CA1248734A - Process of the preparation of a hydrogen-rich gas - Google Patents
Process of the preparation of a hydrogen-rich gasInfo
- Publication number
- CA1248734A CA1248734A CA000463445A CA463445A CA1248734A CA 1248734 A CA1248734 A CA 1248734A CA 000463445 A CA000463445 A CA 000463445A CA 463445 A CA463445 A CA 463445A CA 1248734 A CA1248734 A CA 1248734A
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- Prior art keywords
- gas
- hydrogen
- catalyst
- preparation
- steam
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-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/868—Chromium copper and chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/005—Spinels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
- C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
A B S T R A C T
PROCESS OF THE PREPARATION OF A HYDROGEN-RICH GAS
The present invention relates to a process for the preparation of a hydrogen-rich gas, which is carried out by transforming a carbon monoxide-containing gas with steam. The conversion is effected in the presence of a catalyst containing a spinel whose composition corresponds to the formula [CuxMn-(1-x)FeyCr(1-y)]O4 in which O < X < 1 and O < Y < 2. Preferably an oxide or an alkali metal or of vanadium is added to the catalyst. The process of invention applies to industrial pro-cesses for the preparation of hydrogen.
PROCESS OF THE PREPARATION OF A HYDROGEN-RICH GAS
The present invention relates to a process for the preparation of a hydrogen-rich gas, which is carried out by transforming a carbon monoxide-containing gas with steam. The conversion is effected in the presence of a catalyst containing a spinel whose composition corresponds to the formula [CuxMn-(1-x)FeyCr(1-y)]O4 in which O < X < 1 and O < Y < 2. Preferably an oxide or an alkali metal or of vanadium is added to the catalyst. The process of invention applies to industrial pro-cesses for the preparation of hydrogen.
Description
73~
PROCESS OF THE PREPARATION OF A HYDROGEN-RICH GAS
The present invention relates to a process for the pre-paration of a hydrogen-rich gas carried out by transforming a carbon monoxide-containing gas with steam according -to the wa-ter-gas shift reaction:
CO + H2O ~ 2 2 This conversion, which constitutes an important part in most of the industrial processes for the preparation of hydrogen, is generally effected in two steps in the presence of a catalyst. The first conversion step, which is performed at a temperature of over 300C, is known as water-gas shift reaction at elevated temperature.
In the second conversion step, the water-gas shift reaction at low temperature, a temperature below 300C is used. As most of the catalysts proposed hitherto for the water-gas shift reac-tion are only sufficiently active in a fairly limited temperature range, it is customary to use different catalysts in each of the two conversion steps as mentioned above.
It has now been found that certain spinels are excellent catalysts for the water-gas shift reaction both in low and high temperature operations.
The invention therefore relates to a process for the preparation of a hydrogen-rich gas, which is carried out by transforming a carbon monoxide-containing gas with steam, charact-erized in that the reaction is performed at a temperature from ~' ~
~7~
-la- 63293-2452 175to 500C, a pressure of 10 to 100 bar, a space velocity of 1,500 to 4,500 litres of gas per hour per litre of catalyst at normal temperature and pressure and in a molar ratio of steam in relation to carbon monoxide of 0.5 to 50, and that the conversion is effected in the presence of a catalyst containing a spinel whose composition corresponds to the formula CuxMn(l_x)FeyCr(l-y)o4 in which O < X < 1 and O< Y <2.
~.."' oJ~
The catalysts used according to the inveneion are conveniently obtained by kneading a mixed powder of the metals~containing constituents together with water or by precipitating the me~als-containing constituents in the desired proportion starting from a solucion of their salts, for preference a solution of carbonates and/or nitrates, by drying the kneaded paste or the precipi~ate and subsequently calcining it, for preference at a temperature from 400 to 1000 C for a period of three to 20 hours. It has moreover been found that it is possible to stabilize the above-mentioned cata-lysts by adding an oxide of at lea9t one alkali metal and~or ofvanadium. Catalysts containing these constituents retain their activity longer during use, and as a result it is less frequently n~cessary to regenerate or replace them. It is advantageous to use catalysts containing from 0.1 to 15% by weight of ~i20, ~a20, K20, Rb20, Cs20 and/or V205.
