CN103359732A - Integrated food grade/industrial grade carbon dioxide recovery device and recovery process - Google Patents
Integrated food grade/industrial grade carbon dioxide recovery device and recovery process Download PDFInfo
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- CN103359732A CN103359732A CN2013102527804A CN201310252780A CN103359732A CN 103359732 A CN103359732 A CN 103359732A CN 2013102527804 A CN2013102527804 A CN 2013102527804A CN 201310252780 A CN201310252780 A CN 201310252780A CN 103359732 A CN103359732 A CN 103359732A
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Abstract
The invention relates to an integrated food grade/industrial grade carbon dioxide recovery process, which is characterized by comprising the following steps of: pressurizing feed gases containing carbon dioxide, and then introducing the pressurized feed gases into a desulfurizing tower for coarse desulfurization, and drying the gases by a dryer; exchanging heat between the dried materials with liquid ammonia in a liquefier, condensing carbon dioxide and rectifying the carbon dioxide in a rectifying tower; discharging a non-condensable gas in the feed gases in the rectifying tower through a pressure control valve at the top of the tower; after the carbon dioxide liquid at the bottom of the tower is heated in a reboiler through gas ammonia, evaporating the non-condensable gas in the liquid again to the rectifying tower and discharging the non-condensable gas, and supercooling the carbon dioxide liquid in the reboiler through a subcooler, thereby obtaining industrial grade carbon dioxide product; and if food grade carbon dioxide is required to be produced, performing fine desulfurization on the coarsely desulfurized materials in a fine desulfurization system before drying in the dryer, wherein the total sulfur content of the obtained food grade carbon dioxide product is less than 0.1 ppm. The process is capable of realizing production of industrial grade and food grade carbon dioxide products at the same time, and further is high in efficiency, low in energy consumption and convenient to operate.
Description
Technical field
The present invention relates to the chemical industry environmental protection technical field, particularly a kind of device and technique thereof that can reclaim simultaneously food grade, technical grade carbonic acid gas.
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 continuously carbon dioxide, a large amount of dischargings of carbonic acid gas, cause Global Greenhouse Effect, the environmental hazard that causes is highly visible, 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 the Carbon emission system, and is Japanese then accelerated the research of Utilization of Carbon Dioxide aspect, plans the Independent Industrial system of setting up take carbonic acid gas as industrial chemicals with 10 years.
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 hundred million ton/years of the not enough l of the carbonic acid gas utilization of discharging, the recycling of therefore studying carbon dioxide is just very important.The configuration of existing carbon dioxide recovery system, in accordance all is configured by the maximum gas production rate of carbonic acid gas, but the demand major part of carbonic acid gas is the technical grade carbonic acid gas, and the technical grade carbonic acid gas is not done strict demand to the sulphur content index.The demand of food-grade carbon-dioxide is mainly from food beverage industry, and its demand fluctuates along with the variation in season, and food-grade carbon-dioxide strictly controls total sulfur content less than 0.1ppm, owing to containing COS, H in the industrial carbon dioxide tail gas
2The impurity such as S are promoted to food grade with the technical grade carbonic acid gas, and the technological problems that needs to solve is to need to increase complicated sulfur removal technology and increase energy consumption.Therefore food grade, technical grade carbonic acid gas because of demand, require standard 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 the same technique.
Summary of the invention:
Need to increase complicated sulfur removal technology and the problem of energy consumption in the food-grade carbon-dioxide product process in order to solve to produce, the invention provides the technique that a kind of direct liquefaction reclaims carbonic acid gas, can measure as required in same technique and switch manufacture level, food-grade carbon-dioxide product, the food-grade carbon-dioxide total sulfur content of producing is less than 0.1ppm.Reach technique simple, efficient improves, Energy Intensity Reduction, easy to operate purpose.
Integrated food grade, technical grade carbon dioxide recovering apparatus, comprise carbon dioxide compressor, thionizer, smart desulphurization system, moisture eliminator, liquefier, rectifying tower, reboiler, supercooler that the mass transport direction connects successively, between thionizer and moisture eliminator, connecting tube is set, on this pipeline valve is set.
Described smart desulphurization system comprises temperature raising device, hydrolysis tower and purifier that the mass transport direction connects successively.
Integrated food grade, technical grade carbon dioxide recovery technique after the compressed machine of unstripped gas that contains the carbonic acid gas of 77%-83% volume fraction is pressurized to 2-4MPa, passes into the thick sweetening agent of the thick desulfurization utilization of thionizer and remove H in the unstripped gas
2S;
Described unstripped gas is industrial carbon dioxide tail gas, preferably from the emptying end gas of low-temperature rectisol.
