CN1125775C - Process for recovering food-class CO2 from tail gas generated in preparing Na2S2O4.2H2O powder - Google Patents
Process for recovering food-class CO2 from tail gas generated in preparing Na2S2O4.2H2O powder Download PDFInfo
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- CN1125775C CN1125775C CN01129769A CN01129769A CN1125775C CN 1125775 C CN1125775 C CN 1125775C CN 01129769 A CN01129769 A CN 01129769A CN 01129769 A CN01129769 A CN 01129769A CN 1125775 C CN1125775 C CN 1125775C
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Abstract
The present invention provides a method for recycling food-class CO2 from sodium dithionite production tail gases, which is characterized in that the process comprises the procedures of solvent absorption and recovery by activated carbon, alkali and water washing, acid solution washing by potassium permanganate, secondary adsorption purification by active carbon, combination fine desulphurization by hydrolyst, absorption drying dewatering by a molecular sieve and rectification purification for removing hydrogen component gases. Via practical proof, the present invention is mature, safe and reliable and has the advantages of high yield, high purification purify and obvious economic benefit, and the present invention changes waste into valuable.
Description
The present invention relates to from the tail gas of producing vat powder, reclaim food-class CO
2Method.
Our company adopts sodium formate method to produce vat powder.Vat powder formal name used at school V-Brite B, English name are Sodium dithionite or Sodium hydrosulfite (being called for short SD), CA registration number 7775-14-6.It is industrial famous reductive agent, mainly as fabrics printing and dyeing and papermaking bleaching.
Sodium formate method is produced vat powder with excessive sodium formiate (excessive 10%) and liquid SO
2Do in the reactor of solvent at 80% (V) methanol aqueous solution, 80 ± 2 ℃ of temperature, the synthetic vat powder of intermittent type batch reaction produces stoichiometric CO simultaneously under the non-pressurized condition
2Gas.This strand gas in synthesis procedure as exhaust emissions.The synthetic anti-principle of vat powder sees that reaction equation 1..Technological process of production block diagram is seen accompanying drawing 1.The art of this patent only relates to the synthesis procedure discharge tail gas, and its purification is recycled into food-class liquid CO
2Technology, and do not relate to the technology that vat powder is produced.
There is U.S. Clariant company in the producer that whole world sodium formate method is produced SD; There are German BASF AG, RVC (Clariant) company, Idrosol company in Europe; Mitsubishi gas company, the Hansol company of Korea S, the Tamil Nadu company of India and GulshanChemical Bhiooaid company, their industrial scale is about ten thousand tons/year of 1-3.5, also have units such as one-tenth, chemical plant, Hefei and Yantai Jin He in domestic Wuxi masses, Wujiang Jiu Zhou, the Hunan, their industrial scale is ten thousand tons/year of 1-3.And the scale of our company is 160,000 tons/year, and two 80,000 tons/year production line is arranged.Big like this industrial scale makes CO
2The very big purification of gas emissions is reclaimed and is had very large economy benefit.
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 sodium formate method produces the synthesis tail gas of vat powder and purify and reclaim food-class CO
2Report.
Owing to have impurity in the synthesis material, also have complicated generation of paying reaction, therefore make the CO that discharges synthetic pot
2Exhaust gas component is very complicated, contains a large amount of poisonous and hazardous materials, substantially exceeds the emission standard of country.In order to protect environment, simultaneously also in order to increase economic benefit of enterprises, our company reclaims synthesis tail gas.The major ingredient of synthesis tail gas sees attached list 1.
The objective of the invention is to turns waste into wealth, and the subduction environmental pollution is started from the tail gas of producing vat powder and reclaimed food-class CO
2Method.
The object of the present invention is achieved like this:
Synthesis tail gas purifies the operation that reclaims solvent recuperation (gac), alkali, water washing, potassium permanganate (KmnO
4) the acidic solution washing, gac secondary-cleaned, hydrolyst make up smart desulfurization and handle, and operations such as molecular sieve drying and middle pressure rectifying purifying purify the process flow diagram that reclaims and see accompanying drawing 2.
Gac solvent recuperation operation is to reclaim methyl alcohol in the synthesis tail gas, methyl-formiate etc., and it is obvious to organic removal effect, and process using two tower absorption alternate runs switched once in 2-5 hour, 120 ℃ of regeneration of steam desorptions.The absorption operational conditions is a normal temperature, gas space speed 500-1000h
-1After solvent recuperation, the average removal rate of methyl alcohol is 75% in the tail gas, and the EO average removal rate is 90%, and the average removal rate of thiomethyl alcohol is 60%, and the average removal rate of methyl-formiate is 80%.
