CA1077718A - Process of producing a fuel gas by the catalytic reaction of methanol and water vapor - Google Patents
Process of producing a fuel gas by the catalytic reaction of methanol and water vaporInfo
- Publication number
- CA1077718A CA1077718A CA285,992A CA285992A CA1077718A CA 1077718 A CA1077718 A CA 1077718A CA 285992 A CA285992 A CA 285992A CA 1077718 A CA1077718 A CA 1077718A
- Authority
- CA
- Canada
- Prior art keywords
- gas
- catalyst
- water vapor
- weight
- methanol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/08—Production of synthetic natural gas
-
- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J23/78—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 alkali- or alkaline earth metals
-
- 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
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
-
- 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
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
-
- 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
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
-
- 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
Abstract
ABSTRACT OF THE DISCLOSURE :
The production of a methane-containing fuel gas is carried out by supplying water vapor and vaporized methanol under superatmospheric pressure on a nickel catalyst, the water vapor and vaporized methanol being supplied at a weight ratio of about 0.5 to 1.5 and at inlet temperature of about 300 to 500°C to a reactor and being reacted therein under adiabatic conditions and under a pressure in the range of about 10 to 40 bars; the nickel catalyst contains 25-50% by weight nickel in the form of the compound Ni5MgAl2O9, 5-40% by weight high-alumina cement, and at least 5% by weight zirconium dioxide.
The product gas leaving the reactor at temperatures of about 500 to 700°C is subsequently cooled. The process of the invention has the advantage of producing a gas having a high calorific value without the supply of air so that the carbon monoxide content of the product gas is minimized.
The production of a methane-containing fuel gas is carried out by supplying water vapor and vaporized methanol under superatmospheric pressure on a nickel catalyst, the water vapor and vaporized methanol being supplied at a weight ratio of about 0.5 to 1.5 and at inlet temperature of about 300 to 500°C to a reactor and being reacted therein under adiabatic conditions and under a pressure in the range of about 10 to 40 bars; the nickel catalyst contains 25-50% by weight nickel in the form of the compound Ni5MgAl2O9, 5-40% by weight high-alumina cement, and at least 5% by weight zirconium dioxide.
The product gas leaving the reactor at temperatures of about 500 to 700°C is subsequently cooled. The process of the invention has the advantage of producing a gas having a high calorific value without the supply of air so that the carbon monoxide content of the product gas is minimized.
Description
This invention relates to a process of producing a methane-containing fuel gas by a reaction of methanol and water vapor under superatmospheric pressure on a nickel-containing catalyst.
Town gas or a fuel gas which can be used as a sub-stitute for natural gas can be produced by known processes, which can be carried out with high efficiency and result in a gas which is of excellent quality and suitable for being supplied to existing pipe systems for distribu-ting natuxal gas or town gasO It is also known that the capacity of napththa-cracking plants used to produce fuel gas can be increased at times of peak demand by an addition of methanol. In such an instance, vaporized methanol is added to cracked gas, which contains water vapor and is at a temperature of about 400C. The mixture is then catalytically reacted on a catalyst which is suitable for the shift-conversion of CO. In this way, a gas having a high calori~ic value is produced so that the capacity of existing cracking plants can be increased by about 25 to 30%.
The use of methanol as the only starting material in the production of gas having a high calorific value is problematic when the gas is to be used to meet basic demands because methanol is expensive. On the other hand, methanol is highly suitable for producing gas because methanol can be transported and stored in a simple mannerO For this reason, methanol is preferred in a supply system to meet peak demands, e.g., in winter~
In a known process, fuel gas for peak demands is produced by a catalytic reaction of methanol and water vapor.
. In that process, methanol, water vapor, and air are supplied at inlet temperature of about 350C and are reacted on a high-nickel catalyst on an alumina support. Air is supplied at acontrolled rate mainly in order to produce a gas which has the desired calorific value. ~n the other hand, the supply of air .
~7~7~
has the disadvantage that the produc-t gas has an excessively high density so tha-t considerable quantities of CO2 must be scrubbed therefrom. The supply of air has also the resul-t that the gas leaving the cracking reactor is at an excessively high temperature and for this reason has an undesirably high CO
content, which must be converted in a succeeding shift conversion stage. The high reaction temperatures reached in the known process impose a high stress on the catalyst material and cause the same to be deteriorated wi-thin relatively short -time.
