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CN115504861B - Coupling CO 2 Process method for preparing methanol by hydrogenation - Google Patents

Coupling CO 2 Process method for preparing methanol by hydrogenation Download PDF

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CN115504861B
CN115504861B CN202211159305.8A CN202211159305A CN115504861B CN 115504861 B CN115504861 B CN 115504861B CN 202211159305 A CN202211159305 A CN 202211159305A CN 115504861 B CN115504861 B CN 115504861B
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methanol
gas
synthesis unit
reactor
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CN115504861A (en
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张大洲
张宗飞
彭杰
卢文新
苏静
刘波
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China Wuhuan Engineering Co Ltd
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    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15Preparation 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
    • C07C29/151Preparation 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
    • C07C29/1516Multisteps
    • C07C29/1518Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15Preparation 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
    • C07C29/151Preparation 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
    • C07C29/152Preparation 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

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Abstract

The invention provides a coupling CO 2 The technical method for preparing methanol by hydrogenation comprises the steps of purifying hydrogen-rich tail gas to obtain purified hydrogen; for CO in tail gas of boiler 2 The gas is trapped and purified to obtain purified CO 2 Gas, CO to be purified 2 The gas is divided into n strands; purified hydrogen and a first stream of purified CO 2 The gas respectively enters a first methanol synthesis unit to react to obtain crude methanol, and the gas product after the reaction of the first methanol synthesis unit and a second stream of purified CO 2 The gas respectively enters a second methanol synthesis unit to react to obtain crude methanol, and the crude methanol enters a downstream methanol refining unit by analogy. The whole process is simple in technology, easy to operate, mild in reaction condition and CO 2 The single-pass conversion rate is high, a circulating gas compressor is not required to be arranged, the comprehensive energy consumption is low, the additional value of industrial tail gas can be improved, the carbon emission is reduced, the methanol production cost is obviously reduced, and the method is particularly suitable for methanol production devices with the tonnage of more than ten thousand tons.

Description

Coupling CO 2 Process method for preparing methanol by hydrogenation
Technical Field
The invention belongs to the technical field of carbon neutralization and carbon reduction, and in particular relates to a coupling CO 2 Process for preparing methanol by hydrogenationA method of manufacturing the same.
Background
The massive consumption of fossil energy by humans results in the emission of a huge amount of the greenhouse gas CO into the atmosphere 2 Causes greenhouse gas effect and causes the temperature to rise year by year, so the academia and industry in recent years are actively searching for reducing fossil energy consumption and CO 2 The measures of emissions, in general, mainly comprise three technical routes: firstly, the energy structure is improved, the dependence on fossil energy is reduced, and renewable energy sources such as solar energy, wind energy, nuclear energy, biomass fuel and other zero-carbon technologies are actively developed; secondly, by optimizing the existing process route, a novel carbon reduction process technology with low energy consumption is developed, and the process emission of chemical reaction is reduced; thirdly, developing CO in the process of utilizing fossil energy 2 Is used for trapping, utilizing or storing technology, reducing CO discharged into atmosphere 2 I.e. a layout application of the carbon negative technique.
Methanol is taken as one of important basic organic chemical raw materials, the annual demand is huge, the national methanol productivity is 9738.5 ten thousand tons and the national methanol productivity is 7816.38 ten thousand tons by 2021, the national methanol device takes a coal-to-methanol route as a main part because of the resource characteristics of rich coal, lean oil and less gas in China, the generally adopted flow is coal gasification to obtain synthetic gas, the hydrogen-carbon ratio in the synthetic gas is regulated in a changing way, then raw gas with the hydrogen-carbon modulus ratio of 1.98-2.2 is obtained after purification, desulfurization and decarbonization, and then the raw gas enters the methanol device for reaction to generate methanol. In the above-mentioned shift process, 1mol of CO is produced while 1mol of hydrogen is produced 2 Resulting in inefficient use of carbon elements in the raw coal and large amounts of carbon emissions. CO captured by utilizing industrial byproduct hydrogen and industrial flue gas 2 The hydrogenation reaction is used for preparing methanol, thus realizing CO 2 The recycling of resources reduces the emission of industrial carbon, and can realize the storage and application of hydrogen resources.
