CN113277511B - Production process for preparing electronic grade high-purity carbon dioxide by purifying synthesis gas - Google Patents
Production process for preparing electronic grade high-purity carbon dioxide by purifying synthesis gas Download PDFInfo
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 57
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 51
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 44
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000007789 gas Substances 0.000 claims abstract description 109
- 238000000746 purification Methods 0.000 claims abstract description 46
- 239000012043 crude product Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims description 50
- 239000001257 hydrogen Substances 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 28
- 238000010521 absorption reaction Methods 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- 230000008929 regeneration Effects 0.000 claims description 14
- 238000011069 regeneration method Methods 0.000 claims description 14
- 238000005261 decarburization Methods 0.000 claims description 11
- 238000011084 recovery Methods 0.000 claims description 10
- 238000009833 condensation Methods 0.000 claims description 9
- 230000005494 condensation Effects 0.000 claims description 9
- 239000007791 liquid phase Substances 0.000 claims description 5
- 239000012071 phase Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000012856 packing Methods 0.000 claims description 3
- 238000005262 decarbonization Methods 0.000 abstract description 12
- 230000009286 beneficial effect Effects 0.000 abstract description 6
- 239000003245 coal Substances 0.000 abstract description 6
- 238000012824 chemical production Methods 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000002912 waste gas Substances 0.000 abstract description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 65
- 229910002091 carbon monoxide Inorganic materials 0.000 description 65
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 39
- 238000002474 experimental method Methods 0.000 description 22
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 14
- 238000009835 boiling Methods 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 229910001868 water Inorganic materials 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000006096 absorbing agent Substances 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- -1 moisture Chemical compound 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Gas Separation By Absorption (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a production process for preparing electronic grade high-purity carbon dioxide by purifying synthesis gas, which comprises the following steps: decarbonizing the synthesis gas by a wet decarbonizing device to obtain a high-content CO 2 crude product; the crude product with high content of CO 2 enters a CO 2 purification device to obtain high-purity electronic grade CO 2; other component gases are subjected to wet decarbonization and then enter a low-temperature rectification device to respectively obtain high-content CH 4 and high-content CO; wherein, the high-content CH 4 enters a CH 4 purification device to obtain high-purity electronic grade CH 4; wherein the high-content CO enters a CO purification device to obtain high-purity electronic grade CO. The invention has the beneficial effects that: the invention utilizes the wet decarbonization device, the purification device and the low-temperature rectification device to separate and purify the synthesis gas, so that some gases reach high-purity electronic grade. The synthesis gas produced in the coal chemical production is adopted, so that the waste gas recycling value is improved, and the pollution to the environment is reduced.
Description
Technical Field
The invention relates to the technical field of high-purity gas preparation, in particular to a production process for preparing electronic grade high-purity carbon dioxide by purifying synthesis gas.
Background
Electronic gases are widely used in various process flows for semiconductor, panel and solar energy manufacture, and are commonly used for chemical vapor deposition, ion implantation, photoresist printing, diffusion, etching, doping, and the like. Along with the development of the industries, the requirements for the electronic special gas are continuously increased, most markets of the electronic special gas are monopolyed abroad, and in particular, the electronic special gas is monopolyed by foreign enterprises for over 90 percent as a key material required by the field of integrated circuits, and the localization requirements for the special gas are urgent.
Meanwhile, a plurality of crude raw materials of the electron special gas come from coal chemical industry, chlor-alkali chemical industry, synthetic ammonia and other large chemical industry, and the electron special gas is provided with rich and cheap raw materials. Wherein, the coal chemical industry synthesis gas contains a large amount of methane, carbon monoxide, hydrogen and carbon dioxide. If the raw materials are directly purified to prepare the high-purity electronic grade methane, carbon monoxide, hydrogen and carbon dioxide, the production cost of the high-purity gas can be reduced, the added value of the product can be improved, and the method is a suitable path for developing the high-purity electronic grade methane.
