and fractional yifcld of products using a 
Co-Th-kieselguhr catalyst are reproduced in Figure I. 


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Figure t * Effect of Pressure on Hydrocarbon Yields 



Weeks of Operation 


Figure II--* Effect of Pressure on Catalyst Life 
















































- 21 - 


A pressure of 5 - 15 atmospheres gives the greatest 
degree of conversion and also the highest yield of 
solid and liquid hydrocarbons. 

The effect of pressure on the durability of 
a cobalt catalyst was shown by Fischer and Pichler (12). 
The results are shovm in graphical form in Figure II. 

At both low and high pressures, the effectiveness of 
the catalyst decreases markedly in the first few weeks. 

A pressure of 5 - 15 atmospheres appears to be the 
optimum for maintaining the life of the catalyst. These 
results have been confirmed with iron. Komarewsky and 
Riesz (23) report, however, that these pressures are 
unsuitable for operating with nickel catalysts. 

The space velocities employed are in compari¬ 
son with catalysts for other syntheses, extremely low, 
being, in general practice, in the range of 100 - 150 
per hour. This leaves much room for improvement. 

Fischer and Pichler (12) have investigated the effect 
of varying the throughput on the yield of liquid hydro¬ 
carbons obtained from a Co-Th-kieselguhr catalyst. 

Their plotted results are shown in Figure III. 

At the maximum point in the space-time-yield 
curve, the yield of oil is only 60 grams per cubic 
meter of gas indicating incomplete conversion. If 
one-pass operation is practiced, such yields are 
probably not economical. Aside from this, another 






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- 22 - 


factor limits the space velocities. Since the reaction 
is strongly exothermic, a high space velocity presents 
a serious heat exchange problem. If the heat of 
reaction cannot be dissipated effectively, this causes 
local heating of the catalyst, resulting in the sinter¬ 
ing and deactivation of the active centres. German 
industry has attempted to solve the heat transfer 
problem by using a relatively inert catalyst, high 
space velocities, and recycling. However, the forma¬ 
tion of gaseous inert products (CH 4 , CO 2 ) leads to 
serious recycling difficulties. Two stage operation 
appears to be the compromise (30, 31). 




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- 23 - 






























































- 24 - 


Fischer and co-workers (15) have studied 
the effect of varying the CO:Hg ratio in the synthesis 
gas. They recommend that the stoichimetrical mixture 
containing 33.3^ CO and 66.6 % Hg is the most desirable 
one, giving the maximum yield of products per cubic 
meter of raw gas per unit time. In addition this 
ratio gives the highest degree of conversion to liquid 
hydrocarbons. 

The reaction rate decreases as the COiHg 
ratio rises above this optimum. The yield of liquid 
products increases as does the unsaturation. On the 
other hand, a low CO:Hg ratio results in a greater 
degree of conversion and more saturation. The effect 
of the CO:Ho ratio can be somewhat minimized, however, 
by the proper selection of a specific reaction temp¬ 
erature - this temperature being higher for CO rich 
gases than for Hg rich gases. 

Inert gases like nitrogen have only a diluent 
effect and do not affect the reaction materially. 

Type of Products 

The type of products obtained in the Fischer- 
Tropsch process depend upon both the operating con- 

1 * 

ditions and the catalyst employed. The effect of 
varying the operating conditions has already been 
qualitatively shown. The products obtained from the 



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- 25 - 


two general types of catalyst (iron; and cobalt, 
nickel) show considerable differences. Most of the 
literature deals with cobalt catalysts; data on iron 
catalyst products are relatively scanty. 

Napthali (26) has reported that cobalt 
catalysts give a more saturated product than the iron. 
Fischer (11) using a cobalt catalyst obtained the 
following primary product or Kogasin. 


Table II 

Analysis of Kogasin 


Fraction 

B.Pt. °C 

% by Tift • 

% of Olefins 

C 3 and C 4 

Belov/ 30 

8 

50 

gasoline 

30 - 200 

60 

30 

Diesel Oil 

Over 200 

22 

10 

Paraffin Wax 


10 



Kogasin is largely composed of straight chain 
saturated and unsaturated hydrocarbons. The gasoline 
fraction constitutes 60 % of the total product but has 
a low octane number. 

On the other hand, the U.S. Bureau of Mines 
(32) find that at 7 atmospheres, and using a cobalt 
catalyst, the product had the following approximate 
composition by weight: 








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Fraction 


and 


20 

40 - 150°C B.Pt. 

30 

150 - 370°C B.Pt.(Diesel Gut) 

40 

above 370°C 


These sets of data should be regarded as 
only illustrative of the type of product obtained. 

The character of the various fractions have been 
revealed by several investigators (26, 30, 32). The 
diesel oil cut may be removed by simple distillation. 

It is of good quality, having a high cetane number due 
to the straight chain character of the hydrocarbons in 
this fraction. The paraffin wax differs in properties 
from that obtained from petroleum but can be put to the 
same uses. It is characterized by a high melting point 
and contains relatively high proportions of long straight 
chain hydrocarbons. The gasoline fraction may be in¬ 
creased by reforming and cracking the primary product in 
conventional petroleum plant equipment. The octane 
number can also be raised by these methods. Egloff, 
Nelson and Morrell (7), by means of thermal treatment 
and catalytic polymerizations, obtained 84,5% of 66 
octane gasoline from a kogasin oil which originally had 
an octane number of only 20. 





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4 


Little is known about the product from iron 
catalysts except that a higher percentage of olefins 
(and hence a higher octane number) is found in the 
primary product. 

The development of new catalysts to direct 
the reaction towards specific products has been 
recently reported (6). Of particular interest is the 
so-called "iso-synthesis M in which iso-paraffins are 
produced directly. High octane gasoline fractions 
are obtained which may be converted to aviation fuel. 

The literature reveals the wide versatility 
of the Fischer-Tropsch synthesis. A large variety of 
products is possible through the proper choice of 
catalysts and operating conditions. 

Mechanism of the Reaction 

The overall chemical reaction over Ni, Co 
catalysts differs from that over Fe catalysts mainly 
in the by-products produced. Along with hydrocarbons 
the latter yield CC >2 while the former give principally 
HgO. The reactions - assuming formation of paraffin 
hydrocarbons only - may be represented by the follow¬ 
ing equations. 

1) For the Co and Ni catalysts 

nCO -»- ( 2n +1) H -—.> CnH 2n+2 +nH 2 0 

2) For the Fe catalysts 

2n CO + (n 4 1) H 2 -—» CnH 2n+2 4nC02 






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- 28 - 


This difference in behaviour has been one of the main 
difficulties in the determination of the reaction 
mechanism. Much research has been done on this question 
and several theories have been advanced. 

In 1926 F. Fischer and H. Tropsch (17) follow¬ 
ing their initial production of paraffin hydrocarbons 
from water gas postulated that the catalytic process 
involves the formation of a carbide, rich in carbon 
(Fe^C^ or FegCg) which is later converted to methylene 
groups. The overall effect may be represented by: 

3 CO + 3H 2 —> C0 2 4 H 2 0 +- 2CH 2 
The methylene groups polymerize in the presence of 
hydrogen to form the paraffinic compounds. An Fe - Co 
contact mass was used in their investigation and, as 
a result, both CO 2 and H 2 0 were present. In a later 
paper Fischer (10) reiterated his initial idea but 
suggested an alternative. He stated that the methylene 
groups first polymerize to extremely high molecular 
weight hydrocarbons. These are subsequently cracked 
into compounds with high vapour pressures and carried 
off the catalytic surface. The actual mechanism is 
suggested as follows: 

CO + Me - > MeC + MeO 

MeC +* MeO +■ 2H 2 ——2Me +• CHg 4 - HgO 
However, it is probably more correct to assume that 
the original carbide is merely reduced to a lower 




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- 29 - 


carblde rather than to the metal. No attempt was made 
to explain the COg formation. 

In an endeavour to explain the formation of 
oxygenated compounds, Elvin and Nash (8) advanced in 
1926 an alternative theory. The hypothetical formation 
of methanol is postuluted as the intermediate reaction 
for obtaining both hydrocarbons and oxygenated compounds 
(acids, alcohols, ketones and aldehydes). This, how¬ 
ever, is not supported by thermodynamic considerations. 
This theory has found some support with Japanese investi¬ 
gators (3). 

The presence of carbides in catalysts was 
confirmed by experiments (22) involving the Garb idl¬ 
ing and reduction of the three metals, Ni, Go and Fe. 

Up to certain critical temperatures, when treated with 
CO, all three form metallic carbides which can be 
reduced completely, giving CH^ as a product. Above 
these temperatures (which are but slightly higher than 
the optimum for the synthesis) elementary carbon is 
formed which, by carrying away active centres and 
producing irreducible residues, tend to poison the 
catalyst. There is evidence to indicate that the 
carbides are the real catalyst bodies. 

Craxford (1, 2) in supporting and developing 
Fischer’s carbide theory, has presented a detailed 
mechanism of the reaction. He argued against the 




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- 30 - 

formation of hydrocarbons by simple carbiding and 
reduction as expressed by the following reactions: 

1) 2C o ■+• 2G0 -^ C o 2 C ~f~ C 0 g 

2) OogC *f Hg > CHg-f 20o 

First both reactions are too slow to account for the 
rate of the overall reaction: 

3) CQ + H 2 -^ CH 2 + H 2 0 

Secondly over Co catalysts the production of HgO can¬ 
not be explained by equations 1) and 2). 

As a result of experiments involving the 
rate of ortho-para conversion of hydrogen on the surface 
of an active Co-Th-kieselguhr catalyst, Craxford con¬ 
cluded that the reaction forming hydrocarbons proceeds 
by way of molecular Hg. The following steps in the 
reaction (shown diagrammatically in Figure IV) have 
been suggested: 

1) CO is chemisorbed to the surface and reduced 
by molecular Hg to form the carbide. 

2) The carbide is reduced by Hg to form methylene 
groups. 

3) In the presence of large amounts of chemisorbed 
H 2 , the methylene groups are immediately reduced to 
methane; with smaller amounts long chain hydrocarbons 


are formed 





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-31- 


Legend: oooooo Yan der Waal Adsorption 

- Chemisorption 


(1) Chemisorption of CO 



Reduction of Chemisorbed CO 
by H 2 to give Carbide 


H 2 h 2 o 

: c : 

O o 



(2) Reduction of the Carbide to Chemisorbed Methylene 

I-I 2 

o 

o __ 


( 3 ) 


a 


Presence of a Large Amount of Chemisorbed H 2 


Hj 


H 


CH 2 


CH, 


b. Presence of a Small Amount- of Chemisorbed iL 


CHo CHo 


-OHo — CE ft --CE*~ 


h-2 

CE a -GE a -CE a -S CHa-CHa-GHj 


CH a -OE 2 -CH 3 H CE a -CE a -CE 2 



o 

o 

o 

o 


CEa-CHo-CHs E 


CE a -CE a -CE a 


CE a -CE=CE a . 

> 


Figure IY - Mechanism of the Synthesis of Hydrocarbons 

(Craxford) 
























































-32- 


This mechanism supports Fischer's idea of 
the formation of high molecular weight hydrocarbons 
subsequently followed by hydrogenation or 'cracking'. 
Further experiments involving the breaking down of 
ethane, propane, and butane (mixed with the requisite 
amount of H 2 ) into CH^ over a freshly reduced Fischer 
catalyst substantiated this view. 

While Co catalysts are usually considered 
very active for the water gas shift reaction: 

C0 + H 2 0 —¥ co 2 +h 2 

the primary oxygenated compound is water rather than 
C0 2 . No other explanation for this phenomenon is 
given other than to assume the reaction is inhibited 
by the operating conditions of the Fischer - Tropsch 
synthesis. Vi/hen the temperature is raised to 250 - 
300°C, C0 2 is again produced exclusively, with no 
hydrocarbons save methane. 

To conclude then, while the Craxford 
mechanism is valuable, it is nevertheless complicated 
and is so far limited to Co catalysts. 

Herington and Woodward (21) conclude that 
the Fischer - Tropsch catalysts possess two types of 
active centres: 

(a) Type A (probably cobalt carbide) which is 
responsible for the formation of methylene groups. 



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33- 


(b) Type B (probably cobalt metal) which is 
responsible for the adsorption of Hg to liberate the 
products from the catalytic surface. 

Myddleton (25) has offered an explanation for 
the difference in the by-products with Ni, Go, and 
Pe catalysts on the basis of the chemical bonding of 
the CO to the surface. With dual bonding to adjacent 
atoms (as in the case of cobalt and nickel) HgO is 
produced whereas with single attachment (as with Fe) 

CO 2 is produced. Further experimental evidence is 
needed to support this claim. 

In general, the carbide theory, advanced by 
Fischer and developed by Craxford, appears to be the 
most acceptable at the present time. This mechanism 
has been developed primarily for Go catalysts and 
little work in this connection has been done with 
Fe catalysts. It is almost certain, however, that 
the formation of iron carbides plays an important role 
in the mechanism of the latter. 