CO/CO 2 The hydrogenation to prepare methanol is exothermic reaction, the traditional methanol synthesis process generally adopts a single tubular reactor, raw material gas and a large amount of circulating gas are mixed and enter the reactor to participate in the reaction, and the circulating gas has the functions of reducing the carbon concentration at an inlet and improving CO/CO 2 Conversion, however, the recycle ratio of the tail gas is generally large, resulting in high energy consumption. Compared with the process for preparing methanol by CO hydrogenation, the unit mole of CO 2 The reaction heat release amount for preparing methanol by hydrogenation is small, and CO 2 The molecular inertness, better requirements on the catalyst performance, and the single pass conversion is often lower, so that the CO is necessary from the reaction process point of view 2 The hydrogenation technology for preparing methanol is considered separately.
CO+2H 2 →CH 3 OH+90.64KJ/mol
CO 2 +3H 2 →CH 3 OH+H 2 O+48.02KJ/mol
Patent CN114082287a discloses a method and system for direct hydrogenation of flue gas, hydrogen from electrolyzed water to produce hydrogen, and direct hydrogenation of flue gas to produce methanol and/or synthetic ammonia. Patent CN113956131A discloses a method for realizing the CO-production of methanol/glycol by coupling coal chemical industry and green hydrogen, which reduces the coal consumption and simultaneously reduces the CO of the process by partially replacing the green hydrogen generated by electrolysis water with the ash hydrogen generated by coal gasification 2 Discharging; oxygen generated by electrolysis of water is used for ethylene glycol, so that the air separation load is reduced; the invention is provided with the hydrogen storage device and the energy storage device, and can ensure continuous supply of hydrogen and oxygen when the power generation system cannot be continuously used, thereby meeting the requirement of continuous production. Patent CN114394883a discloses a method for preparing methanol by gasification coupling green electricity and green hydrogen of pulverized coal waste boiler to realize near zero carbon emission, and the consumption of fossil energy is reduced by generating electricity from new energy and electrolyzing water to produce hydrogen. Patent CN113292394B discloses a system for preparing methanol by coke oven gas coupling garbage incineration power generation, which couples the coke oven gas to the garbage incineration power generation process, and utilizes CO generated in the garbage incineration process 2 But also solves the problem of CO in the process of preparing methanol from coke oven gas 2 Source problems, reducing carbon emissions. Patent CN112194566A discloses a device and a process for synthesizing methanol based on carbon dioxide hydrogenation, wherein the reaction temperature in a reactor is 200-300 ℃, the reaction pressure is 5-10MPa, the circulation ratio of tail gas is 1.0-1.5, and the power consumption is increased.
Although at present CO 2 Various researches are carried out on various links of hydrogenation comprehensive utilization, but hydrogen involved in methanol productionGas production, CO 2 Capturing CO 2 The hydrogenation and methanol refining parts are independently researched or improved, and the reaction characteristics of each procedure are not subjected to systematic analysis optimization. Thus, in order to achieve CO in industrial exhaust 2 Is needed to develop a coupling CO, which reduces the carbon emission and simultaneously reduces the production cost and the comprehensive energy consumption of methanol 2 A process technology for preparing methanol by hydrogenation.
Disclosure of Invention
The invention aims to solve the technical problems and provide a CO 2 Coupling CO with high single pass conversion rate and low comprehensive energy consumption 2 A process method for preparing methanol by hydrogenation.