Aiming at the problems, the prior art discloses some technical schemes for purifying synthesis gas, as follows:
1. For example, china patent discloses a method for preparing hydrogen and high-purity carbon monoxide by separating synthesis gas (publication No. CN 104528647A), wherein the synthesis gas is a pretreated mixed gas; the method comprises the following steps: h2 and low boiling point impurities are separated from the top of the tower through rectification, CH 4、O2 and high boiling point impurities are separated from the bottom of the tower through secondary rectification, N2 and non-removed high boiling point impurities are separated from the top of the tower through tertiary rectification, and CO is separated from the bottom of the tower through tertiary rectification; the energy transmission process accompanied by the process is realized by the absorption and the release of heat of the separated N2 circulation loop. The invention also provides a device for the method, which mainly comprises continuous rectifying equipment of the dehydrogenation tower C1, the deoxidization-methane tower C2 and the denitrification tower C3 and related equipment for realizing energy transfer. The invention overcomes the defects of the traditional method, saves equipment investment, reduces energy consumption, improves the added value of products and realizes the circular economic effect.
2. The process for the production of carbon dioxide and hydrogen from synthesis gas is disclosed in chinese patent publication No. CN200780020668.0, the hydrogen plant (1) having a synthesis gas reactor (10), a water gas shift reactor (14) downstream of the synthesis gas reactor to form a synthesis gas stream (12), and a hydrogen pressure swing adsorption unit (20) to produce a hydrogen product (22) recovered from the synthesis gas stream. According to the invention, carbon dioxide is separated from the synthesis gas stream in a vacuum pressure swing adsorption system (80) to produce a hydrogen-enriched synthesis gas stream (76) and a crude carbon dioxide stream (82), and the crude carbon dioxide stream is then purified by a sub-ambient temperature distillation process to produce a carbon dioxide product (756). A hydrogen synthesis gas feed stream (78) to the hydrogen pressure swing adsorption unit is formed at least in part from the hydrogen enriched stream.
Although the above technical scheme has a certain improvement scheme for purifying synthesis gas to a certain extent, the following problems also exist:
1. The method has the defects of low separation efficiency, unstable product purity and the like, and the process for producing high-purity methane by using natural gas has the defect of high production cost;
2. the purification purity of the synthesis gas is not high, and the requirement of high purity of electronic grade is not met.
Therefore, it is necessary to propose a process for preparing electronic grade high purity carbon dioxide by purifying synthesis gas.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a production process for preparing electronic grade high-purity carbon dioxide by purifying synthesis gas so as to solve the problems.
The production process for preparing the electronic grade high-purity carbon dioxide by purifying the synthesis gas comprises the following steps:
s1, decarbonizing the synthesis gas by a wet decarbonizing device to obtain a high-content CO 2 crude product;
S2, the high-content CO 2 crude product enters a CO 2 purification device to obtain high-purity electronic grade CO 2;
S3, other component gases enter a low-temperature rectification device after wet decarburization to respectively obtain high-content CH 4 and high-content CO;
S4, enabling the high-content CH 4 to enter a CH4 purification device to obtain a high-purity electronic grade CH 4;
s5, enabling the high-content CO to enter a CO purification device to obtain high-purity electronic grade CO.
Preferably, the tail gas of the cryogenic rectification plant is hydrogen.
Preferably, the wet decarbonization device comprises an absorption tower, a high-pressure flash tank, a low-pressure flash tank, a regeneration tower, a first semi-lean liquid pump, a second semi-lean liquid pump, a recovery liquid pump and a lean liquid pump, wherein the high-pressure flash tank is arranged on the low-pressure flash tank, the bottom of the absorption tower is respectively communicated with the first semi-lean liquid pump and the low-pressure flash tank through a hydraulic turbine, the first semi-lean liquid pump is respectively communicated with the middle position of the absorption tower, the high-pressure flash tank and the second semi-lean liquid pump, the second semi-lean liquid pump is connected with the regeneration tower through a heat exchanger, and the top of the regeneration tower is communicated with the high-pressure flash tank.