The abova-mentioned catalysts can be used as such:
they will be advantageously applied in the form of particles having a length and/or a diameter of 0.2 to 0.6 mm. ~owever, it is also possible to precipitate the catalysts an a carrier and to use them on this carrier, after drying and calcination, for the water~gas conversion reaction. If desired, aluminium trloxide can be used as carrler; the quanti~y of carrier will suitably be such that it conseitutes from 40 to 80Z by weight of the total catalyst.
The water-gas conver~ion reaction, which in principle may take place at temperatures ranging from 175 ~o 500 C, ls generally performed in practice in severa1 steps, for reasons of reactlon rate and state of equilibriu~, partly above 300 C (water-gas conversion reaction at eleva~ed temperat~re) and partly below 300 C (water-gas shift reaction at low te~pera~ure~. For preference the reaction is performed by passing the gas to be transformed through two or more reactors a~ a temperature ranging from 300 to 500 C, the sald reactors containing a catalyst for water-gas shift reaction at elavated temperature, and subsequenely passing the mixture of partially cransformed gas through a reactor at a temperature ranging from 175 ~o 300 C, the said r~actor containing a catalyst for water-gas shift reaction at low tempera~ure.
j If the water-gas shift process is applied to several steps at different temperatures, partly above and partly below 300 C, a process according to the invention ls an~way preferred for ~he step at low temperature. Since the catalysts used to be used according to the in~ention generally feature a sufficient activity and stability also above 300 C, it is advantageous to use a catalyst according to the invention in all the steps of the water-gas shift reaction, both above and below 300 C.
- The pressure at which the water-gas shift reaction is perfor~ed may vary between wide limits. The reaction is for preference performed at a pressure in the range from 10 to 100 bar in particular from 20 to 80 bar. The quantity of steam present in ~he gas mixture subjected to the water-gas shift reaction is for prefersnce from 0.5 to 50 moles per mole of carbon monoxide.
The rate at which ehe gas is to be eransformed is passed over 2a the catalyst may vary between wide limits, but is for preference fro~ 1,500 to 4~500 litres of gas per hour per litre of catalyst, at normal temperature and pressure.
As has already been m~ntioned, the preparation of hydrogen-rich gas by conversion of a carbon monoxide-containing gas with steam according to the water-gas shift reaction for~s an important part of most of the industrial proc~sses for the preparation of hydrogen. The process according to the invention is very ser~iceable as part of such a process for the preparation of hydrogen. The carbon monoxlde-containing gas is generally obeained in these processes by incomplete combustion of a hydrocarbon or a mixture of hydrocarbons with oxygen. It is preferred to add steam as a modifler to the mixture. The incomplete combustion yields a crude gas which comprises principally car6On monoxide and hydrogen.
:, , : -, The mixture of hydrocarbons used is for preference a petroleum fraction. Petroleum fractions, both from distillation and residual, are serviceable for this purpose. U~der certain condi~ions, coal, for example in the form of a slurry in a hydrocarbon oil, may also be used as feed. It is customary in most of the processes to withdraw heat from the crude gases leaving the combustion reactor and which are at a very elevated temperature.
This can be effected very conveniently by causing heat to be exchanged by the gases with the water in a waste heat boiler; as a result high-pressure steam is formed and the temperature of the crude gas falls.
According to the starting maeerial selected and the conditions uset in the combustion reactor, the gas thus cooled which, however, ls still at a relatively high te~perature, can contain a IS conslderable quantity of soot.
Because of ~he rapid clog~ing of the catalyst by the soot, the latter has to be removed from the gas before the latter ~s sub~ected to the water-gas catalytic shift reaction, if a conventional reactor is used. However, since re~ently a reactor has been available which allows the catalyeic transformatlon of gases containing solid impurlties, such as soot, without the catalyst becoming rapidly clogged by the solid impurities. In this reactor, which contains hollow channels for gas in which the gas can circulate and whose walls are gas-per~eable, the catalyst is present behind the walls. Thi~ reactor is based on the princlple that the constituent~ to be transformed present 1~ the gas ~pread out f rom the gas channels, through the walls of these channels, come into contact with the catalyst, and spread out again in the gas channels after conversion.