The invention provides a coupling CO 2 The process method for preparing methanol by hydrogenation comprises the following steps:
1) Purifying the hydrogen-rich tail gas to obtain purified hydrogen as a hydrogen source;
2) For CO in tail gas of boiler 2 The gas is trapped and purified to obtain purified CO 2 Gas is used as carbon source and purified CO 2 The gas is divided into n strands;
3) Purified hydrogen and a first stream of purified CO 2 The gas respectively enters a first methanol synthesis unit 101 to react to obtain crude methanol, and the gas product after the reaction of the first methanol synthesis unit 101 and a second stream of purified CO 2 The gas respectively enters the second methanol synthesis unit 102 to react to obtain crude methanol, and the gas product after the reaction of the n-1 methanol synthesis unit and the n-th purified CO are analogically 2 The gas respectively enters an n-th methanol synthesis unit to react to obtain crude methanol; the gas product after the reaction of the n-th methanol synthesis unit enters a tail methanol synthesis device to react to obtain crude methanol;
4) The crude methanol synthesized by the first methanol synthesis unit 101, the crude methanol synthesized by the second methanol synthesis unit 102, … …, the crude methanol synthesized by the nth methanol synthesis unit and the crude methanol synthesized by the tail methanol synthesis unit are mixed and then enter a downstream methanol refining unit.
Further, the first methanol synthesis unit 101, the second methanol synthesis unit 102, the … … and the nth methanol synthesis unit have the same structure and comprise a first methanol reactor R101, a first high-pressure separation tank S101 and a first low-pressure separation tank S102, the gas reacted by the first methanol reactor R101 is cooled in multiple stages in sequence and then enters the first high-pressure separation tank S101, and the liquid product of the first high-pressure separation tank S101 enters the first low-pressure separation tank S102 to flash gas to obtain crude methanol; the gas product separated by the first high-pressure separation tank S101 is heated by heat exchange and then enters the next first methanol reactor R101.
Further, the tail methanol synthesis apparatus includes m tail methanol synthesis units 200 connected in series in sequence, each tail methanol synthesis unit 200 including a second methanol reactor R201, a second high-pressure separation tank S201, and a second low-pressure separation tank S202; the gas product separated by the first high-pressure separation tank S101 in the nth methanol synthesis unit is heated by heat exchange and then enters the second methanol reactor R201 in the first tail methanol synthesis unit 200, the gas reacted by the second methanol reactor R201 is sequentially cooled in multiple stages and then enters the second high-pressure separation tank S201, the liquid product of the second high-pressure separation tank S201 enters the second low-pressure separation tank S202 to flash gas to obtain crude methanol, and the flash gas separated by the second high-pressure separation tank S201 enters the second methanol reactor R201 in the second tail methanol synthesis unit 200; and by analogy, the liquid product of the second high-pressure separation tank S201 in the mth tail methanol synthesis unit 200 enters the second low-pressure separation tank S202 to flash gas, so that crude methanol is obtained, and the flash gas separated by the second high-pressure separation tank S201 is discharged to a fuel removing pipe network.
Further, the heat released by the reaction in the second methanol reactor R201 in each of the tail methanol synthesis units 200 is removed by the boiler feed water, and then enters the steam drum S203 to be separated into gas and liquid to generate medium pressure saturated steam.
Further, the hydrogen-rich tail gas is purified by a purifier ST201, the purified hydrogen is pressurized by a second booster C102 and then enters a first methanol synthesis unit 101 through heat exchange, and the hydrogen-rich tail gas is derived from a propane dehydrogenation device; the tail gas of the boiler sequentially passes through CO 2 Trapping unit ST101, CO 2 Purification unitST102 is compressed to the reaction pressure and divided into n strands of CO 2 The gas is used as a carbon source for synthesizing methanol, and the first strand of CO 2 The gas enters a first methanol synthesis unit 101 and a second CO 2 The gas enters the second methanol synthesis unit 102, … … and the nth strand CO 2 The gas enters an nth methanol synthesis unit.
Further, the operating temperature of each first methanol reactor R101 is 210-300 ℃, the operating pressure is 5-20 MPa, and the airspeed is 4000-10000 h -1
Further, the second methanol reactor R201 in each of the tail methanol synthesis units 200 is operated at a temperature of 235 to 325 ℃, an operating pressure of 7 to 20MPa, and a space velocity of 8000 to 15000h -1
Further, if n is 2, the first CO 2 Gas and second CO 2 The gas volume fraction ratio is 0.5:1-5:1.