Preferably, the high-pressure flash tank is connected with a recovery liquid pump through a separator, the recovery liquid pump is respectively connected with the high-pressure flash tank and a heat exchanger, and the heat exchanger is communicated with the lean liquid pump.
Preferably, the lean liquid pump is connected with the top of the absorption tower through a cooler.
Preferably, a low-pressure steam reboiler is connected between the bottom and the middle of the regeneration tower.
Preferably, the CO2 purification device comprises a combined adsorber, a light-removal rectifying tower, a heavy-removal rectifying tower and a buffer tank, wherein the combined adsorber is communicated with the heavy-removal rectifying tower through the light-removal rectifying tower, the heavy-removal rectifying tower is communicated with the buffer tank, and the buffer tank is communicated with the inflatable bottle through a film press.
Preferably, the cryogenic rectification plant comprises a tower tank, a rectification pipe and a circulating condensation tank, wherein the circulating condensation tank is arranged on the tower tank through the rectification pipe, and a circulating cooling pipe is arranged in the circulating condensation tank.
Preferably, a feed inlet is arranged at the side edge of the middle part of the rectifying tube, a liquid phase outlet is arranged at the bottom of the tower tank, and a gas phase outlet is arranged at the top of the circulating condensing tank.
Preferably, the rectifying tube is filled with a packing layer.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention utilizes the wet decarbonization device, the purification device and the low-temperature rectification device to separate and purify the synthesis gas, so that some gases reach high-purity electronic grade.
2. The synthesis gas produced in the coal chemical production is adopted, so that the waste gas recycling value is improved, and the pollution to the environment is reduced.
Drawings
FIG. 1 is a schematic illustration of a synthesis gas purification process for the production of electronic grade high purity carbon dioxide in accordance with the present invention;
FIG. 2 is a schematic diagram of a wet decarburization device according to the present invention;
FIG. 3 is a block diagram of a CO 2 purification unit of the present invention;
FIG. 4 is a block diagram of a cryogenic rectification plant of the invention;
Reference numerals in the drawings: 1. a wet decarbonization device; 2. a CO2 purification device; 3. cryogenic rectification plant; 4. a CO purification device; 5. CH 4 purification unit; 101. an absorption tower; 102. a high pressure flash tank; 103. a low pressure flash tank; 104. a regeneration tower; 105. a first semi-lean liquid pump; 106. a second semi-lean liquid pump; 107. a recovery liquid pump; 108. a lean liquid pump; 109. a hydraulic turbine; 110. a heat exchanger; 111. a cooler; 112. a separator; 113. a low pressure steam reboiler; 201. a combined adsorber; 202. a light component removing rectifying tower; 203. a heavy-removal rectifying tower; 204. a buffer tank; 205. a film press; 206. filling a gas cylinder; 301. a tower tank; 302. a circulating condensing tank; 303. a rectifying tube; 304. a feed inlet; 305. a circulating cooling pipe; 306. a gas phase outlet; 307. a liquid phase outlet; 308. and a filler layer.
Detailed Description
It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
Embodiments of the invention are described in detail below with reference to the attached drawings, but the invention can be implemented in a number of different ways, which are defined and covered by the claims.
As shown in fig. 1 and in combination with fig. 2 and fig. 4, a process for preparing electronic grade high purity carbon dioxide by purifying synthesis gas comprises the following steps:
S1, decarbonizing the synthesis gas by a wet decarbonizing device 1 to obtain a high-content CO 2 crude product;
S2, the crude product of the high-content CO 2 enters a CO 2 purification device 2 to obtain high-purity electronic grade CO 2;
s3, other component gases enter a low-temperature rectification device 3 after wet decarburization to respectively obtain high-content CH 4 and high-content CO;
S4, enabling the high-content CH 4 to enter a CH 4 purification device 5 to obtain a high-purity electronic grade CH 4;
s5, enabling the high-content CO to enter a CO purification device 4 to obtain high-purity electronic grade CO.