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-34- 


IIX EXPERIMENTAL EQUIPMENT 


The Fischer-Tropsch process is composed of* 
essentially two distinct stages - the preparation of 
the synthesis gas and its conversion into suitable 
hydrocarbons. The description of the equipment may 
also be divided in this manner. The preparation of 
the synthesis gas will be described in detail in the 
Appendix. The emphasis in this section will be 
placed on the equipment used in the actual synthesis. 

Catalyst testing is carried out on a pilot 
plant basis and the equipment is operated continuously 
for long periods - extending into several months. The 
following requirements must be satisfied - the passage 
of water gas at extremely low space velocity (100-150 
per hour) over a catalyst column at medium pressures 
(100 psi.) and temperatures (200° - 250°C) with good 
control in general but particularly with respect to 
temperature. 

Much of the present design, the reaction 
converter, and the recovery system in particular, has 







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-35- 


been based on the experience of the U.S. Bureau of 
Mines (Department of the Interior) Pittsburg, Pa. 
However, at the University of Alberta, much more 
automatic control (especially in the control of gas 
flow) had to be incorporated into the design. This 
was necessary because only a comparatively small 
staff was available for work on this project. There 
are six individual catalyst testing units, each of 
which may be operated nearly automatically^and 
independentlyof each other. 

(a) General Flow S heet 

Before giving a detailed description of 
the individual pieces of equipment, a short disciission 
of the general flow sheet (Figure V) will be first 
presented. This will afford an overall picture of the 
whole process and will bring out the relationships 
between the various pieces of equipment. Only a brief 
descriptive paragraph on the synthesis gas production 
will be given here. 

Methane and oxygen, in the volumetric ratio 
2 : 1, are passed simultaneously into gasholder A, 
the flow being measured by two capillary type flowmeters. 
The mixed gases are passed at a controlled rate over a 
nickel catalyst heated to 1000°G in the electric furnace 
B. Here the conversion into synthesis gas occurs, the 




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-36- 


main reaction being 

2 CH 4 + 0 2 -* 2 CO +4 H 2 

The exit gas is purified (of H 2 S and C0 2 ) by a caustic 
scrubber C and is then stored in gasholder D. This 
low pressure gas is compressed to 100 psi. guage and 
held in the high pressure storage tank E. The pressure 
here is maintained constant by automatic control, the 
movement of a Bourdon tube actuating a relay and magnetic 
switch in the power supply to the compressor. High 
pressure synthesis gas, after being dried in the alumina 
dryer F, is passed into a header common to all six units. 

The gas flow to each unit is indicated by the 
pressure drop across a capillary-tube flowmeter, the 
pressure drop being indicated on a mercury manometer, 
equipped with high, low and intermediate contacts. 

The manometer contacts are part of an electrical 
circuit which operates a motor driven control needle 
valve G s designed to keep the flow constant within 
narrow limits. The gas passes into the reaction 
chamber of the converter H containing a column of 

© 

catalyst. The catalyst bed (approximately 16 inches 
in length) is supported inside a inch iron pipe. 

1 

The catalyst temperature is held constant by a liquid 
boiling at constant pressure in a jacket surrounding 
the reactor. This outer jacket forms part of a closed 
system which also includes the water-cooled reflux 





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-37- 



Fi qxto T - General flow sheet for testing of Fis olier 

Tropscli c-t^lysts. 








































































































































38 



Figure VI - Front View of Catalyst Testing Units 











- 39 


Figure VII - Main Panel Board and. 
Equipment for Synthesis Gas Preparation 















-40- 


condenser K and the ballast chamber L. The tempera¬ 
ture of the boiling liquid is changed by varying the 
pressure of an inert gas in this system. 

The liquid and solid products of the synthesis 
are partially separated and collected in the two pots 
M and N. The hydrocarbons with boiling points higher 
than 100°C (at 100 psi.) are collected in a steam- 
coil- jacketed pot M; the hydrocarbons with boiling 
points between 0°C and 100°C (at 100 psi.) in the ice- 
jacketed pot N. Pressure is maintained constant in 
the unit by a back pressure regulator P. The gaseous 
products, in passing through this valve, are reduced 
from 100 psi. to about atmospheric pressure. Water 
and carbon dioxide are removed by a calcium chloride 
dryer R and a caustic scrubber S respectively. The 
volume of the residue gases is measured by a Precision 
Wet Test Meter T. 

For purposes of reduction and reactivation 
of the catalyst, and for the maintainence of a reducing 
atmosphere over the catalyst during 11 shut-downs 1 *, a 
hydrogen supply is included in the flow sheet. Hydrogen 
from a high pressure storage cylinder is discharged at 
a controlled rate and at pressures slightly above 
atmospheric through a two stage pressure-reduction 
valve. Passage of the hydrogen over metallic copper 
at 250° - 3Q0°C in the furnace J serves to remove any 


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-41- 


oxygen, while activated charcoal in the scrubber V 
preferentially adsorbs any high molecular weight 
gases^leaving relatively pure hydrogen gas. A common 
header services all units. 

(b) Description of Synthesis Equipment 

This section is not intended to give a 
detailed description of all the major pieces of syn¬ 
thesis equipment used in these investigations. 

General descriptions will be given of common equip¬ 
ment and details will be given only for equipment 
that presents new design or new unique features. The 
equipment required in the preparation of the synthesis 
gas will be discussed in the Appendix. Special 
features incorporated into the design to control the 
experimental conditions - temperature, pressure and 
rate of flow - will be dealt with in the next sub¬ 
section on w Instrumentation and Controls. 9 *. 

Since the Fischer-Tropsch process involves 
the synthesis of gas under pressure, two types of 
storage are required - a low and high pressure storage. 
A conventional water-seal type gasholder D serves as 
the low pressure reservoir (Figure V) and a pressure 
tank E as the high pressure reservoir. 

Gasholder D has a capacity of approximately 
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-42- 


to maintain a gas pressure of about one inch of water* 
Two safety devices, in the form of upper and lower 
limit switches, have been incorporated into the design* 
The lower limit switch consists of a "microswitch’* 
and is attached to the outer fixed drum of the gas¬ 
holder. It is actuated by the floating drum when it 
reaches its lower position and breaks the electrical 
circuit of the compressor motor, thus eliminating the 
possibility of water being drawn accidentally into 
the gas compressor. The upper limit switch consists 
of a microswitch attached to the top of one of the 
gasholder guides and is actuated by the floating drum 
when near the full position. A warning bell is sounded 
and steps are taken to reduce or discontinue synthesis 
gas production. 

The high pressure reservoir E consists of a 
standard compressed air receiver, approximately 15 
inches in diameter and 60 inches long, of about 6 cu. 
ft. capacity. The pressure is indicated by a Bourdon 
tube pressure guage and is maintained constant to 
within 0.5 to 1 psi. by means of an adapted Mercoid 
Pressure Control operating on the compressor motor 
circuit. 

The gas is compressed by a small single- 
acting compressor with a 2 inch stroke and a lj inch 
piston. It is fitted with a solid plunger-type 



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piston, an external packed gland, and poppet type 
valves. There are no piston rings. Lubrication is 
supplied by gravity through the intake valve. The 
compressor, driven by a J h.p. 1700 r.p.m. induction 
motor through a belt drive, operates intermittently, 
always under pressure, transferring the gas from the 
gasholder to the pressure storage in response to the 
mercoid control. A check valve in the discharge 
line allows the compressor to be unloaded and prevents 
leakage from the high pressure storage. 

The AlgOg drier F is a two foot length of 
2 inch standard iron pipe, filled with dehydrated 
alumina and is wound with a heating coil, the whole 
being encased in Q5% magnesia pipe insulation. Water 
is removed from the synthesis gas at room temperature. 
The heating coil permits the reactivation of the alumina 
at a temperature of 300°C. 

The six converter units, identical in both 
design and construction, are connected to common 
headers but isolated one from the other so that the 
operating conditions may be varied in each. They are 
constructed of standard-weight, butt-weld iron pipe 
and standard malleable iron pipe fittings. Each 
unit consists of principally three sections: 

(1) the catalyst chamber (2) temperature control 
system (3) liquid product recovery system. A 


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drawing of the converter and its accessories is shown 
in Figure VIII. 

The catalyst tube A is a | inch standard 
pipe 27 inches long. Screwed on the upper end is the 
catalyst chamber head B, machined from a 2 inch 
hexagonal steel bar. A thermocouple well C of j inch 
steel tubing, screwed into the head, extends the 
length of the chamber. Provision is also made in the 
head for the introduction of the catalyst into the 
converter. A piece of 3/8 inch pipe D with a fine 
wire screen welded to its upper end, is screwed into 
the lower end of the column and serves as a support 
for the catalyst. The gas enters the unit through a 
i inch pipe E and passes down through the catalyst 
bed. Connection is made to a Bourdon-type pressure 
guage by means of a J inch tee which also serves as 
a connection for the gas feed line. 

A heating jacket F, 20 inches long of 22- 
inch standard pipe with ^ inch steel plate ends^is 
welded to the catalyst tube. A liquid, heated 
electrically by a resistance coil encircling the jacket, 
is kept boiling within the jacket maintaining the 
catalyst tube at a constant and uniform temperature. 

The boiling temperatures are controlled by the pressure 
in the heating jacket. The temperature of the liquid 
i 3 observed by means of a thermocouple inserted in the 


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-46- 


thermocouple well G. The liquid level is indicated 
by an open end sight gauge H. When necessary the 
valve J shuts off connection between the chamber and 
the gauge, allowing pressure or vacuum to be built 
up in the former and allowing the latter to be drained. 
To prevent excessive heat loss, the jacket and 
catalyst column are covered with 85^ magnesia pipe 
insulation K with asbestos cement at each end. A J- 
inch pipe L with its upper end enclosed by a water 
condenser M is connected to the jacket and serves as 
a reflux column for the boiling liquid. At the upper 
end of this column is a Fenwal thermoswitch U which 
breaks the heating circuit if the hot vapours rise 
too high^in case of failure of the cooling water 

supply. Here also are connections to: (1) a compound 

» 

Bourdon tube pressure gauge (range of 30 in. Hg vacuum 
to 60 psi.) (2) a ballast tank made from an 18 inch 
length of 3 inch pipe and (3) a natural gas header 
common to all six units and connected to a high 
pressure gas storage. The liquids used in the con¬ 
verters depended upon the temperatures required, and 
were tetralin, dowtherm and a paraffin oil of initial 
boiling point of 360°C (700 mm Hg). 

The recovery of liquid products is accom¬ 
plished in two stages - in steam-heated and ice- 
jacketed condensers R and S resulting in a rough 


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-47- 


separation of heavy waxes and low boiling hydrocarbons. 
Both pots made from 2j inch pipe, 7 and 8 inches long, 
are only slightly different in design. Condenser R 
has several turns of ^ inch copper tubing encircling 
it and is insulated with 85$ magnesia pipe insulation. 
Steam passing through the copper tubing maintains the 
temperature at approximately 100°C. Both pots are 
equipped with J- inch drain valves to permit the 
removal of the liquid products. Pipe unions, connect¬ 
ing the pots to. one another and to the adjoining 
equipment, enable the removal of either one of the 
condensers. 

The residue gases are bled off continuously 
by the Cash back-pressure control valve T. These are 
standard Cash model 1935, size in which the 
makers replaced the usual bronze seat by a metal-com¬ 
position seat. The control desired, from 100 - 0 
psi. gauge, and the small quantities of gas flowing 
necessitated experimentation with the seat. The 
material known as ”vulcanized fibre’* was found most 
suitable, giving perfect control without drifting 
and complete shut-off. It is probable that the valve 
floats continuously when passing the small amount of 
gas involved. 

The expanded gases are treated for removal 
of water and carbon dioxide, the residue gases after 


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measurement by a standard Precision Wet Test Meter 
being discharged to the atmosphere. Water is adsorbed 
in calcium chloride in Schwartz ground glass stoppered 
U-tubes; carbon dioxide is removed in a standard 
potassium hydroxide solution contained in a fritted 
glass type gas washing bottle (500 cc). Two driers 
and two scrubbers in parallel, suitably connected by 
stop-cocks so that either drier or scrubber can be 
used, make up this phase of the system. A continuous 
gravity-type gas sampler (not shown on the general 
flow sheet), placed immediately before the gas meter, 
gives a representative sample of the residue gases. 

The rate of sampling is regulated by a capillary placed 
in the liquid discharge. A 10$ NagSO^ and 10$ HgSO^. 
solution is used as the confining liquid. 

Saran tubing (a vinylidene chloride plastic) 
is used for connections betn/een the various pieces of 
the equipment. Its strength (at low temperatures only) 
and its flexibility make it an ideal conduit particu¬ 
larly where many short circuitous leads are required. 
Saran tubing and fittings are used to connect together 
the header, the flowmeter, the mercury manometer, the 
control valve, the catalyst column and the- pressure 
gauge in the high pressure synthesis gas stream. 

They also form an integral part of the temperature 
control system, connecting the methane leader and the 
ballast tank to the main assembly. 