Or if n is 3, the first CO 2 Gas, second stream of CO 2 Gas, third strand CO 2 The volume part ratio of the gases is 1:1:0.5-5:1:1.
Further, the first methanol reactor R101 is a chilled methanol reactor, four catalyst beds 1.1 are vertically arranged in a reactor body of the chilled methanol reactor, a distributor 1.2 is arranged between every two adjacent catalyst beds 1.1, an air inlet 1.3 is arranged on the outer side surface of the reactor body and above each distributor 1.2, and each CO stream is provided with a gas inlet 2 The gas is divided into four branches, wherein the three branches are respectively input in one-to-one correspondence with the three gas inlets 1.3, and the last branch is mixed with purified hydrogen and then directly enters the reactor body;
or the first methanol reactor R101 is a tubular methanol reactor.
Further, the second methanol reactor R201 in each of the tail methanol synthesis units 200 is a tube type methanol reactor.
The invention has the advantages that: the invention has simple whole-flow process, easy operation, mild reaction condition and CO 2 The single-pass conversion rate is high, and a circulating gas compressor is not required to be arrangedThe comprehensive energy consumption is low, the additional value of industrial tail gas can be improved, the carbon emission is reduced, the methanol production cost is obviously reduced, and the method is particularly suitable for methanol production devices with the tonnage of more than one megaton.
Drawings
FIG. 1 is a schematic diagram of the coupling CO of the present invention 2 A flow diagram of a process method for preparing methanol by hydrogenation;
FIG. 2 is a flow chart of a second embodiment of the present invention;
FIG. 3 is a flow chart of a third embodiment of the present invention;
FIG. 4 is a schematic diagram of the chilled methanol reactor of FIG. 1.
Wherein, the purifier ST201 and CO 2 Trapping unit ST101, CO 2 A purification unit ST102, a first supercharger C102, and a second supercharger C101;
a first methanol synthesis unit 101, a second methanol synthesis unit 102, a first methanol reactor R101, a first high-pressure separation tank S101, a first low-pressure separation tank S102;
a tail methanol synthesis unit 200, a dimethanol reactor R201, a second high pressure separation tank S201, a second low pressure separation tank S202, and a steam drum S203;
a first heat exchanger E101, a second heat exchanger E102, a third heat exchanger E103, a fourth heat exchanger E104, a fifth heat exchanger E105, a sixth heat exchanger E201, a seventh heat exchanger E202, an eighth heat exchanger E203, a ninth heat exchanger E204, a tenth heat exchanger E301, an eleventh heat exchanger E302, a twelfth heat exchanger E303, a thirteenth heat exchanger E304, a fourteenth heat exchanger E401, a fifteenth heat exchanger E402, a sixteenth heat exchanger E403;
catalyst bed 1.1, distributor 1.2, gas inlet 1.3.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and perfectly described below with reference to the drawings in the present embodiment, and the described embodiments are only for more detailed description and should not be construed as limiting the present invention in any way.
Coupling CO 2 The process method for preparing methanol by hydrogenation comprises the following steps:
as shown in fig. 1, the hydrogen-rich tail gas of the propane dehydrogenation device (PDH) is purified by a purifier ST201 to remove water and a small amount of low-carbon hydrocarbon substances in the hydrogen-rich tail gas, the purified hydrogen is used as a hydrogen source, pressurized (for example, to 8.5-15.5 MPa) by a second booster C102, and then subjected to heat exchange (for example, to 210-220 ℃) by a first heat exchanger E101; the boiler flue gas is sequentially subjected to CO 2 Trapping unit ST101, CO 2 After the purification unit ST102, the mixture enters a first booster C101 to be compressed to the reaction pressure (such as 8.5-15.5 MPa), and CO 2 The trapping can be adsorption method, absorption method or membrane separation method, and CO 2 The purification mainly comprises the steps of removing sulfur impurities, avoiding catalyst poisoning, and adopting dry desulfurization, adsorption desulfurization or catalytic oxidation desulfurization. And purified hydrogen, purified CO 2 The total hydrogen carbon modulus of the gas is 2.99-3.5.