The reactor described above is e~tremely serviceable if the carbon monoxide-containing gas to be tran formed in the process according to the invention contains soot. According eo the soot content of the gas, some of the soot, may, if desired, be separated from the gas in advance.
:` :
J~3~
Upon comple~ion or the water-gas conversion reaction, the resultant hydrogen-rich gas for che preparation of pure hydrogen mus~ be purified again. If the crude gaseous ~ixture leaving the combustion reactor contained sulphur and/or soot, while no sulphur and/or soot has been removed or only some of the soot has been rPmoved before the water-gas conversion reaction, the sulphur and/or the soot must still be removed from the hydrogen-rich gas.
The purification of the hydrogen-rich gas further comprises in particular the removal of carboxylic anhydride ormed and of non-transformed carbon monoxide.
The following non-limitative examples will show clearly how the invention can be carried out.
~ . ~
A catalyst having a composition as defined by the formula ~CuO 5MnO 5Fel gCrO 1)4 was prepared by 8rinding 57-5 g MnC03, 120-75 g Cu(~03)~,3H20, 175.6 g Fe203,1.4H20 (15107 g based on anhydrous Fe203) and 40.0 g Cr(N0~)3.9H20 to obtain a powder, kneading this po~der with 66 cm water during 35 minutes and by drying the resultant paste at 110 C for 4 hours. The mass was subsequently calcined by gradually increasing the temperature to 300 C during about 20 hours and by keeping the temperature at 300 C during 2 hours.
By means of X-ray diffraction it has been found that the resultant mixed oxides had assumed the crystalline shape of a spinel.
The calcined material was screened, and the particles of a diameter from 0.4 to 0.6 mm were used for the conversion of carbon monoxide into hydrogen with steam.
To this end, a gas having the followlng composition, together with steam, was passed over a bed ormed by the cataly~t par~icles:
tdJ 3 ~
% by vol.
The following reaction conditions were used:
Temperature 250 C
Pressure 40 bar Space Velocity 1,500 litres at normal temperature and pressure/l of catalyst/h Steam/gas molar ratio ~V/V) 0.65 63% of the carbon monoxide present in the gas was transformed during the process according to the following reaction:
CO + H20 ~ H2 + CO~
A catalyst having a composition as de~ned by the formula:
85(Cuo 5MnO 5Fel gCro 1)4 12R2-3 2 5 (P
weight) was prepared by grinding. 57.5 g MnC03, 1~0.75 g Cu(~03)2,3H20, 175-6 g Fe203.1.4H20 (151-7 g on anhydrous oxide basis), 40.0 g Cr(~O3)3.9H20, 48.6 g K2C03 and 10.66 g NH4V03 and using the same procedure as in Example 1.
~he calcined material was screened, and the partlcles of a diameter from 0.4 to 0.6 mm were used for the conversion of carbon monoxide into hydrogen with steam, using the same reac~ion conditions as described in Example 1.
In ehis case, 75% of carbon monoxide present in the ga~ was transformed durlng the process, thus showing ehe advan~ageous effect of adding an oxide of alkalimeeal and vanadium on the catalyst activity ~t low temperature.
3~
In this example the catalyst described in Example 2 was used for the conversion of carbon monoxide with steam at higher temperature: 350 C.
S The gas composition was the same as in Example 1 and the following reaction conditions were used:
Temperature 350 C
Pressure 40 bar Space Velocity 1,500 lltres at normal temperature and pressure/l of catalyst/h.
Steam/gas molar ratio (V/V) 0.65 The activity and stability of the catalysts are shown in the following table:
C0 conversion at thermadynamic 68 equilibrium (%) . . . _ . .
C0 conversion (%) after 10 h on stream 64 50 h 62 100 h 61 150 h 59 200 h 58 As shown in the table, ~he use of a catalyst according to the invention leads to an aetive and stable opera~ion at 350 C. about 94% of the thermodyna~ic equilibrium value for C0 converslon had been reached, with an activlty loss with t~me on stream of about 3%
C0 conversion per 100 h.
PROCESS OF THE PREPARATION OF A HYDROGEN-RICH GAS
The present invention relates to a process for the pre-paration of a hydrogen-rich gas carried out by transforming a carbon monoxide-containing gas with steam according -to the wa-ter-gas shift reaction:
CO + H2O ~ 2 2 This conversion, which constitutes an important part in most of the industrial processes for the preparation of hydrogen, is generally effected in two steps in the presence of a catalyst. The first conversion step, which is performed at a temperature of over 300C, is known as water-gas shift reaction at elevated temperature.