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-49- 


(c) Instrumentation and Control 

The electric power required for operation 
is supplied to a main panel board and from here to 
the individual units. The instrumentation of the 
main panel board is shown in Figure IX (a). Power 
from a 110 volt line passes through a two pole line 
switch A to the various units. A fuse B inserted in 
the line protects the power supply. Across this 
supply and in parallel are a light C and a relay D 
which together serve as an alarm system. When the 
power is on, the light glows and the relay is 
actuated, opening the battery circuit containing the 
bell E. A power failure causes the light to go out 
and the bell to ring. The other bell F is common to 
all six convertors and rings when the automatic 
temperature and pressure controls on any of the units 
fail to function properly. The latter alarm is also 
connected to a microswitch G, which is actuated when¬ 
ever the gasholder for the synthesis gas rises too 
high. 

The thermocouple system is shown in Figure 
IX (b). The cold junction H, the constantan header 
K, and the potentiometer L are common to all units. 
Individual copper leads are used for each thermo¬ 
couple. These are connected to the main circuit 
through a pair of single gang eleven position rotary 
switches M and H. 



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and alarm system. (b) Thermocouple system. 


















































-51- 


One rotary switch connects the thermocouples giving 
the catalyst bed temperatures; the other, the jacket 
temperatures. Each set of thermocouples (R and S) 
is connected as shown. 

Each individual unit is designed to maintain 
certain predetermined operating conditions continuously 
for long periods of time. There are three main opera¬ 
tional controls: 

1) Automatic control of synthesis gas flow. This 
flow must be steady and easily measurable. 

2) Temperature control - the maximum range of 
deviation in catalyst temperature is 15 centigrade 
degrees. 

i 

3) Pressure control - a constant pressure of 
100 psi. must be maintained in the reaction system 
and at the same time the residue gases must be bled 
off continuously. 

These controls will be discussed in turn. 

1. Flow Control 

The chief difficulties of automatic flow 
control arose as a result of the extremely small 
flows encountered. A gas space velocity of 150/hour 
(normally used in the Fischer-Tropsch synthesis) 
corresponds to an absolute flov/ of only about 0.4 
cc./sec. for the volume (70 cc.*s) of catalyst space 





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used, when measured at the operating pressure of 
100 psi. gauge. The literature reveals no previous 
attempts to use automatic flow control on such low 
rates. 

For automatic control, there must be a 
primary measuring instrument which will respond 
quickly to changes in the rate of flow. This 
response must then operate a control instrument to 
correct the flow. In this case, the measuring 
instrument is a capillary type pressure flowmeter. 

A diagrammatic drawing of the latter, together with 
a description of its design and calibration will be 
shown in the Appendix. It is sufficient at this 
point to state that the rate of gas flow is indicated 
by a pressure drop across the capillary, this being 
measured by a mercury manometer. 

The instrumentation and wiring is shown in 
Figure X (a). The two mercury arms of the Merriam 
3-contact manometer A are connected to an electrical 
circuit operating a small electric motor B. The 
latter is a 1/50 H.P. reduction gear motor, induction 
type, delivering 29 r.p.m. on the output shaft. The 
driving mechanism of the valve stem is linked to the 
motor shaft by a 24 to 1 worm and worm wheel, the 
valve drive rotating at 1.2 r.p.m. 


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- 55 - 


The motor, the control valve, and the flow¬ 
meter are all mounted on an angle iron, which is in 
the form of an inverted L. Their spatial relation¬ 
ships are indicated in a photograph - Figure XII. 

The valve and mechanism are illustrated in 
Figure XIII. The brass valve drive shaft B is mounted 
in a steel bearing block C. Female threads (24 to the 
inch) at its lower end connects the drive shaft to a 
brass thrust shaft D. The latter, with one of its 
hexagonal sides bearing against the brass bar S, is 
prevented from rotating. For every revolution of the 
drive shaft, there is imparted to D a vertical move¬ 
ment of approximately 1/24 of an inch. This is in 
turn transmitted to the steel valve stem F. The 
needle of the latter has a very small taper of only 
0.034 (inches /inch), thus permitting fine control. 
There is, however, a definite lag (fixed by means of 
the threaded nut on top of the valve stem) between 
the action of the motor and the response of the valve 
stem. This lag improves the control characteristics 
of the valve by matching the lag in the flowmeter- 
manometer system. A gland G and the packing H keep 
the valve pressure-tight. The valve body K is 
machined from a lj inch hexagonal brass bar. The 
synthesis gas enters at L and leaves at M, making the 
valve self-cleaning. 


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- 58 - 


There is provision made to prevent the 
valve from binding in either the extreme open or 
closed positions. The drive shaft B operates a brass 
cam N. This cam is machined from a !-§- inch hexagonal 
brass bar and has internal threads, four to the inch, 
fitting similar threads on the drive shaft B. Rotary 
motion'is prevented by the brass bar E. As the drive 
shaft turns, the cam moves up or down. At either 
extreme of its travel, the cam actuates the microswitch 
P, breaking the motor circuit and ringing the warning 
bell. 

The motor operating circuits are fed through 

(F vc^.Xol') 

an operating switch C -"a 3 gang, 6 pole, rotary type. 
Only three poles are used, each alternate pole being 
open. In two of these three switch positions, the 
motor is operated manually to either open or close the 
valve. In the third position, the relays D and E and 
the manometer A are brought into the circuit and the 
motor is operated by automatic control. These revers¬ 
ing relays are connected such that the circuit through 
one actuates the field of the other. Thus when one is 
open, the other is necessarily closed and short circuits 
are prevented. A fuse further protects the motor and 
circuit. 

Considerable difficulties have arisen with 


the control value, due largely to the smallness of the 


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- 59 - 


flows involved. The slight coasting of the motor, the 
lag in response of the mercury manometer, the inertia 
of the mercury are all important factors when dealing 
with such low rates of flow and were overcome in 
part by test and experience. 

Upon actual trial runs, it was found that 
the maximum allowable pressure drop across the control 
valve were only about one pound per square inch. If 
this value we^fc exceeded, the mercury in the manometer 
started to hunt i.e. it continued to oscillate over a 
range of several inches. With a high pressure drop 
across the valve, the valve stem operated in a nearly 
closed position, resulting in a proportionately large 
percentage of throttling per increment of vertical 
motion. If the pressure drop was less than one pound 
per square inch, however, the control was excellent. 

The valve stem quickly found, and remained at, the 
equilibrium position corresponding to the existing 
flow and pressure. 

It became clear that satisfactory automatic 
flow control required that the pressure variation in 
the supply reservoir be not more than a pound per 
square inch. This was accomplished by means of pressure 
actuated, position relays located in the relay circuit 
of a magnetically operated compressor starting switch. 
The movement of the Bourdon tube (in an adapted mercoid 




if 


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- 60 - 


pressure control gauge attached to the reservoir) is 
magnified and translated into a lateral motion of a 
metal contact strip. The latter moves between two 

f 

electrical contacts which, in turn, are connected 
through two relays to the magnetic switch relay. As 
the pressure in the reservoir drops, one contact is 
made starting the compressor. As the pressure is 
raised, the other contact breaks the circuit, stopping 
the compressor. The supply pressure was maintained 
constant within half a pound per square inch. The 
service required of the compressor motor is a difficult 
one. A future design would involve improvements in the 
flow control valve and continuous compressor operation 
with control by an unloading device. 

2. Pressure Control 

In normal operation, the pressure in the 
system must be kept at 100 psi. gauge. This is done 
using a Cash type 1935 back pressure regulator. This 
can be adjusted to maintain the desired pressure dif¬ 
ferential between the system and the discharge - in 
this case 100 psi. Other pressures can be used but 
only if the same for all converters. Improvement in 
the flow control value to the extent necessary to 
permit wide variations in pressure between converters 
does not seem possible. Back pressure regulators 






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- 61 - 


between the synthesis gas header and the individual 
units would be the solution. 

3. Temperature Control 

Temperature control is obtained by the 
method devised by Downs. The temperature of the 
catalyst tube is kept constant by an outer jacket of 
boiling liquid. Three liquids have been used - dow- 
therm when operating at 250°C, tetralin at 200°C and 
for activations, a paraffin fraction having an initial 
boiling point of 360°C. The electrical heating 
circuit is shown in Figure X (b). The outer jacket 
is heated by a resistance coil K, (total resistance 
of 20 ohms) which is connected in series with a 
rheostat* L. The heat input to the jacket is manually 
controlled to be slightly above that required to keep 
the fluid boiling, the vapors being condensed in a 
water-jacketed condenser. Connected to the latter is 
a ballast chamber whose purpose is to eliminate surges 
due to changes in the vapor position. The volume of 
the ballast is about ten times that of the condenser. 

The temperature of the boiling liquid is 
controlled by varying the pressure in the condenser 
system. An inert atmosphere of methane is maintained 
above the liquid. Pressures greater than atmospheric 
are obtained from a high pressure methane storage; 







, 

, 

. 

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- 62 - 


vacua from a water pump. It is possible to vary the 
pressure in the system from 26 inches of mercury 
vacuum to 40 psi. gauge. For dov/therm this corres¬ 
ponds to a temperature range of 180°C to 330°C, and 
for tetralin 130° - 280°C. 

There are two thermocouples in each con¬ 
verter - one in the boiling liquid, the other in the 
catalyst bed. The latter may be adjusted to give 
temperature readings throughout the whole length of 
the catalyst bed. 

An alarm mechanism is incorporated into the 
electrical heating circuit to prevent the liquid from 
boiling out of the jacket. This may arise from one of 
two causes: the stoppage of the water flow or the 
supply of too much heat to the boiling liquid. A 
reversible thermal switch M in the top of the con¬ 
denser is set to break contact in the heating circuit 
at 70°C. If any hot vapors reach the top, the 
thermoswitch opens breaking the circuit. The light 
N goes off and the bell rings. Thus in the event of 
water failure, the action of the thermal switch would 
prevent any undue temperature rise and, by intermittent 
action, maintain approximate temperature control. 

There is no warning bell if the heating coil 
burns out but there is an increased brightness in the 
signal light. 


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. 







IV CATALYSTS AND THEIR PREPARATION 


In these investigations five catalysts in 
all were tested. Except for two of these, very little 
is known of their preparation. Two catalysts, a 
Co-Th and a Ni-Mn, were prepared by the Harshaw Chemical 
Co. of Cleveland, Ohio, and a third was an ammonia iron 
base catalyst supplied by the Alberta Nitrogen Products 
Ltd. of Calgary, Alberta. The other two catalysts, 
one of pure iron and the other iron-copper, were pre¬ 
pared by an under-graduate student (29) as part of 
another project, following the procedures laid down 
by the U.S. Bureau of Mines. 

The Bureau of Mines No. 10 Iron catalyst was 
prepared according to methods developed by the U.S. 
Bureau of Mines. Two solutions were made up separately 
at 70°C. Solution I consisted of 1012 grams of 
C.P. FeCNO^Jg* SHgO dissolved in 3 litres of distilled 
water; solution II was 571 grams of C.P.K 2 CO 3 dissolved 
in a litre of distilled water. With both solutions at 
70°C, solution II was added slowly to I over a period 












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- 64 - 


of 20 minutes. The temperature of the mixture was 
to be maintained at 70°C throughout the preparation. 

The slurry was made up to 6 litres, the supernatant 
liquid decanted. The slurry was again made up to 6 
litres, the supernatant liquid again decanted. This 
was to be repeated until the nitrate concentration was 
less than 1 part in 16,000 as indicated by a 
diphenylamine test. Nitrate in larger concentrations 
turns a diphenylamine solution a distinct blue. Accord¬ 
ing to instructions sixteen decantations should have 
been sufficient but, in practice, even after thirty 
decantations, the wash water gave a weak nitrate test. 

At this point washing was considered complete. 

The precipitation and washing was carried 
out over a period of a week, during which time the 
temperature of the slurry may have varied over a range 
of 10 - 15 degrees. It is thought that this long 
period of digestion may have had a detrimental effect 
upon the catalyst. 

The slurry was filtered in a large Buckner 
filter and washed several times on the filter paper. 

The cake was placed upon a porous plate and allowed to 
dry slov/ly at room temperature for five days, open to 
the atmosphere. It was then placed in an electric 
oven. The temperature was raised slowly to 150OC over 
a period of five hours and held for an additional 24 


. 

' • -i. ' j°OV d:<i tiznl&uctlu$i od c;i 

. '•id'll 3 o . 

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fci . , I 

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so . ■ ■ . • 


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- 65 - 


hours, The dried catalyst was ground to pass through 
a 50 mesh sieve. A yield of 193 grams was obtained. 

Nine grams of small flake graphite was added as a 
lubricant and the catalyst was pelletted into small 
tablets 7/32 inches in diameter and 3/32 inches thick. 
The graphite has no catalytic action; it is inert. 

The second catalyst. Bureau of Mines No. 24 
Fe-Cu, was prepared by the co-precipitation of Fe(0H)g 
and CuCO^ from a sulphate solution with KgCO^. It 
was prepared in a manner almost Identical with that of 
the iron catalyst above. Similar solutions were used, 
the only difference being that solution I with the 
same iron concentration had CuSO^ added to give an 
Fe-Gu ratio of 4:1. Precipitation and washing was 
the same except that the slurry was blown 10 - 15 
minutes with air before each decantation. Some of the 
iron is oxidized to the ferric state. Sixteen decan¬ 
tations were performed. The catalyst was mixed with 
graphite and pelletted. 

