CN110228792B - Deep decarburization process for synthesis gas - Google Patents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/18—Absorbing units; Liquid distributors therefor
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
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- C—CHEMISTRY; METALLURGY
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
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- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2257/304—Hydrogen sulfide
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Abstract
A synthesis gas deep decarburization process, transform gas is led into a separator through a pipeline, the separator is led into a winding heat exchanger through a pipeline, the winding heat exchanger is led into a desulfurization and decarburization tower through a pipeline, one part of purified gas led out from the decarburization and desulfurization tower is led into a fine decarburization tower for deep decarburization, and the other part of purified gas is led into a special winding heat exchanger methanol removal synthesis device through a special separator; the deep decarbonization purified gas is led to a PSA device through a winding heat exchanger through a pipeline, and purge gas generated by an ethylene glycol device is led to a methanol synthesis device through a pipeline; rich methanol in the fine decarbonizing tower is fed into the desulfurizing decarbonizing tower, the rich methanol in the desulfurizing decarbonizing tower is introduced into the heat exchanger and the heat regenerating system via pipeline, the acid gas in the heat regenerating system is filtered by the sulfur recovering unit, and the poor methanol produced in the heat regenerating system is returned to the heat exchanger, the fine decarbonizing tower and the desulfurizing decarbonizing tower for further absorbing hydrogen sulfide and CO after being cooled2Introducing the sewage of the thermal regeneration system into a water separation system; the invention can greatly reduce the equipment investment and has lower decarburization operation cost.
Description
Technical Field
The invention relates to the production field of ethylene glycol products by using a non-petroleum process route, in particular to a deep decarburization process for synthesis gas.
Background
Ethylene glycol is also known as "glycol" or "1, 2-ethylene glycol", EG for short, and has the chemical formula (CH2OH)2, which is the simplest diol. Is an important organic chemical raw material, and is mainly used for producing polyester fibers (PET), plastics, rubber, polyester paint, nonionic surfactants, solvents, lubricants and the like.
At present, two main preparation technical routes of ethylene glycol are provided: firstly, the petroleum route adopts an ethylene oxide hydration method, has the advantages of mature technology, wide application range and 90 percent of yield, has obvious defects, depends on petroleum resources, is closely hooked with the cost of the ethylene glycol product and the international oil price, has higher cost,and the water consumption is large; the other method is a technical route for preparing the ethylene glycol from coal, namely preparing synthetic gas from the coal, and then using carbon monoxide (CO) and hydrogen (H) in the synthetic gas2) Preparing ethylene glycol from the raw material. The technology for preparing the ethylene glycol from the coal can effectively relieve the contradiction between supply and demand of the ethylene glycol in China and can improve the high-efficiency clean conversion utilization level of coal resources. However, the existing preparation process of the feed gas for preparing the ethylene glycol from the coal still needs to be improved, and the feed gas for preparing the ethylene glycol requires CO and H2The content of the ethylene glycol is more than 99.0 percent, and the requirement on gas quality is higher, so that how to efficiently produce the ethylene glycol feed gas meeting the high-standard gas quality requirement is a technical problem which is urgently needed to be solved at present.
Disclosure of Invention
The invention aims to provide a synthesis gas deep decarburization process with reasonable process and higher synthesis efficiency.
