CN113563159A - Process and device for preparing methanol from water gas - Google Patents
Process and device for preparing methanol from water gas Download PDFInfo
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- CN113563159A CN113563159A CN202110997803.9A CN202110997803A CN113563159A CN 113563159 A CN113563159 A CN 113563159A CN 202110997803 A CN202110997803 A CN 202110997803A CN 113563159 A CN113563159 A CN 113563159A
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 311
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910001868 water Inorganic materials 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 14
- 239000007789 gas Substances 0.000 claims abstract description 134
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 130
- 239000001257 hydrogen Substances 0.000 claims abstract description 130
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 126
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 119
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 114
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 59
- 238000000746 purification Methods 0.000 claims abstract description 36
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000002309 gasification Methods 0.000 claims abstract description 13
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 7
- 239000002002 slurry Substances 0.000 claims abstract description 6
- 150000003568 thioethers Chemical class 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 44
- 238000004519 manufacturing process Methods 0.000 claims description 22
- 238000006460 hydrolysis reaction Methods 0.000 claims description 17
- 230000007062 hydrolysis Effects 0.000 claims description 16
- 230000005540 biological transmission Effects 0.000 claims description 11
- 238000009826 distribution Methods 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 9
- 239000013589 supplement Substances 0.000 claims description 8
- 230000001502 supplementing effect Effects 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 230000006835 compression Effects 0.000 claims description 6
- 238000007906 compression Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000008213 purified water Substances 0.000 claims description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 5
- 230000005611 electricity Effects 0.000 claims description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 238000012932 thermodynamic analysis Methods 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 239000012495 reaction gas Substances 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052799 carbon Inorganic materials 0.000 abstract description 11
- 238000005406 washing Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
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- 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
- C07C29/152—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 reactor used
-
- 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
-
- 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
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process and a device for preparing methanol from water gas comprise a water gas slurry gasification device, wherein water gas generated by the gasification device is washed and separated and then enters a purification device to remove sulfides and part of carbon dioxide, and tail gas discharged by the purification device passes through CO2Separation device for separating CO2Separated and then enters CO2The gas pressurizing device pressurizes, the hydrogen enters the synthesis tower B to react with the hydrogen sent by the hydrogen replenishing device to generate methanol, and the hydrogen amount is adjusted by a hydrogen flow control valve entering the synthesis tower B. The invention can improve the hydrogen content of the synthesis device and effectively utilize the carbon element in the water gas.
Description
Technical Field
The invention belongs to the technical field of methanol preparation, and particularly relates to a process and a device for preparing methanol from water gas.
Background
The water gas generated by gasifying the multi-component slurry is used as a raw material by coal chemical enterprises to prepare the methanol through the processes of conversion, purification, synthesis, rectification and the like. In the synthesis device, the methanol synthesis gas enters a synthesis tower after being pressurized and heated, and CO enter the synthesis tower under the action of a Cu catalyst2And H2The reaction produces methanol and water. Cooling reacted gas to prepare crude methanol, merging part of unreacted gas as circulating gas with fresh synthesis gas, and re-entering the synthesis tower to participate in the synthesis reaction of methanolShould be used.
In the actual production of the process for preparing the methanol from the water gas, CO and CO in the water gas are converted by a conversion device2、H2Adjustment of composition of CO and H2Reaction of O to CO2And H2Increase H2Content, at the same time CO reacts to form CO2Excess CO is purified in a purification device2And simultaneously removing the sulfur compounds, and allowing the prepared synthesis gas to enter a synthesis tower for reaction. In the process of adjusting the H/C ratio of the shift converter, a large amount of CO gas is wasted, and excessive CO is generated2The carbon emission is caused by the emission into the atmosphere, which is not favorable for the reasonable utilization of resources and the environmental protection.
The water gas produced by the gasification device mainly comprises the following components: CO 22—18.1％、CO—43.1％、H2—38.2％、CH40.5%, removing conversion device, washing with low-temperature methanol, and washing with CO2Most of the tail gas is removed and enters a tail gas washing tower to be discharged, and CO in the tail gas is discharged2The content can reach more than 85 percent, and the CO can pass through2Separation device for separating CO2And pressurizing after purification, and reacting with hydrogen generated by photovoltaic hydrogen production at high temperature and high pressure under the action of a catalyst to produce methanol.