It is an object of the invention -to carry out -the process described first hereinbefore in such a manner tha-t a supply of air is not required and that the carbon monoxide eontent of the produe-t gas is minimized. This is accomplished aecording to the invention by supplying water vapor and vaporized methanol under superatmospheric pressure on a nickel eatalyst, the water vapor and vaporized me-thanol being supplied at a weight ratio of about 0.5 to 1.5 and at inlet -temperature of about 300 to 500C to a reactor and being reaeted -therein under adiaba-tie conditions and under a pressure in the range of about 10 to 40 bars; the niekel eatalyst eon-tains 25-50% by weight niekel in the form of the compound Ni5MgA12Og, 5-40% by weight high-alumina eement, and at least 5% by weight zireonium dioxide. The produet gas leaving -the reactor at temperatures of about 500 to 700C is subsequently eooled.
This proeess results in a produet gas whieh has typically a earbon monoxide eontent below 5% by volume based on dry gas. After a sufficien-t cooling of the gas and a condensation of wa-ter vapor therefrom, -the gas can be used as town gas wi-thout need for a further conversion of gas constituents.
For a production oE certain grades of town gas having an upper heating value of 4000 to 5000 kcal per s-tandard m3, the process according -to the invention is carried out in such 1~ .
~(:97~7~8 .
a manner that the product gas is withdrawn from the reactor at temperatures of 580 to 700C and is cooled and part of the carbon dioxide is removed from the gas to an extent which depends on the desired density of the town gas.
When a natural gas substitute which contains more than 90% by volume of methane (on a dry basis) is desired, the hot product gas resulting from the catalytic cracking of methanol is cooled to 250 to 350C and is reacted in at least one methanat-ing stage with water vapor on a nickel-containing catalyst material, whereafter the methanated gas is scrubbed to remove surplus carbon dioxide. The methanation is carried out under conditions known per se.
The catalytic reaction of methanol and water vapor in the process according to the invention is considerably improved by the use of the above type of catalyst.
A first embodiment of such a catalyst will be described hereinafter. This catalyst contains the compounds Ni5MgA12Og and ZrO2 at a weight ratio of 13:1 and also contains a high-alumina cement, which amounts to 306 of the total weight of the catalyst. The high-alumina cement has the Eollowing composition in percent by welght : 26.4 CaO, 71.9 A12O3 , 0.2 Fe2O3, 0.2 MgO, 0.4 Na2O, 0.07 SiO2(and traces of K, Cr, Cu, Mn, Ni and also Pb). The desirable catalyst of this first embodiment is produced as follows :
Within 15 minutes, solution II is added to suspension I.
The suspension and solution have the following compositions:
Suspension I
1250 g sodium carbonate in 6 1 wa-ter containing 37.5 g ZrO2 Solution II
30 250 g Mg(NO3)2. 6H2O
1 .~`, ~ , . ~
7771~3 1280 g Ni(N03)2. 6H20 690 g Al(N03). 9H20 in 6 1 water The resulting precipitate consisting of Ni5Mg(OH)16.
C03.4H20 on zirconium dioxide is filtered o-ff, washed to remove all alkali, dried at 110C for 12 hours anc~ then calcined at 400C
for four hours to produce a calcine which contains nickel oxide, magnesia, alumina and zirconium dioxide as support components.
350 g of the calcine and 150 g high-alumina cement are mixed in a dry state. When 60g of water have been added to the mixture, the same is compacted to form 3x3 mm tablets, which are then briefly watered and are subsequently caused to set completely by being stored in a moist state at 40C in a closed system for si~ days. The resulting tablets have an end face crushing strength of 46~ kg/cm and a bul]~ density of 1.57 kg/l. In the oxidic state, the catalyst has a nickel content of 28.7% by weight. Before the catalyst is used, it is reduce~. This can be accomplished by a treatment with hydrogen or other reducing gases.
A second embodiment of a desirable catalyst contains the compounds Ni5MgA1209, ZrO2 and a-A1203 at a weight ratio of 12:1:2 and also contains the high-alumina cement explained above, in an amount of 15% of the total weight of the catalyst. The catalyst of this second embodiment is duced as follows :
Solutions I and II are continuously combined with suspension III at a temperature of 60C and in such a manner tha~ the pH value of the solution does not decreas~ below 8.5.
The solutions and -the suspension have the followin~ compositions:
Solution I
~ .