The technical scheme of the invention is that,
a deep decarburization process for synthesis gas is characterized in that: (1) the conversion gas is cooled and subjected to heat exchange, then is introduced into the separator through a pipeline, the gas outlet of the separator is introduced into the winding heat exchanger through a pipeline, the gas outlet of the winding heat exchanger is introduced into the desulfurization and decarbonization tower through a pipeline, a special pipeline is arranged on the decarburization and desulfurization tower, part of purified gas from the desulfurization and decarbonization tower is introduced into the fine decarburization tower, the other part of purified gas is introduced into the special winding heat exchanger through the special separator, and then is treated by the special winding heat exchanger, and the gas is introduced into the methanol synthesis device; after passing through a pipeline, one part of the gas treated by the fine decarburization tower is led into a winding heat exchanger to recover cold energy and then enters a special separator to enter a PSA device to provide qualified raw material gas for synthesizing ethylene glycol, and the other part of the gas can also be led into the special separator to adjust the air inflow of methanol synthesis; wherein, the purified gas after deep decarburization is led to a PSA device through a winding heat exchanger by a pipeline, the product gas of the PSA device is led to a glycol device production line, the desorbed gas produced by the PSA device is led to a methanol synthesis device, and the exhausted gas produced by the glycol device production line is also led to the methanol synthesis device by a pipeline; (2) the regenerated poor methanol is sent to the top of the fine decarbonization tower through a pipeline after being cooled by a heat exchanger, and CO is adsorbed by the fine decarbonization tower2The low-temperature methanol-rich refluxThe device comprises a decarburization desulfurization tower, wherein rich methanol in the decarburization tower is introduced into a heat exchanger through a pipeline, the heat exchanger is introduced into a thermal regeneration system through a pipeline, acid gas of the thermal regeneration system is filtered by a sulfur recovery device, poor methanol generated by the thermal regeneration system is reversely poured back to the heat exchanger, and sewage of the thermal regeneration system is introduced into a water separation system for subsequent treatment.
The PSA device in the step (1) is used for purifying carbon monoxide and hydrogen.
The invention has the beneficial effects that: can solve the problem of deep decarburization of purified gas, meets the requirement of raw gas of a PSA device, greatly reduces equipment investment and has lower decarburization operation cost.
Drawings
FIG. 1 is a schematic diagram of the synthesis of the process of the present invention.
Detailed Description
Detailed description of embodiments in conjunction with the above figures
A synthesis gas deep decarburization process, (1) the shift gas is cooled and heat exchanged and then is led into a separator through a pipeline, the gas outlet of the separator is led into a winding heat exchanger through a pipeline, the gas outlet of the winding heat exchanger is led into a desulfurization and decarburization tower through a pipeline, a special pipeline is arranged on the decarburization and desulfurization tower to lead one part of the purified gas from the desulfurization and decarburization tower into a fine decarburization tower, the other part of the purified gas is led into a special winding heat exchanger through a special separator, and then the gas is led into a methanol synthesis device after being processed by the special winding heat exchanger; after passing through a pipeline, one part of the gas treated by the fine decarburization tower is led into a winding heat exchanger to recover cold energy and then enters a special separator to enter a PSA device to provide qualified raw material gas for synthesizing ethylene glycol, and the other part of the gas can also be led into the special separator to adjust the air inflow of methanol synthesis; wherein, the purified gas after deep decarburization is led to a PSA device through a winding heat exchanger by a pipeline, the product gas of the PSA device is led to a glycol device production line, the desorbed gas produced by the PSA device is led to a methanol synthesis device, and the exhausted gas produced by the glycol device production line is also led to the methanol synthesis device by a pipeline; (2) the regenerated poor methanol is sent to the top of the fine decarbonization tower through a pipeline after being cooled by a heat exchanger, and CO is adsorbed by the fine decarbonization tower2The low-temperature rich methanol flows back to the decarburization and desulfurization tower for decarburization and desulfurizationThe rich methanol in the sulfur decarbonization tower is introduced into a heat exchanger through a pipeline, the heat exchanger is introduced into a heat regeneration system through a pipeline, acid gas of the heat regeneration system is filtered by a sulfur recovery device, poor methanol generated by the heat regeneration system is reversely poured back to the heat exchanger, and sewage of the heat regeneration system is introduced into a water separation system for subsequent treatment.
