CN103359732B - Integration food grade, technical grade carbon dioxide recovering apparatus and recovery process - Google Patents
Integration food grade, technical grade carbon dioxide recovering apparatus and recovery process Download PDFInfo
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- CN103359732B CN103359732B CN201310252780.4A CN201310252780A CN103359732B CN 103359732 B CN103359732 B CN 103359732B CN 201310252780 A CN201310252780 A CN 201310252780A CN 103359732 B CN103359732 B CN 103359732B
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- carbon dioxide
- gas
- grade
- technical grade
- food
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 145
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 62
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 61
- 238000011084 recovery Methods 0.000 title claims abstract description 7
- 230000010354 integration Effects 0.000 title description 4
- 239000007789 gas Substances 0.000 claims abstract description 40
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 27
- 239000011593 sulfur Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 13
- 230000023556 desulfurization Effects 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 235000011089 carbon dioxide Nutrition 0.000 claims description 22
- 230000007062 hydrolysis Effects 0.000 claims description 18
- 238000006460 hydrolysis reaction Methods 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 230000003009 desulfurizing effect Effects 0.000 claims description 6
- 230000008929 regeneration Effects 0.000 claims description 6
- 238000011069 regeneration method Methods 0.000 claims description 6
- 235000003599 food sweetener Nutrition 0.000 claims description 5
- 239000003765 sweetening agent Substances 0.000 claims description 5
- 239000004927 clay Substances 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003317 industrial substance Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
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- Carbon And Carbon Compounds (AREA)
Abstract
The present invention relates to integrated food grade, technical grade carbon dioxide recovery technique, it is characterized in that carbonated unstripped gas is after supercharging, pass into the thick desulfurization of thionizer, drying device is dry; Dried material enters liquefier, and with liquefied ammonia heat exchange, carbon dioxide condensing also enters rectifying tower and carries out rectifying; Non-condensable gases in rectifying tower Raw gas is released by the pressure controlled valve of tower top; Carbon dioxide liquid at the bottom of tower enters reboiler after the heating of gas ammonia, and in liquid, non-condensable gases is again evaporated to rectifying tower and releases, the carbon dioxide liquid in reboiler through supercooler cross cold after obtain technical grade carbon dioxide product; If desired produce food-grade carbon-dioxide, then the material after thick desulfurization was introduced into fine de-sulfur system fine de-sulfur before entering moisture eliminator drying; Gained food-grade carbon-dioxide product total sulfur content is at below 0.1ppm.This technique can realize the production of technical grade, food-grade carbon-dioxide product at the same time, and efficiency is high, and energy consumption is low, easy to operate.
Description
Technical field
The present invention relates to technical field of environmental protection in chemical industry, particularly a kind ofly can reclaim food grade, the device of technical grade carbonic acid gas and technique thereof simultaneously.
Background technology
Along with China's industrial expansion, the quantity discharged of carbonic acid gas is rising year by year, numerous boilers, kiln, roasting kiln, the bodies of heater such as calcining furnace, discharge carbon dioxide continuously, a large amount of discharges of carbonic acid gas, cause Global Greenhouse Effect, the environmental hazard caused is attracted worldwide attention, therefore accelerate the recovery of research carbonic acid gas and reduce discharging day by day urgent, the U.S., Britain and Germany have have all studied and defined Carbon emission system, Japanese then accelerate the research of Utilization of Carbon Dioxide aspect, planning with within 10 years, to set up with carbonic acid gas is the Independent Industrial system of industrial chemicals.
Carbonic acid gas is a kind of important industrial chemicals, the industries such as food, light industry, metallurgy, chemical industry all need a large amount of carbon dioxides, but the carbonic acid gas utilization of discharge is less than l hundred million tons/year, the recycling therefore studying carbon dioxide is just very important.The configuration of existing carbon dioxide recovery system, in accordance is all configured by the maximum gas production rate of carbonic acid gas, but the demand major part of carbonic acid gas is technical grade carbonic acid gas, and technical grade carbonic acid gas is strict with sulphur content index.The demand of food-grade carbon-dioxide is mainly from food beverage industry, and its demand fluctuates along with the change in season, and food-grade carbon-dioxide strictly controls total sulfur content and is less than 0.1ppm, due in industrial carbon dioxide tail gas containing COS, H
2the impurity such as S, are promoted to food grade by technical grade carbonic acid gas, and the technological problems that need solve needs to increase complicated sulfur removal technology and increases energy consumption.Therefore food grade, technical grade carbonic acid gas because of demand, require that standard is different, prior art generally needs to reclaim respectively to the carbonic acid gas of these two kinds of different stages, is difficult to be fused in same technique.
