CN118142444A - System for preparing methanol by carbon dioxide one-step hydrogenation - Google Patents
System for preparing methanol by carbon dioxide one-step hydrogenation Download PDFInfo
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- CN118142444A CN118142444A CN202211508500.7A CN202211508500A CN118142444A CN 118142444 A CN118142444 A CN 118142444A CN 202211508500 A CN202211508500 A CN 202211508500A CN 118142444 A CN118142444 A CN 118142444A
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 588
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 55
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 55
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 32
- 239000007789 gas Substances 0.000 claims abstract description 134
- 239000002994 raw material Substances 0.000 claims abstract description 33
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 31
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 31
- 238000001816 cooling Methods 0.000 claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 238000011084 recovery Methods 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 33
- 239000001257 hydrogen Substances 0.000 claims description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims description 33
- 239000012071 phase Substances 0.000 claims description 33
- 238000010992 reflux Methods 0.000 claims description 29
- 239000002826 coolant Substances 0.000 claims description 19
- 239000007791 liquid phase Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 9
- 238000004891 communication Methods 0.000 claims description 7
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 abstract description 36
- 230000008569 process Effects 0.000 abstract description 21
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000001760 fusel oil Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005261 decarburization Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
Classifications
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/06—Flash distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/32—Other features of fractionating columns ; Constructional details of fractionating columns not provided for in groups B01D3/16 - B01D3/30
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/32—Other features of fractionating columns ; Constructional details of fractionating columns not provided for in groups B01D3/16 - B01D3/30
- B01D3/322—Reboiler specifications
-
- 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
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application relates to a system for preparing methanol by one-step hydrogenation of carbon dioxide, which comprises the following components in sequence: the feed gas pretreatment unit comprises a gas compressor and a feed gas preheating device; the raw material gas pretreatment unit inputs raw material gas into the methanol synthesis tower; a cooling unit, by which the crude methanol synthesized in the methanol synthesis tower is cooled; a methanol separator for separating unreacted gas in the crude methanol cooled by the cooling unit; a low pressure flash tank for separating non-condensable gases in the crude methanol; the preheating unit is used for preheating the crude methanol treated by the low-pressure flash tank; and the rectification unit is used for rectifying the crude methanol. Therefore, the system for preparing the methanol by the carbon dioxide one-step hydrogenation can implement the whole process of the process for preparing the methanol by the carbon dioxide hydrogenation by the one-step method.
Description
Technical Field
The application relates to the field of chemical industry, in particular to a method for preparing methanol by one-step hydrogenation of carbon dioxide.
Background
The important component for realizing the combination of carbon neutralization target technology in China by greatly developing carbon dioxide capturing and utilizing and sealing technology is the only technical choice for low-carbon utilization of fossil energy in China. Among the processes of recycling the carbon dioxide, the process for preparing the methanol by hydrogenating the carbon dioxide is relatively simple, the reaction condition is mild, and the industrial scale-up risk of the process is low by referring to the mature industrial process for preparing the methanol by using the synthesis gas. The methanol can be converted into downstream products such as olefin, aromatic hydrocarbon, gasoline and the like through a catalytic means, and is an ideal bulk chemical product for replacing traditional resources such as petroleum, natural gas and the like. Therefore, the hydrogenation of carbon dioxide to prepare methanol is an effective means for solving the problem of carbon dioxide emission and realizing the chemical utilization of carbon dioxide.
In theory, two main technological routes exist for preparing methanol by hydrogenation of carbon dioxide: firstly, preparing methanol by a one-step method of directly hydrogenating carbon dioxide; the method comprises the following steps: the method comprises the steps of converting carbon dioxide into CO through an inverse water-gas shift reaction, and obtaining the final product methanol by utilizing the traditional process for preparing the methanol from the synthetic gas.
Both processes of the two-step process are industrial mature processes, but the required synthesis temperature is high and the energy consumption is high. The one-step process is characterized in that temperature transformation is not needed, the energy consumption is relatively low, but a full-flow system for preparing methanol by one-step method is not available in the field.
Disclosure of Invention
The embodiment of the application provides a system for preparing methanol by one-step hydrogenation of carbon dioxide, which aims to solve the technical problem that a full-flow system for preparing methanol by one-step method is lacked in the field.
In a first aspect, an embodiment of the present application provides a system for preparing methanol by one-step hydrogenation of carbon dioxide, including:
The feed gas pretreatment unit comprises a gas compressor and a feed gas preheating device;
the raw material gas pretreatment unit inputs raw material gas into the methanol synthesis tower;
a cooling unit, by which the crude methanol synthesized in the methanol synthesis tower is cooled;
A methanol separator for separating unreacted gas in the crude methanol cooled by the cooling unit;
A low pressure flash tank for separating non-condensable gases in the crude methanol;
the preheating unit is used for preheating the crude methanol treated by the low-pressure flash tank;
And the rectification unit is used for rectifying the crude methanol.