Nothing is known of the two Harshaw catalysts, 
A5 and A124, except that cobalt and nickel are the 
bases with thoria and manganese respectively as pro¬ 
moters. The pellets were In the form of cylinders, 

3/32” diameter and 1/8 1 ’ long. 

The ammonia catalyst Is prepared by fusing 
iron oxide, prepared from "drum scrap" steel sheet. 


, • 


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il ' r . • '4-. • ... . . . 

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- 66 - 


with suitable promoters, crushing and screening the 
resultant mass to J” - 3/8” mesh. The exact procedure 
is not known. The following analysis of this 
ammonia catalyst was supplied by the maker: 


Si0 2 - 1.4/ 

MgO - trace to 

0 .2/ 

K 2 0 - 1.7/ 

CuO - trace to 

0 .2/ 

A1 2 0 3 -1.7/ 

Fe - 67.7/ 



For present purposes, this catalyst was crushed again 
and that portion retained between 6 and 10 mesh sieves 
tested as a Fischer-Tropsch catalyst. 


- 

, 

. 


■ . - 'j V ■ 

. . 

- 







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. * . 

- 








- - 

V 


-* 









, •• . . ■ 







V ANALYTICAL METHODS AND OPERATIONAL TECHNIQUES 


The procedure followed in testing the 
catalysts was based primarily on the U.S. Bureau of 
Mines technique. These methods were developed 
empirically and slight deviations are permissible 
provided that a careful record is kept at all times 
of the experimental conditions. In general* the 
methods of handling the iron type and the cobalt type 
catalysts differed considerably. 

After the units had been tested and the 
leaks reduced to a negligible quantity* the catalyst 
chambers were filled with catalyst pellets, forming 
a column approximately 16 inches long and 0.6 inches 
in diameter. In some cases porcelain chips were used 
to support from below and cover the top of the 
catalyst bed* primarily to insure uniformity of 
temperature over the length of the catalyst column. 



: . . . .. 




V 






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-68- 


Reduction and Conditioning of the Catalyst 

The system was first flushed with hydrogen 
and the rate of flow adjusted to give a space velocity 
of 20 - 25/hour. (Space velocities are based on the 
volume of the empty catalyst chamber, not on the 
actual volume of the catalyst). In the first experi¬ 
ments, a slo?/ stream of methane passing through the 
outer jacket constituted the heating medium. The 
heat supply was controlled manually with a rheostat. 
The temperature of the catalyst bed was raised quickly 
to 100°G and then slowly over a period of 20 hours 
to 360° - 380°C. During this time, the jacket temp¬ 
erature was kept 20 - 30 centigrade degrees above the 
catalyst temperature, insuring the proper rate of 
heating. Reduction was completed by holding the 
catalyst temperature at 360° - 380°C for 4 hours. 

There were two difficulties encountered in 
the use of a methane heating medium. First, it was 
difficult to raise the catalyst temperature at a 
uniform rate and secondly, there was a considerable 
temperature differential over the length of the 
catalyst column, the top and bottom portions being 
30 - 40 centigrade degrees cooler than the middle. 

For these reasons, in the later experiments, a high 
boiling point liquid was used in the outer jacket as 
the heating medium. This liquid was the residue 







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- 69 - 


obtained after distilling off all the lighter fractions 
(up to 375°C) from a gas oil or petrolatum. 

The conditioning procedures for iron and for 
cobalt catalysts were quite different. In the former 
case, after reduction, the temperature was reduced to 
220°C and synthesis gas at 100 psi. and space velocity 
of 150/hr. was admitted, replacing the hydrogen. The 
temperature was adjusted to give a contraction of 13$ 
(20$ in the case of a water gas having a C 0 :H 2 ratio 
of 1:1)* Yftien it became steady at this value, the 
temperature was raised slowly over a period of 48 
hours to 250°C or to a temperature such that the con¬ 
traction was approximately 40$. The catalyst was now 
completely conditioned and ready for operation. After 
a cobalt catalyst had been reduced, it was allowed to 
cool to 160°C and synthesis gas admitted at one 
atmosphere and space velocity of 100/hour. The temp¬ 
erature was adjusted to give 20$ contraction and held 
for 4 hours. The temperature was raised until 30$ 
contraction and again maintained for 4 hours. This 
was repeated until a 60$ contraction was reached. 

The most active cobalt catalysts operate at 

-x $ contraction = 

Vol.of Feed Qas - Vol.of COg - free Residue Gas ^ . 


Vol. of Feed Gas 



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- 70 - 


approximately 190°C. The synthesis gas pressure was 
raised to 100 psi. and production started with an 
initial contraction of about 70^. 

Method of Operation 

When the automatic controls were function¬ 
ing properly, the operation of the process (as 
distinguished from the analytical work involved) 
required comparatively little attention. All the 
units were started on production Sunday midnight and 
operated continuously until Saturday morning. During 
week-ends, the temperature of the catalyst was lowered 
15 centigrade degrees and a slight but positive flow 
of hydrogen maintained over the catalyst. A normal 
weekly run was approximately 125 hours. At the end 
of the week, the liquid and solid hydrocarbon products 
were removed from the pots, weighed, and stored for 
analysis. 

Iron catalysts were operated with a gas 
space velocity of 150/hour for the first four weeks 
and 100/hour thereafter. Cobalt catalysts utilized 
a space velocity of 100/hour throughout their whole 
life. 

Good iron catalysts maintain their activity 
for periods of months, while cobalt catalysts become 
slowly deactivated (noted by a decrease in the per- 





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- 71 - 


centage contraction). Low temperature reactivations 
of the latter were carried out periodically, usually 
once a week. The pressure was allowed to fall to 
atmospheric and the synthesis gas replaced by hydrogen. 
The temperature was raised 15 degrees above operating 
temperature and hydrogen passed over the catalyst at 
a space velocity of 200 - 300/hour for two hours. 

The unit was put on production again by cooling to 
operating temperature and replacing the hydrogen by 
synthesis gas at 100 psi. 

Iron catalysts are never reactivated. 

Aside from the analyses, the work of the 
operator normally consisted of the following: 

(a) the preparation of the synthesis gas, (b) a 
periodic checkup of the recovery system, especially 
with regards to the operation of the scrubber and the 
residue gas proportional sampler, (c) check on the 
proper functioning of the automatic controls, and 
(d) periodic readings of the experimental conditions. 

In the project's initial stages, however, considerable 
difficulties were encountered in setting up the 
various operational controls (particularly in the 
regulation of the gas flow) and this, together with 
the maintenance of the equipment, required a large 
part of the operator's time. 










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- 72 - 


Flowmeter readings were recorded every hour 
(and the contraction calculated) while temperature 
and pressure readings were taken every three or four 
hours. By means of these and other operating data, 
it was possible to follow the progress of the catalyst 
testing and to note any changes in the experimental 
conditions. A sample operating sheet is shown on the 
next page. 

Analyses and Material Balances 

Examination of the flowsheet indicates one 
feed and three product streams. The synthesis and 
residue gases flowed continuously while the light and 
heavy liquid products were removed from the ice- 
jacketed and steam-jacketed pots once a week. Overall 
material balances, therefore, had to be based upon at 
least a week’s operation. 

The synthesis gas was analyzed once every 
two or three days in a standard Burell Gas Analysis 
Apparatus. The percentages of COg (by KOH), Hg and 
CO (by oxidation over CuO) were determined directly, 

Ng by difference. A careful check was kept on the 
H 2 :C0 ratio which ideally is 2;1 but in actual practice 
ran slightly higher, around 2.03. 

The residue gas contained water vapor, COg, 
hydrocarbons (CH 4 , CgHg, & 3 Hq), Ng, and unconverted 



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Exp*t No. 
Catalyst 


— 2. 


tore Fe (_%■«* M ' * 
9 !• fc ^ • 


OPERATING SHEET 

-FRZ-T-- 


Date: 


1 /h' 


i 

Time 

B AM 

9 

10 

11 

12 

1_PM 

2 

3 

4 

5 

6 

7 

8 

9 

10 

11 

12 

1 M 

2 

3 

4 

5 

i 6 

7 

tressures 

























Reactor D s ^-* 

gauge 

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Barometer 

Tot 







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lox 



lox 



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TEMPERATURES 




















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Catalyst 1 

141 







att 




141 



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Catalyst 2 

t.4£ 



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144 




x(A 



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Catalyst 3 

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XiN 




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Jacket °C 

24£ 


l 

245 








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144 



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Gasmet er °C 

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piormeter L 

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” Total 

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Reactor No. - S 

NoMinal Pressure - t«=c pA. 

Nominal Temperature - 2 . 4 , 5 'cl 

.Nominal Plow Rate - s. Ht 


Notes: 


Notesi 


Notes: 




























































































































































! 




















- 74 - 


Hg and CO. The water was removed by a CaCl^ U-tube 
drier, and determined by weighing. It was necessary 
to weigh these driers only once a week since the 
water content of the residue gases was comparatively 
low. The C0 2 was removed by a caustic scrubber, and 
determined by titration. The scrubber liquid con¬ 
sisted of 250 cc’s of a 3N solution of KOH. Only 
half of the total strength of the KOH could be 
effectively utilized since, beyond that point, some 
COg passed unabsorbed through the scrubber. An 
aliquot part (10 cc’s) of spent solution was titrated 
against IK HC1 to both the phenolphthalein and methyl 
orange end points. The difference represented the 
molar equivalent of COg. 

A proportional sampler collected a daily 
2-litre sample of carbon dioxide-free residue gas. 

This sample was analyzed in a Burell Apparatus for 
co 2 , Hg and CO (over CuO), hydrocarbons (burning with 
oxygen over a hot platinum wire) and Kg (by difference). 
The hydrocarbon content was expressed in terms of 
methane and ethane although it was realized that some 
higher hydrocarbons may have been present. 

The liquid products collected each week 
were allowed to accumulate until in sufficient 
quantities to be analyzed. In both of these fractions, 
considerable water was present which was removed in a 


■ ' ... ... ■ ■ ..v: 


/ . • j O • : . ; 


* 





. 







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iii GO -B 

■ 

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r * • 




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: ■ • C .. ■ 1 : . 

■ ■ 1 ’ . . v 




- 75 - 


separatory funnel. The liquids were filtered to 
remove solid impurities. 

The water in each case was tested for the 

following: 

a) acidity - hy titration with a weak solution 
of NaOH. 

b) a distillation to detect the presence of 
alcohols and other low boiling fractions, 

c) density - accurately by density bottles. 

The oil fractions collected were tested 

for: 

a) density 

b) aniline point - to determine the degree of 
unsaturation. 

c) refractive index. 

d) an A.S.T.M. distillation, modified because 
of the small quantities involved. 

The wax fraction was tested only for density. 


•' . : ■' ; «. i . .... 

: j .. .... . ■ .i. >. '. ■ 


. 


, 




. U- • ;i.:' v/ i 


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- 76 - 


VI EXPERIMENTAL RESULTS 


Since the present investigation involves 
the testing of specific catalysts, each must be 
reported separately with respect to treatment and 
results. Five catalysts were tested: 

1) Pure iron 

2) Iron-copper 

3) Promoted iron (ammonia) 

4) Cobalt-thoria 

5) Nickel-manganese 

The reduction, conditioning, behavior, and yields 
will be discussed for each catalyst. 

The feed or synthesis gas, common to all 
units, was found to have the average composition: 

CO 2 0,3% by volume 

Eg 64.4^ 

CO 31.5 fo 

Ng 3,8% 

Hg/CO 2.04:1 



.... . . J ' . ■ -iq ' 

v ■•.: . . "’0 i M 

■. ■■. ■' ; : , ; .'J .0 Li;i; ■ 

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; H 

• : 

■ 

. , 

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-• ' 





, 













• . 







- 77 - 


This gas was used in the testing of all catalysts and 
the daily variation was on the average not more than 
about 2/6. 

During the coiirse of the experimental runs, 
it was suspected that the feed gas may have contained 
some catalyst poisons, either oxygen or sulphur. 
Sensitive tests failed to detect the presence of 
either. In testing for oxygen, the feed gas was pas¬ 
sed over white phosphorus freshly distilled and 
deposited from the red allotrope. Ho luminescence * 
was visible indicating the absence of oxygen in 
quantities greater than one part in a million (20). 

In testing for sulphur, it was assumed that, if present, 
sulphur would occur as hydrogen sulphide. A measured 
quantity of gas (several cubic feet) was passed through 
a caustic scrubber, the solution acidified and titrated 
with an 0.005 N-Ig solution using starch as an indica¬ 
tor. Close agreement of the titration of the sample 
and a blank indicated a negligible amount, at the most, 
of sulphur in the gas. 

1. Iron Catalyst (Bureau of Min e s #10) 

Source of catalyst - prepared at the University of 
Alberta. 

Weight of catalyst - 71,5 gms. 

Volume of chamber occupied by catalyst - 62.2 cc. 





■ -V: uOi;^ Vi-V/ tfCil 

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. 

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2>dr: p. &£ . . ' v : ' . 

