CN1130246C - Refining and recovering process for industrial by-product halogen hydride gas - Google Patents
Refining and recovering process for industrial by-product halogen hydride gas Download PDFInfo
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- CN1130246C CN1130246C CN00103388A CN00103388A CN1130246C CN 1130246 C CN1130246 C CN 1130246C CN 00103388 A CN00103388 A CN 00103388A CN 00103388 A CN00103388 A CN 00103388A CN 1130246 C CN1130246 C CN 1130246C
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Abstract
The present invention relates to a refining and recovery technology for by-product halogen hydride gas. The technology is characterized in that the by-product halogen hydride gas is introduced from the bottom of a tower and is in counterflow contact with circulation washing solvents introduced from the top of the tower, such as concentrated saturated hydrochloric acid, in the tower, and then impurities contained in HCl gas are removed by reactions, dissolution and washing. The refined HCl gas escapes from the top of the tower and enters an absorption system, and then the HCl gas is absorbed with water to produce the finished hydrochloric acid.
Description
Often be accompanied by the generation of a large amount of byproduct hydrogen chloride gas in organic and inorganic chemical industry are produced, industrial often water absorption or neutralization are handled simply.Because hydrogen chloride produces in course of reaction, gas phase can be carried a certain amount of raw material, product intermediate and accessory substance secretly, and the acid that water absorption byproduct hydrogen chloride obtains can only be worked as spent acid and be handled the transfer that pollutes and the waste of resource.
The refining common treating method of byproduct hydrogen chloride is to remove high-boiling components with shell and tube condenser cooling earlier.Because mass transfer is insufficient, gas flow rate is big, and heat-transfer effect is bad, and the impurity of carrying secretly can not Ex-all, can not fundamentally solve the refining problem of hydrogen chloride.Some factory adopts many still series connection, improves raw material availability, because gas flow is big, the gas-liquid contact is insufficient, DeGrain.Contain 10% organic impurities in the hydrogen chloride tail gas as by-product in the production processes of chloroacetic acid.
And most of systems have the certain vacuum degree, and perhaps the tail gas outlet pressure is lower, thereby adopt the fluid-tight mode to allow gas pass liquid layer and realize that absorption is restricted.A kind ofly will be of great importance if invent at the general hydrogen chloride gas refining plant of most of system.Moreover, if can be reduced to the impurity in the hydrogen chloride gas below 0.1%, then can make full use of the hydrogen chloride resource, the change spent acid is useful industrial acid, even reagent acid, thereby alleviates the deficiency of domestic chlorine resource.
Disclose the method for many refining hydrochloric acid in the prior art, for example, US4786488 discloses and has a kind ofly put forward the method that the hydrochloric acid of a carbon chlorohydrocarbon impurity comes purifying hydrochloric acid with HCl gas gas.In this patent, being intended to hydrochloric acid liquid that gas carries enters the tower of filling concentrated hydrochloric acid liquid from the top of bubble tower packed bed, and at the bottom of tower, hydrochloric acid is heated to boiling by evaporimeter, generation is used for the HCl gas that gas is carried chlorohydrocarbon, described HCl gas is with chlorohydrocarbon, upwards, discharge, and the hydrochloric acid that gas was carried takes out at the bottom of tower from cat head by bubble tower.But this method is not suitable for direct purification gaseous by-product hydrogen chloride, the refining hydrochloric acid that obtains.
The present invention is based in the hydrogen chloride gas most of organic and inorganic impurity can be dissolved in the respective media, or its raw material or intermediate can and be trapped with the respective media reaction, for example in the monoxone tail gas except containing HCl, also contain vinegar acyl chlorides, chloracetyl chloride, S
2Cl
2, they can generate acetic acid and monoxone with water reaction, separate out sulphur, generate HCl simultaneously, and hydrogen chloride gas has sizable boiling-point difference with these medium solutions, have proposed the employing tower and have made with extra care hydrogen chloride.
Fig. 1 is a HCl process for refining flow chart, and wherein 1,2 is treating column; 3,4 is circulating tank; 5,6 is circulating pump; 7,8 is piping filter; 9,10 is fluid flowmeter.