1250 g sodium carbonate in 6 1 water Solution II
255 g Mg(N03)2.6H20 1280 g Ni(No3)2.6H20 ~L~777~
690 g Al(NO3)3.9H2O in 6 1 water Suspension III
-43.2 g zirconium dioxide and 74~0 g ~- A12O3 in 3 1 water.
The resulting precipitate i~ filtered ofE and the filter cake is washed and then dried at 110C for 12 hours and is subsequently calcined at 400C for 4 hours.
425 g of the resulting calcine are mixed with 75 g high-alumina cement in a dry state. After an addition of 75 g water to the mixture the latter is compacted to`form 3 x 3 mm tablets. The catalyst is shortly watered and then dried at 110C for 12 hours. After this treatmen-t, the catalyst has an end face crushing strength of 453 kg/cm2 and a bulk density of 1.52 kg/l. In the oxidic state, the catalyst contains 30.3% by weight of nickel. The catalyst is reduced beEore it is used.
Preferred embodiments of the invention will now be described in greater detail with reference to the following examples and the accompanying drawing which represents a flow -diagram of a process according to the invention.
Referring first to the drawing methanol to be cracked is supplied in conduit 1 and is forced by pump 2 into conduit 3 and conducted in the same through a plurality of heating stages into a shaft reactor 4. The methanol is first heated in a heat exchanger 5 and is then conducted in conduit 6 to another heat exchanger 7 and is vaporized therein. Methanol vapor then flows in conduit 8 to a heater 9 and thereafter in conduit 10 to the reactor 4.
The water vapor required for the catalytic reaction in the reactor 4 comes from the steam accumulator 12 and is added to the methanol through conduit 11. The reactor 4 contains a fixed bed consisting of the catal~st material. In the reactor ~, the reaction is carried out under autothermic, acliaba-tic ~LC3 777~3 conditions. Product gas leaving the reactor 4 through conduit 13 contains water vapor and owing to the exothermic reaction in the reactor is at a temperature of 500-700C, which is higher than the inlet temperature of the material to be reacted~
The product gas flowing in conduit 13 is first cooled in a waste heat boiler 14, from which the product gas is conducted in conduit 15 to the heat exchanger 7. From the latter, the product gas is conducted in conduitl6 to a feed water preheater 3L~777~
17. Further cooling stages for the product gas consist of the heat exchanger 5, a fresh water preheater 18, and an air cooler 19. The cooled product gas in the conduit 20 may be directly used as town gas.
When it is desired to produce certain grades of town gas, the gas flowing in conduit 20 is fed to a known scrubber for the removal of surplus carbon dioxide. If the gas is to be prQcessed to produce a natural gas substitute, the product gas is fed to a single- or multi-stage methanating plant. ~n that case, C02 is scrubbed off before or behind the last methanating stage.
The water vapor required for the reaction is produced as follows: The feed water, which may consist, e.g., of condensate recovered from the gas, is conducted in conduit 25 through the fresh water preheater 18 and is then collected in the feed water container 25, in which the water is degasified and from which the water is fed through conduit 27, pump 28 and conduit 29 to the preheater 17. From the latter, the water is fed through conduit 30 to the steam accumulator 12. Condensate formed in the steam accumulator 12 flows through a conduit 31 and a branch conduit 32 to the heater 9, in which the water vapor is vaporized by heating means, not shown. The steam flows in conduits 33 and 34 back to the accumulator 12. Another portion of the condensate in conduit 31 is conducted in conduit 35 to the waste heat boiler 14 and is at least partly vaporized there and fed through conduit 36 to the return conduit 34.
Example 1 Town gas is produced in a laboratory system correspond-ing to the flow scheme shown on the drawing. 1 kg methanol per hour is fed in conduit 1 to pump 2 and is pressurized to the gas-producing reaction pressure of 24 bars~ The methanol flows in conduit 3 to the heat exchanger 5 and is preheated there to ~L~7771~3 150C by cracked gas~ which is thus cooled. The preheated methanol is vaporized in the heat exchanger 7. Process steam, at a saturated-steam temperature is admixed from conduit 11 at a rate of 1 kg/h to the methanol vapor flowing in conduit 8. The mixture is then heated to a temperature of 460C in the fired heater 9. At this temperature, the mixture enters the cracking shaft reactor 4, which contains the catalyst that has been described hereinbefore as the first embodiment of a preferred catalyst.
