CN1234595C - Method for refining hydrochloric acid as byproduct in procedure for producing chemical products of chlorinated hydrocarbons - Google Patents
Method for refining hydrochloric acid as byproduct in procedure for producing chemical products of chlorinated hydrocarbons Download PDFInfo
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- CN1234595C CN1234595C CN200410014429.2A CN200410014429A CN1234595C CN 1234595 C CN1234595 C CN 1234595C CN 200410014429 A CN200410014429 A CN 200410014429A CN 1234595 C CN1234595 C CN 1234595C
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- hydrochloric acid
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- desorption
- product hydrochloric
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000006227 byproduct Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000000126 substance Substances 0.000 title claims abstract description 13
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 title claims abstract description 8
- 239000000047 product Substances 0.000 title abstract description 7
- 238000007670 refining Methods 0.000 title abstract 2
- 229920005989 resin Polymers 0.000 claims abstract description 50
- 239000011347 resin Substances 0.000 claims abstract description 50
- 238000003795 desorption Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000010521 absorption reaction Methods 0.000 claims abstract description 16
- 238000001179 sorption measurement Methods 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 3
- 239000003463 adsorbent Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 230000008929 regeneration Effects 0.000 claims description 3
- 238000011069 regeneration method Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 44
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 abstract description 27
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 abstract description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 7
- 238000011084 recovery Methods 0.000 abstract description 6
- 239000005416 organic matter Substances 0.000 abstract 4
- 229960002415 trichloroethylene Drugs 0.000 abstract 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 abstract 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 13
- 229940117389 dichlorobenzene Drugs 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000010828 elution Methods 0.000 description 6
- 229960004756 ethanol Drugs 0.000 description 6
- 229960000935 dehydrated alcohol Drugs 0.000 description 4
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 4
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 3
- 229940073608 benzyl chloride Drugs 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CAHQGWAXKLQREW-UHFFFAOYSA-N Benzal chloride Chemical compound ClC(Cl)C1=CC=CC=C1 CAHQGWAXKLQREW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920001429 chelating resin Polymers 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000013341 scale-up Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000406668 Loxodonta cyclotis Species 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000013332 literature search Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
Abstract
一种氯代烃类化工产品生产过程中副产盐酸的精制方法，它由下列步骤组成：(A)吸附：将含几十至几百mg/L有机物(苯、甲苯、氯苯、三氯乙烯等)的工业副产盐酸经过滤后，在流量为1～20BV/h，温度为0～50℃的条件下，经过装填有苯乙烯-二乙烯苯共聚的大孔吸附树脂的吸附塔，使副产盐酸中的有机物被吸附在树脂上，吸附之后的副产盐酸无色透明，有机物含量可降至1mg/L以下，(B)脱附：用水蒸汽作为脱附剂，将步骤A中吸附了有机物的大孔吸附树脂脱附再生，脱附温度为110～150℃，脱附时间为2～16h，(C)回收：脱附汽、液经冷凝和油水分离，回收有机物，水相可返回氯化氢吸收工段生产副产盐酸。A kind of refining method of by-product hydrochloric acid in the production process of chlorinated hydrocarbon chemical products, it is made up of following steps: (A) adsorption: will contain tens to hundreds of mg/L organic matters (benzene, toluene, chlorobenzene, trichloro Ethylene, etc.) industrial by-product hydrochloric acid is filtered, and under the condition of flow rate of 1-20BV/h and temperature of 0-50°C, it passes through the adsorption tower filled with macroporous adsorption resin of styrene-divinylbenzene copolymerization, Make the organic matter in the by-product hydrochloric acid be adsorbed on the resin, the by-product hydrochloric acid after the adsorption is colorless and transparent, and the organic matter content can be reduced to below 1mg/L, (B) desorption: use water vapor as a desorbing agent, the The macroporous adsorption resin that has adsorbed organic matter is desorbed and regenerated. The desorption temperature is 110-150°C, and the desorption time is 2-16 hours. (C) Recovery: desorbed vapor and liquid are condensed and separated from oil and water, and the organic matter is recovered, and the water phase It can be returned to the hydrogen chloride absorption section to produce hydrochloric acid as a by-product.
Description
One. technical field
The present invention relates to contain the process for purification of the technical hydrochloric acid of chlorinated hydrocarbon organic impurities, particularly, be meant the process for purification of the industrial by-product hydrochloric acid that generates in organic chemical industry's process of producing product such as Benzene Chloride, dichlorobenzene, trichlorobenzene, Benzyl Chloride, benzyl dichloride and trieline.