Alkali, washing step are that sour gas such as SO are removed in washing
2And other water-soluble and soluble substance such as methyl alcohol, methyl-formiates etc. that vapour pressure is lower.Be used in rare Na of 5% earlier
2CO
3Aqueous solution drip washing tail gas adopts the tap water drip washing tail gas that cleans again, is countercurrent washing, and operational conditions is normal temperature, normal pressure, gas space velocity 500-1200h
-1Tail gas is SO after washing
2Clearance be 95-99%, the average removal rate of methyl-formiate is 50%, the average removal rate 20% of thiomethyl alcohol, the rate of on average going of methyl alcohol is 85%, the average removal rate of EO is 70%.
Potassium permanganate acidic solution washing tail gas is to utilize KMnO
4The strong oxidizing property of acidic solution is removed impurity easily oxidized in the tail gas such as thiomethyl alcohol, SO
2Deng, KMnO
4Strength of solution is 5-10g/L, uses rare H
2SO
4Transfer pH to 1-2, normal temperature, normal pressure carry out adverse current drip washing to tail gas from top to bottom, and the tail gas air speed is 800-1500h
-1, through KMnO
4The thiomethyl alcohol clearance is 100% in the tail gas of acidic solution washing back, and the methyl-formiate average removal rate is 75%, SO
2Clearance＞99%.
The gac secondary-cleaned is to utilize the adsorptive power of gac to remove a small amount of organism that still has in the tail gas, adopts adsorption/desorption to hocket on the technology, desorption 120-130 ℃ of purging of steam, and normal temperature, normal pressure during absorption, gas space velocity is 500-1000h
-1, tail gas methyl alcohol average removal rate behind the gac secondary-cleaned is 45%, methyl-formiate clearance 100%, COS average removal rate are 65%.
Hydrolyst combination is smart takes off that to handle be carbonylsulfide (COS＜2 * 10 with the difficult trace that removes in the tail gas
-6Mol/mol=is under the hydrolyst effect, catalytic hydrolysis is that H2S removes again, present technique adopts T504 hydrolyst and iron oxide fine desulfurizer EF-2 combination (the Hubei chemistry provides) can remove the COS in the tail gas fully, 50-100 ℃ of operational conditions temperature, pressure 1.8-2.5Mpa, the about 300-800h of gas space velocity
-1, 2. reaction equation sees.COS＜0.05 * 10 in the synthesis tail gas after the smart desulfurization of hydrolysis is handled
-6Mol/mol.
The molecular sieve adsorption drying removes the moisture in the synthesis tail gas, organic impurity and micro-sulfide that can also the absorbed portion denier when adsorption bed that our company adopts 3A molecular sieve and 13X molecular sieve to load in mixture removes moisture, sieve adsorpting bed employing adsorption/desorption alternately switches and carries out, the absorption operational conditions is a normal temperature, pressure 1.8-2.5Mpa, gas space velocity 800-1500h
-1, adopt 150 ℃ of warm air blowoff complete during regeneration until the water desorption.By methyl alcohol clearance 100% after the molecular sieve adsorption, moisture removal rate＞90%.
Purification column is to press under the 1.8-2.5Mpa condition rectifying to remove in temperature 40-50 ℃ to compare CO in the tail gas
2Light fraction is as O
2, N
2, CH
4Deng, advance O in the tail gas of purification column
2Content is 0.2-0.5%, N
2Content is 1-2%, and purified back clearance all＞99% can be removed 30-50% with trace methane in the tail gas and ethene simultaneously.Discharge CO in the gas this moment
2Yield is 50-70%.
Through above each operation whole process treatment S D synthesis tail gas, CO
2Yield is 50-70%.