The product gas which leaves the reactor 4 in conduit 13 at a rate of 1,29 standard m3 per hour and at a temperature of 630C and a pressure of 20 bars has the following composition in % by volume on a dry basis:
C0 21.7 C0 4.4 H2 45.7 CH4 28.2 That gas also contains 1.03 standard m3 water vapor per standard m3 of dry gas. The product gas is subsequently cooled in several heat exchangers and is finally available in conduit 20 with the following properties, which are typical of a town gas:
Net calorific value 4200 kcal per standard m3 Density 0.727 kg per standard m3 Relative density, based on air 0.562 The gas is delivered at a pressure of 18 bars and a temperature of 40C~ Under these conditions, the gas is saturated with water vapor.
Examnle 2 To produce a natural gas substitute, the product gas which is available behind the heat exchanger 5, with its entire water vapor content of 1.03 standard cubic meters per standard cubic meter of dry gas, is supplied at an inlet temperature of .
~ 8 ~L~777~3 260C to a wet methanating stage. The methanated gas leaving the first methanating stage at a rate of 0.7 standard m3 per standaxd m3 of product gas and at 480C has the following composition in % by volume on a dry basis :
C2 24.6 C0 0.6 H2 22.1 CH4 52.7 ~ That gas also contains 1.665 s-tandard m3 water vapor per standard m3 of dry gas. The gas is cooled to 250C in a waste heat boiler and is then fed to a second wet methanating stage, in which a gas having the following composition in percent by volume on a dry basis is produced at a rate of 0.82 standard m3 per standard m3 of gas leaving the first methanating stage:
C2 25.0 C0 less than 0.1 OEI~ 70.0 In both methanating stages, a known catalyst is used, which contains 40/0 by weight nickel on a support consisting of ~rO2-A1203. The gas leaving the second methanating stage contains 2.14 standard m3 per standard m3 of dry gas and is at a temperature of 330C. After being cooled to 250C, this gas flows through a further methanating stage, in which a gas having on a dry basis the following composition in percent by volume is produced at a rate of 0~97 standard m3 per standard m3 of gas from the preceding stage:
C2 25.0 C0 less than 0.1 H2 1.6 CH4 73.4 In the third methanating stage, the same catalyst is used as g 777~3 in the preceding stages~ The product gas from the third methana ting stage is scrubbed with hot potash in order to remove surplus CO20 The scrubbed gas has the following composition in % by volume:
97 CH4, 2 H2 and 1 C02 and constitutes a natural gas substitute~
-- 10 -- ' , . .
Town gas or a fuel gas which can be used as a sub-stitute for natural gas can be produced by known processes, which can be carried out with high efficiency and result in a gas which is of excellent quality and suitable for being supplied to existing pipe systems for distribu-ting natuxal gas or town gasO It is also known that the capacity of napththa-cracking plants used to produce fuel gas can be increased at times of peak demand by an addition of methanol. In such an instance, vaporized methanol is added to cracked gas, which contains water vapor and is at a temperature of about 400C. The mixture is then catalytically reacted on a catalyst which is suitable for the shift-conversion of CO. In this way, a gas having a high calori~ic value is produced so that the capacity of existing cracking plants can be increased by about 25 to 30%.
The use of methanol as the only starting material in the production of gas having a high calorific value is problematic when the gas is to be used to meet basic demands because methanol is expensive. On the other hand, methanol is highly suitable for producing gas because methanol can be transported and stored in a simple mannerO For this reason, methanol is preferred in a supply system to meet peak demands, e.g., in winter~
In a known process, fuel gas for peak demands is produced by a catalytic reaction of methanol and water vapor.
. In that process, methanol, water vapor, and air are supplied at inlet temperature of about 350C and are reacted on a high-nickel catalyst on an alumina support. Air is supplied at acontrolled rate mainly in order to produce a gas which has the desired calorific value. ~n the other hand, the supply of air .
~7~7~
has the disadvantage that the produc-t gas has an excessively high density so tha-t considerable quantities of CO2 must be scrubbed therefrom. The supply of air has also the resul-t that the gas leaving the cracking reactor is at an excessively high temperature and for this reason has an undesirably high CO
content, which must be converted in a succeeding shift conversion stage. The high reaction temperatures reached in the known process impose a high stress on the catalyst material and cause the same to be deteriorated wi-thin relatively short -time.