In some embodiments of the application, the system for producing methanol by one-step hydrogenation of carbon dioxide further comprises a methanol recovery tower, wherein the methanol recovery tower is communicated with the low-pressure flash tank and the rectification unit, the low-pressure flash tank guides non-condensable gas into the methanol recovery tower, the methanol recovery tower washes the non-condensable gas through desalted water, and guides the washed desalted water into the rectification unit.
In some embodiments of the application, the system for preparing methanol by one-step hydrogenation of carbon dioxide further comprises a hydrogen recovery unit, wherein the hydrogen recovery unit is communicated with the methanol recovery tower and the raw material gas pretreatment unit, and is used for recovering hydrogen in the non-condensable gas after washing in the methanol recovery tower and guiding the hydrogen into the raw material gas pretreatment unit.
In some embodiments of the application, the gas compressor comprises a first gas compressor for compressing carbon dioxide and a second gas compressor in communication with the methanol separator for compressing unreacted gas output by the methanol separator; and/or the number of the groups of groups,
The raw material gas preheating device is a first heat exchange device, the first heat exchange device is also communicated with the methanol synthesis tower and the cooling unit, a cooling medium of the first heat exchange device is the raw material gas, a heating medium of the first heat exchange device is crude methanol output from the methanol synthesis tower, and the crude methanol exchanges heat with the raw material gas and then is input into the cooling unit.
In some embodiments of the application, the cooling unit comprises a second heat exchange device, the cold medium of the second heat exchange device is desalted water, and the heat medium is crude methanol; and/or the number of the groups of groups,
The cooling unit comprises an air cooler and a water cooler which are communicated.
In some embodiments of the application, the rectification unit comprises a pre-column, a pressurization column, a medium pressure column, and an atmospheric column in communication with each other.
In some embodiments of the application, the pre-tower is connected to the methanol recovery tower, and the scrubbed desalted water in the methanol recovery tower is introduced into the pre-tower and scrubbed of the gas phase within the pre-tower.
In some embodiments of the present application, a first heat exchange type reboiler is communicated with the top of the pressurizing tower, a pressurizing tower reflux tank is also communicated with the first heat exchange type reboiler, the pressurizing tower reflux tank is communicated with the upper part of the pressurizing tower, the gas phase at the top of the pressurizing tower is used as a heat medium of the first heat exchange type reboiler and is input into the first heat exchange type reboiler, after exothermic condensation, is input into the pressurizing tower reflux tank, a part of the gas phase is condensed back into the pressurizing tower, and the rest of the gas phase is output to form refined methanol; the lower part of the medium pressure tower is communicated with the first heat exchange type reboiler through a first pipeline and a second pipeline which are mutually independent, the liquid phase of the medium pressure tower is used as a cooling medium of the first heat exchange type reboiler, the cooling medium is input into the first heat exchange type reboiler through the first pipeline, and after absorbing heat in the first heat exchange type reboiler, the cooling medium is input into the bottom of the medium pressure tower through the second pipeline.
In some embodiments of the application, the top of the medium-pressure tower is communicated with a second heat exchange type reboiler, the second heat exchange type reboiler is also communicated with a medium-pressure tower reflux tank, the medium-pressure tower reflux tank is communicated with the upper part of the medium-pressure tower, the gas phase at the top of the medium-pressure tower is used as a heat medium of the second heat exchange type reboiler to be input into the second heat exchange type reboiler, after exothermic condensation, the gas phase is input into the medium-pressure tower reflux tank, a part of the gas phase is condensed back into the medium-pressure tower, and the rest of the gas phase is output to form refined methanol; the lower part of the atmospheric tower is communicated with the second heat exchange type reboiler through a third pipeline and a fourth pipeline which are mutually independent, and the liquid phase of the atmospheric tower is used as a cooling medium of the second heat exchange type reboiler and is input into the second heat exchange type reboiler through the third pipeline, absorbs heat in the second heat exchange type reboiler, and is input into the bottom of the atmospheric tower through the fourth pipeline.