Further, the tail gas of the cryogenic rectification plant 3 is hydrogen.
The adoption of the further technical scheme has the beneficial effects that: as raw material for synthesizing ammonia or for removing PSA section to make high-purity hydrogen.
Further, the wet decarbonization device 1 comprises an absorption tower 101, a high-pressure flash tank 102, a low-pressure flash tank 103, a regeneration tower 104, a first semi-lean liquid pump 105, a second semi-lean liquid pump 106, a recovery liquid pump 107 and a lean liquid pump 108, wherein the high-pressure flash tank 102 is arranged on the low-pressure flash tank 103, the bottom of the absorption tower 101 is respectively communicated with the first semi-lean liquid pump 105 and the low-pressure flash tank 103 through a hydro turbine 109, the first semi-lean liquid pump 105 is respectively communicated with the middle position of the absorption tower 101, the high-pressure flash tank 102 and the second semi-lean liquid pump 106, the second semi-lean liquid pump 106 is connected with the regeneration tower 104 through a heat exchanger 110, and the top of the regeneration tower 104 is communicated with the high-pressure flash tank 102.
Further, the high-pressure flash tank 102 is connected to a recovery liquid pump 107 through a separator 112, the recovery liquid pump 107 is connected to the high-pressure flash tank 102 and a heat exchanger 110, and the heat exchanger 110 is communicated with a lean liquid pump 108.
Further, the lean liquid pump 108 is connected to the top of the absorption tower 101 through a cooler 111.
Further, a low pressure steam reboiler 113 is connected between the bottom and the middle of the regeneration tower 104.
Further, the CO 2 purification device 2 includes a combined adsorber 201, a light-removal rectifying tower 202, a heavy-removal rectifying tower 203 and a buffer tank 204, the combined adsorber 201 is communicated with the heavy-removal rectifying tower 203 through the light-removal rectifying tower 202, the heavy-removal rectifying tower 203 is communicated with the buffer tank 204, and the buffer tank 204 is communicated with the gas-filled bottle 206 through a film press 205.
The adoption of the further technical scheme has the beneficial effects that: the combined adsorber 201 includes a desulfurization adsorber, an activated carbon adsorber, and a deoxidization adsorber, which remove sulfide, moisture, oxygen, and other impurities, respectively, wherein a buffer tank is used to buffer dynamic fluctuations of system gases.
Further, the cryogenic rectification plant 3 comprises a tower tank 301, a rectification tube 303 and a circulating condensation tank 302, wherein the circulating condensation tank 302 is arranged on the tower tank 301 through the rectification tube 303, and a circulating cooling tube 305 is arranged in the circulating condensation tank 302.
Further, a feed inlet 304 is provided at a side edge of the middle part of the rectifying tube 305, a liquid phase outlet 307 is provided at the bottom of the tower tank 301, and a gas phase outlet 306 is provided at the top of the circulating condensing tank 302.
Further, the rectifying tube 303 is filled with a packing layer 308.
The adoption of the further technical scheme has the beneficial effects that: the filler layer 308 is made of Polyethylene (PE) plastic filler, and the filler layer 308 enables liquid to flow along the surface of the filler to form a liquid film, the liquid film is dispersed in continuously flowing gas, and a gas-liquid two-phase contact surface is arranged on the surface of the liquid film of the filler.
Wherein the tail gas of the low-temperature rectification device 3 is mostly hydrogen, and is used as a raw material for synthesizing ammonia or a raw material for removing PSA (pressure swing adsorption) working section and preparing high-purity hydrogen.
Wherein the crude methane obtained from cryogenic rectification plant 3 may be sold as natural gas or as a feedstock for electronic grade methane.