It is an object of the invention -to carry out -the process described first hereinbefore in such a manner tha-t a supply of air is not required and that the carbon monoxide eontent of the produe-t gas is minimized. This is accomplished aecording to the invention by supplying water vapor and vaporized methanol under superatmospheric pressure on a nickel eatalyst, the water vapor and vaporized me-thanol being supplied at a weight ratio of about 0.5 to 1.5 and at inlet -temperature of about 300 to 500C to a reactor and being reaeted -therein under adiaba-tie conditions and under a pressure in the range of about 10 to 40 bars; the niekel eatalyst eon-tains 25-50% by weight niekel in the form of the compound Ni5MgA12Og, 5-40% by weight high-alumina eement, and at least 5% by weight zireonium dioxide. The produet gas leaving -the reactor at temperatures of about 500 to 700C is subsequently eooled.
This proeess results in a produet gas whieh has typically a earbon monoxide eontent below 5% by volume based on dry gas. After a sufficien-t cooling of the gas and a condensation of wa-ter vapor therefrom, -the gas can be used as town gas wi-thout need for a further conversion of gas constituents.
For a production oE certain grades of town gas having an upper heating value of 4000 to 5000 kcal per s-tandard m3, the process according -to the invention is carried out in such 1~ .
~(:97~7~8 .
a manner that the product gas is withdrawn from the reactor at temperatures of 580 to 700C and is cooled and part of the carbon dioxide is removed from the gas to an extent which depends on the desired density of the town gas.
When a natural gas substitute which contains more than 90% by volume of methane (on a dry basis) is desired, the hot product gas resulting from the catalytic cracking of methanol is cooled to 250 to 350C and is reacted in at least one methanat-ing stage with water vapor on a nickel-containing catalyst material, whereafter the methanated gas is scrubbed to remove surplus carbon dioxide. The methanation is carried out under conditions known per se.
The catalytic reaction of methanol and water vapor in the process according to the invention is considerably improved by the use of the above type of catalyst.
A first embodiment of such a catalyst will be described hereinafter. This catalyst contains the compounds Ni5MgA12Og and ZrO2 at a weight ratio of 13:1 and also contains a high-alumina cement, which amounts to 306 of the total weight of the catalyst. The high-alumina cement has the Eollowing composition in percent by welght : 26.4 CaO, 71.9 A12O3 , 0.2 Fe2O3, 0.2 MgO, 0.4 Na2O, 0.07 SiO2(and traces of K, Cr, Cu, Mn, Ni and also Pb). The desirable catalyst of this first embodiment is produced as follows :
Within 15 minutes, solution II is added to suspension I.
The suspension and solution have the following compositions:
Suspension I
1250 g sodium carbonate in 6 1 wa-ter containing 37.5 g ZrO2 Solution II
30 250 g Mg(NO3)2. 6H2O
1 .~`, ~ , . ~
7771~3 1280 g Ni(N03)2. 6H20 690 g Al(N03). 9H20 in 6 1 water The resulting precipitate consisting of Ni5Mg(OH)16.
C03.4H20 on zirconium dioxide is filtered o-ff, washed to remove all alkali, dried at 110C for 12 hours anc~ then calcined at 400C
for four hours to produce a calcine which contains nickel oxide, magnesia, alumina and zirconium dioxide as support components.
350 g of the calcine and 150 g high-alumina cement are mixed in a dry state. When 60g of water have been added to the mixture, the same is compacted to form 3x3 mm tablets, which are then briefly watered and are subsequently caused to set completely by being stored in a moist state at 40C in a closed system for si~ days. The resulting tablets have an end face crushing strength of 46~ kg/cm and a bul]~ density of 1.57 kg/l. In the oxidic state, the catalyst has a nickel content of 28.7% by weight. Before the catalyst is used, it is reduce~. This can be accomplished by a treatment with hydrogen or other reducing gases.
A second embodiment of a desirable catalyst contains the compounds Ni5MgA1209, ZrO2 and a-A1203 at a weight ratio of 12:1:2 and also contains the high-alumina cement explained above, in an amount of 15% of the total weight of the catalyst. The catalyst of this second embodiment is duced as follows :
Solutions I and II are continuously combined with suspension III at a temperature of 60C and in such a manner tha~ the pH value of the solution does not decreas~ below 8.5.
The solutions and -the suspension have the followin~ compositions:
Solution I
~ .