In some embodiments of the present application, a heat pump compressor is connected to the top of the atmospheric tower, the heat pump compressor is connected to a third heat exchange reboiler, the third heat exchange reboiler is connected to the lower part of the atmospheric tower, the third heat exchange reboiler is also connected to an atmospheric tower condenser, the atmospheric tower condenser is connected to an atmospheric tower reflux tank, the atmospheric tower reflux tank is connected to the upper part of the atmospheric tower, after the gas phase at the top of the atmospheric tower is input into the heat pump compressor, the gas phase is compressed by the heat pump compressor and then is input into the third heat exchange reboiler for heat exchange, and then is input into the atmospheric tower condenser for cooling, a part of the condensed liquid flows back into the upper part of the atmospheric tower, and the rest of the condensed liquid is output to form refined methanol; the third heat exchange type reboiler is also communicated with the bottom of the atmospheric tower, the liquid phase at the bottom of the atmospheric tower is used as a cooling medium to be input into the third heat exchange type reboiler, and the liquid phase is absorbed in the third heat exchange type reboiler and then is input into the bottom of the atmospheric tower.
Compared with the prior art, the technical scheme provided by the embodiment of the application has the following advantages:
The embodiment of the application provides a system for preparing methanol by one-step hydrogenation of carbon dioxide, which is characterized in that a raw material gas pretreatment unit, a methanol synthesis tower, a cooling unit, a methanol separator, a low-pressure flash tank, a preheating unit and a rectifying unit which are sequentially communicated are arranged, so that the system can perform raw material gas pretreatment and methanol synthesis, and perform post-treatment and rectification on formed crude methanol, and therefore, the system for preparing methanol by one-step hydrogenation of carbon dioxide provided by the embodiment of the application can implement the whole process of preparing methanol by one-step hydrogenation of carbon dioxide.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the application and together with the description, serve to explain the principles of the application.
In order to more clearly illustrate the embodiments of the application or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, and it will be obvious to a person skilled in the art that other drawings can be obtained from these drawings without inventive effort.
Fig. 1 is a schematic structural diagram of a system for preparing methanol by one-step hydrogenation of carbon dioxide according to an embodiment of the present application.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more apparent, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Unless specifically stated otherwise, the terms used herein should be understood as meaning as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. In case of conflict, the present specification will control.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present application are commercially available or may be prepared by existing methods.
The hydrogenation of carbon dioxide to prepare methanol mainly has two technological routes, one of which is to prepare methanol by a one-step method of direct hydrogenation of carbon dioxide, and no full-flow system for preparing methanol by one-step method exists in the prior art.
The technical scheme provided by the embodiment of the application aims to solve the technical problems, and the overall thought is as follows:
the embodiment of the application provides a system for preparing methanol by one-step hydrogenation of carbon dioxide, which comprises the following components in sequence:
The feed gas pretreatment unit comprises a gas compressor and a feed gas preheating device;
A methanol synthesis tower 21, wherein the raw material gas pretreatment unit inputs raw material gas into the methanol synthesis tower 21;
A cooling unit by which the crude methanol synthesized in the methanol synthesis tower 21 is cooled;
A methanol separator 4 for separating unreacted gas in the crude methanol cooled by the cooling unit;
A low pressure flash tank 5 for separating non-condensable gases in the crude methanol;
A preheating unit for preheating the crude methanol treated by the low pressure flash tank 5;
And the rectification unit is used for rectifying the crude methanol.
The feed gas mainly comprises carbon dioxide and hydrogen. The carbon dioxide is high-concentration carbon dioxide obtained from low-temperature methanol washing decarburization and natural gas decarburization in the coal chemical industry, and the purity of the carbon dioxide product of a flue gas carbon dioxide capturing device is 90-100%, preferably 99-100% after capturing before combustion, oxygen-enriched combustion and combustion. The hydrogen is from green hydrogen produced by renewable energy sources, garbage gasification hydrogen production, fossil fuel hydrogen production, byproduct hydrogen of a refining device, purified hydrogen and recovered hydrogen in the methanol production process. The purity is 90-100%, preferably 99-100%.
The pretreatment of the feed gas mainly comprises pressurizing and preheating the feed gas.
In addition to the reaction products methanol and water vapor, the outlet gas of the methanol synthesis column 21 contains unreacted hydrogen, carbon dioxide, a small amount of CO, an inert gas, and a small amount of reaction by-products in the ppm order. The outlet gas temperature of the synthesis column is 210-240 ℃, preferably 225-235 ℃.
The methanol separator 4 mainly realizes a gas-liquid separation function, can be selected according to a conventional mode in the field, and as a practical matter, the methanol separator 4 can be a gas-liquid separation tank with a foam remover at the top.
The low pressure flash tank 5 is used to initially separate most of the non-condensable gases in the crude methanol, reducing the load on the rectification unit.
The embodiment of the application provides a system for preparing methanol by one-step hydrogenation of carbon dioxide, which is provided with a raw material gas pretreatment unit, a methanol synthesis tower 21, a cooling unit, a methanol separator 4, a low-pressure flash tank 5, a preheating unit and a rectifying unit which are sequentially communicated, so that the system can perform raw material gas pretreatment and methanol synthesis, and perform post-treatment and rectification on formed crude methanol.