Introducing H into the purified synthesis gas2Increasing H in syngas2The content and the H/C ratio in the synthesis gas are adjusted, the methanol synthesis reaction is facilitated, the carbon element in the water gas is effectively utilized, and the yield of the methanol is improved. H recovered by conventional hydrogen recovery apparatus2The amount is smaller and the adjustment to the H/C ratio is the least useful.
In the process of preparing methanol from raw water gas, the water gas is adjusted to CO and CO by a conversion device2And H2The shift gas is washed and purified by methanol and then enters a methanol synthesis device to generate methanol. H is added during the component adjustment of the converter2O, carrying out CO + H2O→H2+CO2Reaction, hydrogen element in water is utilized to generate H2But partial conversion of the available gas CO to CO2Carbon element is discharged outside the purification device and is not effectively utilized, so that the waste of the carbon element is caused, the yield of products is limited, and greenhouse gas is increasedThe discharge of the body is not beneficial to environmental protection.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a process and a device for preparing methanol from water gas, which can improve the hydrogen content of a synthesis device and effectively utilize carbon element in water gas.
In order to achieve the purpose, the invention adopts the technical scheme that:
a device for preparing methanol from water gas comprises a water gas slurry gasification device 1, wherein water gas generated by the gasification device 1 is washed and separated and then enters a purification device 2 to remove sulfides and part of carbon dioxide, and tail gas discharged by the purification device 2 passes through CO2Separation device 10 separates CO2Separated and then enters CO2The gas pressurizing device 11 pressurizes, the hydrogen gas enters the synthesis tower B12 to react with the hydrogen gas sent by the hydrogen replenishing device to generate methanol, and the amount of the hydrogen gas is adjusted by the hydrogen gas flow control valve 15 entering the synthesis tower B.
The hydrogen supplementing device comprises a photovoltaic power transmission and distribution device 5, a hydrolysis hydrogen production device 6 and a hydrogen pressurizing device 7 which are connected in sequence, wherein electric energy generated by the photovoltaic power transmission and distribution device 5 is sent to the hydrolysis hydrogen production device 6 to carry out electric hydrolysis on purified water to obtain pure hydrogen, and the pure hydrogen is pressurized by the hydrogen pressurizing device 7 and then sent to the methanol synthesis device for reaction;
the high-pressure hydrogen produced by the hydrogen replenishing device is sent to a hydrogen replenishing position 8 on an inlet pipeline of a methanol synthesis tower A4, the synthesis gas produced by the purifying device 2 and the hydrogen produced by the hydrogen replenishing device react in a synthesis tower A4 to produce crude methanol, and the crude methanol produced by a synthesis tower B12 are sent to a methanol rectifying device 13 to produce methanol products.
And a synthesis gas on-line analyzer 9 is arranged on an inlet pipeline of the methanol synthesis tower A4, the synthesis gas on-line analyzer 9 analyzes gas components, and the opening of a hydrogen flow control valve 14 entering the synthesis tower A is used for adjusting the supplement amount of a hydrogen supplement position 8.
A process for preparing methanol from water gas comprises the following steps;
the water gas generated by the gasification device 1 is washed and separated and then enters the purification device 2 for removing sulfide and partial carbon dioxideAnd the exhaust tail gas discharged by the purification device 2 contains a large amount of CO2Volume content is more than or equal to 85%, through CO2The separation device 10 separates N in the tail gas2Removing impurities and purifying CO2，CO2The content is more than or equal to 99.9 percent, and the content is measured by CO2The gas pressurizing device 11 is pressurized to the reaction pressure of 8.8-9.2MPa of the synthesis tower, and the hydrogen gas enters the synthesis tower B12 together with the hydrogen gas sent by the hydrogen replenishing device, and the hydrogen gas flow rate is according to CO2The gas flow is adjusted by controlling the opening of the hydrogen flow control valve 15, the reaction is carried out under the action of catalyst at high temperature and high pressure, crude methanol is generated after cooling, unreacted gas is taken as circulating gas and enters a synthesis device for reaction through circulating compression, and H is generated simultaneously due to the reaction20, so the crude methanol is sent to a methanol rectifying device 13 for purification, and the water is removed to generate a methanol product.