For vacuum and pressure-fired system, it is suitable adopting the packed tower rectification flow, for example chlorine Refining the present invention that can adopt as shown in Figure 1 of by-product hydrogen chloride gas in the acetic acid production process Technological process.
Process description:
1. the impure HCl gas that comes out by production system, entering from HCl treating column 1 bottom, is 10-60 ℃ in the tower temperature, is preferably in 20-40 ℃ the tower and the circulation cleaning solvent counter current contacting that enters from cat head, by reaction, dissolving and washing, remove most of impurity contained in the HCl gas.
2. the HCl gas behind the primary purification, come out from HCl treating column 1 top, utilize pressure reduction, enter HCl treating column 2 from the bottom, in temperature is 10-60 ℃, be preferably in 20-40 ℃ the tower and the circulation cleaning solvent counter current contacting in tower that enters from cat head,, thoroughly remove impurity contained in the HCl gas by reaction, dissolving and washing.HCl gas after refining is made finished product hydrochloric acid by the cat head extraction to the absorption of absorption system water.
3. the circulation cleaning solvent adopts saturated hydrochloric acid.Earlier saturated hydrochloric acid is joined in the circulating tank 4, carry through circulating pump 6, remove mechanical admixture contained in the circulating solvent and gel, floccule through piping filter 8, regulate flows through flowmeter 10 again, add, contact with up HCl back flow of gas at Ta Nei from HCl treating column 2 tops, remove impurity contained in the HCl gas, the circulation cleaning solvent that has dissolved impurity goes out from tower bottom flow, gets back to circulating tank 4, and then recycles.
4. when the impurity in the circulating tank 4 reaches finite concentration (acetic acid, monoxone concentration reach 10%-30%) possibly can't thoroughly remove the impurity in the HCl gas again.At this moment, with the circulating solvent of circulating tank 4, replenish new saturated hydrochloric acid in the circulating tank 4 again as HCl treating column 1.
5. the circulating solvent in the circulating tank 3 is carried and piping filter 7 filtrations through circulating pump 5, and carries by flowmeter 9, enters from HCl treating column 1 top, and the circulation cleaning solvent that has dissolved impurity goes out from tower bottom flow, gets back to circulating tank 3, and then recycles.Be recycled to impurity content and reach finite concentration (decide according to the system situation, its limiting case is that the water in the hydrochloric acid all reacts with vinegar acyl chlorides, chloracetyl chloride, generates corresponding acetic acid and monoxone), discharge turns back to production system or handles as spent acid.
Fig. 2 is chlroacetone by-product HCl process for refining flow chart, and wherein 1 is circulation flow reactor; 2 are The micropore distributor; 3 is circulating tank.
Also can circulation type gas purification tower mode, for example, when producing chlroacetone for the dyestuff factory The byproduct hydrogen chloride tail gas that produces can adopt technological process of the present invention as shown in Figure 2.
Process description:
1. the impure HCl gas that is come out by production system, from circulation flow reactor bottom through the micropore branch The cloth device enters, and is 10-60 ℃ in temperature, be preferably in 20-40 ℃ the reactor with from reaction The circulation cleaning solvent counter current contacting that the device top enters is by reaction, dissolving and washing, thoroughly Remove impurity contained in the HCl gas.
2. the HCl gas after making with extra care comes out from the circulation flow reactor top, to the HCl absorption system, and The circulation cleaning solvent comes out to get back to the circulating tank from the circulation flow reactor bottom.
HCl gas purification tower of the present invention adopts continuous multi-stage countercurrent equipment (plate column) or continuous Contact adverse current equipment (packed tower).
It is that gas and cleaning solvent can be realized repeatedly at Ta Nei that the present invention adopts the foundation of tower equipment The washing balance, the filler of certain altitude can be equivalent to the washing of tens grades even tens grades, guarantees Impurity react with the circulation cleaning solvent fully and be dissolved in the circulation cleaning solvent, from And impurity is removed to greatest extent.
By the tower height of selecting to suit, reaction is carried out fully, it is qualified to obtain at cat head Refining hydrogen chloride gas, the hydrogen chloride gas after making with extra care absorbs through gas absorbing device and obtains Elaboration hydrochloric acid.