In some embodiments of the present application, the system for preparing methanol by one-step hydrogenation of carbon dioxide further comprises a methanol recovery tower 8, wherein the methanol recovery tower 8 is communicated with the low-pressure flash tank 5 and the rectification unit, the low-pressure flash tank 5 introduces non-condensable gas into the methanol recovery tower 8, the methanol recovery tower 8 washes the non-condensable gas by desalted water, and introduces the washed desalted water into the rectification unit.
The methanol recovery column 8 can wash and recover methanol from the noncondensable gas.
In some embodiments of the present application, the system for preparing methanol by one-step hydrogenation of carbon dioxide further comprises a hydrogen recovery unit 9, wherein the hydrogen recovery unit 9 is communicated with the methanol recovery tower 8 and the raw material gas pretreatment unit, and the hydrogen recovery unit 9 is used for recovering hydrogen in the non-condensable gas after washing in the methanol recovery tower 8 and introducing the hydrogen into the raw material gas pretreatment unit.
The hydrogen recovery unit 9 may perform hydrogen recovery using a conventional hydrogen recovery method in the art, and may recover hydrogen gas using membrane separation or Pressure Swing Adsorption (PSA) separation, for example.
In some embodiments of the application, the gas compressor comprises a first gas compressor 11 and a second gas compressor 12, the first gas compressor 11 is used for compressing carbon dioxide, the second gas compressor 12 is communicated with the methanol separator 4, and the second gas compressor 12 is used for compressing unreacted gas output by the methanol separator 4; and/or the number of the groups of groups,
The raw material gas preheating device is a first heat exchange device 13, the first heat exchange device 13 is also communicated with the methanol synthesis tower 21 and the cooling unit, a cooling medium of the first heat exchange device 13 is the raw material gas, a heating medium of the first heat exchange device 13 is crude methanol output from the methanol synthesis tower 21, and the crude methanol exchanges heat with the raw material gas and then is input into the cooling unit.
The gas phase from the methanol separator 4 is mostly recycled to the methanol synthesis column 21 by the second gas compressor 12, so that the total conversion rate can be improved, and the recycle ratio is 3 to 7, preferably 4 to 5.
The crude methanol condensed and separated in the methanol separator 4 contains, in addition to methanol and water, dissolved gas and part of impurities (reaction by-products) produced by the reaction, and is sent to a methanol rectifying unit.
After the first gas compressor 11 compresses the carbon dioxide, hydrogen is input into the first gas compressor, and the hydrogen is combined and input into the second gas compressor 12, and the second gas compressor 12 compresses the gas phase mixture of the carbon dioxide, the hydrogen and the methanol separator 4 to 5-10MPaG, preferably 7-10MPaG.
The crude methanol synthesized in the methanol synthesis column 21 is outputted as an outlet gas having a temperature of 210 to 240 ℃, preferably 225 to 235 ℃. After preheating the synthesis column inlet gas in the first heat exchange device 13, the temperature is reduced to 110-140 ℃, preferably 120-130 ℃.
The heat exchange between the crude methanol and the raw material gas can utilize the waste heat in the crude methanol to achieve the energy-saving effect. The feed gas is preheated to 180-250 c, preferably 200-230 c.
In some embodiments of the present application, the cooling unit includes a second heat exchange device 31, the cold medium of the second heat exchange device 31 is desalted water, and the heat medium is crude methanol; and/or the number of the groups of groups,
The cooling unit includes an air cooler 32 and a water cooler 33 in communication.
The desalted water subjected to heat exchange in the cooling unit can be used as desalted water for washing in the methanol recovery tower 8, the temperature of the desalted water is increased after heat exchange, and the washing effect is better.
After passing through the air cooler 32 and the water cooler 33, the temperature of the crude methanol is reduced to 40 to 43 ℃.
In some embodiments of the application, the methanol synthesis column 21 is an isothermal shell-and-tube reactor, the feed gas being reacted within the tube side of the isothermal shell-and-tube reactor; the shell side of the isothermal shell-and-tube reactor is communicated with a steam drum 22, and the steam drum 22 drives water to be used as a heat exchange medium to take away heat in the shell side; the drum 22 is also connected to the second heat exchange device 31 and feeds water vapour into the cooling medium of the second heat exchange device 31.
The methanol synthesis column 21 is an isothermal shell-and-tube reactor, the tubes are filled with catalyst, and water outside the tubes circulates between the shell side and the drum 22. The reaction of hydrogen and carbon dioxide occurs in the tube side filled with the catalyst, and the released reaction heat is taken away by boiling water of the shell side. Thus, the system is maintained in an approximately isothermal state, which ensures high conversion while eliminating the risk of possible deactivation of the catalyst due to excessive temperatures.