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-78- 


Reduction ; The catalyst temperature was brought up 
slowly over a period of 20 hours to 360 - 380°C in 
an atmosphere of hydrogen. This temperature range 
was maintained for 4 hours. Heating was by transfer 
across a slow stream of methane passing through the 
outer jacket. Although the middle three quarters of 
the catalyst column was at 380°C the top and bottom 
portions were as much as 50 degrees lower. 

Conditioning : On reducing the catalyst temperature 

to 225°C and admitting synthesis gas- at 100 psi. gauge, 
no apparent contraction occurred. The temperature 
was raised in 5 degree increments over a period of 
48 hours to 250°C. The conditioning then proceeded 
as follows: 


Temp. 

Percentage 

Total hrs. 

oc 

Contraction 

operation 

250 

13 $ 

78 

254 

18 $ 

86 

260 

20% 

92 

268 

Initially 30$ increasing 

to 38$ 

Operation: 

In order to maintain the necessary con- 

traction. 

operation was carried on at 

268°C, even 

though thi 

s temperature is higher than 

that recommended 


by the Bureau of Mines. Table III shows the operating 












. 

. 

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a . . . . ■ i b .. °< ; 


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r • • • ■’ t ■. •.» 

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- 79 - 


conditions and contractions for each successive 
week of testing. 


Table III 


Weekly Operation with 

the pure Iron 

Catalyst 

Week 

No. 

Temp. 

°C 

Space 
Velocity 
hrs.“1 

Contraction 

. . 

Flow 

Control 

1 


Activation 


2 

269 

150 

39 

Good 

3 

269 

150 

38 

Good 

4 

265 

150 

35 

Good 

5 

265 

150 

35-40 

Unsteady 

6 

253 

150 

25 

Good 

7 

265 

150 

35 

Good 

8 

266 

100 

55 

Good 

9 

266 

100 

52 . 

Fair 


Reactivation and Operation : Although the catalyst 
was giving the proper contractions, it was evident 
that this was due mainly to the methane formation and 
the water gas shift reaction. At the end of nine 
weeks, the catalyst was given a high temperature 
reactivation. Hydrogen at one atmosphere and space 
velocity of 20 - 25/hour was passed through the 








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- 80 - 


catalyst bed. The temperature of the latter was 
raised quickly to 360°C and held for 4 hours. 

After reactivation, synthesis gas at 100 
psi. was admitted and the unit operated at 250°C for 
two more weeks. Although contractions were high, 
there was no increase in liquid hydrocarbon yields 
and it was decided that no useful purpose would be 
served in further continuing the test. 

Yields The yields of the various products are shown 
in Table IV. 

Table IV 

Weekly Yield of Products from the pure Iron Catalyst 
gms./cubic metre of gas at N.T.F. 

Week Liquid Fraction Off - gas 

No. Heavy Light CH^ GgH^ GOg **2® 


1 Activation 


2 

03 

• 

O 

7.7 

41 

62 

w 

■w 

3.9 

3 

0.8 

9.8 

40 

43 


28.6 

4 

1.4 

9.4 

29 

48 


6.8 

5 

1.7 

9.1 

26 

48 


18.8 

6 

5.1 

5.4 

21 

11 

108 

14.8 

7 

1.4 

8.0 

31 

44 

180 

22.2 

8 


4.9 

38 

32 

153 

26.9 

9 


1.2 

35 

34 

145 

14.7 


Reactivation 





10 

0.1 

6.5 

55 

22 

222 

38.0 

11 

3.6 

5.9 

46 

24 

154 

25.4 


•* Figures are unavailable for the first few weeks since 
much CO 2 was passing through the scrubber unabsorbed. 













•+ 








- 81 - 


Analyses : Pour distinct products from the synthesis 
were analyzed namely, the residue gas, the light 
liquid fraction, the heavy liquid fraction, and the 
water. 


a) The residue gas had the following average 
composition (COg unadsorbed): 


Component 


co 2 

% 

CO 

ch 4 

°sP« 


Volume Per cent 

1S.1 

55.3 

5.4 

8.8 

5.6 

4.8 


There were no significant trends in the gas composi¬ 
tion during the course of the catalyst testing except 
that, after the high temperature reactivation, the 
gaseous hydrocarbons and carbon dioxide content 
increased slightly. 

b) The light liquid fraction analyzed as follows 

1) Density at 25°C - 0.7164 gms/cc. 

2) Aniline point - 66.9°C. 

3) Refractive index - 1.4112 

4) Distillation - see Figure XIV 

5) Odour indicates possible oxygenated com¬ 
pounds . 

6) Average molecular weight - 130. 





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- 82 - 


c) The heavy liquid fraction showed the follow¬ 
ing properties: 

1) Density at 25°C - 0.7734. 

2) Wo solid products precipitated in this 
fraction at room temperature. 

d) The water had the following characteristics: 

1) Density at 25°C - 0.9968 indicating 
practically pure water. 

2) Traces of acids: Acid normality - 0.004. 

3) Traces of a low boiling point liquid on 
distillation. 

Discussion of Results 

1) Even at the beginning of the testing, there 
were positive indications of the poor behaviour of 
this iron catalyst. These may be listed as follows: 

a) Formation of appreciable quantities of 
water - not usually expected from active iron catalysts. 

b) Low yields of liquid hydrocarbons - about 
a sixth of the yields obtained by the U.S. Bureau of 
Mines. 

c) Comparatively high yields of gaseous 
hydrocarbons indicating the methane reaction. 

d) High COg production, indicating the water 
gas shift reaction. 

e) In order to obtain the contraction 
normally expected from this catalyst, operating 









- 83 - 


temperatures 15° - 20° higher than those reported as 
optimum in the literature were required* 

There is a possibility that the inactivity 
of the catalyst may have been due to poisoning either 
by sulphur or oxygen. However, delicate tests have 
failed to reveal the presence of either in the 
synthesis gas. In the case of sulphur poisoning, un¬ 
less there is a comparatively high concentration of 
hydrogen sulphide in the feed gas (which is unlikely), 
the poisoning should take some length of time. In 
the initial stages, the literature reports that the 
liquid hydrocarbon yields actually increase. However, 
this catalyst was inactive from the very beginning. 
Initial oxygen poisoning is unlikely but a possibility. 

Some parts of the catalyst may have been 
improperly reduced. However, thi3 is insufficient 
to account wholly for its poor behavior. 

The third possibility is that the catalyst 
was originally inactive due to contamination in its 
preparation. Further, the long time of digestion 
(several days) may have affected the physical condi¬ 
tion of the catalyst, perhaps in the state of sub¬ 
division . 

2) Until the eighth week the total liquid yields 
remain substantially constant, at which time they 
dropped sharply with a corresponding increase in 


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-84- 


methane production. The few original active centres 
were apparently deactivated either by poisoning, 
carbiding or carbonyl formation. 

3) High temperature reactivation failed to 
restore the activity of the iron catalyst. This is 
in agreement with the literature. The subsequent 
high contractions are due almost entirely to methane 
formation and the water gas shift reaction. 

4) The liquid hydrocarbon products were entirely 
oil. Ho wax was precipitated. 

5) Correlation of the aniline point and the 
average molecular weight indicates that the light 
liquid product contained some unsaturated and pos¬ 
sibly some cyclic compounds. The refractive index 
tends to substantiate this. 

2• Iron-Copper Catalyst (Bureau of Mines #2 4) 

Source of catalyst - prepared at the 
University of Alberta. 

Weight of catalyst - 76.3 gms. 

Volume of chamber occupied by catalyst - 58 cc. 
Reduction : This catalyst was reduced in the same way 
as the iron catalyst described previously, i.e. at 
360 - 380°C for 4 hours in an atmosphere of hydrogen. 
The same difficulties were encountered. 





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-86- 


Conditioning : Synthesis gas at 100 psi. was admitted 
at (catalyst temperature of 223°C. The progress of 
the conditioning is recorded below: 


Temp. 

°C 

Percentage 

Contraction 

Total hrs. 
operation 

223 

0 


230 

11 

16 

237 

16 

34 

245 

20 

58 

250 

25 

62 


Despite the low contraction, it was decided 
to operate in the region of 250°C, since the litera¬ 
ture reveals that at slightly higher temperatures 
carbiding and carbonyl formation quickly deactivate 
the catalyst. 

Operation : Operation proceeded at a pressure of 100 

psi. gauge and a gas space velocity of 150/hr. The 
results are shown in tabular form below: 








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-86- 


Table V 

Weekly Operation with the Fe-Cu Catalyst 


Week 

No. 

Temp. 

°C 

Contraction 

<sf 
/0 

Plow 

Control 

1 

Activation 



2 

250 

23-25 

Fair 

3 

250 

22-25 

Fair 

4 

255 

29-31 

Fair 

5 

255 

25-35 

Unsteady 

6 

255 

30-40 

Unsteady 


The contraction is apparently temperature 
sensitive. The unsteadiness of flow during the last 
two weeks of operation obscured the contraction but 
indications point to increasing contraction. 
Reactivation and Operation : At the end of the sixth 
week, in an endeavour to improve its activity, the 
catalyst was given a high temperature reactivation at 
360°C for 4 hours. Although the resulting contraction 
was higher (58 - 60^), there was no improvement in the 
liquid hydrocarbon yield. It was concluded that the 
catalyst had been permanently deactivated. Testing 
was discontinued. 

Yields: The yields per cubic meter of synthesis gas 

of the variour fractions for each successive week are 


shown in Table VI 











. >/v,. 




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r/j 


. 



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i 



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: . /< , 






-87- 


Table VI 

Weekly Yields of Products from Pe-Cu Catalyst 
Sms./cubic metre of gas at N.T.P . 


Week 

No. 

Liquid 

Product 


Off-gas 

H 2 0 

Heavy 

Light 

ch 4 

°£= 6 

co 2 

1 

Activation 





2 

6.6 

5.8 

8.0 

11.0 

53.7 

25.3 

3 

5.6 

5.3 

9.3 

9.7 

62.6 

24.7 

4 

6.2 

7.7 

26.2 

20.1 

86.2 

23.1 

5 

5.1 

2.9 

22.4 

32.8 

89.5 


6 


3.7 

32.5 

23.1 

154.5 

3.7 


High 

Temperature Reactivation 


7 


5.5 

19.6 

40.8 

197 

28.6 

8 


8.9 

17.4 

37.6 

149 

19.0 


Analysis of Products : (a) Table VII shows the change 
in composition of the residue gas during the catalyst 
testing. 


















-88- 


Table VII 

Composition of Off-Gas from Fe-Cu Catalyst 

- Volume % - 


Week 


No. 

co 2 

CH 4 

C 2 H 6 

CO 

H 2 

H 2 

1 

Activation 





2 

4.4 

1.8 

1.3 

24.3 

63.0 

5.2 

3 

5.4 

2.2 

1.2 

24.8 

63.1 

3.3 

4 

8.7 

6.3 

2.6 

18.4 

62.1 

1.9 

5 

11.9 

7.6 

5.8 

14.0 

57.9 

2.8 

6 

20.3 

9.4 

3.5 

13.3 

51.3 

2.2 


High Temperature Reactivation 


7 

29.7 

5.8 

6.6 

4.8 

50.0 

3.1 

8 

22.8 

6.1 

6.9 

4.4 

57.6 

3.2 

(b) The light liquid 

fraction analysed 

as follows: 

1) Density at 25 

|°C - 0.7537 gms./cc. 



2) Aniline point - 63.2°C. 

3) Refractive index - 1.4189. 

4) Distillation - see Figure XIV. 

5) Odour - suggestive of oxygenated organic 
compounds• 


6) Average molecular weight - 130. 






•; -•' o. 



Vi:: O’ 


. 





- 











. 





0 ... 













-89- 


(c) The heavy liquid fraction exhibited the following 
properties: 

1) Density at 25°C - 0.7856 gms./cc. 

2) White solid at room temperatures. 

(d) The water showed the following characteristics: 

1) Density at 25°C - 0.9840 gms./cc. 

(Pure water - 0.9940 gms./cc.) 

2) Traces of acid: Acid normality - 0.004. 

3) Traces of a low boiling point liquid on 
distillation. 

Discussion of Results : 

1) The overall behavior of the Pe-Gu catalyst was 
very similar to that of the pure iron with respect 

to water formation, low yields of liquid hydrocarbons, 
high yield of gaseous hydrocarbons, high carbon 
dioxide production, and lower contraction than that 
normally expected at the operating temperatures. The 
low activity of this catalyst may be explained in the 
same manner as above. 

2) As testing proceeded, the activity of the catalyst 
decreased continuously. Table VI shows the progressive 
decline in liquid and solid product yields and the 
increase in production of carbon dioxide and gaseous 
hydrocarbons. It is clear that the reactions favoring 
the water gas shift and methane formation became pre¬ 
dominant after a few weeks 1 operation. 













o 













-90- 


3) As before high temperature reactivation failed to 
improve the activity of the catalyst. 

4) Approximately half of the condensible hydrocarbon, 
product was solid wax at room temperature. 

5) The aniline point and average molecular weight 
indicated some unsaturation in the light product. 

3. Iron base Ammonia Catalyst . 

Source of catalyst - Alberta Nitrogen Products Ltd. 
Weight of catalyst - 187.6 grams. 