Photovoltaic power transmission and distribution device 5 in the hydrogen supplement device fully utilizes local photo-thermal to generate electricity, the generated electric energy is sent into hydrolysis hydrogen production device 6 to carry out electric hydrolysis on purified water, and 2H2O＝2H2+O2And the prepared pure hydrogen is dried and dehumidified and then is respectively sent into a synthetic tower A4 and a synthetic tower B12 for reaction.
The main components of the synthesis gas produced by the purification device 2 are CO and CO2、H2The purification apparatus 2 removes a large amount of CO2,CO2The content of the methanol is controlled to be 4 percent, the H/C ratio in the synthesis gas is unchanged, in order to enable the H/C to reach 2.05-2.15, high-pressure hydrogen produced by a hydrogen replenishing device is sent to a hydrogen replenishing position 8 on an inlet pipeline of a methanol synthesis tower A4 through a pipeline, gas components are analyzed according to an online synthesis gas analyzer 9, the replenishing amount of the hydrogen replenishing device 8 is adjusted by adjusting the opening of a hydrogen flow control valve 14 of the synthesis tower A, the index of the synthesis tower gas is optimized to the maximum extent, the synthesis gas and the hydrogen produced by the hydrogen replenishing device react in the synthesis tower A4, crude methanol is produced after cooling, unreacted gas is used as circulating gas and enters the synthesis device for reaction through circulating compression, and the crude methanol is sent to a methanol rectification device 13 for purification, so that the product methanol is produced.
When H is substituted2When the inlet of the synthesis tower of the synthesis device is supplemented, the hydrogen content of the synthesis gas entering the synthesis tower can be improved, and the synthesis reaction of methanol: CO +2H2＝CH3OH、CO2+3H2＝CH3OH+H2O is the reaction of gas volume reduction, and the right amount of H is added in the reaction according to the thermodynamic analysis of chemical reaction2Can also effectively promote the methanol synthesis and improve the yield of the methanol.
The invention has the beneficial effects that:
the method of the invention aims at the problems that the content of hydrogen in water gas is low, the H/C ratio is low, the content of effective gas CO is reduced by a conversion device, and most CO produced2The problems of carbon element waste and methanol yield limitation caused by removing in a purification device are improved, and a method for improving the methanol yield by directly supplementing hydrogen in a synthesis device without a conversion device is provided. The method cancels a conversion device, reduces the equipment investment and the maintenance cost, and the water gas directly enters a purification device to remove sulfide and partial carbon dioxide to prepare qualified synthesis gas. The hydrogen supplementing pipeline is arranged at the position of the inlet pipeline of the synthesis tower, an online gas component analysis device is arranged behind the hydrogen supplementing pipeline on the inlet pipeline of the synthesis tower, and the flow of the supplemented hydrogen is adjusted according to online gas component analysis data so as to achieve the optimal reaction H/C ratio.
The method has the following main effects: 1. the replacement device is eliminated, the equipment purchase and maintenance cost can be reduced, and the H does not need to be increased2Content of effective gas CO into CO2The utilization rate of carbon element is improved, and the effective gas quantity is increased. 2. Capturing and purifying CO in discharged tail gas2And the methanol is separated and pressurized and then reacts with H2 to generate methanol, so that the yield of the methanol is improved, carbon elements are effectively utilized, and the carbon emission is reduced. 3. When H is substituted2When the synthesis device is supplemented, the hydrogen content in the synthesis gas is effectively improved, the content of CO is reduced, the optimal reaction H/C ratio is achieved, and the yield of methanol is improved. 4. The hydrogen produced by photovoltaic hydrogen production is called green hydrogen, and accords with the strategic direction of national energy conservation and emission reduction.
Drawings
FIG. 1 is a schematic structural diagram of the present invention.