The reaction of gas in tower, according to the separate sources of gas, the circulation cleaning solvent of its mechanism and employing is also different.With the monoxone by-product hydrogen chloride gas is example, made full use of the reaction of water (or water vapour) with acyl chlorides, chloracetyl chloride, sulfur dichloride, contact by the continuous flow upstream of water with production of chloroacetic acid tail gas, vinegar acyl chlorides in the tail gas, chloracetyl chloride and water reaction are generated acetic acid and monoxone, be dissolved in the water and enrichment, and then recycled.Sulfur dichloride and water reaction generation sulphur is removed through piping filter in the tail gas.
Gas source among the present invention can be the hydrogen chloride gas of production process by-product, also can be the hydrogen chloride gas that the spent acid after the absorption obtains through gasification.
The circulation cleaning solvent that the present invention mentions can be water, acetic acid, and the employed raw material of the course of reaction of by-product hydrogen chloride and intermediate, product or higher is arranged, and easily dissolves other solvent of impurity in the hydrogen chloride gas.Circulation cleaning solvent as the refining employing of by-product hydrogen chloride in the production of chloroacetic acid can be water, watery hydrochloric acid, saturated hydrochloric acid or acetic acid, preferred saturated hydrochloric acid.The hydrogen chloride useful raw materials of by-product or product such as benzene, chlorobenzene equal solvent wash refining in the chlorobenzene production process.
The material of tower adopts corresponding resistant material according to the characteristic of different systems among the present invention.Filler in the tower is all kinds filler of acid corrosion-resistant, and the height of filler is generally 2 to 20 meters, and concrete height is decided according to condition such as pressure, tolerance, gas speed and the refining quality that will reach of system.
The mode that can adopt single tower also can adopt multitower series connection or tower to connect among the present invention with still, the circulation cleaning solvent is single medium during single-tower rectifying, the circulation cleaning solvent that adopts multitower series connection or tower and still series system to adopt is multiple medium.
The hydrogen chloride gas treating column adopts continuous multi-stage countercurrent equipment (plate column) or Continuous Contact adverse current equipment (packed tower), and outlet has the system of higher malleation also can adopt the tower or water conservancy diversion cartridge type gas purification tower of bubbling for tail gas.
Temperature during purification operations of the present invention is lower than the boiling point of cleaning solvent, generally with material non-crystallizable and energy-conservation be principle, can suitably reduce operating temperature.
Below adopt the mode of embodiment that the present invention is carried out non-limiting explanation.
Making with extra care of [industrial implementation example 1] monoxone tail gas by-product hydrochloric acid
Adopt technological process of the present invention shown in Figure 1 that tail gas in the production of chloroacetic acid is carried out refinement treatment.Contain impurity such as acetic acid, chloracetyl chloride, vinegar acyl chlorides and sulfur dichloride in the handled monoxone tail gas, the about 2-5% of content.During refinement treatment, the inlet amount of HCl gas is controlled at 50-100 liter/second, and the diameter for the treatment of column 1,2 is 500mm, and temperature is 20-30 ℃ in the tower, and the circulation cleaning solvent is saturated hydrochloric acid, its flow-control the 1000-1200 liter/hour.Refining through two-stage, the content of hydrochloric acid of gained is 36.5%, and in the HCl total acid, the purity of hydrochloric acid is 99.85%, and organic impurity content is less than 0.1%.The refining hydrochloric acid water white transparency that obtains reaches the industrial synthesis hydrochloric acid standard.
By-product hydrochloric acid is refining in [industrial implementation example 2] chlroacetone production process
Adopt technological process of the present invention shown in Figure 2 that HCl tail gas in the chlroacetone production is carried out refinement treatment.Contain acetone, monochloroacetone and dichloroacetone (1,1 one dichloroacetone and 1,3-dichloroacetone) in the handled accessory substance HCl tail gas, the about 2-3% of its content.During refinement treatment, HCl gas feed amount is controlled at 500 liters/minute, and the temperature of circulation flow reactor is 20-30 ℃, and the circulation flow reactor diameter is 400mm, and the circulation cleaning solvent is saturated hydrochloric acid, its flow-control the 15-20 liter/minute.After refining, the purity of the refining hydrochloric acid of gained reaches 99.9%, and organic impurity content reaches the industrial synthesis hydrochloric acid quality less than 0.1%.Adopting circulation type gas purification tower shown in the accompanying drawing 2, is cleaning solvent with saturated hydrochloric acid, and the purity of the refining hydrochloric acid of gained reaches 99.9%, and organic impurity content reaches the industrial synthesis hydrochloric acid quality less than 0.1%.