Volume of chamber occupied by catalyst - 75 cc. 
Reduction : Reduction with hydrogen was the same as 

that for the other four catalysts. The temperature 
was raised over a period of twenty hours to 362°C and 
maintained for four hours. In the final stages, a 
high boiling point gas oil was used as the heating 
medium and no difficulties were encountered in main¬ 
taining a fairly constant temperature throughout the 
whole catalyst bed. 

Conditioning : Temperatures were lowered to 220°C and 

conditioning was commenced at 100 psi. gauge pressure. 

At 249°C a contraction of 3% was obtained which remained 
unchanged even with temperatures as high as 292°C. The 
test was then discontinued. 

Yields : No liquid products, either water or oil, were 
obtained. Only a small amount of methane in the residue 








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80 

70 

60 

50 

40 

30 

20 

10 

0 


































































































































































































































































































































































































































































































































































































































































































































































































































































































































































- 92 - 


gas indicated any sign of hydrocarbon synthesis. 
Discussion : This catalyst, reduced and conditioned 

as described above, has proven to be an inert Fischer- 
Tropsch catalyst. Possibly the temperatures were not 
high enough to reduce sufficiently the fused iron 
oxide mass. When this catalyst is used for the 
synthesis of ammonia, reduction is carried out at 
temperatures approximating 500°C. With the present 
equipment, this temperature would be very difficult 
to obtain. 

This catalyst is of the type used in the 
^iso^-synthesis which involves a relatively inert 
catalyst, low yields per pass, high space velocities, 
and recycling. Such a catalyst would probably be 
difficult to test in a one-pass system. 

4. Cobalt-Thoria Catalyst 

Source of catalyst - Harshaw Chemical Co., Ltd. 

Weight of catalyst - 51.4 grams. 

Volume of chamber occupied by catalyst - 58 cc. 
Reduction : The catalyst was reduced with hydrogen 

as described above by raising the temperature slowly 
over a period of 20 hours to 360 - 380°C and held for 
4 hours. A stream of methane through the jacket 
acted as the heat transfer medium. 






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- 93 - 


Conditioning : Synthesis gas was admitted at atmospheric 
pressure and space velocity of 100/hr. to the catalyst 
maintained at 161°C. No perceptible contraction was 
obtained. The catalyst temperature was raised slowly 
over a period of 175 hours to 190°C and the first 
contraction of 5$ was obtained. Over a period of 
six days, the temperature was raised to 19S, 206, 

210 and 215°C with corresponding increases in contrac¬ 
tion of 8 - 9, 10, 16 and 17$ respectively. No 
further increases in temperature were made in view of 
reports that temperatures above 215°C favor carbon 
formation and catalyst deactivation. The desired 
60$ contraction was not obtained at atmospheric 
pressure. 

Operation : Operation was begun at 216°C, a space 
velocity of 100/hr. and a pressure of 100 psi. gauge. 

A high initial contraction of over 60$ was attained 
which decreased quite sharply over a period of 40 
hours to approximately 32$ (Figure XVa). Subsequent 
operation at temperatures of 209°C and 200°C show 
the same effect of deactivation, the contraction be¬ 
ing lower throughout the operation for lower tempera¬ 
tures . 

Low Temperature Reactivation : At the completion of 
each run, usually at the end of each week, the 
catalyst was reactivated by passing hydrogen through 





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- 94 - 


the bed at temperatures fifteen degrees above opera¬ 
ting temperatures. The catalyst activity was revived. 
High Temperature Reactivati on: At the end of the 
eighth week, the catalyst was given a high temperature 
treatment i.e. hydrogen was passed through it at 350 - 
370°C for four hours. This treatment increased the 
contraction even above that obtained initially. This 
effect may be observed in Figure XV b. 

Yields: 

Table VIII 


Wk 

Ho 

Yields 

of Products 

from Co 

-Th Catalyst 

- . 


h 2 o 

Oper. 
. Temp. 
. °C 

Vol. of 
Feed Gas 
Cu.M # 

Liquid 

Product 

Light 

Off-Gas 

Heavy 

ch 4 

c 2 E 6 

co 2 

1 

Activation 





2.3 

11.3 

2 

Activation 





5.2 

19.0 

3 

215 

0^89 

20.2 

7.2 

19 

13 

4.9 

78.8 

4 

210 

0.85 

21.5 

7.2 

14 

5 

4.7 

25 

5 

• *200 

0.85 

6.6 

2.3 

13 

3 

0.5 

30 

6 

213 

0.67 

11.0 

3.3 

21 

14 


27 

7 

213 

0.47 

13.2 

2.8 

25 

5 

8.9 

46 

8 

213 

0.92 

14.5 

4.0 

41 

23 

14.6 

42 



High Temperature Reactivation 

• 



9 

200 

0.62 

17 

3.6 

15 

11 

9.1 

71 

10 

200 

0.75 

17 

2.0 

23 

6 

12.1 

63 




Measured at U.T.P 




















- 95 - 


Yields shown above are those actually obtained during 
each week's operation. Yields computed upon a unit 
volume of gas serve no useful purpose because of rapidly 
changing yields other than to show that greater yields 
per unit volume are obtained during the initial stages 
of each run when conversion is high. 

Analysis of Products 

(a) There were no significant trends in the composition 
of the residue gas during the course of the test. A 
typical analysis is shown below (Sample #6R23): 


iponent 

Volume % 

co 2 

0.5 

H 2 

57.9 

CO 

29.4 

CH 4 

6.5 

C 2 H 6 

1.9 

N 2 

3.8 


The results of the analysis of the light 
and heavy products and the water revealed: 

(b) Light Fraction: 

1) Density @ 25°C - 0.7207 gms./cc. 

2) Refractive index - 1.4093 

3) Aniline point - 74.0°C 

4) Distillation - see Figure XIV 

5) Odour - suggestive of oxygenated organic 
compounds 

6) Average molecular weight - 85. 






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- 97 - 


(c) Heavy Fraction: 

1) Density @ 25°C - 0.7668 gms./cc. 

2) This fraction was a thick suspension of wax 
in oil. 

(d) Water: 

1) Density - same as pure water. 

2) Acidity - 0.004 N. 

3) Distillation - very similar to that of pure 
water. 

Discussion : The behavior of this Co-Th catalyst dif¬ 
ferent in several respects from that of proven cobalt 
catalysts. 

1) In the conditioning at atmospheric pressure, 
the desired contraction could not be obtained even 
with a temperature as high as 214°C. 

2) Operation indicated a very short life catalyst. 
The initially high contraction dropped very rapidly 

- 20$ in 20 hours. A drop of 10$ in four days is 
normally expected from a good catalyst. 

3) The yields of liquid hydrocarbons are about a 
quarter to a fifth of that reported in the literature. 
These Ioy/ values may be explained partly by operation 
for considerable lengths of time at low contractions, 
normally the catalyst is reactivated when the contrac¬ 
tion drops from 70 to 60 per cent. During these tests 
contractions as low as 20 - 30 per cent were allowed. 







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- 98 - 


Low liquid yields account for the high gaseous - liquid 
hydrocarbon ratio in the products. 

4) A high gaseous - liquid hydrocarbon ratio was 
obtained. This may be due to the method of condition¬ 
ing. The desired 60$ contraction would not be obtained 
at atmospheric pressure even with a temperature as high 
as 214°C. Pressure operation at 216°C gave an 
immediate 60$ contraction. This stidden increase in the 
rate of reaction, as exhibited by the increase from 
17 - 60$ contraction, may have favored, to some extent, 
the production of gaseous in preference to liquid 
hydrocarbons. This is the "methane reaction" reported 
by Herington and Woodward (21). 

Low temperature reactivation restored the 
catalyst to approximately its original activity. High 
temperature treatment did not increase the activity 
much above that obtained by low temperature reactiva¬ 
tion. The relative contractions were much higher but 
the liquid yield increase only slightly. The yield 
of liquid hydrocarbons dropped sharply during the fourth 
and fifth weeks suggesting that the catalyst had been 
poisoned possibly by oxidation. Reactivations restored 
the catalyst’s activity as the yields in the succeeding 
weeks showed a gradual increase in both liquid and 
gaseous hydrocarbons. 




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- 99 - 


A definite increase in carbon dioxide produc¬ 
tion indicated a change in the catalyst favoring the 
water gas shift reaction. The high temperature 
reactivation did not improve the catalyst in this 
respect. 

This catalyst produced an oil with a much 
lov/er average molecular weight than that from the two 
iron catalysts but at the same time produced a consid¬ 
erable quantity of solid waxes. The aniline point and 
refractive index indicate that the oil is highly 
paraffinic in character. The distillation curve, the 
average molecular weight and the denisty show that 
the oil from the cobalt catalyst was more highly satura- 
ted than that from the two iron catalysts. This 
agrees with reports in the literature. 

The short life of the catalyst may be due to 
the presence of only a few highly active centres upon 
the catalytic surface. The condition may be due to 
improper reduction or improper activation. During 
operation a few centres may become deactivated by 
waxing, this effect being accentuated because of the 
small number. On the other hand, the short life may 
be an intrinsic property of this particular catalyst. 


I 


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-100 


5. The Hickel-Manganese Catalyst 
Source of catalyst - Harshaw Chemical Co. 

Weight of catalyst - 67.6 grams 

Volume of chamber occupied by catalyst - 70cc. 

Reduction : The catalyst was reduced with hydrogen at 

a temperature of 358°C. A gas oil heating medium was 

used. 

Conditioning : The catalyst temperature was lowered 

to 160°C and synthesis gas was admitted at a space 
velocity of 100/hr. and at atmospheric pressure. A 
very small contraction was detected. Temperatures 
were raised slov;ly and corresponding increases in the 
contraction were obtained. 


Temperature 

°C 

% 

Contraction 

Total hrs 
Operation 

172 

5 

5 

183 

8 

24 

198 

15 

35 

205 

23 

38 

211 

31 

42 

218 

41 

48 

230 

57 

54 


Operation : Pressure was raised to 100 psi. and opera¬ 

tion commenced at 230°C with a 73$ contraction. This 
dropped to 59$ over a period of 10 hours. 


A low 
















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- 101 - 


temperature reactivation was then carried out at 240°C. 
Hydrogen was passed through the catalyst during the 
shutdown over the week end. Operation was recommenced 
under the same pressure conditions but only 47$ con¬ 
traction was obtained. This decreased to zero over a 
period of IS hours. 

The catalyst viras given another low tempera¬ 
ture reactivation and operated at atmospheric pressure 
at 231°C. A contraction of 11$ was obtained and it 
decreased in time. Increasing temperatures to 239, 

254 and 262°G increased the contraction to 13, 20 
and 22$ respectively. These contractions however, 
decreased with continued operation. This concluded 
tests upon the Hi-Mn catalyst. 

Yields : Wo yield of liquid hydrocarbons, except one 
and a half cubic centimetres of light oil, produced 
during conditioning, was obtained. The residue gas 
analysis revealed high ethane and methane formation. 
Water and some carbon dioxide was produced. 

D iscussion : This catalyst was activated according to 

the method prescribed by the U.S. Bureau of Mines for 
cobalt catalysts. Although the desired initial con¬ 
tractions were obtained, the decrease in contraction 
with time and the extremely low yield of liquid 
hydrocarbons indicated that, operating under these 
conditions, this Wi-Mn catalyst was ineffective in 
promoting the Fischer-Tropsch synthesis. 






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- 102 - 


Low temperature reactivations failed to 
restore the activity of the catalyst for either 
pressure or atmospheric operation. The loss of 
activity may be due to one or more reasons: 

i 

1) Poisoning by oxygen or sulphur. Delicate 
tests fail to indicate either in quantities large 
enough to be detrimental. 

2) Too high a temperature employed. To obtain 
the desired contraction, the temperature had to be 
raised to 230°C. This is considerably higher than 
the optimum reported by Fischer (15) (190° - 210°C). 
The high yield of gaseous products, methane and 
ethane, with little or no liquid products also 
supports this vieif. 

3) Loss of active centres by carbonyl formation. 
Komarewsky and Riesz (23) report that nickel catalysts 
soon lose their activity at medium pressures due to 
the loss of active centres in the formation of nickel 
carbonyl. Nickel carbonyl is very volatile and thus 
removes the active centres irreversibly. 




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- 103 - 


VII SUMMARY AND CONCLUSIONS 


Five catalysts have been tested for their 
ability to promote the Fischer-Tropsch synthesis. 

Their performance and characteristics have been studied 
and discussed. Under the conditions of the tests, 
none of them has proven to be an effective Fischer- 
Tropsch catalyst. Poisoning is a possible explanation 
of their poor behavior. However, sensitive tests have 
failed to detect the presence of either oxygen or 
sulphur in the synthesis gas. The catalysts exhibit 
some signs of poisoning but the evidence is confusing 
and inconclusive. 

In the preparation of the Bureau of Mines’ 
catalysts, the digestion and washing stages extended 
over several days with possible temperature fluctuations. 
This deviation in procedure may have affected the 
activity of the catalysts. 

The percentage contraction of the synthesis 
gas in passing over a catalyst is not a positive 
criterion of catalyst preformance. In practically all 



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- 104 - 


cases, although the normal contraction was reached, 
the liquid hydrocarbon yields were much lower than 
expected. With comparatively inactive catalysts, the 
methane reaction and the water gas shift reaction 
appeared to predominate, giving high yields of gaseous 
products. 