1250 g sodium carbonate in 6 1 water Solution II
255 g Mg(N03)2.6H20 1280 g Ni(No3)2.6H20 ~L~777~
690 g Al(NO3)3.9H2O in 6 1 water Suspension III
-43.2 g zirconium dioxide and 74~0 g ~- A12O3 in 3 1 water.
The resulting precipitate i~ filtered ofE and the filter cake is washed and then dried at 110C for 12 hours and is subsequently calcined at 400C for 4 hours.
425 g of the resulting calcine are mixed with 75 g high-alumina cement in a dry state. After an addition of 75 g water to the mixture the latter is compacted to`form 3 x 3 mm tablets. The catalyst is shortly watered and then dried at 110C for 12 hours. After this treatmen-t, the catalyst has an end face crushing strength of 453 kg/cm2 and a bulk density of 1.52 kg/l. In the oxidic state, the catalyst contains 30.3% by weight of nickel. The catalyst is reduced beEore it is used.
Preferred embodiments of the invention will now be described in greater detail with reference to the following examples and the accompanying drawing which represents a flow -diagram of a process according to the invention.
Referring first to the drawing methanol to be cracked is supplied in conduit 1 and is forced by pump 2 into conduit 3 and conducted in the same through a plurality of heating stages into a shaft reactor 4. The methanol is first heated in a heat exchanger 5 and is then conducted in conduit 6 to another heat exchanger 7 and is vaporized therein. Methanol vapor then flows in conduit 8 to a heater 9 and thereafter in conduit 10 to the reactor 4.
The water vapor required for the catalytic reaction in the reactor 4 comes from the steam accumulator 12 and is added to the methanol through conduit 11. The reactor 4 contains a fixed bed consisting of the catal~st material. In the reactor ~, the reaction is carried out under autothermic, acliaba-tic ~LC3 777~3 conditions. Product gas leaving the reactor 4 through conduit 13 contains water vapor and owing to the exothermic reaction in the reactor is at a temperature of 500-700C, which is higher than the inlet temperature of the material to be reacted~
The product gas flowing in conduit 13 is first cooled in a waste heat boiler 14, from which the product gas is conducted in conduit 15 to the heat exchanger 7. From the latter, the product gas is conducted in conduitl6 to a feed water preheater 3L~777~
17. Further cooling stages for the product gas consist of the heat exchanger 5, a fresh water preheater 18, and an air cooler 19. The cooled product gas in the conduit 20 may be directly used as town gas.
When it is desired to produce certain grades of town gas, the gas flowing in conduit 20 is fed to a known scrubber for the removal of surplus carbon dioxide. If the gas is to be prQcessed to produce a natural gas substitute, the product gas is fed to a single- or multi-stage methanating plant. ~n that case, C02 is scrubbed off before or behind the last methanating stage.
The water vapor required for the reaction is produced as follows: The feed water, which may consist, e.g., of condensate recovered from the gas, is conducted in conduit 25 through the fresh water preheater 18 and is then collected in the feed water container 25, in which the water is degasified and from which the water is fed through conduit 27, pump 28 and conduit 29 to the preheater 17. From the latter, the water is fed through conduit 30 to the steam accumulator 12. Condensate formed in the steam accumulator 12 flows through a conduit 31 and a branch conduit 32 to the heater 9, in which the water vapor is vaporized by heating means, not shown. The steam flows in conduits 33 and 34 back to the accumulator 12. Another portion of the condensate in conduit 31 is conducted in conduit 35 to the waste heat boiler 14 and is at least partly vaporized there and fed through conduit 36 to the return conduit 34.
Example 1 Town gas is produced in a laboratory system correspond-ing to the flow scheme shown on the drawing. 1 kg methanol per hour is fed in conduit 1 to pump 2 and is pressurized to the gas-producing reaction pressure of 24 bars~ The methanol flows in conduit 3 to the heat exchanger 5 and is preheated there to ~L~7771~3 150C by cracked gas~ which is thus cooled. The preheated methanol is vaporized in the heat exchanger 7. Process steam, at a saturated-steam temperature is admixed from conduit 11 at a rate of 1 kg/h to the methanol vapor flowing in conduit 8. The mixture is then heated to a temperature of 460C in the fired heater 9. At this temperature, the mixture enters the cracking shaft reactor 4, which contains the catalyst that has been described hereinbefore as the first embodiment of a preferred catalyst.