If need to generate the technical grade carbonic acid gas, then the material after the thick desulfurization directly enters moisture eliminator and carries out drying; Dried material enters liquefier, and with the liquefied ammonia heat exchange, carbon dioxide condensing also enters rectifying tower and carries out rectifying; Non-condensable gases in the rectifying tower Raw gas is evaporation upwards, emits by the pressure controlled valve of cat head; Carbon dioxide liquid at the bottom of the rectifying tower enters reboiler; After the heating through the reboiler gas ammonia, non-condensable gases again is evaporated to rectifying tower and emits in the liquid, and the carbon dioxide liquid in the reboiler is crossed through supercooler and obtained the technical grade carbon dioxide product after cold; 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, adsorbs respectively, regeneration and warm-up operation; The regeneration gas of adsorber adopts the rectifying tower top noncondensable gas, heats and passes into adsorber regeneration by the external electric process furnace.
If need to produce food-grade carbon-dioxide, then the material after the thick desulfurization was introduced into the desulfurization of smart desulphurization system essence before entering the moisture eliminator drying; Gained food-grade carbon-dioxide product total sulfur content is below 0.1ppm.
Described smart desulphurization system comprises temperature raising device, hydrolysis tower and purifier successively according to flow direction of material.In the temperature raising device material is heated, 50-80 ℃ of controlled hydrolysis tower bed temperature makes the COS hydrolysis become H in hydrolysis tower
2S removes the H that hydrolysis generates by the desulfurizing agent in the purifier
2S.
Desulfurizing agent in the thick sweetening agent of thionizer and the purifier can be activated carbon, 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 by switching annexation in same device, easy to operate.
(2) production line at the technical grade carbon dioxide product increases simple smart desulphurization system production food-grade carbon-dioxide product, and the food-grade carbon-dioxide total sulfur content of producing is less than 0.1ppm, the method has solved to produce needs to increase complicated sulfur removal technology and the problem of energy consumption in the food-grade carbon-dioxide product process, technique is simple, Energy Intensity Reduction, 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.
Description of drawings
Fig. 1 is apparatus structure schematic diagram of the present invention.
Embodiment
Specify embodiments of the present invention 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 Figure 1, the technique of using this device manufacture grade carbon-dioxide product is as follows:
Contain the tail gas process water separator that volume fraction is the carbonic acid gas of 77%-83% from low-temperature rectisol, enter compressor boost to 2-4MPa, enter the thick desulfurization of thionizer, material after the 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, adsorb respectively, regeneration and warm-up operation.The regeneration gas of adsorber adopts the noncondensable gas of rectifying tower top, heats and passes into adsorber regeneration by the external electric process furnace.Dried material enters liquefier, carry out heat exchange with liquefied ammonia, carbon dioxide condensing also enters rectifying tower and carries out rectifying, non-condensable gases in the rectifying tower Raw gas such as nitrogen, methane, carbon monoxide etc. are evaporation upwards, pressure controlled valve by rectifying tower top is emitted, and goes front system unstripped gas to carry out heat exchange.Carbon dioxide liquid at the bottom of the rectifying tower enters reboiler, and after the heating through the reboiler gas ammonia, non-condensable gases is evaporated to rectifying tower again in the liquid, and emits by the stripping section in the rectifying tower, rectifying section, overhead condenser.Carbon dioxide liquid in the reboiler is crossed through supercooler and is entered the technical grade storage tank as the technical grade carbon dioxide product after cold.Technical grade carbon dioxide product purity reaches 99.99%.
Embodiment 2
With reference to shown in Figure 1, the technique of using this device production food-grade carbon-dioxide product is as follows: be that the carbon dioxide tail gas of 77%-83% is through water separator from the low-temperature rectisol volume fraction, enter compressor boost to 2-4MPa, enter the thick desulfurization of thionizer, material after the thick desulfurization is before entering moisture eliminator, through smart desulphurization system, total sulfur is controlled at below the 0.1ppm.The essence desulphurization system comprises temperature raising device, hydrolysis tower and purifier.Material after the thick desulfurization is introduced into the temperature raising device, laggardly enters hydrolysis tower, enters purifier again.In the temperature raising device material is heated, 75 ℃ of controlled hydrolysis tower bed temperatures make the COS hydrolysis become H in hydrolysis tower
2S removes the H that hydrolysis generates by the desulfurizing agent in the purifier
2S.Food-grade carbon-dioxide product total sulfur content is below the 0.1ppm.
Embodiment 3
Except following content, all the other are all identical with embodiment 2.The unstripped gas that adopts is produced 50-80 ℃ of food-grade carbon-dioxide control of product hydrolysis tower bed temperature from industrial carbon dioxide tail gas, makes the COS hydrolysis become H in hydrolysis tower
2S removes the H that hydrolysis generates by the desulfurizing agent in the purifier
2S.Food-grade carbon-dioxide product total sulfur content is below the 0.1ppm.