In this example, the purified CO 2 The gas is split into 2 streams, thus two sets of methanol synthesis units are required, and the first stream of CO 2 Gas and second CO 2 The gas volume fraction ratio is 0.5:1-5:1; meanwhile, the tail methanol synthesis device comprises 2 tail methanol synthesis units which are sequentially connected in series.
First CO 2 H in a cold state after heat exchange 2 The mixture enters a first methanol reactor R101 in a first methanol synthesis unit 101, the operation temperature of the first methanol reactor R101 is 210-300 ℃, the operation pressure is 5-20 MPa, and the airspeed is 4000-10000 h -1 The method comprises the steps of carrying out a first treatment on the surface of the The gas reacted by the first methanol reactor R101 sequentially passes through a second heat exchanger E102, a third heat exchanger E103 and a fourth heat exchanger E104 for multi-stage cooling and then enters a first high-pressure separation tank S101, the liquid product of the first high-pressure separation tank S101 enters a first low-pressure separation tank S102 to flash out part of the gas, crude methanol is obtained, and the flash gas is discharged to a boiler; the gas product separated by the first high-pressure separation tank S101 is subjected to heat exchange and temperature rise by the fifth heat exchanger E105 and then enters the first methanol reactor R101 in the second methanol synthesis unit 102.
At the same time, the second strand of CO 2 The gas inlet enters a first methanol reactor R101 in a second methanol synthesis unit 102, and the operation temperature of the first methanol reactor R101 is 210-300 ℃ and the operation is carried outPressure is 5-20 MPa, airspeed is 4000-10000 h -1 The method comprises the steps of carrying out a first treatment on the surface of the The gas reacted by the first methanol reactor R101 sequentially passes through a sixth heat exchanger E201, a seventh heat exchanger E202 and an eighth heat exchanger E203 for multi-stage cooling and then enters a first high-pressure separation tank S101, and a liquid product of the first high-pressure separation tank S101 enters a first low-pressure separation tank S102 to flash out part of the gas to obtain crude methanol; the gas product separated by the first high-pressure separation tank S101 is heated to 235-255 ℃ through heat exchange of a ninth heat exchanger E204, then enters a second methanol reactor R201 of the first tail methanol synthesis unit 200, the gas reacted by the second methanol reactor R201 sequentially passes through a tenth heat exchanger E301, an eleventh heat exchanger E302 and a twelfth heat exchanger E303 to be cooled in multiple stages, then enters a second high-pressure separation tank S201, the liquid product of the second high-pressure separation tank S201 enters a second low-pressure separation tank S202 to flash gas, crude methanol and flash gas are obtained, the flash gas is discharged to a boiler, and the flash gas separated by the second high-pressure separation tank S201 enters the second methanol reactor R201 in the second tail methanol synthesis unit 200 through a thirteenth heat exchanger E304; the gas reacted by the second methanol reactor R201 in the second tail methanol synthesis unit 200 sequentially passes through a fourteenth heat exchanger E401, a fifteenth heat exchanger E402 and a sixteenth heat exchanger E403, is cooled in multiple stages and then enters a second high-pressure separation tank S201, the liquid product of the second high-pressure separation tank S201 enters a second low-pressure separation tank S202 to flash gas to obtain crude methanol, the flash gas is discharged to a boiler, the flash gas separated by the second high-pressure separation tank S201 is discharged to a fuel removing pipe network, and the liquid product of the second high-pressure separation tank S201 enters a second low-pressure separation tank S202 to flash gas to obtain crude methanol.
The second methanol reactor R201 in each tail methanol synthesis unit 200 is of a tubular structure, the operating temperature is 235-325 ℃, the operating pressure is 7-20 MPa, and the airspeed is 8000-15000 h -1 The heat released by the reaction in the second methanol reactor R201 in each tail methanol synthesis unit 200 is removed by boiler feed water and then enters a steam drum S203 to be separated in gas-liquid separation to produce medium pressure saturated steam.