Wherein the crude carbon monoxide obtained by the cryogenic rectification plant 3 can be used as a raw material for a coal chemical industry conversion section or as a raw material for high-purity electronic grade CO.
Compared with the prior art, the invention has the beneficial effects that:
1. The invention utilizes the wet decarbonization device 1, the purification device and the cryogenic rectification device 3 to separate and purify the synthesis gas, so that some gas reaches high-purity electronic grade.
2. The synthesis gas produced in the coal chemical production is adopted, so that the waste gas recycling value is improved, and the pollution to the environment is reduced.
Wherein the composition (volume%) of the synthesis gas is: 32 to 67 percent of hydrogen (H 2), 10 to 57 percent of carbon monoxide (CO), 2 to 28 percent of carbon dioxide (CO 2), 0.1 to 14 percent of methane (CH 4) and 0.6 to 23 percent of nitrogen (N 2).
Wherein the boiling point of hydrogen is: -252.77 ℃; the melting point is as follows: -259.2 ℃;
The boiling point of carbon monoxide is: -191.5 ℃; the melting point is as follows: -205 ℃;
the boiling point of carbon dioxide is: -78.5 ℃; the melting point is as follows: -56.6 ℃;
The boiling point of methane is: -161.5 ℃; the melting point is as follows: -182.5 ℃;
the boiling point of nitrogen is: -196 ℃; the melting point is as follows: -210 ℃;
The working principle is as follows: the synthesis gas is decarbonized by a wet decarbonizing device 1 to obtain a crude product with high content of CO 2 (96 percent); the crude product with high content of CO 2 enters a CO 2 purification device 2 to obtain high-purity electronic grade CO 2 (99.999 percent); other component gases (methane, carbon monoxide and hydrogen) are subjected to wet decarburization and then enter a low-temperature rectification device 3 to respectively obtain high-content CH 4 (97%) and high-content CO (96%); wherein, the high-content CH 4 enters a CH 4 purification device 5 to obtain high-purity electronic grade CH 4 (99.999 percent); wherein the high-content CO enters the CO purification device 4 to obtain high-purity electronic grade CO (99.999%).
The purity of the electron-grade gas is usually above 5N grade, namely above 99.999%.
Wherein the wet decarburization device adopts an MDEA decarburization method, which comprises the following steps: methyldiethanolamine, commonly known as N-methyldiethanolamine (R 2CH3 N), has the structural formula: HOCH 2CH2NCH3CH2CH2 OH.
The solvent is colorless or yellowish viscous liquid, has small toxicity, boiling point 247 ℃, is easy to dissolve in water and alcohol and ether, has strong absorption capacity on acid gases such as carbon dioxide and the like under certain conditions, has small reaction heat, low desorption temperature and stable chemical property, is a novel solvent with excellent performance for selective desulfurization and decarbonization, and has the advantages of high selectivity, low solvent consumption, obvious energy-saving effect, difficult degradation and the like.
The decarburization principle is as follows:
The pure MDEA solution does not react with C0 2, but its aqueous solution reacts with CO 2 as follows:
CO2+H20＝H++HCO3- (1)
R2CH3N+H+＝R2CH3NH+ (2)
The formula (1) is controlled by a liquid film, the reaction rate is very slow, and the formula (2) is instantaneous reversible reaction, so that the formula (1) is a control step of absorbing CO by MDEA, and in order to accelerate the reaction rate, 1% -3% of an activating agent R2' NH is generally added into a solution, so that the carbon dioxide absorption process of the MDEA solution is changed, and the reaction is as follows:
R2 'NH+CO2＝R2'NCOOH (3)
R2 'NCOOH+R2CH3N+H2O＝R2 'NH+R2CH3NH++HCO3 - (4)
(3)+(4):
R2CH3N+CO2+H20＝R2CH3NH++HCO3-；
From formulas (3) - (5), the activator absorbed CO 2, transferred CO 2 to the liquid phase, and the MDEA was regenerated, the MDEA molecule contained a tertiary amine group, absorbed CO, and formed bicarbonate, and the heat required for regeneration was much lower than that required for the amino acid salt formed by the primary amine.