Summary of the invention:
Need to increase complicated sulfur removal technology and the problem of energy consumption to solve to produce in food-grade carbon-dioxide product process, the invention provides the technique that a kind of direct liquefaction reclaims carbonic acid gas, can measure as required and switch manufacture level, food-grade carbon-dioxide product in same technique, the food-grade carbon-dioxide total sulfur content produced is less than 0.1ppm.Reach technique simple, efficiency improves, and energy consumption reduces, easy to operate object.
Integration food grade, technical grade carbon dioxide recovering apparatus, comprise carbon dioxide compressor, thionizer, fine de-sulfur system, moisture eliminator, liquefier, rectifying tower, reboiler, supercooler that mass transport direction connects successively, connecting tube is set between thionizer and moisture eliminator, this pipeline arranges valve.
Described fine de-sulfur system, comprises temperature raising device, hydrolysis tower and purifier that mass transport direction connects successively.
Integration food grade, technical grade carbon dioxide recovery technique, the unstripped gas of the carbonic acid gas containing 77%-83% volume fraction is pressurized to after 2-4MPa through compressor, passes into the thick desulfurization of thionizer and utilizes thick sweetening agent to remove H in unstripped gas
2s;
Described unstripped gas is industrial carbon dioxide tail gas, preferably from the emptying end gas of low-temperature rectisol.
If desired generate technical grade carbonic acid gas, then the material after thick desulfurization directly enters moisture eliminator and carries out drying; Dried material enters liquefier, and with liquefied ammonia heat exchange, carbon dioxide condensing also enters rectifying tower and carries out rectifying; Non-condensable gases in rectifying tower Raw gas upwards evaporates, and is released by the pressure controlled valve of tower top; Carbon dioxide liquid at the bottom of rectifying tower enters reboiler; After the heating of reboiler gas ammonia, in liquid, non-condensable gases is again evaporated to rectifying tower and releases, the carbon dioxide liquid in reboiler through supercooler cross cold after obtain technical grade carbon dioxide product; Gained technical grade carbon dioxide product purity reaches 99.99%.
Moisture eliminator comprises three adsorbers, in-built molecular sieve and aluminum oxide, dealcoholysis agent.
Described adsorber can carry out blocked operation, carries out respectively adsorbing, regenerating and warm-up operation; The regeneration gas of adsorber adopts rectifying tower top noncondensable gas, is undertaken heating and passing into adsorber regeneration by external electric process furnace.
If desired produce food-grade carbon-dioxide, then the material after thick desulfurization was introduced into fine de-sulfur system fine de-sulfur before entering moisture eliminator drying; Gained food-grade carbon-dioxide product total sulfur content is at below 0.1ppm.
Described fine de-sulfur system comprises temperature raising device, hydrolysis tower and purifier successively according to flow direction of material.Heat material in temperature raising device, controlled hydrolysis tower bed temperature 50-80 DEG C, makes COS hydrolysis become H in hydrolysis tower
2s, removes the H of hydrolysis generation by the desulfurizing agent in purifier
2s.
Desulfurizing agent in the thick sweetening agent of thionizer and purifier can be activated carbon, and also can be modified clay, can also be modified zeolite, preferred gac.
Beneficial effect: (1) the present invention realizes the production of technical grade, food-grade carbon-dioxide product in same device by switching annexation, easy to operate.
(2) on the production line of technical grade carbon dioxide product, increase simple fine de-sulfur system produce food-grade carbon-dioxide product, and the food-grade carbon-dioxide total sulfur content produced is less than 0.1ppm, this method solving to produce in food-grade carbon-dioxide product process needs to increase complicated sulfur removal technology and the problem of energy consumption, technique is simple, energy consumption reduces, the method level of automation is high, and waste discharge is few.
(3) this technique can obtain the carbonic acid gas of direct liquefaction, improves carbon dioxide product yield and output, is conducive to environment protection.
Accompanying drawing explanation
Fig. 1 is apparatus structure schematic diagram of the present invention.
Embodiment
Embodiments of the present invention are illustrated below with reference to accompanying drawing.
