CA1053706A - Process for the preparation of methanol - Google Patents
Process for the preparation of methanolInfo
- Publication number
- CA1053706A CA1053706A CA232,465A CA232465A CA1053706A CA 1053706 A CA1053706 A CA 1053706A CA 232465 A CA232465 A CA 232465A CA 1053706 A CA1053706 A CA 1053706A
- Authority
- CA
- Canada
- Prior art keywords
- gas
- temperature
- carbon dioxide
- hydrogen
- 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.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/1516—Multisteps
- C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A B S T R A C T
A process for the preparation of methanol, comprising the following steps:
(1) Preparation of a hydrogen- and carbon monoxide-containing gas by partial combustion of a carbonaceous material.
(2) Conversion of carbon monoxide with steam into carbon dioxide and hydrogen in the gas obtained according to step (1).
(3) Separation of part of the carbon dioxide from the gas obtained in step (2).
(4) Reaction of remaining gaseous carbon dioxide with hydrogen to form methanol.
(5) Drying of the resultant methanol.
A process for the preparation of methanol, comprising the following steps:
(1) Preparation of a hydrogen- and carbon monoxide-containing gas by partial combustion of a carbonaceous material.
(2) Conversion of carbon monoxide with steam into carbon dioxide and hydrogen in the gas obtained according to step (1).
(3) Separation of part of the carbon dioxide from the gas obtained in step (2).
(4) Reaction of remaining gaseous carbon dioxide with hydrogen to form methanol.
(5) Drying of the resultant methanol.
Description
The invention relates to a process for the preparation of methanol. This process comprises the following steps.
(1) Preparation of a hydrogen- and carbon monoxide-containing gas by partial combustion of a carbonaceous material.
(1) Preparation of a hydrogen- and carbon monoxide-containing gas by partial combustion of a carbonaceous material.
(2) Conversion of carbon monoxide with steam into carbon dioxide and hydrogen in the gas obtained according to step (1).
(3) Removal of part of the carbon dioxide from the gas obtained in step (2).
(4) Reaction of remaining gaseous carbon dioxide with hydrogen to form methanol.
(5) Drying of the resultant methanol.
The partial combustion according to step (1) of the process according to the invention can be carried out in any desired manner. A survey of the known processes for the preparation of hydrogen and carbon monoxide-containing gases by partial combustion of coal or oil is given in "Ullmann's Enzyklopadie der technischen Chemie" Volume 10 (1958), pp. 360-458. Several processes for the partial combustion of carbonaceous material are used on a commercial scale. If the starting material is liquid, it is preferred to use the "Shell Gasification Process" for step (1) of the process according to the invention. In the case of solid starting material it ~053706 is advantagçous to use the "Koppers~Totzek Process".
As feed for the process according to the invention any carbonaceous material can be used. By carbonaceous material is meant any fuel consisting substantially of chemically bound or unbound carbon. This material may contain oxygen, sulphur, hydrogen, nitrogen, metals and/or ash. Such a starting material comprises, for example, lignite, bituminous coal, sub-bituminous coal, anthracite, coke, mineral oil or a fraction thereof, oil derived from tar sand and oil derived from bituminous shale.
If the feed is solid, it is preferably first rendered into powder form before being converted by partial combustion, so that the partial combustion proceeds more rapidly and more completely. The particle size of this powder is advantageously so selected that 70% of the solid feed can pass a 200-mesh sieve.
During the partial combustion according to step (1) of the process according to the invention, the carbonaceous feed is converted with oxygen into a gas mixture which substantially comprises hydrogen and carbon monoxide.
The purity of the oxygen is preferably at least 90%
by volume, nitrogen, carbon dioxide and argon being admitted as impurities. Steam may be supplied as temperature moderator. A quantity of 5-150% by volume of steam, ~0537~6 based on the oxygen, is suitably added to the oxygen or to the reaction mixture.