In some embodiments of the present application, the rectification unit comprises a pre-column 71, a pressurization column 72, a medium pressure column 73, an atmospheric column 74 in communication with each other.
Multistage rectification is beneficial to recovering more methanol.
The pre-column 71 is operated at a pressure of 0.15 to 0.4MPag, preferably 0.2 to 0.3MPag. The medium pressure column 73 is operated at a pressure of 0.3 to 0.5MPag, preferably 0.35 to 0.45MPag. And the reflux ratio of each tower is regulated to meet the national standard or AA-grade methanol requirement of the refined methanol at the top of the tower.
In some embodiments of the present application, the pre-tower 71 is connected to the methanol recovery tower 8, and the desalted water having been washed in the methanol recovery tower 8 is introduced into the pre-tower 71 and the gas phase in the pre-tower 71 is washed.
The desalted water methanol concentration at which the washing is completed is low and has a suitable temperature suitable for further washing the gas phase in the pre-tower 71.
In some embodiments of the present application, the pre-tower 71 is further connected to a first condenser 711 and a pre-tower 71 reflux tank, the pre-tower 71 reflux tank is connected to a second condenser 712, the pre-tower 71 reflux tank is used for collecting and inputting the reflux methanol of the first condenser 711 and the second condenser 712 into the pre-tower 71, the second condenser 712 is connected to the methanol recovery tower 8, and the gas phase in the second condenser 712 is combined with the non-condensable gas and then washed together.
The primary condenser 711 may use an air cooler 32 or a water cooler 33 with an outlet temperature of 40 to 65 c, preferably 50 to 55 c, to condense and reflux a large amount of methanol, and the secondary condenser 712 is provided for recovering as much entrained methanol as possible, and the secondary condenser 712 uses the water cooler 33 with an outlet temperature of 40 to 50 c, preferably 40 to 43 c.
In some embodiments of the present application, a first heat exchange type reboiler 722 is connected to the top of the pressure tower 72, the first heat exchange type reboiler 722 is further connected to a pressure tower reflux tank 721, the pressure tower reflux tank 721 is connected to the upper portion of the pressure tower 72, the gas phase at the top of the pressure tower 72 is used as a heat medium of the first heat exchange type reboiler 722 and is input into the first heat exchange type reboiler 722 after exothermic condensation, a part of the gas phase is condensed back into the pressure tower 72, and the rest of the gas phase is output to form refined methanol; the lower part of the medium pressure column 73 is communicated with the first heat exchange type reboiler 722 through a first pipeline 733 and a second pipeline 734 which are mutually independent, the liquid phase of the medium pressure column 73 is used as a cooling medium of the first heat exchange type reboiler 722 to be input into the first heat exchange type reboiler 722 through the first pipeline 733, absorbs heat in the first heat exchange type reboiler 722, and then is input into the bottom of the medium pressure column 73 through the second pipeline 734.
In some embodiments of the present application, a second heat exchange type reboiler 732 is connected to the top of the medium pressure column 73, the second heat exchange type reboiler 732 is further connected to a medium pressure column reflux tank 731, the medium pressure column reflux tank 731 is connected to the upper part of the medium pressure column 73, the gas phase at the top of the medium pressure column 73 is used as a heat medium of the second heat exchange type reboiler 732 and is input into the second heat exchange type reboiler 732 after exothermic condensation, a part of the gas phase is condensed and flows back into the medium pressure column 73, and the rest of the gas phase is output to form refined methanol; the lower part of the atmospheric tower 74 is communicated with the second heat exchange type reboiler 732 through a third pipeline 745 and a fourth pipeline 746 which are independent of each other, and the liquid phase of the atmospheric tower 74 is used as a cooling medium of the second heat exchange type reboiler 732 and is input into the second heat exchange type reboiler 732 through the third pipeline 745, absorbs heat in the second heat exchange type reboiler 732, and is input into the bottom of the atmospheric tower 74 through the fourth pipeline 746.