Reference numerals: (1) coal water slurry gasification device, (2) purification device, (3) synthesis gas compressor, (4) methanol synthesis tower A and (5)Photovoltaic power transmission and distribution equipment, (6) -hydrolysis hydrogen production device, (7) -hydrogen pressurization device, (8) -hydrogen supplement point, (9) -synthesis gas on-line analyzer, (10) -CO2Separation apparatus (11) -CO2Gas pressurizing device, (12) -methanol synthesis tower B, (13) -rectifying device, (14) -hydrogen flow control valve entering synthesis tower A and (15) -hydrogen flow control valve entering synthesis tower B
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
As shown in fig. 1: a process and equipment for preparing methanol from water gas comprise a water gas slurry gasification device (1), wherein water gas generated by the gasification device (1) is washed and separated and then enters a purification device (2) to remove sulfide and partial carbon dioxide. The exhaust tail gas discharged by the purification device (2) passes through CO2Separation device (10) for separating CO2Separated and then enters CO2The gas pressurizing device (11) pressurizes, the hydrogen enters the synthesis tower B (12) to react with the hydrogen sent by the hydrogen replenishing device to generate methanol, and the hydrogen flow is adjusted by a hydrogen flow control valve (15) which enters the synthesis tower B.
The hydrogen supply device consists of a photovoltaic power transmission and distribution device (5), a hydrolysis hydrogen production device (6) and a hydrogen pressurization device (7). The electric energy generated by the photovoltaic power transmission and distribution device (5) is sent to a hydrolysis hydrogen production device (6) to carry out electric hydrolysis on the purified water to obtain pure hydrogen, and the pure hydrogen is pressurized by a hydrogen pressurization device (7) and then sent to a methanol synthesis device to carry out reaction.
High-pressure hydrogen produced by the hydrogen replenishing device is sent to a hydrogen replenishing position 8 on an inlet pipeline of a methanol synthesis tower A (4), gas components are analyzed according to a synthesis gas online analyzer (9), and the opening of a hydrogen flow control valve (14) entering the synthesis tower A is used for adjusting the replenishing amount of the hydrogen replenishing device 8. The synthesis gas produced by the purification device 2 reacts with the hydrogen produced by the hydrogen supply device in the synthesis tower A (4) to produce crude methanol, and the crude methanol produced by the synthesis tower B (12) are sent into a methanol rectification device (13) together to produce the methanol product.
The device of the invention supplements hydrogen to the photovoltaic hydrogen production device to produce hydrogen which is sent into the synthesis device by pressurization. The hydrogen production raw material source of water is stable, no pollution is caused, and the purity of the hydrogen obtained by the water electrolysis is higher and can reach more than 99.9 percent.
The hydrogen is in a vaporization state, and the system pressure of the hydrogen supplementing and synthesizing device is 8.8-9.2 MPa.
The H/C ratio of the synthetic tower A is 2.05-2.15, and the H/C ratio of the synthetic tower B is slightly more than 3. The optimal reaction ratio is achieved, and the maximum productivity of the methanol is realized.
The invention discharges CO in the tail gas discharged by the purification device (2)2Separating to prepare high-purity CO2After being pressurized, the hydrogen gas is reacted with hydrogen gas generated by a photovoltaic hydrogen production system in a synthesis tower B under the action of a high-temperature high-pressure catalyst to generate CO2+3H2＝CH3OH+H2The ratio of O to H/C is slightly larger than 3, the gas after reaction is cooled to generate crude methanol, and the crude methanol is sent to a rectifying device (13) for dehydration to prepare refined methanol; the unreacted gas is compressed by the circulating gas and sent back to the synthesis tower B for circulating reaction.