Desulfurizing agent in the thick sweetening agent of embodiment 1-3 thionizer and the purifier is activated carbon, modified clay, and any of modified zeolite is conventional sorbent material, need not additionally to describe.
Claims (7)
1. integrated food grade, technical grade carbon dioxide recovering apparatus, it is characterized in that the carbon dioxide compressor, thionizer, smart desulphurization system, moisture eliminator, liquefier, rectifying tower, reboiler, the supercooler that comprise that the mass transport direction connects successively, between thionizer and moisture eliminator, connecting tube is set, on this pipeline valve is set.
2. integrated food grade according to claim 1, technical grade carbon dioxide recovering apparatus is characterized in that described smart desulphurization system, comprise temperature raising device, hydrolysis tower and purifier that the mass transport direction connects successively.
3. based on claim 1 or 2 described integrated food grade, the integrated food grade of technical grade carbon dioxide recovering apparatus, technical grade carbon dioxide recovery technique, after it is characterized in that containing the compressed machine supercharging of unstripped gas of carbonic acid gas, pass into the thick sweetening agent of the thick desulfurization utilization of thionizer and remove H in the unstripped gas
2S;
If need to generate the technical grade carbonic acid gas, then the material after the thick desulfurization directly enters moisture eliminator and carries out drying; Dried material enters liquefier, and with the liquefied ammonia heat exchange, carbon dioxide condensing also enters rectifying tower and carries out rectifying; Non-condensable gases in the rectifying tower Raw gas is evaporation upwards, emits by the pressure controlled valve of cat head; Carbon dioxide liquid at the bottom of the rectifying tower enters reboiler; After the heating through the reboiler gas ammonia, non-condensable gases again is evaporated to rectifying tower and emits in the liquid, and the carbon dioxide liquid in the reboiler is crossed through supercooler and obtained the technical grade carbon dioxide product after cold; Gained technical grade carbon dioxide product purity reaches 99.99%;
If need to produce food-grade carbon-dioxide, then the material after the thick desulfurization was introduced into the desulfurization of smart desulphurization system essence before entering the moisture eliminator drying; Gained food-grade carbon-dioxide product total sulfur content is below 0.1ppm.
4. integrated food grade according to claim 3, technical grade carbon dioxide recovery technique is characterized in that described unstripped gas is industrial tail gas, and the volume fraction of carbonic acid gas is 77%-83%, and the raw gas pressure after the supercharging is 2-4MPa.
5. integrated food grade according to claim 3, technical grade carbon dioxide recovery technique is characterized in that in smart desulphurization system, 50-80 ℃ of controlled hydrolysis tower bed temperature.
6. integrated food grade according to claim 3, technical grade carbon dioxide recovery technique is characterized in that the thick sweetening agent of thionizer and the desulfurizing agent in the purifier are activated carbon, modified clay, any of modified zeolite.
7. integrated food grade according to claim 3, technical grade carbon dioxide recovery technique is characterized in that described moisture eliminator comprises three adsorbers, and in-built molecular sieve and aluminum oxide, dealcoholysis agent are adsorbed respectively, regeneration and warm-up operation; The regeneration gas of adsorber adopts the rectifying tower top noncondensable gas, heats and passes into adsorber regeneration by the external electric process furnace.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| US9409846B2 (en) | 2013-03-15 | 2016-08-09 | Celanese International Corporation | Process for separating product gas using carbonylation processes |
| CN105883807A (en) * | 2016-04-11 | 2016-08-24 | 辽宁洁镁科技有限公司 | Method for purifying carbon dioxide as by-product in magnesite processing |
| 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 |
| 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 |
| CN110015664A (en) * | 2019-04-24 | 2019-07-16 | 华东能源环保股份有限公司 | A kind of efficient purification system of food-grade carbon-dioxide and its technique |
| CN110217794A (en) * | 2019-05-09 | 2019-09-10 | 上海启元空分技术发展股份有限公司 | A kind of production method and its process units of high-purity carbon dioxide |
| CN115159524A (en) * | 2022-07-06 | 2022-10-11 | 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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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US9409846B2 (en) | 2013-03-15 | 2016-08-09 | 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 |
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| 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 |
| 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 |
| CN110015664A (en) * | 2019-04-24 | 2019-07-16 | 华东能源环保股份有限公司 | A kind of efficient purification system of food-grade carbon-dioxide and its technique |
| 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 |
| CN110217794A (en) * | 2019-05-09 | 2019-09-10 | 上海启元空分技术发展股份有限公司 | A kind of production method and its process units of high-purity carbon dioxide |
| CN115159524A (en) * | 2022-07-06 | 2022-10-11 | 重庆朗福环保科技有限公司 | Carbon dioxide recovery and liquefaction process and system thereof |
| 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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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 Soap (Group) Co., Ltd. |