The ratio of lean solution to semi-lean solution is generally 1/3-1/6, which is determined by the partial pressure of CO 2 in the raw material, and the partial pressure of CO 2 is high, and the ratio can be higher (such as 1/6), so that the heat consumption is reduced, and the temperature of the lean solution is generally 55-70 ℃.
The semi-lean solution is generally 70-80 ℃, the liquid inlet temperature is high, the heat energy consumption is low, but the excessive temperature affects the bottom temperature of the absorption tower, so that the absorption capacity of the solution is reduced, but the heat energy consumption is increased, and the optimal solution temperature ratio is provided for different working conditions of raw gas. The purification degree can be ensured, the physical properties of the water-based heat-absorbing agent can be fully utilized, and the heat energy consumption of the water-based heat-absorbing agent can be reduced to the minimum.
When the absorption pressure is 2.7MPal, the CO 2 can be removed to below 0.005, the heat energy consumed by the CO 2 with the purification degree of less than 0.1 depends on the partial pressure of the CO 2 in the raw material gas, the partial pressure is higher, the heat energy consumption is low, generally, in a process of removing the CO 2 in an adiabatic manner, the heat energy is not required in principle, but the stable absorption and analysis temperature is required to be maintained, and the temperature is required to be maintained by the heat balance among the raw material gas, the purified gas and the regenerated gas, usually because the regenerated gas takes more heat, the heat is required to be supplemented (such as low energy such as hot water).
The solubility of nonpolar gases such as hydrogen, nitrogen, methanol, CH 4 and other higher hydrocarbon compounds in MDEA solution is low, so that the loss of purified gas is small, but when the absorption pressure is high, CO 2 in regenerated gas is less than 98%, for example, the absorption pressure is 2.7MPa, high-pressure flash steam is used in the process to improve the purity of CO 2, the flash pressure is selected according to the purity requirement, 96% of left CO 2 can be recovered, the purity can reach 99.5, and when the absorption pressure is less than 1.8MPa, high-pressure flash evaporation is not needed in the process, and CO 2 with the purity of more than 98.5% can be obtained.
The working principle of the wet decarburization device 1 is as follows: methyl Diethanolamine (MDEA) is placed in the absorption tower, carbon dioxide enters the absorption tower and is absorbed into amino salt and carbonic acid by the methyl diethanolamine, then after a series of pressurization and purification, the carbonic acid is separated into carbon dioxide and water by heating, so that the purification effect on the carbon dioxide is achieved, and other gases cannot be absorbed by the Methyl Diethanolamine (MDEA), so that the carbonic acid can be separated from the carbon dioxide.
The high-content carbon dioxide is obtained after decarbonization by the wet decarbonization device 1, and then the high-content carbon dioxide is further purified by a purification device to obtain the pure electronic grade carbon dioxide.
After the high-content CO 2 enters the CO 2 purification device 2, firstly, some sulfides and moisture are removed through the combined absorber 201, then, light component gases (hydrogen, methane and nitrogen) are removed through the light component removal rectifying tower 202, the specific principle is that the carbon dioxide (CO 2) is condensed by utilizing a condensing pipe in a mode that the boiling point of the carbon dioxide is higher than that of the light component gases, and other light component gases are condensed, so that the separation effect is achieved; finally, heavy component gas (impurities such as moisture, benzene and the like) is removed by the heavy component removal rectifying tower 203, the specific principle is that the boiling point of carbon dioxide is lower than that of the heavy component, the carbon dioxide liquid is heated by a circulating pipe heating mode, so that the carbon dioxide is gasified, the heavy component gas is not liquefied to perform a separation effect, and the separated heavy component gas is filled into the gas filling cylinder 206 by the membrane press 205.