Making with extra care of [industrial implementation example 3] dimethylphosphite by-product hydrochloric acid
Adopt technological process of the present invention shown in Figure 1 that HCl gas in the dimethylphosphite production is carried out refinement treatment.Contain impurity such as phosphorus trichloride, methyl alcohol, chloromethyl ester and dimethylphosphite, the about 3-8% of content in the handled dimethylphosphite by-product HCl gas.During refinement treatment, the inlet amount of HCl gas is controlled at 100-200 liter/second, and the diameter for the treatment of column 1,2 is 700mm, and temperature is 20-30 ℃ in the tower, and the circulation cleaning solvent is saturated hydrochloric acid, its flow-control the 2000-2400 liter/hour.Refining through two-stage, the content of hydrochloric acid of gained is 36.5%, and in the HCl total acid, the purity of hydrochloric acid is 99.9%, and organic impurity content is less than 0.1%.The refining hydrochloric acid water white transparency that obtains reaches the industrial synthesis hydrochloric acid standard.
Claims (12)
1. the method for byproduct hydrogen chloride gas in the refining chemical process, it is characterized in that byproduct hydrogen chloride gas feeds at the bottom of by tower, with the circulation cleaning solvent counter current contacting in tower that enters from cat head, by reaction, dissolving and washing, remove the impurity that contains in the HCl gas, the circulation cleaning solvent goes out from tower bottom flow, recycles, and the HCl gas after refining is by the cat head extraction, enter absorption system, water absorbs, and makes finished product hydrochloric acid.
2. according to the process of claim 1 wherein, the source of described hydrogen chloride gas can be the production process byproduct hydrogen chloride gas, also can be the hydrogen chloride gas that the spent acid after absorbing obtains through gasification.
3. according to the process of claim 1 wherein the mode of the single tower of refining employing of described hydrogen chloride gas or multitower series connection, still series connection.
4. according to the method for claim 3, wherein, when adopting single-tower rectifying, the circulation cleaning solvent is single medium.
5. according to the method for claim 3, wherein, when adopting multitower series connection or tower to connect with still, the circulation cleaning solvent is single or the multimedium system.
6. according to the process of claim 1 wherein, described hydrogen chloride gas treating column adopts continuous multi-stage countercurrent equipment or Continuous Contact adverse current equipment.
7. method according to claim 6, wherein, described continuous multi-stage countercurrent equipment is meant that plate column etc. has the equipment of multistage mass transfer balance,
8. method according to claim 6, wherein, described Continuous Contact adverse current equipment is meant that packed tower etc. has the equipment of continuous mass transfer balance.
9. according to the process of claim 1 wherein, when the tail gas outlet has the system of higher malleation, adopt the tower or water conservancy diversion cartridge type gas purification tower of bubbling.
10. according to the process of claim 1 wherein, described circulation cleaning solvent is water, watery hydrochloric acid, saturated hydrochloric acid, acetic acid, benzene or chlorobenzene.
11. according to the process of claim 1 wherein, the operating temperature of described hydrogen chloride gas treating column is 10-60 ℃.
