CN1125774C - Process for recovering food-class CO2 by adding alkaline tail gas to mother liquid of sodium salt of pyrosulfurous acid - Google Patents
Process for recovering food-class CO2 by adding alkaline tail gas to mother liquid of sodium salt of pyrosulfurous acid Download PDFInfo
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- CN1125774C CN1125774C CN01129768A CN01129768A CN1125774C CN 1125774 C CN1125774 C CN 1125774C CN 01129768 A CN01129768 A CN 01129768A CN 01129768 A CN01129768 A CN 01129768A CN 1125774 C CN1125774 C CN 1125774C
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Abstract
The present invention provides a method for recovering food grade CO2 by adding alkaline tail gas to mother liquor of sodium metabisulfite. The present invention is characterized in that the mother liquor of sodium metabisulfite is prepared by a calcined soda method; the mother liquor of sodium metabisulfite is stirred with calcined soda to react; after alkali washing, water washing, and the purification of molecular sieves of active carbon, light gas is removed in a purification tower through fractionating; the liquor food grade CO2 is prepared by compression. The present invention has the advantages of high safety and reliability, low cost, high productivity, obvious economic benefit and creativity.
Description
The present invention relates to from useless tail gas, reclaim CO
2Method, particularly join alkali tail gas recycle food-class CO from the pyrosulphite mother liquid of sodium
2Method.
The U.S. has the waste gas of glassmaking furnace to reclaim food-class CO according to the retrieval
2, Japan has the waste gas of glutamic acid fermentation to reclaim food-class CO
2, Japan and domestic all have to produce in the urea reclaim food-class CO
2, also have high concentration CO from burning and exhausting
2Waste gas reclaims CO through transformation absorption (PSA)
2Report, do not see that so far soda ash method Sodium Pyrosulfite joins the alkali tail gas clean-up and reclaim food-class CO
2Report.
The production method of Sodium Pyrosulfite has soda ash method and soda processes, and the production method of my company is conventional soda ash method.Because industrial scale is big, the CO of discharging
2The tail gas amount is many, and reclaiming has economic worth.
The objective of the invention is turns waste into wealth, and starts from the pyrosulphite mother liquid of sodium and joins alkali tail gas recycle food-class CO
2Method.
The object of the present invention is achieved like this:
The main component of pyrosulphite mother liquid of sodium is sodium bisulfite (NaHSO
3), be the aqueous solution of content 36～40%, its pH value is 4.5～4.8, density is 1.30～1.40g/cm
3The reaction of it and soda ash is:
The mass ratio of the add-on of control mother liquor and soda ash is 4.2～5.0: 1, and with 4.5～4.8: 1 is advisable; Control terminal point PH is 4.3～5.0, is advisable with 4.5～4.8; 60～70 ℃ of temperature of reaction are advisable with 65 ± 2 ℃; This moment, the main component of feed liquid was Na
2SO
3The aqueous solution, wherein Na
2CO
3Content is 0～0.2%, NaHCO
3Content is 0～1.0%, at this moment CO
2Factor of created gase the highest, reach 90～95%, the air-generating reaction time is 20～40 minutes.
Because 2. reaction produces CO
2So, join CO in the tail gas that alkali discharges
2Be main component, usually＞90%, the toxic substance of environment protection control such as SO in this strand tail gas
2, H
2S etc. are allow compliance with emission standards all, does emptying in the past and handles.
Reducing greenhouse body quantity discharged is the responsibility of this enterprise, and also in order to increase economic benefit of enterprises, CO advances to purify to reclaim with this strand tail gas in our company
2, adopt the technical process of accompanying drawing 1.
Joining the alkali exhaust gas component is:
CO
2＞90% total sulfur (SO
2+ H
2S)＜10 * 10
-6(V/V)
Moisture＜5% total hydrocarbon (with methanometer)＜10 * 10
-6(V/V)
O
2+N
2＜5％
Remove solubility and acidic substance by alkali, washing step, as SO
2, H
2S etc., alkali cleaning is 5% Na
2CO
3Dilute alkaline soln drip washing, normal temperature, gas space velocity are 500～1000h
-1Washing is 500～1000h for tap water drip washing, normal temperature, the gas space velocity of cleaning
-1
Active carbon purifying adopts fixed-bed type, handle the total hydrocarbon of removing in the tail gas by active carbon purifying, tail gas after washing enters air bag and is compressed and enters fixed-bed type active carbon purifying device, carries out further smart desulfurization, and operational conditions is that normal temperature, gas space velocity are about 500～1000h
-1
Remove moisture in the tail gas by the 3A molecular sieve adsorption, molecular sieve drying adopts absorption, desorption alternate run, and operational conditions is a normal temperature, and gas space velocity is 500～1200h
-1, regeneration condition is that 150 ℃ of warm air blowoff are complete until the moisture desorption.