In some embodiments of the present application, a heat pump compressor 744 is connected to the top of the atmospheric tower 74, the heat pump compressor 744 is connected to a third heat exchange reboiler 743, the third heat exchange reboiler 743 is connected to the lower part of the atmospheric tower 74, the third heat exchange reboiler 743 is also connected to an atmospheric tower condenser 742, the atmospheric tower condenser 742 is connected to an atmospheric tower reflux tank 741, the atmospheric tower reflux tank 741 is connected to the upper part of the atmospheric tower 74, the gas phase at the top of the atmospheric tower 74 is input into the heat pump compressor 744, compressed by the heat pump compressor 744, then is input into the third heat exchange reboiler 743 as a heat medium, is input into the atmospheric tower condenser 742 for cooling, is input into the atmospheric tower reflux tank 741 after cooling, a part of the condensed liquid flows into the upper part of the atmospheric tower 74, and the remaining part of the condensed liquid is output to form refined methanol; the third heat exchange reboiler 743 is further connected to the bottom of the atmospheric tower 74, and the liquid phase at the bottom of the atmospheric tower 74 is fed into the third heat exchange reboiler 743 as a cooling medium, and is fed into the bottom of the atmospheric tower 74 after absorbing heat in the third heat exchange reboiler 743.
When the alcohol content in the liquid phase at the bottom of the atmospheric tower 74 is less than 500ppm, the liquid phase is discharged as process water.
Fusel oil can be extracted from the middle side part of the atmospheric tower 74, and the extraction amount of the fusel oil can be adjusted by adjusting the lateral line of the atmospheric tower 74.
In some embodiments of the application, the pre-tower 71 is further in communication with a first steam reboiler 714 and a condensate reboiler 715.
In some embodiments of the application, the pressurization tower 72 is also in communication with a second steam reboiler 723.
In some embodiments of the present application, the preheating unit may use process water, refined methanol, low pressure steam condensate of a steam reboiler as a heat source. As an example, the preheating unit includes a process water heat exchanger 61, a refined methanol heat exchanger 62, and a condensate heat exchanger 63 which are sequentially communicated, and the crude methanol outputted from the low pressure flash tank 5 sequentially passes through the process water heat exchanger 61, the refined methanol heat exchanger 62, and the condensate heat exchanger 63 as a cooling medium, and the process water heat exchanger 61 uses the collected process water as a heating medium; the refined methanol heat exchanger 62 takes the collected refined methanol as a heat medium, and if the refined methanol is still in a gaseous state, the refined methanol is subjected to exothermic condensation; the condensate heat exchanger 63 uses low pressure steam condensate from the first steam reboiler 714 as a heat medium.
The low-pressure steam condensate of the process water, refined methanol and the first steam reboiler 714 is used as a heat source, so that the preheating can be fully utilized, and the energy consumption is reduced.
It will be appreciated by those skilled in the art that in actual production, the process water, the refined methanol, and the low pressure steam condensate of the first steam reboiler 714 may be transported to the process water heat exchanger 61, the refined methanol heat exchanger 62, and the condensate heat exchanger 63, respectively, through pipelines.
In some embodiments of the application, the condensate reboiler 715 uses low pressure steam condensate of the second steam reboiler 723 as a heat medium.
As will be appreciated by those skilled in the art, the low pressure steam condensate of the second steam reboiler 723 may be piped to the condensate reboiler 715.
The application will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. The experimental procedures, which are not specified in the following examples, are generally determined according to national standards. If the corresponding national standard does not exist, the method is carried out according to the general international standard, the conventional condition or the condition recommended by the manufacturer.
Examples
The carbon dioxide concentration of the carbon dioxide raw material from a certain carbon dioxide liquefying device is 99.9%, the temperature is 40 ℃, the pressure is 2.2MPaG, and the flow rate is 60640kg/h.
The purity of the hydrogen raw material from a certain garbage gasification device is 99.5%, the temperature is 40 ℃, the pressure is 2.2MPaG, and the flow is 8059kg/h.
The carbon dioxide raw material and the hydrogen raw material are mixed and then enter a second gas compressor, unreacted gas from the top of the methanol separator also enters the second gas compressor, the flow rate of the unreacted gas is 168359kg/h, the first gas compressor and the second gas compressor adopt centrifugal compressors, and the power is 8340kW. Compressed to 8.2Mpa, enters a first heat exchanger, is preheated to 205 ℃, and enters a methanol synthesis tower. The catalyst in the methanol synthesis tower is in an initial working condition, and the temperature of the outlet gas of the synthesis tower is 230 ℃ and the pressure is 7.7MPag. After passing through the inlet and outlet heat exchanger, the desalted water preheater, the air cooler and the water cooler in turn, the temperature is reduced to 40 ℃, and the pressure is 7.5Mpag. Then the mixture enters a methanol separator for gas-liquid separation, the liquid phase enters a low-pressure flash tank, and the gas phase is unreacted gas. The outlet pressure of the low pressure flash tank was 0.6MPag and the temperature was 42 ℃. The liquid phase at the outlet of the low-pressure flash tank is crude methanol, the flow rate is 67266kg/h, and the crude methanol enters a methanol rectifying unit. The gas phase sequentially enters a methanol recovery tower and a hydrogen recovery unit, the flow is 501kg/h, and the hydrogen recovery unit adopts a membrane separation device.