Embodiment 1:
Fig. 1 is apparatus structure schematic diagram of the present invention, and with reference to shown in Fig. 1, the technique applying this device manufacture grade carbon-dioxide product is as follows:
Containing volume fraction from low-temperature rectisol is that the tail gas of the carbonic acid gas of 77%-83% is through water separator, enter compressor boost to 2-4MPa, enter the thick desulfurization of thionizer, material after thick desulfurization directly enters moisture eliminator and carries out drying, moisture eliminator comprises three adsorbers, in-built molecular sieve and aluminum oxide, dealcoholysis agent.Three adsorbers carry out blocked operation, carry out respectively adsorbing, regenerating and warm-up operation.The regeneration gas of adsorber adopts the noncondensable gas of rectifying tower top, is undertaken heating and passing into adsorber regeneration by external electric process furnace.Dried material enters liquefier, heat exchange is carried out with liquefied ammonia, carbon dioxide condensing also enters rectifying tower and carries out rectifying, non-condensable gases in rectifying tower Raw gas such as nitrogen, methane, carbon monoxide etc. upwards evaporate, released by the pressure controlled valve of rectifying tower top, go front system unstripped gas to carry out heat exchange.Carbon dioxide liquid at the bottom of rectifying tower enters reboiler, and after the heating of reboiler gas ammonia, in liquid, non-condensable gases is evaporated to rectifying tower again, and is released by the stripping section in rectifying tower, rectifying section, overhead condenser.Carbon dioxide liquid in reboiler through supercooler cross cold after enter technical grade storage tank as technical grade carbon dioxide product.Technical grade carbon dioxide product purity reaches 99.99%.
Embodiment 2
With reference to shown in Fig. 1, applying this device, to produce the technique of food-grade carbon-dioxide product as follows: be that the carbon dioxide tail gas of 77%-83% is through water separator from low-temperature rectisol volume fraction, enter compressor boost to 2-4MPa, enter the thick desulfurization of thionizer, material after thick desulfurization is before entering moisture eliminator, through fine de-sulfur system, total sulfur is controlled at below 0.1ppm.Fine de-sulfur system comprises temperature raising device, hydrolysis tower and purifier.Material after thick desulfurization is introduced into temperature raising device, after enter hydrolysis tower, then enter purifier.In temperature raising device, material is heated, controlled hydrolysis tower bed temperature 75 DEG C, in hydrolysis tower, make COS hydrolysis become H
2s, removes the H of hydrolysis generation by the desulfurizing agent in purifier
2s.Food-grade carbon-dioxide product total sulfur content is below 0.1ppm.
Embodiment 3
Except following content, all the other are all identical with embodiment 2.The unstripped gas adopted, from industrial carbon dioxide tail gas, is produced food-grade carbon-dioxide control of product hydrolysis tower bed temperature 50-80 DEG C, is made COS hydrolysis become H in hydrolysis tower
2s, removes the H of hydrolysis generation by the desulfurizing agent in purifier
2s.Food-grade carbon-dioxide product total sulfur content is below 0.1ppm.
Desulfurizing agent in the thick sweetening agent of embodiment 1-3 thionizer and purifier is activated carbon, modified clay, any one of modified zeolite, is common adsorbents, without the need to being additionally described.
Claims (3)
1. integrated food grade, technical grade carbon dioxide recovering apparatus, it is characterized in that comprising carbon dioxide compressor, thionizer, fine de-sulfur system, moisture eliminator, liquefier, rectifying tower, reboiler, supercooler that mass transport direction connects successively, connecting tube is set between thionizer and moisture eliminator, this pipeline arranges valve.
2. integrated food grade according to claim 1, technical grade carbon dioxide recovering apparatus, is characterized in that described fine de-sulfur system, comprises temperature raising device, hydrolysis tower and purifier that mass transport direction connects successively.
3. based on integrated food grade, the technical grade carbon dioxide recovery technique of the integrated food grade described in claims 1 or 2, technical grade carbon dioxide recovering apparatus, it is characterized in that unstripped gas containing carbonic acid gas is after compressor supercharging, pass into the thick desulfurization of thionizer and utilize thick sweetening agent to remove H in unstripped gas
2s; Described unstripped gas is industrial tail gas, and the volume fraction of carbonic acid gas is 77%-83%, and the raw gas pressure after supercharging is 2-4MPa; Desulfurizing agent in the thick sweetening agent of thionizer and purifier is activated carbon, modified clay, any one of modified zeolite;