In the second conversion step, the water-gas shift reaction at low temperature, a temperature below 300C is used. As most of the catalysts proposed hitherto for the water-gas shift reac-tion are only sufficiently active in a fairly limited temperature range, it is customary to use different catalysts in each of the two conversion steps as mentioned above.
It has now been found that certain spinels are excellent catalysts for the water-gas shift reaction both in low and high temperature operations.
The invention therefore relates to a process for the preparation of a hydrogen-rich gas, which is carried out by transforming a carbon monoxide-containing gas with steam, charact-erized in that the reaction is performed at a temperature from ~' ~
~7~
-la- 63293-2452 175to 500C, a pressure of 10 to 100 bar, a space velocity of 1,500 to 4,500 litres of gas per hour per litre of catalyst at normal temperature and pressure and in a molar ratio of steam in relation to carbon monoxide of 0.5 to 50, and that the conversion is effected in the presence of a catalyst containing a spinel whose composition corresponds to the formula CuxMn(l_x)FeyCr(l-y)o4 in which O < X < 1 and O< Y <2.
~.."' oJ~
The catalysts used according to the inveneion are conveniently obtained by kneading a mixed powder of the metals~containing constituents together with water or by precipitating the me~als-containing constituents in the desired proportion starting from a solucion of their salts, for preference a solution of carbonates and/or nitrates, by drying the kneaded paste or the precipi~ate and subsequently calcining it, for preference at a temperature from 400 to 1000 C for a period of three to 20 hours. It has moreover been found that it is possible to stabilize the above-mentioned cata-lysts by adding an oxide of at lea9t one alkali metal and~or ofvanadium. Catalysts containing these constituents retain their activity longer during use, and as a result it is less frequently n~cessary to regenerate or replace them. It is advantageous to use catalysts containing from 0.1 to 15% by weight of ~i20, ~a20, K20, Rb20, Cs20 and/or V205.
The abova-mentioned catalysts can be used as such:
they will be advantageously applied in the form of particles having a length and/or a diameter of 0.2 to 0.6 mm. ~owever, it is also possible to precipitate the catalysts an a carrier and to use them on this carrier, after drying and calcination, for the water~gas conversion reaction. If desired, aluminium trloxide can be used as carrler; the quanti~y of carrier will suitably be such that it conseitutes from 40 to 80Z by weight of the total catalyst.
The water-gas conver~ion reaction, which in principle may take place at temperatures ranging from 175 ~o 500 C, ls generally performed in practice in severa1 steps, for reasons of reactlon rate and state of equilibriu~, partly above 300 C (water-gas conversion reaction at eleva~ed temperat~re) and partly below 300 C (water-gas shift reaction at low te~pera~ure~. For preference the reaction is performed by passing the gas to be transformed through two or more reactors a~ a temperature ranging from 300 to 500 C, the sald reactors containing a catalyst for water-gas shift reaction at elavated temperature, and subsequenely passing the mixture of partially cransformed gas through a reactor at a temperature ranging from 175 ~o 300 C, the said r~actor containing a catalyst for water-gas shift reaction at low tempera~ure.
j If the water-gas shift process is applied to several steps at different temperatures, partly above and partly below 300 C, a process according to the invention ls an~way preferred for ~he step at low temperature. Since the catalysts used to be used according to the in~ention generally feature a sufficient activity and stability also above 300 C, it is advantageous to use a catalyst according to the invention in all the steps of the water-gas shift reaction, both above and below 300 C.
- The pressure at which the water-gas shift reaction is perfor~ed may vary between wide limits. The reaction is for preference performed at a pressure in the range from 10 to 100 bar in particular from 20 to 80 bar. The quantity of steam present in ~he gas mixture subjected to the water-gas shift reaction is for prefersnce from 0.5 to 50 moles per mole of carbon monoxide.
The rate at which ehe gas is to be eransformed is passed over 2a the catalyst may vary between wide limits, but is for preference fro~ 1,500 to 4~500 litres of gas per hour per litre of catalyst, at normal temperature and pressure.