The crude methanol synthesized in the first methanol synthesis unit 101, the crude methanol synthesized in the second methanol synthesis unit 102, and the crude methanol synthesized in the tail methanol synthesis unit are mixed and then enter the downstream methanol purification unit.
The first methanol reactor R101 is a chilled methanol reactor, as shown in FIG. 4, four catalyst beds 1.1 are vertically arranged in a reactor body of the chilled methanol reactor, a distributor 1.2 is arranged between every two adjacent catalyst beds 1.1, an air inlet 1.3 is arranged on the outer side surface of the reactor body and above each distributor 1.2, and each CO stream is discharged from the reactor 2 The gas is divided into four branches, wherein the three branches are respectively input in one-to-one correspondence with the three air inlets 1.3, and the last branch is mixed with purified hydrogen and then enters the reactor body directly. The second methanol reactor R201 is a tube type methanol reactor, or the first methanol reactor R101 is also a tube type methanol reactor.
Two sets of methanol synthesis units and one set of tail methanol synthesis units may also be employed, as shown in fig. 2, as well as three sets of methanol synthesis units and two sets of tail methanol synthesis units, as shown in fig. 3.
The invention utilizes the discharged CO 2 And recovered H 2 Is characterized by single raw material gas, and is reasonably controlled to enter into the parallel reactor by adopting the method 2 、CO 2 Rather than directly mixing the gases into the feed, such that each reactor inlet H2/CO in parallel 2 The molar ratio is higher than the theoretical value, the catalyst has high single-pass conversion rate at low temperature, the size of a single reactor is obviously reduced, and the reaction condition is mild. The CO is further improved by connecting the tube type methanol reactors in series 2 Is converted into CO after the whole process 2 The conversion rate of (2) is more than or equal to 95%, a circulating gas compressor with high energy consumption and high circulation quantity is omitted, and finally CO is realized 2 And the hydrogenation reaction is effectively coupled with hydrogen.

Claims (6)

1. Coupling CO 2 The process method for preparing methanol by hydrogenation is characterized by comprising the following steps: the process method comprises the following steps:
1) Purifying the hydrogen-rich tail gas to obtain purified hydrogen as a hydrogen source;
2) For CO in tail gas of boiler 2 The gas is trapped and purified to obtain purified CO 2 Gas is used as carbon source and purified CO 2 The gas is divided into n strands;
3) Purified hydrogen and a first stream of purified CO 2 The gas respectively enters a first methanol synthesis unit (101) to react to obtain crude methanol, and the gas product after the reaction of the first methanol synthesis unit (101) and a second stream of purified CO 2 The gas respectively enters a second methanol synthesis unit (102) to react to obtain crude methanol, and then the gas product after the reaction of the n-1 methanol synthesis unit and the n-th purified CO 2 The gas respectively enters an n-th methanol synthesis unit to react to obtain crude methanol; the gas product after the reaction of the n-th methanol synthesis unit enters a tail methanol synthesis device to react to obtain crude methanol;
4) The crude methanol synthesized by the first methanol synthesis unit (101), the crude methanol synthesized by the second methanol synthesis unit (102), … …, the crude methanol synthesized by the nth methanol synthesis unit and the crude methanol synthesized by the tail methanol synthesis unit are mixed and then enter a downstream methanol refining unit;
the first methanol synthesis unit (101), the second methanol synthesis unit (102), the … … and the nth methanol synthesis unit have the same structure and comprise a first methanol reactor (R101), a first high-pressure separation tank (S101) and a first low-pressure separation tank (S102), gas reacted by the first methanol reactor (R101) sequentially enters the first high-pressure separation tank (S101) after being cooled in multiple stages, and liquid products of the first high-pressure separation tank (S101) enter the first low-pressure separation tank (S102) to flash gas to obtain crude methanol; the gas product separated by the first high-pressure separation tank (S101) enters the next first methanol reactor (R101) after heat exchange and temperature rise;