The working principle of the invention is as follows:
the water gas generated by the gasification device (1) is washed and separated and then enters the purification device (2) for removing sulfide and partial carbon dioxide. The exhaust tail gas discharged by the purification device (2) contains a large amount of CO2Volume content is more than or equal to 85%, through CO2The separation device (10) separates N in the tail gas2Removing impurities and purifying CO2，CO2The content is more than or equal to 99.9 percent, and the content is measured by CO2The gas pressurizing device (11) is pressurized to the reaction pressure of 8.8-9.2MPa of the synthesis tower, and the gas and the hydrogen sent by the hydrogen replenishing device enter the synthesis tower B (12), and the hydrogen flow rate is according to CO2The gas flow is adjusted by controlling the opening of the hydrogen flow control valve 15, the reaction is carried out under the action of a catalyst at high temperature and high pressure, crude methanol is generated after cooling, and unreacted gas is taken as circulating gas and enters a synthesis device for reaction through circulating compression. By reaction with simultaneous formation of H20, so the crude methanol is sent to a methanol rectifying device (13) for purification, and the water is removed to generate a methanol product.
The hydrogen supply device consists of a photovoltaic power transmission and distribution device (5), a hydrolysis hydrogen production device (6) and a purification/compression device (7). The photovoltaic power transmission and distribution device (5) fully utilizes local light and heat to generate electricity, the generated electric energy is sent into the hydrolysis hydrogen production device (6) to carry out electric hydrolysis on the purified water, and 2H2O＝2H2+O2And the prepared pure hydrogen is respectively sent into a synthetic tower A (4) and a synthetic tower B (12) for reaction after being dried and dehumidified.
The main components of the synthesis gas produced by the purification device (2) are CO and CO2、H2The purification device (2) removes a large amount of CO2，CO2The content of (A) is controlled to be basically 4%. Because a conversion device is cancelled, the H/C ratio in the synthesis gas is unchanged, in order to enable the H/C to reach 2.05-2.15, high-pressure hydrogen produced by a hydrogen replenishing device is sent to a hydrogen replenishing position (8) on an inlet pipeline of a methanol synthesis tower A (4) through a pipeline, gas components are analyzed according to an online synthesis gas analyzer (9), the replenishing amount of the hydrogen replenishing device (8) is adjusted by adjusting the opening of a hydrogen flow control valve (14) of the synthesis tower A, and the index of the synthesis tower gas is optimized to the greatest extent. The synthesis gas reacts with hydrogen prepared by a hydrogen supplementing device in a synthesis tower A (4), crude methanol is generated after cooling, and unreacted gas is used as circulating gas and enters the synthesis device for reaction through circulating compression. The crude methanol is sent into a methanol rectifying device (13) for purification to prepare the methanol product.
When H is substituted2When the synthesis gas is supplied to the inlet of the synthesis tower of the synthesis device, the hydrogen content of the synthesis gas entering the synthesis tower can be improved. Due to the methanol synthesis reaction: CO +2H2＝CH3OH、CO2+3H2＝CH3OH+H2O is the reaction of gas volume reduction, so the appropriate amount of H is added in the chemical reaction thermodynamic analysis2Can also effectively promote the methanol synthesis and improve the yield of the methanol.
Claims (7)
1. The device for preparing the methanol from the water gas is characterized by comprising a water gas slurry gasification device (1), wherein the water gas generated by the gasification device (1) is washed and separated and then enters a purification device (2) to remove sulfides and part of carbon dioxide, and the tail gas discharged by the purification device (2) passes through CO2Separation device (10) for separating CO2Separated and then enters CO2The gas pressurizing device (11) pressurizes, the hydrogen enters the synthesis tower B (12) to react with the hydrogen sent by the hydrogen replenishing device to generate methanol, and the hydrogen flow is adjusted by a hydrogen flow control valve (15) which enters the synthesis tower B.
2. The device for preparing methanol from water gas according to claim 1, wherein the hydrogen supplementing device comprises a photovoltaic power transmission and distribution device (5), a hydrolysis hydrogen production device (6) and a hydrogen pressurizing device (7) which are connected in sequence, electric energy generated by the photovoltaic power transmission and distribution device (5) is sent to the hydrolysis hydrogen production device (6) to carry out electric hydrolysis on purified water to obtain pure hydrogen, and the pure hydrogen is pressurized by the hydrogen pressurizing device (7) and then sent to the methanol synthesizing device for reaction;
high-pressure hydrogen produced by the hydrogen replenishing device is sent to a hydrogen replenishing position (8) on an inlet pipeline of a methanol synthesis tower A (4), synthesis gas produced by the purifying device (2) and hydrogen produced by the hydrogen replenishing device react in the synthesis tower A (4) to generate crude methanol, and the crude methanol produced by the synthesis tower B (12) are sent to a methanol rectifying device (13) together to produce methanol.