The oxygen is preferably preheated before it is supplied to the carbonaceous fuel. This preheating is suitably carried out by indirect heat exchange, for example with the hot product gas obtained from step (1) of the present process. By preheating, the oxygen is preferably brought to a temperature in the range from 200 to 500C.
After preheating, the hot oxygen is advantageously mixed with the carbonaceous fuel and the oxygen/fuel mixture is introduced into a reactor, preferably in the form of a jet. This reactor preferably comprises an empty steel vessel, the interior of which is lined with heat-resistant material. A preferred reactor is described in the U.K. patent specifications 780,120, 832,385, 850,409 and 967,885.
The partial combustion is preferably carried out at a temperature in the range from 900 to 1800C, which temperature is the result of the reaction between the carbonaceous fuel and oxygen and steam.
In a preferred embodiment the mixture of fuel and oxygen is passed into the reactor at a high velocity.
A suitable linear velocity is in the range from 10 to 200 m/sec. The pressure maintained in the reactor ~053706 may vary within wide limits and is advantageously kept in the range from 1-200 bar abs.
In order to convert into gas as much as possible of the fuel introduced into the reactor, the fuel particles or droplets must be present in the reactor for a certain residence time. It has been found that a residence time betwéen 0.1 and 12 sec. is sufficient to achieve this object.
After the carbonàceous starting material has been converted into gas, this reaction product, which consists substantially of H2, C0, C02 and H20, is discharged from the reactor.
This gas has a high temperature, generally a temperature above 1100C, and may contain impurities such as ash, solid carbonaceous material and hydrogen sulphide.
To permit the removal of any impurities, the gas is preferably first cooled in a boiler in which steam is generated by means of the waste heat.
The solid matter content of the crude gas leaving the boiler is kept low by choosing the conditions in the reactor appropriately. Nevertheless, a reduction in the solid matter content may be desirable, for example if the gas has to be desulphurized, and also `1053706 for the next step of the present process, in which carbon monoxide is converted with steam into carbon dioxide and hydrogen.
To this end the gas is preferably passed through a scrubber in which it is washed with water. An installation of this type is described in the British patent specification 826,209. This washing treatment produces a gas which contains substantially no solid matter and which has a temperature between 20 and 80C.
The gas freed of solid matter has a composition which is usually between the following limits: -Table I
Vol.%
It may be further purified by removing H2S and possibly part of the C02. This purification may be carried out in a known manner.
.
H2S and C02 are preferably removed from the gas by means of the ADIP process or the SULFINOL process, which are described in the U.K. patent specifications 1,444,963, 1,131,989, 965,358, 957,260 and 972,140.
The gas freed of solid matter and H2S has a composition between the following limits:
Table II
Vol.%
co 70 40 H2S 0-0 . 01 It is passed to step t2) of the process according to the invention.
In this step a large part of the carbon monoxide present is converted into carbon dioxide and hydrogen by reaction with steam according to the reaction CO + H20 > C2 ~ H2 This step may be carried out in any desired manner.
It is generally preferred to carry out this conversion in two or three stages in the presence of a catalyst.
~053706 The first stage(s) is (are) suitably carried out at a temperature in the range from 250 to 450C. The final stage is preferably carried out at a temperature in the range from 200 to 400C. In the stage which is carried out at relatively low temperature use is preferably made of a copper-zinc catalyst. In the stage(s) which is (are) carried out at relatively high temperature, use may be suitably made of an iron-chromium catalyst. The pressure may vary within wide limits. The reaction ispreferably carried out at a pressure between 10 and 100 bar.
The amount of steam present in the gas mixture which is subjected to this reaction is preferably 1-20 mol/mol of C0.