If desired generate technical grade carbonic acid gas, then the material after thick desulfurization directly enters moisture eliminator and carries out drying; Dried material enters liquefier, and with liquefied ammonia heat exchange, carbon dioxide condensing also enters rectifying tower and carries out rectifying; Non-condensable gases in rectifying tower Raw gas upwards evaporates, and is released by the pressure controlled valve of tower top; Carbon dioxide liquid at the bottom of rectifying tower enters reboiler; After the heating of reboiler gas ammonia, in liquid, non-condensable gases is again evaporated to rectifying tower and releases, the carbon dioxide liquid in reboiler through supercooler cross cold after obtain technical grade carbon dioxide product; Gained technical grade carbon dioxide product purity reaches 99.99%; In fine de-sulfur system, controlled hydrolysis tower bed temperature 50-80 DEG C; Described moisture eliminator comprises three adsorbers, and in-built molecular sieve and aluminum oxide, dealcoholysis agent, carry out adsorbing, regenerating and warm-up operation respectively; The regeneration gas of adsorber adopts rectifying tower top noncondensable gas, is undertaken heating and passing into adsorber regeneration by external electric process furnace;
If desired produce food-grade carbon-dioxide, then the material after thick desulfurization was introduced into fine de-sulfur system fine de-sulfur before entering moisture eliminator drying; Gained food-grade carbon-dioxide product total sulfur content is at 0.1ppm.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014143840A2 (en) | 2013-03-15 | 2014-09-18 | Celanese International Corporation | Process for separating product gas using carbonylation processes |
| CN104896873A (en) * | 2015-06-17 | 2015-09-09 | 镇江索普天辰碳回收有限公司 | Improved integrated food-grade industrial-grade CO2 recovery device and process |
| CN105883807B (en) * | 2016-04-11 | 2017-03-22 | 辽宁洁镁科技有限公司 | Method for purifying carbon dioxide as by-product in magnesite processing |
| CN106753642A (en) * | 2016-12-22 | 2017-05-31 | 乐陵胜利新能源有限责任公司 | A kind of energy comprehensive utilization system in high-pressure washing Methane decarbonization technique |
| CN106744956A (en) * | 2016-12-22 | 2017-05-31 | 乐陵胜利新能源有限责任公司 | A kind of high-pressure washing methane purification carbon dioxide in process recovery process |
| CN110015664B (en) * | 2019-04-24 | 2022-06-14 | 华东能源环保股份有限公司 | High-efficiency purification system and process for food-grade carbon dioxide |
| CN110217794B (en) * | 2019-05-09 | 2024-07-30 | 上海启元气体发展有限公司 | Production method and production device of high-purity carbon dioxide |
| CN115159524B (en) * | 2022-07-06 | 2023-04-07 | 重庆朗福环保科技有限公司 | Carbon dioxide recovery and liquefaction process and system thereof |
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| CN101181995A (en) * | 2007-11-14 | 2008-05-21 | 辽河石油勘探局 | Medium pressure adsorption deeply-liquefied liquid carbon dioxide reclaiming process |
| CN101607708A (en) * | 2009-07-27 | 2009-12-23 | 申屠晶 | The co-production of technical grade and food-class liquid CO 2 and device |
| CN102765719A (en) * | 2012-07-25 | 2012-11-07 | 新乡市心连心气体有限公司 | Technological method for co-producing industrial-grade carbon dioxide and food-grade carbon dioxide through heat pump rectification |
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2013
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Patent Citations (3)
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|---|---|---|---|---|
| CN101181995A (en) * | 2007-11-14 | 2008-05-21 | 辽河石油勘探局 | Medium pressure adsorption deeply-liquefied liquid carbon dioxide reclaiming process |
| CN101607708A (en) * | 2009-07-27 | 2009-12-23 | 申屠晶 | The co-production of technical grade and food-class liquid CO 2 and device |
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Address after: 212006 Dantu Changgang, Zhenjiang City, Jiangsu Province Co-patentee after: Jiangsu Soap Tianchen Gas Co.,Ltd. Patentee after: JIANGSU SOPO (Group) Co.,Ltd. Address before: 212006 Dantu Changgang, Zhenjiang City, Jiangsu Province Co-patentee before: ZHENJIANG SOPO TIANCHEN CARBON RECYCLING Co.,Ltd. Patentee before: JIANGSU SOPO (Group) Co.,Ltd. |
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Effective date of registration: 20191230 Address after: 212006 No. 88 Qiusuo Road, Jingkou District, Zhenjiang City, Jiangsu Province Co-patentee after: Jiangsu Soap Tianchen Gas Co.,Ltd. Patentee after: JIANGSU SOPO CHEMICAL Co.,Ltd. Address before: 212006 Long Gang, Dantu, Jiangsu, Zhenjiang Co-patentee before: Jiangsu Soap Tianchen Gas Co.,Ltd. Patentee before: JIANGSU SOPO (Group) Co.,Ltd. |
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Effective date of registration: 20240912 Address after: No. 88 Qiusuo Road, Jingkou District, Zhenjiang City, Jiangsu Province, China 212001 Patentee after: JIANGSU SOPO CHEMICAL Co.,Ltd. Country or region after: China Address before: No.88, qiusuo Road, Jingkou District, Zhenjiang City, Jiangsu Province, 212006 Patentee before: JIANGSU SOPO CHEMICAL Co.,Ltd. Country or region before: China Patentee before: Jiangsu Soap Tianchen Gas Co.,Ltd. |