The purified gas and flash gas (containing a large amount of methane, carbon monoxide and hydrogen) which are subjected to wet decarbonization by the wet decarbonization device 1 enter the low-temperature rectification device 2 to separate methane, carbon monoxide and hydrogen, the methane is liquefied by utilizing different modes of respective boiling points and melting points, the liquefied methane is collected for further purification treatment, the carbon monoxide is liquefied at a temperature below-205 ℃, and carbon monoxide liquid is collected for further purification treatment, and the hydrogen can be separated for post-treatment after the liquefaction of other gases is completed due to the fact that the melting point of the hydrogen is reduced and the hydrogen is not liquefied.
The purification treatment of methane adopts a CH 4 purification device, the specific structure composition of which is similar to that of a CO 2 purification device 2, and moisture and sulfide are removed by a combined absorber 201, light component gas is removed by a light component removal rectifying tower 202, and heavy component gas is removed by a heavy component removal rectifying tower 203.
The specific structure composition of the CO purification device 4 is similar to that of the CO 2 purification device 2, namely, the water and sulfide are removed by the combined absorber 201, the light component gas is removed by the light component removal rectifying tower 202, and the heavy component gas is removed by the heavy component removal rectifying tower 203.
In order to more clearly illustrate the technical effects of the process for producing electronic grade high purity carbon dioxide by purifying synthesis gas according to the present invention, the following data of the examples set forth below are provided. It should be understood that the data in the following example set are only to better illustrate the technical effects of the continuous production process of high purity chlorine proposed by the present invention, and are not equivalent to all experimental data.
Comparative experiment 1:
Selecting an experiment group 1 and a comparison group 1, wherein the experiment group 1 is carbon dioxide purified by utilizing the working principle flow of the invention, the comparison group 1 is carbon dioxide purified by utilizing the embodiment corresponding to the comparison document 1 in the background technology, and then the detection equipment is utilized to detect the respective gas components, and the specific experiment results are shown in the following table 1:
table 1 shows the gas composition content of each component after carbon dioxide purification in comparative experiment 1:
| Examples | Carbon dioxide (%) | Other impurity gases (%) |
| Experiment group 1 | 99.99999 | 0.00001 |
| Control group 1 | 99.9 | 0.1 |
The comparison analysis 1 can be obtained by combining the experiment group 1 with the comparison group 1, the purity of the carbon dioxide in the experiment group 1 is higher than that in the comparison group 1, and meanwhile, only a small amount of other impurity gases (hydrogen, nitrogen and the like) are detected in the experiment group 1, so that the technical scheme of the invention can be obtained, the purity of the carbon dioxide can be well improved, and the carbon dioxide purification rate of the comparison group is low, and the carbon dioxide cannot be used as electronic grade gas.
Comparative experiment 2:
Selecting an experiment group 1 and an experiment group 2, wherein the experiment group 1 adopts the working principle flow of the invention to purify the synthesis gas, the experiment group 2 removes a wet desulphurization device on the basis of the experiment group 1, and only uses a low-temperature rectification device and a purification device to purify each gas, and the specific experimental results are shown in the following table:
Table 2 shows the results of comparative experiment 2 for carbon dioxide purity
| Examples | Carbon dioxide (%) | Methane (%) | Carbon monoxide (%) |
| Experiment group 1 | 99.99999 | 99.99999 | 99.99999 |
| Experiment group 2 | 55％ | 80％ | 70％ |
Comparative analysis 2: by combining the experiment group 1 and the experiment group 2, the purification purity of each component gas in the experiment group 1 is higher than that of each component gas in the experiment group, so that the wet decarburization device can influence the purification of carbon dioxide and the purification of other component gases (methane and carbon monoxide).
The foregoing description is only of the preferred embodiments of the present invention and is not intended to limit the scope of the invention, and all equivalent structures or equivalent processes using the descriptions and drawings of the present invention or directly or indirectly applied to other related technical fields are included in the scope of the invention.