After passing the second stage of the present process, the dry gas mixture usually has the following composition:
Table III
Vol.%
C0 0.2 -3 ~o53706 This gas mixture is generally not of suitable composition for use in the production of methanol by hydrogenation of the carbon dioxide and carbon monoxide present. For this reason part of the carbon dioxide must be removed from the gas mixture. This may be effected in any desired manner, such as washing with a physical or chemical solvent for carbon dioxide, or by selective adeorption of the carbon dioxide to solid materials suitable for this purpose. Processes of this type are described in "Ullmanns Enzyklopadie der technischen Chemie" Volume 9 (1958), pp. 756-766.
To remove part of the carbon dioxide, the gas mixture is preferably entirely or partly cooled to a temperature between -10C and -80C and at a pressure between 1 and 200 bar abs. In certain combinations of sufficiently low temperature and sufficiently high pressure, part of the C02 liquefies so that it can be separated in a simple manner. It is therefore indeed preferable to select the combination of temperature and pressure in such a,way bhat liquid CO2 is formed.
However, it is also possible first to render part of the C02 directly into the solid state and subsequently separate it, although this latter treatment is more difficult than the separation of liquid C02.
l~S;~7~6 The conditions are preferably so selected that 50-80%
of the C02 can be separated.
After separation of part of the C02 the gas mixture has the following composition:
Table IV
Vol.%
N2 ~5 This gas mixture is used for the production of methanol according to the reactions (a) C02 3H2 ~ CH30H + H20 (b) C0 + 2H2 CH30H
During these reactions the gas mixture is passed over a catalyst, preferably at a temperature between 300 and 375C
and a pressure between 270 and 350 bar abs. The catalyst used is suitably zinc, copper and/or chromium and/or one or more oxides of Zn, Cu and/or Cr, supported on a carrier.
After the formation of the methanol the reaction product has the following composition:
- ~053706 Table V
Vol.%
The reaction product is subsequently cooled, as a result of which the methanol and the water become liquid and are separated from the still gaseous C02, N2 and A. After drying OI' the liquid product pure methanol is obtained.
The invention will now be further elucidated with reference to the following Example.
EXAMPLE
. . _ The starting material used was coal having the following composition:
% wt.
C73.7 H5.1 8.8 S0.9 N1.6 ash9.9 This coal contained 33.8% by weight of volatile components and also 2.6% by weight of water.
The coal was gasified by partial combustion by means of 0.841 kg of 2 ancl 0.234 kg of steam per kg of anhydrous and ash-free coal. The temperature used was 1100C and the pressure 40 bar abs.
After cooling to 40C and removal of solid matter, the resultant gas had the following composition:
Vol.%
H20 0.18 H2 33.95 C0 62. o8 CO2 1 . 1 9 CH4 1.33 H2S 0.30 N2 0.75 A 0.22 This gas was purified by means of the Sulfinol-process, in which the gas was washed at 40C and 39 bar with a mixture of sulfolane, di-isopropanolamine and water.
The composition of the purified gas was as follows:
Vol.%
H20 0.18 H2 34.46 C0 63.o3 CH4 1.35 N2 o.76 A 0.22 ~053706 The purified gas was subjected to the water gas shift reaction, in which carbon monoxide is converted with steam into carbon dioxide and hydrogen in three stages.
All stages were carried out at a pressure of 38 bar. In the first two stages an iron-chromium catalyst was used. The temperature was 300-400C.
In the final stage use was made of a copper-zinc catalyst at a temperature of 250C.
After drying, the product gas of the water gas shift reaction had the following composition:
Vol .,70 H2 59.66 C0 3.50 C2 38.40 CH4 o.83 N2 0.47 A 0.14 This gas was subsequently cooled at a pressure of 30 bar to a temperature of -50C, as a result of which about half of the C02 present condensed. This liquid C2 was sepa~ated after which the residual gas had the following composition:
105~706 Vol.%
H2 73.21 C0 0.61 C2 24.41 CH4 1.02 N2 0.58 A 0.17 This gas was heated to 350C and passed at this temperature and a pressure of 300 bar abs. over a Zn/Cr203/Al203 catalyst, forming methanol by hydrogenation of the carbon dioxide and carbon monoxide present. After condensation, separation of gaseous components and drying, pure methanol was obtained.