The crude methanol sequentially passes through a process water heat exchanger, a refined methanol heat exchanger and a condensate heat exchanger, and enters a pre-tower after being preheated to 107 ℃. The operating pressure of the pre-column was 0.24Mpa, the operating temperature at the top of the column was 60℃and the operating temperature at the bottom of the column was 111 ℃. The first-stage condenser at the top of the tower adopts an air cooler, the second-stage condenser adopts a water cooler, and the total heat load is-5.4 Gcal/h. The pre-tower was provided with a condensate reboiler and a first steam reboiler with a total heat duty of 5.5Gcal/h. The operation pressure of the pressurizing tower is 0.82Mpag, the operation temperature of the tower top is 133.6 ℃, the flow rate of refined methanol is 10300kg/h, the purity is 99.9%, and the requirements of national standard superior methanol are met. The heat duty of the second steam reboiler at the bottom of the pressurizing tower was 20Gcal/h. The column bottom operating temperature was 150.7 ℃. The pressure column overhead condenser was coupled to a medium pressure column reboiler with a heat duty of-7.5 Gcal/h. The intermediate pressure tower overhead condenser was coupled to an atmospheric tower reboiler with a thermal duty of-7 Gcal/h. The operating pressure of the medium pressure tower is 0.26MPag, the operating temperature of the top of the tower is 108 ℃, and the flow rate of refined methanol is 12590kg/h. The operating pressure of the atmospheric tower is 0.03Mpag, the operating temperature of the tower top is 73 ℃, the flow rate of refined methanol is 10551kg/h, the purity is 99.9%, and the requirements of national standard high-grade methanol are met. The heat pump compressor power is 1MW. The column bottom operating temperature was 118.7 ℃. The condenser of the atmospheric tower adopts an air cooler, and the heat load is-9 Gcal/h. The yield of fusel oil is 450kg/h.
In the embodiment, the steam consumption is 1.02t/t of methanol, the circulating cooling water consumption is 258t/t of methanol, and the electricity consumption is 402kwh/t of methanol.
Various embodiments of the application may exist in a range of forms; it should be understood that the description in a range format is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the application; it is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
In the present application, unless otherwise specified, terms such as "upper" and "lower" are used specifically to refer to the orientation of the drawing in the figures. In addition, in the description of the present specification, the terms "include", "comprising" and the like mean "including but not limited to". Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element. Relational terms such as "first" and "second", and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Herein, "and/or" describing an association relationship of an association object means that there may be three relationships, for example, a and/or B, may mean: a alone, a and B together, and B alone. For the association relation of three or more associated objects described by "and/or", it means that any one of the three associated objects may exist alone or any at least two of the three associated objects exist simultaneously, for example, for a, and/or B, and/or C, any one of A, B, C may exist alone or any two of the three associated objects exist simultaneously or three of the three associated objects exist simultaneously. Herein, "at least one" means one or more, and "a plurality" means two or more. "at least one", "at least one" or the like refer to any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
The foregoing is only a specific embodiment of the application to enable those skilled in the art to understand or practice the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A system for preparing methanol by one-step hydrogenation of carbon dioxide is characterized by comprising the following components in sequence:
The feed gas pretreatment unit comprises a gas compressor and a feed gas preheating device;
the raw material gas pretreatment unit inputs raw material gas into the methanol synthesis tower;
a cooling unit, by which the crude methanol synthesized in the methanol synthesis tower is cooled;
A methanol separator for separating unreacted gas in the crude methanol cooled by the cooling unit;
A low pressure flash tank for separating non-condensable gases in the crude methanol;
the preheating unit is used for preheating the crude methanol treated by the low-pressure flash tank;
And the rectification unit is used for rectifying the crude methanol.
2. The system for producing methanol by one-step hydrogenation of carbon dioxide according to claim 1, further comprising a methanol recovery tower, wherein the methanol recovery tower is communicated with the low-pressure flash tank and the rectification unit, the low-pressure flash tank introduces noncondensable gas into the methanol recovery tower, the methanol recovery tower washes the noncondensable gas by desalted water, and introduces desalted water after washing into the rectification unit.
3. The system for preparing methanol by one-step hydrogenation of carbon dioxide according to claim 1, further comprising a hydrogen recovery unit, wherein the hydrogen recovery unit is communicated with the methanol recovery tower and the raw material gas pretreatment unit, and is used for recovering hydrogen in the noncondensable gas after washing in the methanol recovery tower and guiding the hydrogen into the raw material gas pretreatment unit.