Purification column rectifying is light component such as the O that removes in the tail gas
2, N
2Deng, 40～50 ℃ of operational conditions tower still temperature, pressure 1.8～2.5Mpa discharges CO in the gas
2Content is 70～80%.
Through above each operation purifying treatment CO
2Yield reaches 60～75%.
Tail gas after purified tower is handled, the last compressed high purity liquid CO that is frozen into
2Product, product meets the food-class CO that Coca-Cola issued in 1999 fully through the gaseous mass supervision and inspection center check of bright designing institute of State Standard Matter Research Centre and the Ministry of Chemical Industry
2The new standard of additive.Quality sees attached list 1.
The liquid CO of this recovery
2Product has obtained Department of Health of Guangdong Province's food hygiene licence, has been applied to Zhujiang River beer at present and has made drink additive.
Embodiment:
Get pyrosulphite mother liquid of sodium 3.5L (d=1.370g/cm
3, pH value 4.78, NaHSO
3Content 36.5%) in the closed reaction flask of 5L band gas port, violent stirring is reacted, and adds soda ash (＞99%) 97.5g, 60 ℃ of temperature of reaction, endpoint pH 7.2, NaCSO in the feed liquid of reaction back
3Be 0, Na
2CO
3Content is 0.054%, produces CO this moment
2Gas 207L (25 ℃), factor of created gase 92%.
Discharge CO
2Gas is handled its CO through the glass active carbon purifying device of ф 35 * 450mm and the molecular sieve adsorption device of ф 35 * 450mm
2Content＞99.98%, total hydrocarbon＜1 * 10
-6Mol/mol, total sulfur＜1 * 10
-6Mol/mol, moisture＜1 * 10
-6Mol/mol, N
2+ O
2＜1 * 10
-6Mol/mol.
Reclaim CO
2Quality see attached list
Process flow diagram of the present invention is seen accompanying drawing 1, reclaims CO
2Quality is seen attached list
The present invention is safe and reliable through facts have proved, cost is low, the productive rate height, and remarkable in economical benefits is to have initiative invention.
Subordinate list reclaims CO
2Quality
| Project | Unit | Coca-Cola New Set | Middle one-tenth product measured value | Remarks |
| Carbonic acid gas | ％ | ＞99.9 | ＞99.98 | Bright institute |
| O 2 | ×10 -6mol/mol | ≤30 | ＜10 | Bright institute |
| Moisture | ×10 -6mol/mol | ≤20 | ＜10 | Bright institute |
| Oxynitride | ×10 -6mol/mol | ≤2.5 | ＜0.1 | Mark thing center |
| Aromatic compound | ×10 -6mol/mol | ≤0.02 | ＜0.02 | Mark thing center |
| Total hydrocarbon (with methanometer) | ×10 -6mol/mol | ≤50 | 3.9 | Mark thing center |
| Non-volatile organic remnants | ×10 -6mol/mol | ≤5 | ＜1 | Mark thing center |
| Non-volatile remnants | ×10 -6w/w | ≤10 | 0.08 | Mark thing center |
| Acetaldehyde | ×10 -6mol/mol | ≤0.2 | 0.02 | Mark thing center |
| Carbon monoxide | ×10 -6mol/mol | ≤10 | ＜1 | Mark thing center |
| Total sulfur (in sulphur) | ×10 -6mol/mol | ≤0.1 | 0.08 | Mark thing center |
| COS | ×10 -6mol/mol | ≤0.1 | 0.04 | Mark thing center |
| H 2S | ×10 -6mol/mol | ≤0.1 | 0.05 | Mark thing center |
| SO 2 | ×10 -6mol/mol | ≤1 | 0.05 | Mark thing center |
| Phosphuret-(t)ed hydrogen | ×10 -6mol/mol | ＜0.3 | ＜0.1 | Mark thing center |
| Ammonia | ×10 -6mol/mol | ≤2.5 | 0.2 | Bright institute |
| Acidity | By test | Meet | Bright institute | |
| Aqueous solution outward appearance | Water white transparency | Water white transparency | Bright institute | |
| Smell | Free from extraneous odour | Free from extraneous odour | Bright institute | |
| Taste and smell in the aqueous solution | Free from extraneous odour | Free from extraneous odour | Bright institute |
Claims (5)
1, a kind ofly joins alkali tail gas recycle food-class CO from the pyrosulphite mother liquid of sodium
2Method, the mother liquor that it is characterized in that producing with the soda ash method Sodium Pyrosulfite is that density is 1.30～1.40g/cm
3, the pH value is 4.5～4.8, NaHSO
3Content is 36～40% the aqueous solution, and the mass ratio of it and soda ash add-on is 4.2～5.0: 1, is 60-70 ℃ of stirring reaction 20-40 minute in temperature of reaction, and endpoint pH is 4.3～5.0.