Claims (7)
1. A production process for preparing electronic grade high-purity carbon dioxide by purifying synthesis gas is characterized by comprising the following steps of: the production process comprises the following steps:
S1, decarbonizing the synthesis gas by a wet decarbonizing device (1) to obtain a high-content CO 2 crude product;
s2, the crude product of the high-content CO 2 enters a CO 2 purification device (2) to obtain high-purity electronic grade CO 2;
S3, other component gases enter a low-temperature rectification device (3) after wet decarburization to respectively obtain high-content CH 4 and high-content CO;
S4, enabling the high-content CH 4 to enter a CH 4 purification device (5) to obtain a high-purity electronic grade CH 4;
S5, enabling the high-content CO to enter a CO purification device (4) to obtain high-purity electronic grade CO;
The wet decarburization device (1) comprises an absorption tower (101), a high-pressure flash tank (102), a low-pressure flash tank (103) and a regeneration tower (104), a first semi-lean liquid pump (105), a second semi-lean liquid pump (106), a recovery liquid pump (107) and a lean liquid pump (108), wherein the high-pressure flash tank (102) is arranged on the low-pressure flash tank (103), the bottom of the absorption tower (101) is respectively communicated with the first semi-lean liquid pump (105) and the low-pressure flash tank (103) through a hydraulic turbine (109), the first semi-lean liquid pump (105) is respectively communicated with the middle position of the absorption tower (101), the high-pressure flash tank (102) and the second semi-lean liquid pump (106), the second semi-lean liquid pump (106) is connected with the regeneration tower (104) through a heat exchanger (110), and the top of the regeneration tower (104) is communicated with the high-pressure flash tank (102);
The CO2 purification device (2) comprises a combined adsorber (201), a light-removal rectifying tower (202), a heavy-removal rectifying tower (203) and a buffer tank (204), wherein the combined adsorber (201) is communicated with the heavy-removal rectifying tower (203) through the light-removal rectifying tower (202), the heavy-removal rectifying tower (203) is communicated with the buffer tank (204), and the buffer tank (204) is communicated with the inflatable bottle (206) through a film press (205);
The cryogenic rectification plant (3) comprises a tower tank (301), a rectification pipe (303) and a circulating condensation tank (302), wherein the circulating condensation tank (302) is arranged on the tower tank (301) through the rectification pipe (303), and a circulating cooling pipe (305) is arranged in the circulating condensation tank (302).
2. A process for producing electronic grade high purity carbon dioxide by purifying synthesis gas according to claim 1, wherein: the tail gas of the cryogenic rectification plant (3) is hydrogen.
3. A process for producing electronic grade high purity carbon dioxide by purifying synthesis gas according to claim 1, wherein: the high-pressure flash tank (102) is connected with the recovery liquid pump (107) through the separator (112), the recovery liquid pump (107) is respectively connected with the high-pressure flash tank (102) and the heat exchanger (110), and the heat exchanger (110) is communicated with the lean liquid pump (108).
4. A process for producing electronic grade high purity carbon dioxide by purifying synthesis gas according to claim 1, wherein: the lean liquid pump (108) is connected with the top of the absorption tower (101) through a cooler (111).
5. A process for producing electronic grade high purity carbon dioxide by purifying synthesis gas according to claim 1, wherein: a low-pressure steam reboiler 113 is connected between the bottom and the middle of the regeneration tower (104).
6. A process for producing electronic grade high purity carbon dioxide by purifying synthesis gas according to claim 1, wherein: the middle side edge position of the rectifying tube (303) is provided with a feed inlet (304), the bottom of the tower tank (301) is provided with a liquid phase outlet (307), and the top of the circulating condensing tank (302) is provided with a gas phase outlet (306).
7. A process for producing electronic grade high purity carbon dioxide by purifying synthesis gas according to claim 1, wherein: the rectifying tube (303) is internally filled with a packing layer (308).
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