The invention gasifies the crude gas (N) from coal2 0.63%、CO66.07%、CO2 5.65%、CH4 0.14%、H226.98%、H2S1000 ppm) after sulfur-resistant wide-temperature shift, shift the gas (N)2 0.57%、CO 22.88%、CO2 30.75%、CH4 0.1%、H2 45.61%、H2S900 ppm) is subjected to heat exchange and temperature reduction and then is introduced into a separator through a pipeline, the cold shift gas from the gas outlet of the winding heat exchanger is introduced into a winding heat exchanger through a pipeline for further temperature reduction, the cold shift gas from the gas outlet of the winding heat exchanger is introduced into a desulfurization and decarbonization tower from the bottom through a pipeline and is fully contacted with low-temperature poor methanol flowing downwards from the top of the tower in the tower, and the low-temperature methanol absorbs H in the shift gas2S、CO2The gas which is easy to absorb, purified gas 1 (N) after desulfurization and decarburization2 0.54%、CO 31.51%、CO2 4.3%、CH4 0.14%、H263.4%) of methanol is discharged from the tower top, and is subjected to gas-liquid separation and winding heat exchanger to normal temperature, and the methanol is pressurized by a synthesis compressor and then is sent to methanol synthesis to produce crude methanol under the action of a catalyst. Absorption of H2S、CO2The rich methanol is sent to the medium-pressure flash tower and the desorption tower from the lower part of the desulfurization and decarbonization tower through pipelines to continuously release and desorb CO in the rich methanol2And a small part of sulfur components, wherein the part of rich methanol is pressurized by a high-pressure pump and then is introduced into a heat exchanger, the heat exchanger is introduced into a heat regeneration system through a pipeline, acid gas in the heat regeneration system is concentrated and then is treated by a sulfur recovery device to recover sulfur, tail gas reaches the standard and is discharged, lean methanol recovered by the heat regeneration system is pressurized by the high-pressure pump and then is reversely cooled continuously by the heat exchanger, and the lean methanol enters the absorption cold-change gas from the top of a desulfurization decarbonization tower to absorb H in the cold-change gas2S and CO2And introducing the methanol water solution of the thermal regeneration system into a water separation system for subsequent treatment.
(2) The pressure swing adsorption PSA process is adopted to purify CO and H in gas2In the case of purificationFor the CO in the purified gas 1 of the prior low-temperature methanol washing process2The process is required to be below 20PPm, and in this case, a fine decarburization tower is added in the low-temperature methanol washing unit, and the process quality is improved by utilizing the existing low-temperature cold energy deep decarburization.
The purified gas in the step (1) can be controlled by a regulating valve, and a part of the purified gas from the desulfurization and decarbonization tower is introduced into a fine decarbonization tower for deep decarbonization, and the part of the purified gas ((N)2 0.55%、CO 32.36%、CO2＜10ppm、CH4 0.12%、H266.97%) is led to a PSA device through a winding heat exchanger and a pipeline, the PSA device purifies carbon monoxide and hydrogen, the purified carbon monoxide and hydrogen are sent to an ethylene glycol device production line to produce ethylene glycol products, and a part of desorption gas from the PSA device and purge gas from the ethylene glycol device are combined with purified gas from a desulfurization and decarbonization tower and then are sent to a methanol synthesis device through a compressor under pressure.
(3) The route of the liquid material in the process is as follows: after the poor methanol from the heat regeneration system is pressurized by a pump, subjected to heat exchange and reduced to a required temperature, the low-temperature poor methanol enters the top of the fine decarbonization tower from top to bottom to be in countercurrent contact with the purified gas entering the bottom, and CO in the purified gas2And the trace sulfur component is absorbed by the low-temperature liquid, and the purified gas is discharged from the top of the tower through a demister to a PSA device; the low-temperature solution at the bottom of the tower is pressurized by a pump and sent to a tower plate at the top of the desulfurization and decarbonization tower, and is in countercurrent contact with the shift gas entering from the bottom from top to bottom, and sulfur components such as hydrogen sulfide and the like and most of CO in the shift gas2Is absorbed and absorbs sulfur and CO2The methanol-rich solution releases CO through continuous depressurization and flash evaporation2And the rich methanol is regenerated into the poor methanol through a thermal regeneration tower, a water fractionating tower and the like.