By means of the process described above, a quantity of 1100 litres of methanol was produced from 1000 kg of anhydrous and ash-free coal.
The partial combustion according to step (1) of the process according to the invention can be carried out in any desired manner. A survey of the known processes for the preparation of hydrogen and carbon monoxide-containing gases by partial combustion of coal or oil is given in "Ullmann's Enzyklopadie der technischen Chemie" Volume 10 (1958), pp. 360-458. Several processes for the partial combustion of carbonaceous material are used on a commercial scale. If the starting material is liquid, it is preferred to use the "Shell Gasification Process" for step (1) of the process according to the invention. In the case of solid starting material it ~053706 is advantagçous to use the "Koppers~Totzek Process".
As feed for the process according to the invention any carbonaceous material can be used. By carbonaceous material is meant any fuel consisting substantially of chemically bound or unbound carbon. This material may contain oxygen, sulphur, hydrogen, nitrogen, metals and/or ash. Such a starting material comprises, for example, lignite, bituminous coal, sub-bituminous coal, anthracite, coke, mineral oil or a fraction thereof, oil derived from tar sand and oil derived from bituminous shale.
If the feed is solid, it is preferably first rendered into powder form before being converted by partial combustion, so that the partial combustion proceeds more rapidly and more completely. The particle size of this powder is advantageously so selected that 70% of the solid feed can pass a 200-mesh sieve.
During the partial combustion according to step (1) of the process according to the invention, the carbonaceous feed is converted with oxygen into a gas mixture which substantially comprises hydrogen and carbon monoxide.
The purity of the oxygen is preferably at least 90%
by volume, nitrogen, carbon dioxide and argon being admitted as impurities. Steam may be supplied as temperature moderator. A quantity of 5-150% by volume of steam, ~0537~6 based on the oxygen, is suitably added to the oxygen or to the reaction mixture.
The oxygen is preferably preheated before it is supplied to the carbonaceous fuel. This preheating is suitably carried out by indirect heat exchange, for example with the hot product gas obtained from step (1) of the present process. By preheating, the oxygen is preferably brought to a temperature in the range from 200 to 500C.
After preheating, the hot oxygen is advantageously mixed with the carbonaceous fuel and the oxygen/fuel mixture is introduced into a reactor, preferably in the form of a jet. This reactor preferably comprises an empty steel vessel, the interior of which is lined with heat-resistant material. A preferred reactor is described in the U.K. patent specifications 780,120, 832,385, 850,409 and 967,885.
The partial combustion is preferably carried out at a temperature in the range from 900 to 1800C, which temperature is the result of the reaction between the carbonaceous fuel and oxygen and steam.
In a preferred embodiment the mixture of fuel and oxygen is passed into the reactor at a high velocity.
A suitable linear velocity is in the range from 10 to 200 m/sec. The pressure maintained in the reactor ~053706 may vary within wide limits and is advantageously kept in the range from 1-200 bar abs.
In order to convert into gas as much as possible of the fuel introduced into the reactor, the fuel particles or droplets must be present in the reactor for a certain residence time. It has been found that a residence time betwéen 0.1 and 12 sec. is sufficient to achieve this object.
After the carbonàceous starting material has been converted into gas, this reaction product, which consists substantially of H2, C0, C02 and H20, is discharged from the reactor.
This gas has a high temperature, generally a temperature above 1100C, and may contain impurities such as ash, solid carbonaceous material and hydrogen sulphide.
To permit the removal of any impurities, the gas is preferably first cooled in a boiler in which steam is generated by means of the waste heat.
The solid matter content of the crude gas leaving the boiler is kept low by choosing the conditions in the reactor appropriately. Nevertheless, a reduction in the solid matter content may be desirable, for example if the gas has to be desulphurized, and also `1053706 for the next step of the present process, in which carbon monoxide is converted with steam into carbon dioxide and hydrogen.