2, recovery food-class CO according to claim 1
2Method, it is characterized in that joining alkali tail gas with 5% Na behind the stirring reaction
2CO
3Dilute alkaline soln is in normal temperature drip washing, and gas space velocity is 500～1000h
-1, with the drip washing of cleaning tap water normal temperature, gas space velocity is 500～1000h again
-1
3, recovery food-class CO according to claim 2
2Method, it is characterized in that tail gas after washing enters air bag and is compressed and enters fixed-bed type active carbon purifying device, be 500～1000h in the gas at normal temperature air speed
-1Smart desulfurization under the condition.
4, recovery food-class CO according to claim 3
2Method, it is characterized in that the tail gas after the smart desulfurization is removed moisture in the tail gas by the 3A molecular sieve adsorption.
5, recovery food-class CO according to claim 4
2Method, it is characterized in that dewatered tail gas removes O in the tail gas with the middle pressure rectifying of 1.8～2.5Mpa in 40-50 ℃ purification column
2, N
2Light constituent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN01129768A CN1125774C (en) | 2001-10-16 | 2001-10-16 | Process for recovering food-class CO2 by adding alkaline tail gas to mother liquid of sodium salt of pyrosulfurous acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN01129768A CN1125774C (en) | 2001-10-16 | 2001-10-16 | Process for recovering food-class CO2 by adding alkaline tail gas to mother liquid of sodium salt of pyrosulfurous acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1356261A CN1356261A (en) | 2002-07-03 |
| CN1125774C true CN1125774C (en) | 2003-10-29 |
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ID=4669431
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN01129768A Expired - Fee Related CN1125774C (en) | 2001-10-16 | 2001-10-16 | Process for recovering food-class CO2 by adding alkaline tail gas to mother liquid of sodium salt of pyrosulfurous acid |
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|---|---|
| CN (1) | CN1125774C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108423681B (en) * | 2018-02-05 | 2021-05-18 | 杭州快凯高效节能新技术有限公司 | Absorption and rectification combined denitration and purification process for carbon capture gas |
| CN111439759A (en) * | 2020-05-23 | 2020-07-24 | 淄博长城化工厂 | Method for producing food-grade potassium sulfite by adopting potassium metabisulfite mother liquor |
| CN112250089A (en) * | 2020-10-29 | 2021-01-22 | 新晃鲁湘钡业有限公司 | Method for producing sodium metabisulfite by utilizing sulfur-containing tail gas |
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2001
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| Publication number | Publication date |
|---|---|
| CN1356261A (en) | 2002-07-03 |
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| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: GUANGDONG ZHONGCHENG CHEMICAL CO., LTD. Free format text: FORMER NAME OR ADDRESS: ZHONGCHENG CHEMICAL CO LTD, GUANGDONG |
|
| CP03 | Change of name, title or address |
Address after: 510730 Guangzhou Guangdong economic and Technological Development Zone transferred to Guangdong Cheng Cheng Chemical Co., Ltd. Patentee after: Guangdong Zhongcheng Chemicals Inc. Address before: 510730 Guangzhou Guangdong economic and Technological Development Zone transferred to Guangdong Cheng Cheng Chemical Co., Ltd. Patentee before: Zhongcheng Chemical Co., Ltd., Guangdong |
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| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20031029 Termination date: 20141016 |
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| EXPY | Termination of patent right or utility model |