Some difference has been found in the products 
from the two types of catalysts. The cobalt catalyst 
yielded a more paraffinic product than the iron. The 
former yielded a high 'percentage of wax as might have 
been expected. The pure iron catalyst yielded only 
oil, while the iron-copper gave some waxes. 

The testing of Fischer-Tropsch catalysts in a ^ 
dynamic system requires special operational techniques. 
These catalysts are characterized by temperature 

s 

sensitivity, low space velocities, pressure operation, 
and high sensitivity to poisoning. No difficulty has 
been found in maintaining and controlling the operating 
temperature. Initial difficulties were experienced in 
maintaining the pressure in the units constant. How¬ 
ever, this was remedied by modifying the Cash-type 
back pressure regulator, replacing the composition 
seats with a hard vulcanized fibre. The special feature 
of the experimental equipment was the use of automatic 
control on these extremely low rates of gas flow. This 
has on the whole performed quite satisfactorily. 


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APPENDIX 


A Preparation of Synthesis Gas 
B Design and Calibration of Flowmeters 
C Short-Time Catalyst Testing in a Static 


System 









.. 




i. 























* 




























- 105 - 


A - PREPARATION OF SYNTHESIS GAS 

The Fischer-Tropsch process, unlike the Ber- 
gius process, is an indirect conversion of carbonaceous 
material to hydrocarbons. This gives the former pro¬ 
cess a distinct advantage in enabling the use of a 
wide variety of raw material. All types of coal, or 
coke, can be used in preparing the synthesis gas, a 
mixture of CO and H2. The waste gases of the large 
steel industries have been suggested as a possible 
source and natural gases have been used on a small 
scale. Large scale industrial development in both 
Germany and Britain has been based on the incomplete 
combustion of coal and coke. However, production from 
natural gas, the apparent cheapest raw material on this 
continent, is still in the experimental stage. 

The simplest and most convenient method of 
preparing synthesis gas for laboratory purposes is by 
the partial oxidation of natural gas with oxygen, 














_ 

. 

. ■ - ' ■ 



:: 







. 





. 


. 


' 

\ 








i 




c 



■» 

.. 'J . " . 




- 



. 



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. •' : r 

- 










: . 

3 







« 





' ■( j ' 


* 

. 

< i '--J "0 


’ 

















- 106 - 


carbon dioxide or steam: 


CH4 + 1/2 02 v 

CO 

-*■ 2H2 

(1) 

CH4 ■+• CO2 ^— 

- v 2C0 

+ 2H2 

(2) 

CH4 -t H20 — 

A CO 

^ 3H 2 

(3) 

These reactions give 

H2:C0 

ratios 

of 2, 1, and 3 respective- 


ly. Since a synthesis gas with a 2:1 ratio was chosen 
for the present program of catalyst testing, reaction (1) 
was employed. 

The preparation of water gas is a batch opera¬ 
tion. Methane (high methane natural gas) and oxygen are 
fed simultaneously into a water-seal type gasholder, A, 
of about 10 cu. ft. capacity (Figure XVI). The rates of 
flow of each gas, measured by glass capillary flowmeters 
B and C, are carefully controlled to give a 2:1 methane- 
oxygen ratio. A high pressure storage, maintained by 
pumping natural gas from a commercial gas line, serves 
as the methane supply; the usual commercial cylinders 
were purchased to provide an oxygen supply. 

When gasholder A is full, the methane and 
oxygen supplies are disconnected. The gas mixture is 
then passed back through flowmeter C to the reaction 
chamber D. The latter is essentially a 3/4-inch quartz 
tube, 18 inches long, and heated by a Multiple Unit 
Electric Furnace, operating on 220-volt supply. A 
6-Inch catalyst bed is located in the middle of the 
tube, with 5 inches of porcelain chips at both ends. 















, 

. ' • .... • 

. 


■ A .. ■ . A" . .. d 

5 •— . ' 

. . 


I 




. ' ' 

\ 

. 


■ .1 , , 


: 5 ■ v. 11:1 ;■ i 




■ 






.... 

« 

■ A .. 

, 

■ 

- 

1 f 



107 




































































































- 108 - 


Thus the catalyst, well inside the furnace, is held, in 
its entirety, at a reasonably uniform temperature. (This 
precaution is necessary since the water gas reaction re¬ 
verses over the catalyst at lower temperatures.) The 
thermocouple well, a l/4-inch quartz tube, containing a 
Pt - Pt 10$ Rh thermocouple extends to the catalyst 
bed. Passing over the nickel catalyst at 900° - 1000OC, 
the CHq and 02 are converted to CO and Hg, with small 
amounts of C02, H20, and H 2 S. Water is removed in the 
water trap S; CO 2 and H 2 S in the caustic scrubber F. 

The caustic scrubber consists of three sec¬ 
tions: the absorption column F, and upper and lower 
storage vessels 0 and K. The first is a 12-inch length 
of 1-1/2 inch glass tubing, packed with 6-mm. diam. 
glass Raschig rings. Glass wool at the top serves to 
give an even distribution of the scrubbing liquid, pre¬ 
venting channelling. Compressed air is used to elevate 
the solution (25$ NaOH) from K to J, This liquid flows 
by gravity at a controlled rate through the scrubber. 

The synthesis gas is purified on passing counter- 
current ly through the scrubber. 

The synthesis gas, carbon monoxlde, hydrogen, 
and a little nitrogen, is stored in a water-seal type 
gasholder, G, of approximately 15 cu. ft. capacity. 

Flow is maintained through this system by a difference 


; ' , 

. , i 

• ' : ' 7 

;i i Jiiti .. I \ro ' '..-.arv' 

' -- , ■ . • 

- ■ 

. 

- 

: ■ • 

? . 

. 

... 

\ 

• - 

c 

■ 

' 

- ..... .... ■■ .. ... 

- : • ;. ' ‘ ‘ . ' ’ ... . L : .;) 'i ,' yjti'I? 

... : 

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( t ... 






- 109 - 


of pressure of 5 - 6 inches of water between the two 
gasholders. 

The catalyst used is pure nickel on porcelain, 
as developed at the University of Alberta in 1926 (la). 

It is prepared by soaking porcelain chips of 4 - 8 mesh 
for a period of 24 hours in a saturated solution of 
nickel nitrate. The chips are removed and heated 
strongly in a nickel crucible until brown fumes are no 
longer evolved. The catalyst, now NiO, is placed in the 
reaction chamber and reduced by heating slowly to 1000OC 
in an atmosphere of hydrogen. 

Oxygen and sulfur, even in very small quan¬ 
tities, are serious poisons to Fischer-Tropsch catalysts. 

Both attack the active centers, permanently deactivating 

i*eiwova\ 

the catalyst. Oxygen^\presents no serious problems. The 
reducing atmosphere in the synthesis gas furnace re¬ 
moves any excess oxygen that may be present. The stor¬ 
age and connecting lines are always under a slight 

positive pressure and any leaks would be outward. Sul- 

re moved 

fur^ however, presents greater difficulties. Fortunately, 
in the reducing atmosphere of the furnace, all the sulfur 
compounds are converted to H 2 S, which is later absorbed 
in the caustic scrubber. Complete removal of the sul¬ 
fur is essential, as even minute quantities (0.1 grains 
per 100 cu. ft. of gas is the upper allowable limit) 
can quickly poison a catalyst. 




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- 110 - 


Little difficulty was experienced in the 
manufacture of this gas. Though methane and oxygen were 
mixed in an exact 2:1 ratio, an analysis of the syn¬ 
thesis gas revealed a product slightly high in hydrogen. 
However, by increasing the proportion of oxygen in the 
mixture, the proper H2:C0 ratio was obtained. This 
ratio could be maintained with a deviation of not more 
than four per cent. 






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- 111 - 


B - DESIGN AND CALIBRATION OF FLOIMET3RS 


One of the commonest methods of determining 
the rate of flow of fluids is to measure the pressure 
drop caused by the insertion of a restricted opening 
into the line. Thus orifice and venturi meters are popu¬ 
lar industrial flow measuring devices. However, for 
laboratory work where the rate of gas flow is small, 
capillary flowmeters have proven the most satisfactory. 
Their behavior is dependable and predictable; the pres¬ 
sure drop easily measurable. 

Since the gas flow in the Fischer-Tropsch 
synthesis is measured under 100 psi. pressure, a flow¬ 
meter of sturdy construction must be employed. Two 
other features are incorporated into the design—a 
separate capillary holder which may be conveniently re¬ 
moved from the main flowmeter block; and provision for 
bypassing the gas while this is being done. 

A schematic drawing of the whole flowmeter 
is shown in Figure XVII. The main body, A, is machined 






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- 112 - 



Figure XVII - ^a'pillury Flowmeter led 






























































































































































- 113 - 


from a 2-inch hexagonal steel bar and has an overall 
length of 6 inches. In the interior of the block a 
brass capillary holder B is threaded and sealed by a 
garlock gasket. The gas passages and pressure taps are 
located as shown on the diagram. 

Three valve stem assemblies, C, D, and E 
(from l/4-inch needle valves) direct the gas flow. The 
brass needle seats directly onjfco the steel edged open¬ 
ings in the flowmeter block. The capillary holder 
chember B is closed by a threaded steel plug G, which is 
tightened with a dolly bar. Pressure taps at H and K 
are connected to a Merriam mercury manometer, which 
indicates the pressure drop across the capillary. Lead 
gaskets seal the valve stems and the steel plug to the 
flowmeter block. 

The brass capillary holder B is threaded 
snugly into chamber E. One end is notched to permit the 
use of a screwdriver for tightening. The capillary L 
(a short length of thermometer stem) is held tightly in 
place by the brass gland and packing consisting of a 
short piece of rubber tubing. 

In normal operation the bypass valve D is 
closed and the other two (C and E) open. The gas enters 
at M, passes into the hollowed section E, through the 
capillary, and discharges through outlet N. On closing 
valves G and E and opening valve D, the cep illary is 


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- 114 - 


taken out of the gas stream and may be removed and 
cleaned without interruption of gas flow to the reactor, 
manual flow control being necessary, of course, during 
this operation. 

Capillary tubing of the proper length and 
diameter had to be chosen to give a suitable pressure 
drop for normal operational flows. Govier (.19) has 
combined in one equation the various factors which 
determine the pressure drop across a capillary tube with 
square ends, through which a fluid is flowing . 

H 3 ..JA- (81pQ, + #& ) 

ZTgI>4 ' 7T 

H s pressure drop across capillary - cms. HgO 

D = diameter of capillary - cms. 

1 st length of capillary - cms. 

p - viscosity of flowing gas - poises 
= density of flowing gas - gm./c.c. 

Q, s rate of flow (under flowing conditions) 
c.c.* s/sec. 

This equation reveals several interesting 
features about capillary flowmeters: 

1) If the end effects are small, then the rela¬ 
tionship between Q, and H is linear. With the low space 
velocities used in the synthesis (of the order 0.4 c.c.*s 
per sec.), this condition is certainly satisfied. There¬ 
fore the second term in the above equation may be neglected. 



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- 115 - 


2) The quantity Q, in the equation refers to the 
volume of gas as measured under flowing conditions, 
i.e., at the average of the upstream and downstream 
pressures. Since the viscosity of a gas is almost 
independent of pressure (up to about 10 atmospheres), 
then the capacity of the flowmeter is roughly proportional 
to the pressure of the flowing gas. 

The design equation may he expressed in the 
following form: 

1 = TT-gP* (4H) 

128 ^uQ, 

In order to determine the proper length of 
capillary to he used, it was decided that synthesis 
gas flowing at 100 psi. gauge, with a space velocity of 
150/hour (or 0.4 c.c.*s/sec. at 8 atmospheres) should 
give a pressure drop of approximately 4 inches of mer¬ 
cury. All the variables except 1 and D (and u in the 
case of the gas mixture) are now known or readily cal¬ 
culable. Data on the viscosity of CO - H 2 mixtures 
are very scanty and the relationship between viscosity 
and composition is obscure. It was finally necessary 
to estimate the value of u, knowing the behavior of 
CO - H 2 and N2 - H 2 mixtures over limited ranges. 

Convenience with regard to the size of the 
flowmeter block limited the length of the capillary to 
a maximum of 12 cms. Preliminary calculations 



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- 116 - 


indicated that only thermometer capillaries had suffi¬ 
ciently small diameters to permit this requirement to 
be satisfied. By sucking up and weighing a measured 
length of mercury in the capillaries, it was possible 
to determine the average diameters. Knowing these 
data, the proper length of capillary in each case was 
determined and the cut capillaries inserted into flow¬ 
meters. 

These capillaries were designed approximately 
and calibrated absolutely under normal operating con¬ 
ditions. The calibrations were carried out for hydrogen 
and synthesis gas at atmospheric pressure, and for the 
latter at 100 psi. gauge. 