To this end the gas is preferably passed through a scrubber in which it is washed with water. An installation of this type is described in the British patent specification 826,209. This washing treatment produces a gas which contains substantially no solid matter and which has a temperature between 20 and 80C.
The gas freed of solid matter has a composition which is usually between the following limits: -Table I
Vol.%
It may be further purified by removing H2S and possibly part of the C02. This purification may be carried out in a known manner.
.
H2S and C02 are preferably removed from the gas by means of the ADIP process or the SULFINOL process, which are described in the U.K. patent specifications 1,444,963, 1,131,989, 965,358, 957,260 and 972,140.
The gas freed of solid matter and H2S has a composition between the following limits:
Table II
Vol.%
co 70 40 H2S 0-0 . 01 It is passed to step t2) of the process according to the invention.
In this step a large part of the carbon monoxide present is converted into carbon dioxide and hydrogen by reaction with steam according to the reaction CO + H20 > C2 ~ H2 This step may be carried out in any desired manner.
It is generally preferred to carry out this conversion in two or three stages in the presence of a catalyst.
~053706 The first stage(s) is (are) suitably carried out at a temperature in the range from 250 to 450C. The final stage is preferably carried out at a temperature in the range from 200 to 400C. In the stage which is carried out at relatively low temperature use is preferably made of a copper-zinc catalyst. In the stage(s) which is (are) carried out at relatively high temperature, use may be suitably made of an iron-chromium catalyst. The pressure may vary within wide limits. The reaction ispreferably carried out at a pressure between 10 and 100 bar.
The amount of steam present in the gas mixture which is subjected to this reaction is preferably 1-20 mol/mol of C0.
After passing the second stage of the present process, the dry gas mixture usually has the following composition:
Table III
Vol.%
C0 0.2 -3 ~o53706 This gas mixture is generally not of suitable composition for use in the production of methanol by hydrogenation of the carbon dioxide and carbon monoxide present. For this reason part of the carbon dioxide must be removed from the gas mixture. This may be effected in any desired manner, such as washing with a physical or chemical solvent for carbon dioxide, or by selective adeorption of the carbon dioxide to solid materials suitable for this purpose. Processes of this type are described in "Ullmanns Enzyklopadie der technischen Chemie" Volume 9 (1958), pp. 756-766.
To remove part of the carbon dioxide, the gas mixture is preferably entirely or partly cooled to a temperature between -10C and -80C and at a pressure between 1 and 200 bar abs. In certain combinations of sufficiently low temperature and sufficiently high pressure, part of the C02 liquefies so that it can be separated in a simple manner. It is therefore indeed preferable to select the combination of temperature and pressure in such a,way bhat liquid CO2 is formed.
However, it is also possible first to render part of the C02 directly into the solid state and subsequently separate it, although this latter treatment is more difficult than the separation of liquid C02.
l~S;~7~6 The conditions are preferably so selected that 50-80%
of the C02 can be separated.
After separation of part of the C02 the gas mixture has the following composition:
Table IV
Vol.%
N2 ~5 This gas mixture is used for the production of methanol according to the reactions (a) C02 3H2 ~ CH30H + H20 (b) C0 + 2H2 CH30H
During these reactions the gas mixture is passed over a catalyst, preferably at a temperature between 300 and 375C
and a pressure between 270 and 350 bar abs. The catalyst used is suitably zinc, copper and/or chromium and/or one or more oxides of Zn, Cu and/or Cr, supported on a carrier.
After the formation of the methanol the reaction product has the following composition:
- ~053706 Table V
Vol.%
The reaction product is subsequently cooled, as a result of which the methanol and the water become liquid and are separated from the still gaseous C02, N2 and A. After drying OI' the liquid product pure methanol is obtained.
The invention will now be further elucidated with reference to the following Example.