As has already been m~ntioned, the preparation of hydrogen-rich gas by conversion of a carbon monoxide-containing gas with steam according to the water-gas shift reaction for~s an important part of most of the industrial proc~sses for the preparation of hydrogen. The process according to the invention is very ser~iceable as part of such a process for the preparation of hydrogen. The carbon monoxlde-containing gas is generally obeained in these processes by incomplete combustion of a hydrocarbon or a mixture of hydrocarbons with oxygen. It is preferred to add steam as a modifler to the mixture. The incomplete combustion yields a crude gas which comprises principally car6On monoxide and hydrogen.
:, , : -, The mixture of hydrocarbons used is for preference a petroleum fraction. Petroleum fractions, both from distillation and residual, are serviceable for this purpose. U~der certain condi~ions, coal, for example in the form of a slurry in a hydrocarbon oil, may also be used as feed. It is customary in most of the processes to withdraw heat from the crude gases leaving the combustion reactor and which are at a very elevated temperature.
This can be effected very conveniently by causing heat to be exchanged by the gases with the water in a waste heat boiler; as a result high-pressure steam is formed and the temperature of the crude gas falls.
According to the starting maeerial selected and the conditions uset in the combustion reactor, the gas thus cooled which, however, ls still at a relatively high te~perature, can contain a IS conslderable quantity of soot.
Because of ~he rapid clog~ing of the catalyst by the soot, the latter has to be removed from the gas before the latter ~s sub~ected to the water-gas catalytic shift reaction, if a conventional reactor is used. However, since re~ently a reactor has been available which allows the catalyeic transformatlon of gases containing solid impurlties, such as soot, without the catalyst becoming rapidly clogged by the solid impurities. In this reactor, which contains hollow channels for gas in which the gas can circulate and whose walls are gas-per~eable, the catalyst is present behind the walls. Thi~ reactor is based on the princlple that the constituent~ to be transformed present 1~ the gas ~pread out f rom the gas channels, through the walls of these channels, come into contact with the catalyst, and spread out again in the gas channels after conversion.
The reactor described above is e~tremely serviceable if the carbon monoxide-containing gas to be tran formed in the process according to the invention contains soot. According eo the soot content of the gas, some of the soot, may, if desired, be separated from the gas in advance.
:` :
J~3~
Upon comple~ion or the water-gas conversion reaction, the resultant hydrogen-rich gas for che preparation of pure hydrogen mus~ be purified again. If the crude gaseous ~ixture leaving the combustion reactor contained sulphur and/or soot, while no sulphur and/or soot has been removed or only some of the soot has been rPmoved before the water-gas conversion reaction, the sulphur and/or the soot must still be removed from the hydrogen-rich gas.
The purification of the hydrogen-rich gas further comprises in particular the removal of carboxylic anhydride ormed and of non-transformed carbon monoxide.
The following non-limitative examples will show clearly how the invention can be carried out.
~ . ~
A catalyst having a composition as defined by the formula ~CuO 5MnO 5Fel gCrO 1)4 was prepared by 8rinding 57-5 g MnC03, 120-75 g Cu(~03)~,3H20, 175.6 g Fe203,1.4H20 (15107 g based on anhydrous Fe203) and 40.0 g Cr(N0~)3.9H20 to obtain a powder, kneading this po~der with 66 cm water during 35 minutes and by drying the resultant paste at 110 C for 4 hours. The mass was subsequently calcined by gradually increasing the temperature to 300 C during about 20 hours and by keeping the temperature at 300 C during 2 hours.
By means of X-ray diffraction it has been found that the resultant mixed oxides had assumed the crystalline shape of a spinel.
The calcined material was screened, and the particles of a diameter from 0.4 to 0.6 mm were used for the conversion of carbon monoxide into hydrogen with steam.
To this end, a gas having the followlng composition, together with steam, was passed over a bed ormed by the cataly~t par~icles:
tdJ 3 ~
% by vol.