It is obvious from the design equation that 
a capillary designed for a space velocity of 150/hour 
for synthesis gas at 8 atmospheres would only permit a 
space velocity of 20 - 30/hour for synthesis gas or 
hydrogen at atmospheric pressure. The latter rate is 
satisfactory for hydrogen, since it is used only in 
reducing^conditioning, and reactivating the catalysts, 
where low space velocities are permissible. These 
capillaries are, however, not suitable for operating 
with water gas at 1 atmosphere—the allowable space 
velocity being too low for effective catalyst testing. 
Nevertheless, a calibration for this last case was 
carried out in order to determine whether or not the 




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- 117 - 


effect of pressure on the behavior of the flowmeter is 
predictable from theoretical considerations. 

The calibrations proved to be a rather 
formidable task because of the small flows involved. 

Any small leaks in the system were sufficient to change 
the flow by several hundred per cent. It was found 
necessary to check for tightness before every set of 
experimental runs. After passing through the flowmeter, 
the rate of gas flow was measured accurately in a 
Precision Wet Test Meter. A stopwatch was used to note 
the time required for the passage of a 1/10 of a cubic 
foot of gas (corresponding to one complete revolution 
of the meter)* This was done in duplicate for three or 
four different rates of flow for each capillary and for 
each set of conditions. Since some single runs took as 
long as two hours, the calibrations were tedious and 
time consuming. 

The rates of flow (measured at atmospheric 
pressure) were then plotted against the pressure dif¬ 
ferentials. A typical set of curves for one capillary 
is shown in Figure XVIII. 

Since the rate of flow Q,' is in this case 
measured under discharge conditions, the graphs show a 
slight curvature. In order to test the validity of 
the design equation, it is necessary to calculate the 
flow rates as measured under the actual flowing conditions. 




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Flow - litres/hour 



Manometer Differential - inohes of Hg# 












































































































































































































































































































































































































































































































































































































































































































































































































































































- 120 - 


These results were then plotted—rate versus 
pressure differential. A typical set of graphs is 
shown in Figure XIX. Six capillaries were calibrated 
and 18 curves drawn. An examination of these curves 
led to the following conclusions: 

1. In all cases the linear relationship between 
the rate of flow Q, (under flowing conditions) and the 
pressure drop^H was confirmed. 

2. The ratios of the slopes of the curves for 
hydrogen (1 atmosphere):synthesis gas (1 atmosphere): 
synthesis gas (8 atmospheres) for all of the six capil¬ 
laries were consistent. This is to be expected since 
these ratios depend only upon the flow characteristics 
(viscosity and density) of the gas being measured. 

The following table shows this clearly—the ratio of 
the slopes being based on a value of unity for the 
hydrogen curve. 

TABLE IX 


Correlation of Slopes of Calibration Curves 


llary No. 

Ratio 

He 

1 atm. 

of Slopes 
CO: 2Hg 

1 atm. 

of Curves 
C0:2B 2 
100 psi 

5 

1.0 

0.59 

0.57 

6A 

1.0 

0.59 

0.57 

6B 

1.0 

0.61 

0.55 

10 

1.0 

0.60 

0.57 

11A 

1.0 

0.60 

0.56 

11B 

1.0 

0.60 

0.56 








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The average deviation is ]e ss than 1$. This 
indicates the correctness of the calibrations. 

3. The slope of the curves Q, « f 04 H) for syn¬ 
thesis gas changed only slightly with an increase in 
pressure from 1 atmosphere to 8 atmospheres—there being 
a decrease in slope of only about 7$. It is therefore 
possible to interpolate and obtain curves for any 
intermediate pressures without incurring any appreciable 
error. 

4. The effect of gas leaks on the calibration 
curves was clearly demonstrated. A leak in the dis¬ 
charge system causes the graph to shift to the right. 

A bypass leak through the capillary holder or through 
the bypass valve changes the slope of the graph. These 
two effects are illustrated in Figure XX. 

5. The results did not agree with the calculated 
values of the basic equation. Deviations were found 

as high as 25$. Therefore, while the equation is of 
much value in the design of capillary flowmeters, with 
flows of this order^the latter should always be 


calibrated absolutely. 




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- 123 - 


C - SHORT-TIME CATALYST TESTING IN A STATIC SYSTEM 


Introduction 

The proper evaluation of a Fischer-Tropsch 
catalyst requires weeks of testing under conditions 
approximating commercial operation. This is time con¬ 
suming and it is desirable to devise a short-time test 
which can he used to predict the catalyst behavior. 
Specifically, what is sought is a correlation between 
the results of these short-time tests and those 
obtained from long term dynamic tests. 

An investigation of this type was started 
but is still only in the preliminary stages and no 
conclusive results are as.yet available. The method 
used involves the reaction of synthesis gas in a static 
system at 1 atmosphere over a reduced but not conditioned 
catalyst. As the adsorption and reaction proceeds, 
giving hydrocarbon products (mainly methane but pos¬ 
sibly some liquids), the pressure in the system drops. 
Pressure-time readings are recorded and plotted. 





- 124 - 


Assuming the initial reaction to be only 


CO + 3H 2 - 

—> CH 4 -+ H 2 0 

or 2C0 + 2H 2 - 

—> CH 4 -h C0 2 


the slope of the curve gives the initial rate of me¬ 
thane synthesis. Ultimately, a correlation between 
these rates and catalyst behavior in liquid production 
will be sought, the absence of any such correlation 
vitiating this method of evaluation. 

Apparatus 

The individual pieces of equipment listed 
below are represented in their proper places in 
Figure XSI. 

A - Storage chamber for the synthesis gas. 

B - P 2 O 5 drier for drying the synthesis gas. 

C - Mercury manometer (vacuum on its right arm) 
to measure the absolute pressure in A. 

D - Activated charcoal to purify the hydrogen. 

E - Reaction chamber. 

F - Copper wire basket, containing the catalyst 
pellets. 

G- - Mercury manometer. 

H - Paraffin wax constant temperature bath, heated 
by a hot plate and two knife heaters (con¬ 
trolled through a rheostat). 


K, L, M - Three-i/ay stopcocks 




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- 126 - 


Procedure 

The copper wire basket F was filled with 
catalyst pellets, weighed, and placed in the reaction 
chamber E. The latter was surrounded by an air bath. 
The whole system, including the storage chamber A, was 
evacuated. Purified hydrogen was admitted into E and a 
slight but positive flow of hydrogen was maintained, 
the latter leaving at N. The catalyst was heated to 
360° - 370° C and held at this temperature foe 4 hours. 
The storage chamber A was filled with synthesis gas and 
the pressure measured on manometer C. After the 
catalyst had been reduced, the air bath was replaced 
by a paraffin wax bath H and the temperaturereduced to 
185°C. The reaction chamber E was evacuated free of 
hydrogen, and synthesis gas from A admitted. The 
final pressure in A was recorded. On admission of the 
synthesis gas into E, the pressure was read on the 
manometer G and the stopwatch started. Pressure-time 
readings were taken, at 1-minute intervals at first, 
and at longer time intervals when the pressure 
readings became steadier. The temperature was main¬ 
tained constant by adjusting the rheostat which was 
connected in series with the knife heaters. Each run 
took from 30 to 60 minutes, depending upon the catalyst. 
Duplicate runs were made at 185°C, 190°C, and 195°C. 







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Results 

Three catalysts were given preliminary test, 

namely; 

(1) Fe-Cu - Bureau of Mines #24. 

(2) Co-Th - Harshaw Chemical Co. Ltd. 

(3) Ni-Mn - Harshaw Chemical Co. Ltd. 

A comparison of the activity of each may he seen in 
Figure XXII. The effect of temperature upon the re¬ 
activity of the cohalt catalyst is shown in Figure XXIII. 
Discussion 

With respect to the Co-Th catalyst in parti¬ 
cular, successive runs at the same temperature gave 
duplicate results. Similar performance was obtained 
after reactivation for four hours with hydrogen. 

Whether this catalyst could he reactivated after cooling 
to room temperature was not investigated. Tests upon 
the Fe-Cu catalyst were inconclusive. 

At the temperatures tested the Fe-Cu was 
much less active than the other catalysts. This is 
probably not a fair comparison since iron catalysts 
operate normally at a temperature of 250°C. The ni¬ 
ckel catalyst revealed a higher activity than the 
cobalt but the per cent contraction was less. Since 
the contraction in the case of the nickel catalyst was 
approximately one half, the methane reaction is 
indicated. The contraction in the case of the cobalt 







- 128 - 



Time— minutes 






























































































































































































































































































































































































































































































































































































































































































































































































































































































































































































Time - minutes 























































































































































































































































































































































































































































































































































































































































































































































































































































































































































































































































- 130 - 


catalyst is 65 per cent, and therefore cannot be ex¬ 
plained wholly by this reaction. Adsorption or the 
formation of higher hydrocarbons are the only two alter¬ 
natives. Figure XXIII indicates that the temperature 
coefficient of reaction is comparatively low. This 
would be the case if, as has been suggested by some 
authors, diffusion were the rate controlling factor. 

Insufficient data have been obtained to 
determine the order of reaction. The same is true at 
this stage of the work with respect to the value of 
these rate measurements as indicative of catalyst per¬ 
formance in the Fischer-Tropsch synthesis. 



















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- 131 - 


BIB LI OGRAPHY 


(la) Boomer, E.H,, Can. Pat. 289,830, (1926). 

(1) Craxford, S.R., Trans. Far. Soc., 35, 946-958 

(1939). “ 

(2) Craxford, S.R. and Rideal, E.K., Jour. Chem. 

Soc., Part II, 1604-1614 (1939). 

(3) Domai. S., Bull. Chem. Soc. Japan, 16., 213 

(1941), C.A. 36, 739 (1942). 

(4) D.R.P. (German patent) 293, 787 (1913). 

(5) D.R.P. , 293, 797 (1913). 

(6) D.R.P., 705, 528 (1938). 

(7) Egloff, G., Nelson, E.F., and Morrell, J.C., 

Ind. Eng. Chem., 29, 555-559 (1937). 

(8) Elwin, O.E. and Nash, A.W., Nature, 118 . 

154 (1926). 

(9) Fischer, F., Brennstoff-Chem., 16, 2 (1936). 

(10) Fischer, F., J. Inst, of Fuel, 10, 10 (1936). 

(11) Fischer, F., Ber., 71, 56-67 (1938). 

(12) Fischer, F. and Pichler, H., Brennstoff-Chem., 

20, 41-61 (1939). 

(13) Fischer, F. and Pichler, H., Brenn. Chemie, 

21_, 285-8 (1940). 

(14) Fischer, F., Roelen, 0., and Feist, ¥., Brenn. 

Chemie, 13, 461-8 (1932). 

(15) Fischer, F., Roelen, 0., and Feist, W., Re¬ 

finer, 22, 429-35 (1943). 

(16) Fischer, F. and Tropsch, H., Brenn. Chemie., 

4, 276-85 (1923). 

(17) Fischer, F. and Tropsch, H., Brenn. Chemie, 2> 

97-104 (1926). 




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- 132 - 


(18) Foster, ti.L,, Oil and Gas Journal, 43, No* 15, 

99-101; No* 17, 46-49; No. 18, 66-69; (1944). 

(19) Govier, G.W., "The production of formaldehyde 

by low pressure oxidation of high-methane 
natural gas", Thesis, Part I, Appendix A, 
University of Alberta (1945). 

(20) Hamon, F., Mayer, A., and Plantefol, L., Ann. 

physio, physicochim. biol., j6, 452-63 (1930). 
C.A. 25, 4292 (1931). 

(21) Herington, E.F.G. and Woodward, L.A., Trans. 

Far. Soc., 35, 958-67 (1939). 

(22) Hofer, L.J.E., "The preparation a.nd properties 

of metal carbides", Bureau of Mines (U.S. 
Department of the Interior) Booklet, July 
(1944), p. 1, 39. 

(23) Komarewsky, V.I. and Riesz, C.H., Refiner, 25 . 

415-22 (1944). 

(24) Myddleton, ¥.1., J. Inst, of Fuel, 11, 477-92 

(1937). 

(25) Myddleton, W.W., J. Inst. Petroleum, 30, 211 

(1944). 

(26) Napthali, M., Refiner, 17, 47-51 (1938). 

(27) Russell, R.P., Hearings before a Subcommittee 

of the Committee on Public Lands and Sur¬ 
veys, United States Senate on Synthetic 
Liquid Fuels, p. 39 (1944). 

(28) Sabatier and Sendereus, Compt. rend., 154 . 514 

(1902). 

(29) Shaw, A.G., "Preparation and Testing of Fischer- 

Tropsch Catalysts", Unpublished report, 

Dept, of Chemistry, University of Alberta, 
(1945). 

(30) Storch, H.H., "The Chemistry of Coal Utilization", 

edited by H.H. Lowry, John Wiley & Sons, 

New York, N.Y., 1945, Vol. II, pp. 1797- 
1845. 

(31) Underwood, A.J.V., Ind. Eng. Chem., 32, 449-53 

(1940). 





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- 133 - 


(32) U 

(33) U 


.S. Bureau of Mines (Department of the Interior), 
Pittsburgh, Penn., Private Communication 
(1944). 

.S. Steel Corporation, "Methods of the Chemists 
of the U.S. Steel Corporation for the 
Sampling and Analysis of Gases”, Booklet, 
Third Edition, p. 106 (1927). 


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