12. according to the process of claim 1 wherein, the material of described hydrogen chloride gas treating column is a resistant material, inner-tower filling material is all kinds filler of acid corrosion-resistant, and the height of filler is 2 to 20 meters.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00103388A CN1130246C (en) | 2000-03-03 | 2000-03-03 | Refining and recovering process for industrial by-product halogen hydride gas |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00103388A CN1130246C (en) | 2000-03-03 | 2000-03-03 | Refining and recovering process for industrial by-product halogen hydride gas |
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| CN1311053A CN1311053A (en) | 2001-09-05 |
| CN1130246C true CN1130246C (en) | 2003-12-10 |
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| CN00103388A Expired - Fee Related CN1130246C (en) | 2000-03-03 | 2000-03-03 | Refining and recovering process for industrial by-product halogen hydride gas |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101185835B (en) * | 2007-08-23 | 2010-08-18 | 周滢 | Method for absorbing and using waste gases hydrogen chloride produced in chemical industrial products |
| CN101274195B (en) * | 2007-12-24 | 2010-06-30 | 天津大学 | Method for removing residual chlorine gas in tail gas in production processes of chloroacetic acid |
| CN101648104B (en) * | 2008-08-13 | 2011-06-22 | 北京格瑞华阳科技发展有限公司 | Technology for reclaiming hydrogen chloride tail gas in chemical production |
| CN101870457B (en) * | 2010-06-29 | 2011-12-28 | 蓝星化工有限责任公司 | Method for purifying by-product hydrogen chloride gas of TDI |
| CN102849681A (en) * | 2012-04-06 | 2013-01-02 | 昊华鸿鹤化工有限责任公司 | Method for removing chlorine included in hydrogen chloride gas |
| CN106310875A (en) * | 2015-07-01 | 2017-01-11 | 启东久星化工有限公司 | System for separating organic matter from mixture of hydrogen chloride and organic matter |
| CN105480948B (en) * | 2015-12-16 | 2018-05-18 | 南京工业大学 | Method and system for recycling byproduct hydrogen chloride in fatty acid or fatty acyl chloride chlorination production process |
| CN106621427A (en) * | 2016-12-08 | 2017-05-10 | 张贵 | Cold evaporation purifying system for by-product hydrochloric acid |
| CN107043090B (en) * | 2017-01-06 | 2019-08-06 | 江苏吉华化工有限公司 | It is a kind of for improve recycling hydrochloric acid in removal rate of sulfur dioxide devices and methods therefor |
| CN108310912A (en) * | 2017-01-18 | 2018-07-24 | 湖北星火化工有限公司 | A kind of processing unit of hydrochloric acid tank tail gas |
| CN114262258B (en) * | 2021-12-23 | 2024-09-03 | 浙江万盛股份有限公司 | Method for preparing dichloropropanol by recycling impurity-containing phosphate flame retardant industrial byproduct HCl |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4629610A (en) * | 1985-05-10 | 1986-12-16 | Dow Chemical Co. | Hydrogen fluoride recovery process |
| US4786488A (en) * | 1982-03-05 | 1988-11-22 | Chemische Werke Huls Aktiengesellschaft | Process for the purification of hydrochloric acids |
| US5352420A (en) * | 1989-04-17 | 1994-10-04 | Krc Umwelttechnik Gmbh | Process for the purification of waste gas having a high chloride content |
| WO1998002402A1 (en) * | 1996-07-17 | 1998-01-22 | Texaco Development Corporation | Method for minimizing hydrogen halide corrosion in a partial oxidation process |
-
2000
- 2000-03-03 CN CN00103388A patent/CN1130246C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4786488A (en) * | 1982-03-05 | 1988-11-22 | Chemische Werke Huls Aktiengesellschaft | Process for the purification of hydrochloric acids |
| US4629610A (en) * | 1985-05-10 | 1986-12-16 | Dow Chemical Co. | Hydrogen fluoride recovery process |
| US5352420A (en) * | 1989-04-17 | 1994-10-04 | Krc Umwelttechnik Gmbh | Process for the purification of waste gas having a high chloride content |
| WO1998002402A1 (en) * | 1996-07-17 | 1998-01-22 | Texaco Development Corporation | Method for minimizing hydrogen halide corrosion in a partial oxidation process |
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Owner name: BEIJING ZIGUANG YING LI CHEMICAL TECHNOLOGY CO., L Free format text: FORMER NAME: QINGHUAZIGUANG YINGLI CHEMICAL TECHNOLOGY CO. LTD., BEIJING |
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Address after: No. 18 Anning East Road, Beijing, Haidian District Patentee after: TH-UNIS Insight Co., Ltd. Address before: Room 506, purple building, Tsinghua University, Beijing Patentee before: Beijing Tsinghua Unisplendour Insight Chemical Technology LLC |
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Granted publication date: 20031210 Termination date: 20100303 |