3. The device for preparing the methanol from the water gas as claimed in claim 2, wherein an on-line synthesis gas analyzer (9) is arranged on an inlet pipeline of the methanol synthesis tower A (4), the on-line synthesis gas analyzer (9) analyzes gas components, and the opening degree of a hydrogen flow control valve (14) of the synthesis tower A is used for adjusting the supplement amount of the hydrogen supplement position (8).
4. A process for preparing methanol from water gas based on the device of any one of claims 1-3, which comprises the following steps;
the water gas generated by the gasification device (1) is washed and separated and then enters the purification device (2) to remove sulfide and partial carbon dioxide, and the exhaust tail gas discharged by the purification device (2) contains a large amount of CO2Volume content is more than or equal to 85%, through CO2The separation device (10) separates N in the tail gas2Removing impurities and purifying CO2，CO2The content is more than or equal to 99.9 percent, and the content is measured by CO2The gas pressurizing device (11) is pressurized to the reaction pressure of 8.8-9.2MPa of the synthesis tower, and the gas and the hydrogen sent by the hydrogen replenishing device enter the synthesis tower B (12), and the hydrogen flow rate is according to CO2The gas flow is adjusted by controlling the opening of a hydrogen flow control valve (15), reacts under the action of a catalyst at high temperature and high pressure, and is cooled to generate crude methanol which is not reactedThe reaction gas as circulating gas is circularly compressed and then enters a synthesis device to react, and H is generated simultaneously due to the reaction20, so the crude methanol is sent to a methanol rectifying device (13) for purification, and the water is removed to generate a methanol product.
5. The process for preparing methanol from water gas as claimed in claim 4, wherein the photovoltaic power transmission and distribution device (5) in the hydrogen supplement device fully utilizes the local light heat to generate electricity, the generated electricity is sent to the hydrolysis hydrogen production device (6) to carry out the electric hydrolysis on the purified water, and 2H2O＝2H2+O2And the prepared pure hydrogen is respectively sent into a synthetic tower A (4) and a synthetic tower B (12) for reaction after being dried and dehumidified.
6. The process for preparing methanol from water gas according to claim 4, wherein the synthesis gas produced by the purification device (2) comprises CO and CO as main components2、H2The purification device (2) removes a large amount of CO2,CO2The content of the methanol synthesis gas is controlled to be 4 percent, the H/C ratio in the synthesis gas is unchanged, in order to enable the H/C to reach 2.05-2.15, high-pressure hydrogen produced by a hydrogen replenishing device is sent to a hydrogen replenishing position (8) on an inlet pipeline of a methanol synthesis tower A (4) through a pipeline, gas components are analyzed according to a synthesis gas on-line analyzer (9), the replenishing amount of the hydrogen replenishing device (8) is adjusted by adjusting the opening degree of a hydrogen flow control valve (14) of the synthesis tower A, the index of the synthesis tower gas is optimized to the maximum extent, the synthesis gas and the hydrogen produced by the hydrogen replenishing device react in the synthesis tower A (4), crude methanol is produced after cooling, unreacted gas is used as circulating gas and enters the synthesis device for reaction through circulating compression, and the crude methanol is sent to a methanol rectification device (13) for purification, and the product methanol is produced.
7. The process of claim 4, wherein when H is used, H is added2When the inlet of the synthesis tower of the synthesis device is supplemented, the hydrogen content of the synthesis gas entering the synthesis tower can be improved, and the synthesis reaction of methanol: CO +2H2＝CH3OH、CO2+3H2＝CH3OH+H2O is a reaction in which the volume of the gas is reduced,from the thermodynamic analysis of chemical reaction, appropriate amount of H is added2Can also effectively promote the methanol synthesis and improve the yield of the methanol.
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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