EXAMPLE
. . _ The starting material used was coal having the following composition:
% wt.
C73.7 H5.1 8.8 S0.9 N1.6 ash9.9 This coal contained 33.8% by weight of volatile components and also 2.6% by weight of water.
The coal was gasified by partial combustion by means of 0.841 kg of 2 ancl 0.234 kg of steam per kg of anhydrous and ash-free coal. The temperature used was 1100C and the pressure 40 bar abs.
After cooling to 40C and removal of solid matter, the resultant gas had the following composition:
Vol.%
H20 0.18 H2 33.95 C0 62. o8 CO2 1 . 1 9 CH4 1.33 H2S 0.30 N2 0.75 A 0.22 This gas was purified by means of the Sulfinol-process, in which the gas was washed at 40C and 39 bar with a mixture of sulfolane, di-isopropanolamine and water.
The composition of the purified gas was as follows:
Vol.%
H20 0.18 H2 34.46 C0 63.o3 CH4 1.35 N2 o.76 A 0.22 ~053706 The purified gas was subjected to the water gas shift reaction, in which carbon monoxide is converted with steam into carbon dioxide and hydrogen in three stages.
All stages were carried out at a pressure of 38 bar. In the first two stages an iron-chromium catalyst was used. The temperature was 300-400C.
In the final stage use was made of a copper-zinc catalyst at a temperature of 250C.
After drying, the product gas of the water gas shift reaction had the following composition:
Vol .,70 H2 59.66 C0 3.50 C2 38.40 CH4 o.83 N2 0.47 A 0.14 This gas was subsequently cooled at a pressure of 30 bar to a temperature of -50C, as a result of which about half of the C02 present condensed. This liquid C2 was sepa~ated after which the residual gas had the following composition:
105~706 Vol.%
H2 73.21 C0 0.61 C2 24.41 CH4 1.02 N2 0.58 A 0.17 This gas was heated to 350C and passed at this temperature and a pressure of 300 bar abs. over a Zn/Cr203/Al203 catalyst, forming methanol by hydrogenation of the carbon dioxide and carbon monoxide present. After condensation, separation of gaseous components and drying, pure methanol was obtained.
By means of the process described above, a quantity of 1100 litres of methanol was produced from 1000 kg of anhydrous and ash-free coal.
Claims (10)
1. A process for the preparation of methanol, characterized in that this process comprises the following steps:
(1) preparing a hydrogen- and carbon monoxide-containing gas by partial combustion of a carbonaceous material, (2) converting substantially all of the carbon monoxide with steam into carbon dioxide and hydrogen in the gas obtained according to step (1), (3) separating part of the carbon dioxide from the gas obtained in step (2), (4) reacting remaining gaseous carbon dioxide with hydrogen to form methanol, and (5) drying the resultant methanol.
(1) preparing a hydrogen- and carbon monoxide-containing gas by partial combustion of a carbonaceous material, (2) converting substantially all of the carbon monoxide with steam into carbon dioxide and hydrogen in the gas obtained according to step (1), (3) separating part of the carbon dioxide from the gas obtained in step (2), (4) reacting remaining gaseous carbon dioxide with hydrogen to form methanol, and (5) drying the resultant methanol.
2. A process as claimed in claim 1, characterized in that partial combustion in step (1) is carried out at a temperature in the range from 900°C to 1800°C, a pressure in the range from 1 to 200 bar abs. and a residence time between 0.1 and 12 sec.
3. A process as claimed in claim 1, characterized in that the partial combustion in step (1) is carried out with oxygen preheated to a temperature in the range from 200 to 500°C.
4. A process as claimed in claim 3, characterized in that a quantity of 5-150% by volume of steam, based on the oxygen, is added to the reaction mixture.
5. A process as claimed in claim 1, 2 or 4, characterized in that hydrogen sulphide is removed from the product gas of the partial combustion.