Synthesis tail gas CO2 content＞99.95% after purified meets the food-class CO that Coca-Cola issued in 1999 fully through checking its quality
2The new quality standard of additive.Check the results are shown in subordinate list 2.(check unit: middle one-tenth chemical institute, middle one-tenth chemical industry quality inspection station)
More than each operation average removal rate of removing impurity gather and see attached list:
Subordinate list
The main component of subordinate list 1 synthesis tail gas
| The composition title | Unit | The result | The composition title | Unit | The result |
| CO 2 | ％ | ＞90 | Methyl-formiate | ×10 -6 mol/mol | 8000～12000 |
| Methane | ×10 -6 mol/mol | ＜10 | SO 2 | 10000～20000 | |
| Ethene | ＜20 | COS | ＜2 | ||
| Methyl alcohol | 1000～2000 | O 2 | ％ | 0.2～0.5 | |
| Thiomethyl alcohol | 500～800 | N 2 | ％ | 1～2 | |
| Oxyethane | 500～800 |
Subordinate list 2 tail gas recycle CO
2Quality
| Project name | Unit | Coca-Cola new standard | Middle one-tenth product measured value | Project name | Unit | Coca-Cola new standard | Middle one-tenth product measured value |
| CO 2 | ％ | ＞99.9 | ＞99.95 | The methane hydrocarbon | ×10 -6 mol/mol | ≤20 | 14 |
| Methyl alcohol | ×10 -6 mol/mol | -- | ＜0.5 | Total sulfur (in sulphur) | ≤0.1 | ＜0.1 | |
| Thiomethyl alcohol | -- | Do not detect | SO 2 | ≤1 | 0.05 | ||
| Methyl-formiate | -- | ＜0.5 | H 2S | ≤0.1 | Do not detect | ||
| Oxyethane | -- | Do not detect | COS | ≤0.1 | 0.03 | ||
| Total hydrocarbon (with methanometer) | ≤50 | 16 |
Subordinate list 3 respectively purifies the recovery process removal of impurity and gathers
| Sequence number | The cleaning section title | Impurity average removal rate % | ||||||||||
| Methane | Ethene | Methyl alcohol | EO | Thiomethyl alcohol | Methyl-formiate | SO 2 | COS | O 2 | N 2 | Moisture | ||
| 1 | The gac solvent recuperation | -- | -- | 75 | 90 | 60 | 80 | -- | -- | -- | -- | -- |
| 2 | Alkali, water washing | -- | -- | 85 | 70 | 20 | 50 | 95-99 | -- | -- | -- | -- |
| 3 | The washing of KMnO4 acidic solution | -- | -- | ＜10 | -- | 100 | 75 | ＞99 | -- | -- | -- | -- |
| 4 | The gac secondary-cleaned | -- | -- | 45 | 100 | -- | ＞99 | -- | 65 | -- | -- | -- |
| 5 | The smart desulfurization combination of hydrolysis | -- | -- | -- | -- | -- | -- | -- | ＞99 | -- | -- | -- |
| 6 | Molecular sieve drying | -- | -- | ＞99 | -- | -- | -- | -- | -- | -- | -- | ＞99 |
| 7 | Press purifying in the low temperature | 50 | 30 | -- | -- | -- | -- | -- | -- | ＞99 | ＞99 | -- |
More than the method for inspection of each cleaning section impurity be: 1. the methods of inspection such as methane, ethene, methyl alcohol, methyl-formiate, oxyethane, thiomethyl alcohol are the vapor-phase chromatography fid detector, GDX-103 chromatographic column, 90 ℃ of column temperatures, 120 ℃ of detector temperatures; 2, SO2, the CO2 method of inspection are vapor-phase chromatography FPD detector, Parapak Ps post, 75 ℃ of column temperatures, 120 ℃ of detector temperatures; 3, O2, the N2 method of inspection are vapor-phase chromatography, TCD detector, 13X molecular sieve column, 60 ℃ of column temperatures.Bridge stream 120mA; 4, the moisture method of inspection is the minute surface dew point method;
Embodiment 1:
At 15m
3Add circulating mother liquor (based on methanol solvate) 3m in the synthesis reactor earlier
3, begin to be stirred in 60-80 minute and slowly to add the methanol aqueous solution that contains sodium formiate 2530Kg and to contain Na
2S
2O
5The methanol aqueous solution of 2610Kg, dripping SO2 concentration then in 120-180 minute is the SO of 380g/L
2One methanol solution 4.5m
3, 80 ± 2 ℃ of control reaction temperature, pressure 0.2Mpa reacts and (can produce 4.7 tons of vat powders like this, and produce CO in 4 hours
21.1 tons of gases).Adopt the water at low temperature condensation reflux liquid in the reaction, come condensation tail gas to contain CO
292% (V) also contains methyl alcohol 860 * 10
-6Mol/mol, methyl-formiate 6500 * 10
-6Mol/mol, SO2 8520 * 10
-6Mol/mol etc., this strand tail gas obtain 99.95% liquid CO through method treatment and purification of the present invention
2Product, yield 70%.