Two. background technology
Hydrochloric acid is a kind of important chemical product, and many absorption through water with hydrogen and chlorine reaction of technical hydrochloric acid produced.In organic chemical industry's process of producing product such as Benzene Chloride, dichlorobenzene, trichlorobenzene, Benzyl Chloride, benzyl dichloride, trieline, generate a large amount of by-product hydrochloric acids, these concentration of hydrochloric acid are about 25～35%, the face light yellow complexion, wherein contain organic impuritys such as benzene, toluene, Benzene Chloride, Benzyl Chloride and trieline, thereby limited its application in industrial production.
Literature search shows, the external activated carbon treatment by-product hydrochloric acid of report mostly, domestic report separates the organism in the trade effluent that contains hydrogenchloride with distillation method, but for macroporous adsorbent resin being used for the organic removal of by-product hydrochloric acid, does not all still have relevant report both at home and abroad.
Three. summary of the invention
The purpose of this invention is to provide a kind of economy, simple and easy to do purifying industrial by-product hydrochloric acid, to remove organic method in the by-product hydrochloric acid.
Technical scheme of the present invention is as follows:
The process for purification of by-product hydrochloric acid in a kind of chlorinated hydrocarbon Chemicals production process, it is made up of the following step: (A) absorption: will contain organic industrial by-product hydrochloric acid after filtering, at flow is 1～20BV/h, temperature is under 0～50 ℃ the condition, process is filled with the adsorption tower of the macroporous adsorbent resin of vinylbenzene-divinylbenzene copolymerization, and the organism in the by-product hydrochloric acid is attracted on the resin, the by-product hydrochloric acid water white transparency after the absorption, organic content can be reduced to below the 1mg/L
(B) desorption: as desorbing agent, will adsorb organic macroporous adsorbent resin desorption and regeneration in the steps A with water vapor, desorption temperature is 110～150 ℃, and desorption time is 2～16h,
(C) reclaim: desorption vapour, liquid reclaim organism through condensation and oily water separation, and water can return hydrogen chloride absorption workshop section and produce by-product hydrochloric acid.
Desorbing agent water vapor in the aforesaid method can replace with organic solvents such as methyl alcohol, ethanol, acetone or Virahols, with methyl alcohol or ethanol during as desorbing agent, desorption temperature is respectively 15～45 ℃ and 20～60 ℃, by organic chemical industry's product and the organic solvent in the rectifying separation recovery desorption liquid, also can be by organic chemical industry's product and the organic solvent in preceding 1/3～preceding 3/5 the desorption liquid of rectifying separation recovery, the desorption liquid of remaining back 2/3～back 2/5 is being applied mechanically in the desorption next time.
Above-mentioned macroporous adsorbent resin is homemade CHA-111 resin with superhigh cross-linking polystyrene structure, JX-101 resin, NDA-150 resin, H-103 resin etc., or U.S. Amberlite XAD-4, XAD-2 resin, perhaps Japanese Diaion HP series macroporous adsorbent resin.Preferably NDA-150 resin and CHA-111 resin.
Process for purification provided by the invention, can make in the by-product hydrochloric acid the organic concentration of chlorinated hydrocarbon from greatly to hundreds of mg/L, reduce to below the 1mg/L to tens mg/L for a short time, organic removal rate can reach more than 99%.Hydrochloric acid water white transparency after the processing, the organic smell of no chlorinated hydrocarbon, economic worth improves, and range of application is widened, and the adsorption treatment process does not have influence for the hydrogen cloride concentration in the by-product hydrochloric acid.Absorption back resin can use repeatedly through desorption and regeneration.
Four. embodiment
Further specify the present invention by the following examples.
Embodiment 1:
10ml (quality about 7 gram) CHA-111 (development chemical plant, changzhou produces, down with) resin is packed in the glass adsorption column of strap clamp cover ( 1.2cm * 30cm).Industrial by-product hydrochloric acid in the benzene chloride production process contains benzene 196mg/L, Benzene Chloride 30.9mg/L, and dichlorobenzene 3.88mg/L, face light yellow complexion, HCl content are 31%.Under the room temperature (25 ℃) with its with the flow of 50ml/h by above-mentioned resin bed.When treatment capacity is 1000mL, the by-product hydrochloric acid water white transparency after the absorption, wherein the concentration of benzene and Benzene Chloride is respectively 0.5mg/L and 0.2mg/L, and dichlorobenzene does not detect.
As desorbing agent, under 55 ℃ of conditions, with the above-mentioned resin bed of flow wash-out of 10ml/h, the ethanol desorption liquid is through the recyclable ethanol of rectifying with the 100ml dehydrated alcohol.Eluted resins is behind distilled water flushing, and at room temperature with the flow of 50ml/h, adsorbing benzene, Benzene Chloride and dichlorobenzene total content once more is the by-product hydrochloric acid of 35.5mg/L, and when treatment capacity was 1550ml, the organism total concn in the absorption effluent liquid was less than 1mg/L.