6. A process as claimed in claim 1, characterized in that the conversion of carbon monoxide with steam in step (2) is carried out in two or three stages, the temperature of the first stage being in the range from 250° to 450°C and the temperature of the final stage in the range from 200° to 400°C.
7. A process as claimed in claim 1, characterized in that at least part of the gas obtained in step (2) is cooled to a temperature at which part of the carbon dioxide condenses or sublimates and the liquid or solid carbon dioxide is separated from the gas.
8. A process as claimed in claim 7, characterized in that the gas is cooled at a pressure between 1 and 200 bar abs. to a temperature between -10 and -80°C.
9. A process as claimed in claim 1, 4 or 8, characterized in that in step (3) 50-80% of the carbon dioxide is separated from the gas.
10. A process as claimed in claim 1, 4 or 8, characterized in that step (4) is carried out at a temperature between 300 and 375°C and a pressure between 270 and 350 bar abs.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL7413747A NL7413747A (en) | 1974-10-21 | 1974-10-21 | PROCESS FOR THE PREPARATION OF METHANOL. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1053706A true CA1053706A (en) | 1979-05-01 |
Family
ID=19822304
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA232,465A Expired CA1053706A (en) | 1974-10-21 | 1975-07-29 | Process for the preparation of methanol |
Country Status (8)
| Country | Link |
|---|---|
| BE (1) | BE834426A (en) |
| CA (1) | CA1053706A (en) |
| FR (1) | FR2288722A1 (en) |
| GB (1) | GB1523797A (en) |
| IN (1) | IN141779B (en) |
| IT (1) | IT1043499B (en) |
| NL (1) | NL7413747A (en) |
| ZA (1) | ZA756602B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57130547A (en) * | 1981-02-06 | 1982-08-13 | Mitsubishi Gas Chem Co Inc | Catalyst for methanol synthesis |
| NL8102840A (en) * | 1981-06-12 | 1983-01-03 | Stamicarbon | METHOD FOR THE PREPARATION OF METHANOL. |
| FR2726821B1 (en) * | 1994-11-16 | 1997-01-03 | Patillet Henri | PROCESS AND APPARATUS FOR THE PRODUCTION OF METHANOL BY GASIFICATION OF CARBONACEOUS MATERIALS |
| DE10214003B4 (en) * | 2002-03-27 | 2005-12-22 | Lurgi Ag | Process for the production of carbon monoxide and methanol |
| CN114907186A (en) * | 2022-04-24 | 2022-08-16 | 中国成达工程有限公司 | Method for directly preparing methanol from carbon dioxide and hydrogen |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1262987B (en) * | 1966-01-22 | 1968-03-14 | Metallgesellschaft Ag | Process for adjusting the carbon dioxide content in methanol synthesis gas |
-
1974
- 1974-10-21 NL NL7413747A patent/NL7413747A/en not_active Application Discontinuation
-
1975
- 1975-07-29 CA CA232,465A patent/CA1053706A/en not_active Expired
- 1975-07-30 IN IN1504/CAL/75A patent/IN141779B/en unknown
- 1975-10-13 BE BE1006954A patent/BE834426A/en unknown
- 1975-10-20 FR FR7531985A patent/FR2288722A1/en active Granted
- 1975-10-20 GB GB42970/75A patent/GB1523797A/en not_active Expired
- 1975-10-20 ZA ZA00756602A patent/ZA756602B/en unknown
- 1975-10-20 IT IT28460/75A patent/IT1043499B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| AU8585675A (en) | 1977-04-28 |
| IN141779B (en) | 1977-04-16 |
| FR2288722B1 (en) | 1978-10-13 |
| ZA756602B (en) | 1976-09-29 |
| GB1523797A (en) | 1978-09-06 |
| IT1043499B (en) | 1980-02-20 |
| BE834426A (en) | 1976-04-13 |
| FR2288722A1 (en) | 1976-05-21 |
| NL7413747A (en) | 1976-04-23 |
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