The present invention is ripe safe and reliable through facts have proved, the productive rate height purifies the purity height, and remarkable in economical benefits is the pioneer invention creation of turning waste into wealth.
Claims (8)
1, a kind ofly from the tail gas of producing vat powder, reclaims food-class CO
2Method, it is characterized in that its technology comprises that charcoal absorption reclaims that solvent, alkali and washing pouring, the washing of potassium permanganate acidic solution, gac second adsorption purify, hydrolyst makes up smart desulfurization, molecular sieve adsorption drying and dehydrating and take off light-component gas at purification column rectifying purifying.
2, recovery food-class CO according to claim 1
2Method, it is characterized in that it is to adopt two tower adsorption/desorption alternate runs that solvent is reclaimed in charcoal absorption, switched once in 2-5 hour, 120 ℃ of regeneration of steam desorptions are at gas at normal temperature air speed 500-1000h
-1Adsorb under the condition.
3, recovery food-class CO according to claim 1
2Method, it is characterized in that it is at normal temperature, normal pressure, gas space velocity 500-1200h that alkali and washing are drenched
-1Condition under earlier with 5% rare Na
2CO
3Aqueous solution adverse current drip washing tail gas is again with cleaning tap water adverse current drip washing tail gas.
4, recovery food-class CO according to claim 1
2Method, it is characterized in that potassium permanganate acidic solution concentration is the 5-10g/ liter, transfer pH1-2 with dilute sulphuric acid, from top to bottom to the drip washing of tail gas adverse current, the tail gas air speed is 800-1500h at normal temperature and pressure
-1
5, recovery food-class CO according to claim 1
2Method, it is characterized in that the gac second adsorption purify to adopt adsorption/desorption to hocket, desorption is with 120-130 ℃ of purging of steam, being adsorbed on normal temperature, normal pressure, gas space velocity is 500-1000h
-1Carry out under the condition.
6, recovery food-class CO according to claim 1
2Method, it is characterized in that hydrolyst makes up that smart desulfurization adopts be T504 hydrolyst and iron oxide fine desulfurizer EF-2 be combined in temperature 50-100 ℃, pressure is 1.8-2.5Mpa, gas space velocity 300-800h
-1Carry out under the condition.
7, recovery food-class CO according to claim 1
2Method, it is characterized in that the molecular sieve adsorption drying and dehydrating is that the adsorption bed that adopts 3A molecular sieve and 13X molecular sieve to load in mixture removes moisture, sieve adsorpting bed be adsorption/desorption alternately switching carry out, be 1.8-2.5Mpa at normal temperature pressure, gas space velocity 800-1500h
-1Adsorb under the condition, adopt 150 ℃ of warm air blowoff during regeneration until water desorption air.
8, recovery food-class CO according to claim 1
2Method, it is characterized in that taking off light component gases at purification column rectifying purifying is at temperature 40-50 ℃, carries out under the middle pressure 1.8-2.5Mpa condition.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN01129769A CN1125775C (en) | 2001-10-16 | 2001-10-16 | Process for recovering food-class CO2 from tail gas generated in preparing Na2S2O4.2H2O powder |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN01129769A CN1125775C (en) | 2001-10-16 | 2001-10-16 | Process for recovering food-class CO2 from tail gas generated in preparing Na2S2O4.2H2O powder |
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|---|---|
| CN1356262A CN1356262A (en) | 2002-07-03 |
| CN1125775C true CN1125775C (en) | 2003-10-29 |
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| CN101670220B (en) * | 2009-09-28 | 2012-12-26 | 烟台金海化工有限公司 | Treatment method for waste gas produced in preparation process of sodium hydrosulfite |
| 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 |
| CN113233463A (en) * | 2021-06-24 | 2021-08-10 | 湖北洁绿环保科技有限公司 | Preparation method for separating and purifying high-purity liquid carbon dioxide |
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Owner name: GUANGDONG ZHONGCHENG CHEMICAL CO., LTD. Free format text: FORMER NAME OR ADDRESS: ZHONGCHENG CHEMICAL CO LTD, GUANGDONG |
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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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