Embodiment 2:
The resin absorption device is with embodiment 1, (dagger-axe moral environmental protection Science and Technology Co., Ltd. of Jiangsu Nanjing University produces to change filling NDA-150 resin into, down together), the by-product hydrochloric acid that the concentration that will contain benzene, chlorobenzene and dichlorobenzene is respectively 204mg/L, 220mg/L and 132mg/L at room temperature passes through resin bed with the flow of 100ml/h, when treatment capacity is 2000ml, the concentration of benzene, chlorobenzene is respectively 0.6mg/L and 0.08mg/L in the effluent liquid, and dichlorobenzene does not detect.
Under 60 ℃ of conditions, with the flow wash-out resin bed of 140ml dehydrated alcohol with 10ml/h, the elutriant peak appears at preceding 60ml, its elution amount accounts for more than 95% of total elution amount, this part elutriant can carry out rectifying, Separation and Recovery ethanol and benzene, chlorobenzene, remaining rear section elutriant can be used for wash-out next time.Eluted resins can reuse behind distilled water flushing.
Embodiment 3:
10ml (quality about 7 gram) CHA-111 resin is packed in the glass adsorption column of strap clamp cover ( 1.2cm * 30cm).Industrial by-product hydrochloric acid in the benzene chloride production process contains benzene 196mg/L, Benzene Chloride 30.9mg/L, and dichlorobenzene 3.88mg/L, face light yellow complexion, HCl content are 31%.Under the room temperature (25 ℃) with its with the flow of 50ml/h by above-mentioned resin bed.When treatment capacity is 1000mL, the by-product hydrochloric acid water white transparency after the absorption, wherein the concentration of benzene and Benzene Chloride is respectively 0.5mg/L and 0.2mg/L, and dichlorobenzene does not detect.
Under 45 ℃ of conditions, with the flow wash-out resin bed of 140ml dehydrated alcohol with 10ml/h, the elutriant peak appears at preceding 80ml, its elution amount accounts for more than 95% of total elution amount, this part elutriant can carry out rectifying, Separation and Recovery methyl alcohol and benzene, chlorobenzene, remaining rear section elutriant can be used for wash-out next time.Eluted resins can reuse behind distilled water flushing.
Embodiment 4:
Adopt the acidproof adsorption column ( 100mm) of inner liner polytetrafluoroethylene to make the scale-up device, NDA-150 resin loading height is that 400mm (the resin humid volume is about 3.1L) carries out scale-up, organic concentration is benzene 6.49mg/L in the raw material by-product hydrochloric acid, chlorobenzene 25.8mg/L, dichlorobenzene 76.1mg/L, under the normal temperature (30 ℃), flow with 15.5L/h passes through resin column, when treatment capacity is 943L, organic concentration is in the by-product hydrochloric acid of absorption back: Benzene Chloride 0.16mg/L, dichlorobenzene 0.23mg/L, benzene does not detect.
Resin after the absorption is with 140 ℃ water vapour stripping 10h, and desorption vapour, liquid carry out oily water separation after condensation, reclaim organism.After the resin column cooling, carry out adsorption operations once more.Be respectively the by-product hydrochloric acid of 6.38mg/L, 24.1mg/L and 59.6mg/L for benzene, chlorobenzene and dichlorobenzene content, when the adsorption treatment amount is 930L, organic concentration in the by-product hydrochloric acid effluent liquid is reduced to: benzene 0.03mg/L, chlorobenzene 0.03mg/L, dichlorobenzene 0.11mg/L.
Embodiment 5:
Device and condition are with embodiment 3, but the flow of adsorption step is 62L/h, and temperature is 0 ℃, and the resin after the absorption is with 110 ℃ water vapour stripping 16h, and its result is substantially the same manner as Example 3.
Embodiment 6:
The resin absorption device is with embodiment 1,10ml (quality about 7 gram) NDA-150 resin is packed in the adsorption column, then the by-product hydrochloric acid that contains the 250mg/L trieline of having an appointment (HCl content about 31%) is passed through resin bed at 10 ℃ of flows with 50ml/h, when treatment capacity is 500ml, the concentration 0.3mg/L of trieline in the effluent liquid, the clearance of trieline reaches more than 99%.
Under 60 ℃ of conditions, with the flow wash-out resin bed of 60ml dehydrated alcohol with 20ml/h, the elutriant peak appears at preceding 20ml, its elution amount accounts for more than 70% of total elution amount, this part elutriant can carry out rectifying, separate and recovery ethanol and trieline, remaining rear section elutriant can be used for wash-out next time.
Embodiment 7:
Change the polymeric adsorbent in embodiment 1 and the example 4 into JX-101 resin (production of Golden Elephant chemical plant, Danyang, Jiangsu) or H-103 resin (Chemical Plant of Nankai Univ.'s production), perhaps Amberlite XAD-4 resin or XAD-2 resin (U.S. Rohm ﹠amp; Haas company provides), perhaps Diaion HP series macroporous adsorbent resin (Japanese Diaion company provide), other operational conditions remain unchanged, and except that every batch processing amount changed, other results were substantially roughly the same.