The above examples are merely examples for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. It is not necessary or necessary to exhaustively enumerate all embodiments herein, and obvious variations or modifications can be made without departing from the scope of the invention.
Claims (2)
1. A deep decarburization process for synthesis gas is characterized in that: (1) the conversion gas is cooled and subjected to heat exchange, then is introduced into the separator through a pipeline, the gas outlet of the separator is introduced into the winding heat exchanger through a pipeline, the gas outlet of the winding heat exchanger is introduced into the desulfurization and decarbonization tower through a pipeline, a special pipeline is arranged on the decarburization and desulfurization tower, part of purified gas from the desulfurization and decarbonization tower is introduced into the fine decarburization tower, the other part of purified gas is introduced into the special winding heat exchanger through the special separator, and then is treated by the special winding heat exchanger, and the gas is introduced into the methanol synthesis device; after passing through a pipeline, one part of the gas treated by the fine decarburization tower is led into a winding heat exchanger to recover cold energy and then enters a special separator to enter a PSA device to provide qualified raw material gas for synthesizing ethylene glycol, and the other part of the gas can also be led into the special separator to adjust the air inflow of methanol synthesis; wherein, the purified gas after deep decarburization is led to a PSA device through a winding heat exchanger by a pipeline, the product gas of the PSA device is led to a production line of an ethylene glycol device, the desorbed gas produced by the PSA device is led to a methanol synthesis device, and the exhausted gas produced by the production line of the ethylene glycol device is also led to the methanol synthesis device by a pipeline; (2) the regenerated poor methanol is sent to the top of the fine decarbonization tower through a pipeline after being cooled by a heat exchanger, and CO is adsorbed by the fine decarbonization tower2And the low-temperature rich methanol flows back to the decarburization and desulfurization tower, the rich methanol in the desulfurization and decarburization tower is introduced into a heat exchanger through a pipeline, the heat exchanger is introduced into a heat regeneration system through a pipeline, acid gas in the heat regeneration system is filtered by a sulfur recovery device, poor methanol generated by the heat regeneration system is reversely poured back to the heat exchanger, and sewage of the heat regeneration system is introduced into a water separation system for subsequent treatment.
2. The deep decarburization process for synthesis gas as claimed in claim 1, wherein: in the step (1), the carbon monoxide and the hydrogen are purified by a PSA device.
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| CN111153769A (en) * | 2020-01-16 | 2020-05-15 | 上海国际化建工程咨询有限公司 | Method and device for producing methanol by using tail gas of ethylene glycol device |
| CN117125673B (en) * | 2023-08-22 | 2024-02-13 | 山东福富新材料科技有限公司 | Large-scale carbon capture system |
| CN117065503A (en) * | 2023-08-22 | 2023-11-17 | 山东福富新材料科技有限公司 | Large-scale carbon trapping method |
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| CN100513301C (en) * | 2006-12-11 | 2009-07-15 | 山西丰喜肥业（集团）股份有限公司临猗分公司 | Purification process of raw material gas for production of synthetic ammonia or methanol production |
| CN102381717B (en) * | 2010-09-01 | 2013-07-31 | 中国石油天然气股份有限公司 | Method for converting natural gas to produce ammonia |
| CN106310888A (en) * | 2015-06-17 | 2017-01-11 | 中国石油化工股份有限公司 | Synthetic gas decarburization method |
| CN104927949B (en) * | 2015-06-19 | 2018-04-20 | 上海国际化建工程咨询公司 | It is a kind of that circulating fluidized bed dry thermally desulfurizing production synthetic natural gas or the method and system of coproduction hydrogen manufacturing are used in combination |
| CN106867586A (en) * | 2015-12-14 | 2017-06-20 | 神华集团有限责任公司 | A kind of gasification of coal and gasification installation |
| CN105948046B (en) * | 2016-04-25 | 2018-06-08 | 华陆工程科技有限责任公司 | A kind of method for being recycled without stripping gas and producing pure hydrogen and pure carbon monoxide simultaneously that gasifies |
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