4. The one-step hydrogenation methanol production system of carbon dioxide according to claim 1, wherein the gas compressor comprises a first gas compressor for compressing carbon dioxide and a second gas compressor in communication with the methanol separator for compressing unreacted gas output from the methanol separator; and/or the number of the groups of groups,
The raw material gas preheating device is a first heat exchange device, the first heat exchange device is also communicated with the methanol synthesis tower and the cooling unit, a cooling medium of the first heat exchange device is the raw material gas, a heating medium of the first heat exchange device is crude methanol output from the methanol synthesis tower, and the crude methanol exchanges heat with the raw material gas and then is input into the cooling unit.
5. The system for preparing methanol by one-step hydrogenation of carbon dioxide according to claim 1, wherein the cooling unit comprises a second heat exchange device, a cooling medium of the second heat exchange device is desalted water, and a heating medium is crude methanol; and/or the number of the groups of groups,
The cooling unit comprises an air cooler and a water cooler which are communicated.
6. The one-step hydrogenation system for producing methanol from carbon dioxide according to any one of claims 1 to 5, wherein said rectifying unit comprises a pre-tower, a pressurizing tower, a medium pressure tower, and an atmospheric tower which are communicated with each other.
7. The system for producing methanol by one-step hydrogenation of carbon dioxide according to claim 6, wherein said pre-tower is connected to said methanol recovery tower, and the desalted water having been washed in said methanol recovery tower is introduced into said pre-tower and the gas phase in said pre-tower is washed.
8. The one-step hydrogenation methanol production system of carbon dioxide according to claim 6, wherein the top of the pressurizing tower is communicated with a first heat exchange type reboiler, the first heat exchange type reboiler is also communicated with a pressurizing tower reflux tank, the pressurizing tower reflux tank is communicated with the upper part of the pressurizing tower, the gas phase at the top of the pressurizing tower is used as a heat medium of the first heat exchange type reboiler and is input into the first heat exchange type reboiler, after exothermic condensation, part of the gas phase is condensed back into the pressurizing tower, and the rest of the gas phase is output to form refined methanol; the lower part of the medium pressure tower is communicated with the first heat exchange type reboiler through a first pipeline and a second pipeline which are mutually independent, the liquid phase of the medium pressure tower is used as a cooling medium of the first heat exchange type reboiler, the cooling medium is input into the first heat exchange type reboiler through the first pipeline, and after absorbing heat in the first heat exchange type reboiler, the cooling medium is input into the bottom of the medium pressure tower through the second pipeline.
9. The one-step hydrogenation methanol production system of carbon dioxide according to claim 6, wherein the top of the medium pressure tower is communicated with a second heat exchange type reboiler, the second heat exchange type reboiler is also communicated with a medium pressure tower reflux tank, the medium pressure tower reflux tank is communicated with the upper part of the medium pressure tower, the gas phase at the top of the medium pressure tower is used as a heat medium of the second heat exchange type reboiler to be input into the second heat exchange type reboiler, after exothermic condensation, the gas phase is input into the medium pressure tower reflux tank, part of the gas phase is condensed back into the medium pressure tower, and the rest of the gas phase is output to form refined methanol; the lower part of the atmospheric tower is communicated with the second heat exchange type reboiler through a third pipeline and a fourth pipeline which are mutually independent, and the liquid phase of the atmospheric tower is used as a cooling medium of the second heat exchange type reboiler and is input into the second heat exchange type reboiler through the third pipeline, absorbs heat in the second heat exchange type reboiler, and is input into the bottom of the atmospheric tower through the fourth pipeline.
10. The one-step hydrogenation methanol production system of carbon dioxide according to claim 6, wherein the top of the atmospheric tower is communicated with a heat pump compressor, the heat pump compressor is communicated with a third heat exchange type reboiler, the third heat exchange type reboiler is communicated with the lower part of the atmospheric tower, the third heat exchange type reboiler is also communicated with an atmospheric tower condenser, the atmospheric tower condenser is communicated with an atmospheric tower reflux tank, the atmospheric tower reflux tank is communicated with the upper part of the atmospheric tower, the gas phase at the top of the atmospheric tower is input into the heat pump compressor, compressed by the heat pump compressor, then is input into the third heat exchange type reboiler for heat exchange, then is input into the atmospheric tower condenser for cooling, is input into the atmospheric tower reflux tank after cooling, and is partially condensed back into the upper part of the atmospheric tower, and the rest is output to form refined methanol; the third heat exchange type reboiler is also communicated with the bottom of the atmospheric tower, the liquid phase at the bottom of the atmospheric tower is used as a cooling medium to be input into the third heat exchange type reboiler, and the liquid phase is absorbed in the third heat exchange type reboiler and then is input into the bottom of the atmospheric tower.
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