Claims (1)
1. the process for purification of by-product hydrochloric acid in the chlorinated hydrocarbon Chemicals production process is characterized in that it is made up of the following step:
(A) absorption: will contain organic industrial by-product hydrochloric acid after filtering, at flow is 1～20BV/h, temperature is under 0～50 ℃ the condition, through being filled with the macroporous adsorbent resin NDA-150 resin of vinylbenzene-divinylbenzene copolymerization or the adsorption tower of CHA-111 resin, organism in the by-product hydrochloric acid is attracted on the resin
(B) desorption: as desorbing agent, will adsorb organic macroporous adsorbent resin desorption and regeneration in the steps A with water vapor, desorption temperature is 110～150 ℃, and desorption time is 2～16h,
(C) reclaim: desorption vapour, liquid reclaim organism through condensation and oily water separation, and water can return hydrogen chloride absorption workshop section and produce by-product hydrochloric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200410014429.2A CN1234595C (en) | 2004-03-25 | 2004-03-25 | Method for refining hydrochloric acid as byproduct in procedure for producing chemical products of chlorinated hydrocarbons |
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| Application Number | Priority Date | Filing Date | Title |
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| CN200410014429.2A CN1234595C (en) | 2004-03-25 | 2004-03-25 | Method for refining hydrochloric acid as byproduct in procedure for producing chemical products of chlorinated hydrocarbons |
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| CN1562733A CN1562733A (en) | 2005-01-12 |
| CN1234595C true CN1234595C (en) | 2006-01-04 |
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| CN200410014429.2A Expired - Fee Related CN1234595C (en) | 2004-03-25 | 2004-03-25 | Method for refining hydrochloric acid as byproduct in procedure for producing chemical products of chlorinated hydrocarbons |
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| CN100591648C (en) * | 2006-12-27 | 2010-02-24 | 贵州蓝天化工有限公司 | Technique for coproducing polyvinyl chloride from by-product hydrogen chloride of trichloroethylene |
| CN101200286B (en) * | 2007-12-05 | 2011-03-23 | 南京大学 | Method for refining byproduct hydrogen chloride during production process of organochlorine products |
| CN101830436B (en) * | 2010-04-29 | 2011-11-09 | 唐山氯碱有限责任公司 | Device for preparing concentrated hydrochloric acid in vinyl chloride conversion procedure |
| 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 |
| CN104058370B (en) * | 2014-06-13 | 2016-04-06 | 王金明 | A kind of method that dimethyldichlorosilane(DMCS) hydrolysis by-product hydrochloric acid is purified |
| CN104192802B (en) * | 2014-08-29 | 2016-01-13 | 浙江大洋生物科技集团股份有限公司 | The by-product hydrochloric acid purifying method of the chloro-6-fluorobenzaldehyde of 2-or analogue |
| CN104445072B (en) * | 2014-10-31 | 2016-05-11 | 浙江衢州巨塑化工有限公司 | A kind of purifying plant of trichloro-ethylene by-product hydrogen chloride and method |
| CN104709879A (en) * | 2015-03-10 | 2015-06-17 | 安徽八一化工股份有限公司 | Process for removing organic matters in byproduct hydrochloric acid in chlorobenzene production |
| CN111606305B (en) * | 2020-06-17 | 2022-02-18 | 山东默锐科技有限公司 | Refining method of byproduct hydrochloric acid in industrial organic synthesis |
| CN111792623A (en) * | 2020-06-23 | 2020-10-20 | 湖南海利化工股份有限公司 | Method for recovering and preparing high-quality hydrochloric acid from waste gas of phosgene reaction system |
| CN112320758A (en) * | 2020-12-01 | 2021-02-05 | 北京钟华鼎盛节能技术有限公司 | Method for purifying trichloroethylene by-product hydrochloric acid |
| CN113499663A (en) * | 2021-08-10 | 2021-10-15 | 西安瀚宇树脂科技有限公司 | Resource treatment and recovery method for shale oil dry distillation refining waste gas |
| CN115414762A (en) * | 2022-09-06 | 2022-12-02 | 安徽东至广信农化有限公司 | Tail gas treatment method for adjacent nitrate workshop |
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| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20050112 Assignee: Jiangsu N&G Environmental Technology Co.,Ltd. Assignor: Nanjing University Contract record no.: 2010320000069 Denomination of invention: Method for refining hydrochloric acid as byproduct in procedure for producing chemical products of chlorinated hydrocarbons Granted publication date: 20060104 License type: Exclusive License Record date: 20100221 |
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| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060104 |