The product gas which leaves the reactor 4 in conduit 13 at a rate of 1,29 standard m3 per hour and at a temperature of 630C and a pressure of 20 bars has the following composition in % by volume on a dry basis:
C0 21.7 C0 4.4 H2 45.7 CH4 28.2 That gas also contains 1.03 standard m3 water vapor per standard m3 of dry gas. The product gas is subsequently cooled in several heat exchangers and is finally available in conduit 20 with the following properties, which are typical of a town gas:
Net calorific value 4200 kcal per standard m3 Density 0.727 kg per standard m3 Relative density, based on air 0.562 The gas is delivered at a pressure of 18 bars and a temperature of 40C~ Under these conditions, the gas is saturated with water vapor.
Examnle 2 To produce a natural gas substitute, the product gas which is available behind the heat exchanger 5, with its entire water vapor content of 1.03 standard cubic meters per standard cubic meter of dry gas, is supplied at an inlet temperature of .
~ 8 ~L~777~3 260C to a wet methanating stage. The methanated gas leaving the first methanating stage at a rate of 0.7 standard m3 per standaxd m3 of product gas and at 480C has the following composition in % by volume on a dry basis :
C2 24.6 C0 0.6 H2 22.1 CH4 52.7 ~ That gas also contains 1.665 s-tandard m3 water vapor per standard m3 of dry gas. The gas is cooled to 250C in a waste heat boiler and is then fed to a second wet methanating stage, in which a gas having the following composition in percent by volume on a dry basis is produced at a rate of 0.82 standard m3 per standard m3 of gas leaving the first methanating stage:
C2 25.0 C0 less than 0.1 OEI~ 70.0 In both methanating stages, a known catalyst is used, which contains 40/0 by weight nickel on a support consisting of ~rO2-A1203. The gas leaving the second methanating stage contains 2.14 standard m3 per standard m3 of dry gas and is at a temperature of 330C. After being cooled to 250C, this gas flows through a further methanating stage, in which a gas having on a dry basis the following composition in percent by volume is produced at a rate of 0~97 standard m3 per standard m3 of gas from the preceding stage:
C2 25.0 C0 less than 0.1 H2 1.6 CH4 73.4 In the third methanating stage, the same catalyst is used as g 777~3 in the preceding stages~ The product gas from the third methana ting stage is scrubbed with hot potash in order to remove surplus CO20 The scrubbed gas has the following composition in % by volume:
97 CH4, 2 H2 and 1 C02 and constitutes a natural gas substitute~
-- 10 -- ' , . .
Claims (5)
1. A process for the production of a methane-containing fuel gas, which comprises supplying water vapor and vaporized methanol under superatmospheric pressure on a nickel catalyst, said water vapor and vaporized methanol being supplied at a weight ratio of about 0.5 to 1.5 and at inlet temperature of about 300 to 500°C to a reactor and being reacted therein under adiabatic conditions and under a pressure in the range of about 10 to 40 bars, said nickel catalyst containing 25-50 %
by weight nickel in the form of the compound Ni5MgAl2O9, 5-40 %
by weight high-alumina cement, and at least 5 % by weight zirconium dioxide, the product gas leaving the reactor at temperatures of about 500 to 700°C being subsequently cooled.
by weight nickel in the form of the compound Ni5MgAl2O9, 5-40 %
by weight high-alumina cement, and at least 5 % by weight zirconium dioxide, the product gas leaving the reactor at temperatures of about 500 to 700°C being subsequently cooled.
2. A process according to claim 1 for producing a town gas having a gross calorific value of 4000 to 5000 kcal per standard m3, characterized in that the product gas is with-drawn from the reactor at temperatures of 580 to 700°C and is cooled and part of the carbon dioxide is removed from the gas to an extent which depends on desired density of the gas.
3. A process according to claim 1 for producing a natural gas substitute which contains more than 90% methane by volume, characterized in that the hot product has resulting from the catalytic cracking of methanol is cooled to 250 to 350°C and is reacted in at least one methanating stage with water vapor on nickel-containing catalyst material, whereafter the methanated gas is scrubbed to remove surplus CO2.
4. A process according to claims 1, 2 or 3, character-ized in that the catalyst contains Ni5MgAl2O9 and ZrO2 at a weight ratio of 13:1 and high-alumina cement in an amount of 30 % of the total weight of the catalyst.