the tail methanol synthesis device comprises m tail methanol synthesis units (200) which are sequentially connected in series, wherein each tail methanol synthesis unit (200) comprises a second methanol reactor (R201), a second high-pressure separation tank (S201) and a second low-pressure separation tank (S202); the gas product separated by a first high-pressure separation tank (S101) in the n-th methanol synthesis unit is heated by heat exchange and then enters a second methanol reactor (R201) in a first tail methanol synthesis unit (200), the gas reacted by the second methanol reactor (R201) is cooled in multiple stages in sequence and then enters the second high-pressure separation tank (S201), the liquid product of the second high-pressure separation tank (S201) enters a second low-pressure separation tank (S202) to flash gas to obtain crude methanol, and the flash gas separated by the second high-pressure separation tank (S201) enters the second methanol reactor (R201) in the second tail methanol synthesis unit (200); by analogy, the liquid product of the second high-pressure separation tank (S201) in the mth tail methanol synthesis unit (200) enters a second low-pressure separation tank (S202) to flash gas to obtain crude methanol, and the flash gas separated by the second high-pressure separation tank (S201) is discharged to a fuel removing pipe network;
purifying and purifying the hydrogen-rich tail gas by a purifier (ST 201), pressurizing the purified hydrogen by a second supercharger (C102), and then exchanging heat to enter a first methanol synthesis unit (101), wherein the hydrogen-rich tail gas is derived from a propane dehydrogenation device; the tail gas of the boiler sequentially passes through CO 2 Capturing unit (ST 101) and CO 2 After the purification unit (ST 102), the mixture is compressed to the reaction pressure and divided into n strands of CO 2 The gas is used as a carbon source for synthesizing methanol, and the first strand of CO 2 The gas enters a first methanol synthesis unit (101) and a second CO 2 The gas enters a second methanol synthesis unit (102), … … and the nth strand CO 2 The gas enters an n-th methanol synthesis unit;
if n is 2, the first CO 2 Gas and second CO 2 The gas volume fraction ratio is 0.5:1-5:1;
or if n is 3, the first CO 2 Gas, second stream of CO 2 Gas, third strand CO 2 The volume part ratio of the gases is 1:1:0.5-5:1:1.
2. The coupled CO of claim 1 2 The process method for preparing methanol by hydrogenation is characterized by comprising the following steps: the heat released by the reaction in the second methanol reactor (R201) in each tail methanol synthesis unit (200) is removed by boiler feed water and then enters a steam drum (S203) for gas-liquid separation to generate medium pressure saturated steam.
3. The coupled CO of claim 1 2 The process method for preparing methanol by hydrogenation is characterized by comprising the following steps: each first methanol reactor (R101) has an operating temperature of 210-300 ℃, an operating pressure of 5-20 MPa and a space velocity of 4000-10000 h -1
4. The coupled CO of claim 1 2 The process method for preparing methanol by hydrogenation is characterized by comprising the following steps: the second methanol reactor (R201) in each tail methanol synthesis unit (200) operates at a temperature of 235-325 ℃, an operating pressure of 7-20 MPa, and a space velocity of 8000-15000 h -1
5. The coupled CO of claim 1 2 The process method for preparing methanol by hydrogenation is characterized by comprising the following steps: the first methanol reactor (R101) is a chilled methanol reactor, four catalyst beds (1.1) are vertically arranged in a reactor body of the chilled methanol reactor, a distributor (1.2) is arranged between every two adjacent catalyst beds (1.1), an air inlet (1.3) is formed in the outer side surface of the reactor body and above each distributor (1.2), and each CO 2 The gas is divided into four branches, wherein the three branches are respectively input in one-to-one correspondence with three gas inlets (1.3), and the last branch is mixed with purified hydrogen and then directly enters the reactor body;
or the first methanol reactor (R101) is a tubular methanol reactor.
6. The coupled CO of claim 1 2 The process method for preparing methanol by hydrogenation is characterized by comprising the following steps: the second methanol reactor (R201) in each of the tail methanol synthesis units (200) is a tube array methanol reactor.
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