The following reaction conditions were used:
Temperature 250 C
Pressure 40 bar Space Velocity 1,500 litres at normal temperature and pressure/l of catalyst/h Steam/gas molar ratio ~V/V) 0.65 63% of the carbon monoxide present in the gas was transformed during the process according to the following reaction:
CO + H20 ~ H2 + CO~
A catalyst having a composition as de~ned by the formula:
85(Cuo 5MnO 5Fel gCro 1)4 12R2-3 2 5 (P
weight) was prepared by grinding. 57.5 g MnC03, 1~0.75 g Cu(~03)2,3H20, 175-6 g Fe203.1.4H20 (151-7 g on anhydrous oxide basis), 40.0 g Cr(~O3)3.9H20, 48.6 g K2C03 and 10.66 g NH4V03 and using the same procedure as in Example 1.
~he calcined material was screened, and the partlcles of a diameter from 0.4 to 0.6 mm were used for the conversion of carbon monoxide into hydrogen with steam, using the same reac~ion conditions as described in Example 1.
In ehis case, 75% of carbon monoxide present in the ga~ was transformed durlng the process, thus showing ehe advan~ageous effect of adding an oxide of alkalimeeal and vanadium on the catalyst activity ~t low temperature.
3~
In this example the catalyst described in Example 2 was used for the conversion of carbon monoxide with steam at higher temperature: 350 C.
S The gas composition was the same as in Example 1 and the following reaction conditions were used:
Temperature 350 C
Pressure 40 bar Space Velocity 1,500 lltres at normal temperature and pressure/l of catalyst/h.
Steam/gas molar ratio (V/V) 0.65 The activity and stability of the catalysts are shown in the following table:
C0 conversion at thermadynamic 68 equilibrium (%) . . . _ . .
C0 conversion (%) after 10 h on stream 64 50 h 62 100 h 61 150 h 59 200 h 58 As shown in the table, ~he use of a catalyst according to the invention leads to an aetive and stable opera~ion at 350 C. about 94% of the thermodyna~ic equilibrium value for C0 converslon had been reached, with an activlty loss with t~me on stream of about 3%
C0 conversion per 100 h.
Claims
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of a hydrogen-rich gas, which is carried out by transforming a carbon monoxide-containing gas with steam, characterized in that the reaction is performed at a temperature from 175 to 500°C, a pressure of 10 to 100 bar, a space velocity of 1,500 to 4,500 litres of gas per hour per litre of catalyst at normal temperature and pressure and in a molar ratio of steam in relation to carbon monoxide of 0.5 to 50, and that the conversion is effected in the presence of a catalyst containing a spinel whose composition corresponds to the formula CuxMn(1-x)FeyCr(1-y)O4 in which O < X< 1 and O< Y < 2.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8316374A FR2553399A1 (en) | 1983-10-14 | 1983-10-14 | Process for the preparation of a hydrogen-rich gas. |
| FR8316374 | 1983-10-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1248734A true CA1248734A (en) | 1989-01-17 |
Family
ID=9293139
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000463445A Expired CA1248734A (en) | 1983-10-14 | 1984-09-18 | Process of the preparation of a hydrogen-rich gas |
Country Status (2)
| Country | Link |
|---|---|
| CA (1) | CA1248734A (en) |
| FR (1) | FR2553399A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4604375A (en) * | 1983-12-20 | 1986-08-05 | Exxon Research And Engineering Co. | Manganese-spinel catalysts in CO/H2 olefin synthesis |
| US5108979A (en) * | 1991-02-25 | 1992-04-28 | Intercat, Inc. | Synthetic spinels and processes for making them |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3899577A (en) * | 1969-07-25 | 1975-08-12 | Inst Francais Du Petrole | Carbon monoxide conversion catalysts |
| FR2054524A1 (en) * | 1969-07-25 | 1971-04-23 | Inst Francais Du Petrole | |
| FR2102662A6 (en) * | 1970-08-13 | 1972-04-07 | Inst Francais Du Petrole | Oxide catalyst partially of spinel structure - for carbon monoxide conversion |
| IT1003097B (en) * | 1973-03-28 | 1976-06-10 | Tokyo Electric Co Ltd | CATALYST TO TREAT EXHAUST GASES OF MOTOR VEHICLES |
-
1983
- 1983-10-14 FR FR8316374A patent/FR2553399A1/en active Pending
-
1984
- 1984-09-18 CA CA000463445A patent/CA1248734A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR2553399A1 (en) | 1985-04-19 |
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