5. A process according to claims 1, 2 or 3, characterized in that the catalyst contains Ni5MgAl2O9, ZrO2 and .alpha.-Al2O3 at a weight ratio of 12:1:2 and high-alumina cement in an amount of 15% of the total weight of the catalyst.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2641113A DE2641113C2 (en) | 1976-09-13 | 1976-09-13 | Process for generating a methane-containing heating gas through the catalytic conversion of methanol with water vapor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1077718A true CA1077718A (en) | 1980-05-20 |
Family
ID=5987774
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA285,992A Expired CA1077718A (en) | 1976-09-13 | 1977-09-01 | Process of producing a fuel gas by the catalytic reaction of methanol and water vapor |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS5335702A (en) |
| AT (1) | AT372669B (en) |
| BR (1) | BR7706069A (en) |
| CA (1) | CA1077718A (en) |
| CH (1) | CH630402A5 (en) |
| DK (1) | DK404977A (en) |
| ES (1) | ES460521A1 (en) |
| FR (1) | FR2364191A1 (en) |
| IT (1) | IT1086077B (en) |
| SE (1) | SE426483B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AR220381A1 (en) * | 1979-04-16 | 1980-10-31 | Sao Paulo Gas | CATALYTIC PROCESS FOR THE GASIFICATION OF ETHANOL WITH STEAM |
| BE884720A (en) * | 1980-08-11 | 1981-02-11 | Catalysts & Chem Europ | METHANOL REFORMING PROCESS AND DEVICE IMPLEMENTED |
| JPS58183563A (en) * | 1982-04-16 | 1983-10-26 | Toshiba Corp | Apparatus for sorting and receiving blank |
| JPH0613720B2 (en) * | 1985-12-27 | 1994-02-23 | 日揮株式会社 | Method for producing methane gas |
| JPH0558721U (en) * | 1992-01-22 | 1993-08-03 | 三井ホーム株式会社 | Wall framework with wiring construction |
| JP2768117B2 (en) * | 1992-03-17 | 1998-06-25 | 日本鋼管株式会社 | Sludge reforming method |
| CN110773174B (en) * | 2019-09-24 | 2020-11-10 | 浙江大学 | Catalyst for preparing gamma-butyrolactone through dehydrogenation of 1, 4-butanediol and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1447974A (en) * | 1972-11-13 | 1976-09-02 | British Gas Corp | Process for the production of gases containing methane from hydro carbons |
| DE2311756A1 (en) * | 1973-03-09 | 1974-09-12 | Basf Ag | PROCESS FOR THE PRODUCTION OF GASES RICH IN METHANE, CARBON OXIDES AND HYDROGEN |
| US3888043A (en) * | 1973-06-25 | 1975-06-10 | Texaco Inc | Production of methane |
| DE2624975A1 (en) * | 1975-07-28 | 1977-02-17 | Engelhard Min & Chem | SINGLE-STAGE CATALYTIC PROCESS FOR PRODUCING FUEL GAS |
-
1977
- 1977-06-03 AT AT0393277A patent/AT372669B/en not_active IP Right Cessation
- 1977-07-05 FR FR7720624A patent/FR2364191A1/en active Granted
- 1977-07-07 ES ES460521A patent/ES460521A1/en not_active Expired
- 1977-08-29 JP JP10352077A patent/JPS5335702A/en active Granted
- 1977-09-01 CA CA285,992A patent/CA1077718A/en not_active Expired
- 1977-09-07 IT IT27318/77A patent/IT1086077B/en active
- 1977-09-12 BR BR7706069A patent/BR7706069A/en unknown
- 1977-09-12 DK DK404977A patent/DK404977A/en not_active Application Discontinuation
- 1977-09-12 CH CH1112577A patent/CH630402A5/en not_active IP Right Cessation
- 1977-09-13 SE SE7710266A patent/SE426483B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| DK404977A (en) | 1978-03-14 |
| SE426483B (en) | 1983-01-24 |
| JPS5335702A (en) | 1978-04-03 |
| ATA393277A (en) | 1983-03-15 |
| FR2364191A1 (en) | 1978-04-07 |
| FR2364191B1 (en) | 1983-09-02 |
| ES460521A1 (en) | 1978-06-16 |
| SE7710266L (en) | 1978-03-14 |
| AT372669B (en) | 1983-11-10 |
| CH630402A5 (en) | 1982-06-15 |
| JPS6160117B2 (en) | 1986-12-19 |
| BR7706069A (en) | 1978-06-06 |
| IT1086077B (en) | 1985-05-28 |
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