CN102849681A - Method for removing chlorine included in hydrogen chloride gas - Google Patents
Method for removing chlorine included in hydrogen chloride gas Download PDFInfo
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- CN102849681A CN102849681A CN2012101015880A CN201210101588A CN102849681A CN 102849681 A CN102849681 A CN 102849681A CN 2012101015880 A CN2012101015880 A CN 2012101015880A CN 201210101588 A CN201210101588 A CN 201210101588A CN 102849681 A CN102849681 A CN 102849681A
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- hydrogen chloride
- chloride gas
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Abstract
The invention, belonging to the field of chemical industry production, discloses a method for removing contained chlorine from a byproduct hydrogen chloride gas generated in the process of producing organic chlorides, comprising the following steps: carrying out reduction reaction upstream on a byproduct hydrogen chloride gas output by the process of producing organic chlorides and a purification solution in a packed tower to remove chlorine, and then conducting freeze drying to obtain a high-purity hydrogen chloride gas with the chlorine content of less than 1ppm. According to the invention, by using a ferrous chloride solution containing satuarated hydrogen chloride as the purification solution to remove chlorine from the hydrogen chloride gas with a chlorine content of less than 5%(v/v) to obtain chlorine, the advantages of simpleness, reliability, fast removing speed, and low energy consumption and cost of purification are achieved, and the method can effectively raise the application value of the byproduct hydrogen chloride gas, broaden the application range of the byproduct hydrogen chloride gas, and the like; and the method can be used for removing chlorine from a synthetic hydrogen chloride gas with a chlorine content of less than 5%(v/v and byproduct hydrogen chloride gases generated from other production processes.
Description
Technical field
The invention belongs to the production method of the high purity chlorination hydrogen in the chemical production field, particularly remove wherein contained chlorine in a kind of byproduct hydrogen chloride gas for gained from the organic chloride production process.Adopt the inventive method can fully remove chlorine contained in the hydrogen chloride gas, produce the high purity chlorination hydrogen that chlorine content is lower than 1ppm, with for the production of Chemicals such as PVC, trichlorosilanes, thus enlarge gained byproduct hydrogen chloride gas in the organic chloride production process use range, improve its using value.
Background technology
High purity chlorination hydrogen can be used for producing the Chemicals such as PVC, trichlorosilane, reagent pure hydrochloric acid.The method production that the hydrogen that the conventional employing of this type of high purity chlorination hydrogen electrolytic process is produced and chlorine are synthetic, as: be disclosedly in CN1165110A, the denomination of invention patent document for " producing the method and apparatus of reagent hydrochloric acid " a kind ofly to remove chlorine in the synthesising hydrogen with tin protochloride at publication number, hydrogenchloride after being purified namely belongs to this type of technology for the production of the processing method of reagent pure hydrochloric acid, although this technology can effectively be removed the chlorine in the synthesising hydrogen: the one, adopt H
2With Cl
2Synthesising hydrogen cost height, the 2nd, tin protochloride is expensive, therefore has the production of hydrogen chloride gas and purifies the high in cost of production disadvantage; And be CN100372756C at notification number, denomination of invention discloses a kind of employing absorption extraction agent (Sulfothiorine 30-40% in the patent document of " method of reagent grade hydrochloric acid ", S-WAT 10-15%, iron protochloride 15-20%, ferrous sulfate 30-40%) and pure water be made into the absorption extraction agent solution of 0.03-0.1%, contact the trace impurity of removing wherein with synthesizing chlorinated hydrogen following current, hydrogen chloride gas after the purification is for the production of the processing method of reagent grade hydrochloric acid, the impurity of the method purifying treatment also mainly is chlorine, and remove the impurity gas such as chlorine by redox reaction, the method exists purification systems complicated, the scavenging agent concentration of selecting is on the low side, technological process by-product waste hydrochloric acid amount is large.In addition, in conventional organic chloride the production of material, also can produce a large amount of byproduct hydrogen chloride gas, still can not be directly used in high-end derived product such as producing PVC, trichlorosilane because containing a small amount of chlorine in the hydrogen chloride gas of this type of by-product, the chlorine that therefore must remove wherein could satisfy derived product requirements such as producing PVC, trichlorosilane; Yet above-mentioned for removing synthesising hydrogen chlorine to produce the method for reagent grade hydrochloric acid, but be difficult to use in this type of byproduct hydrogen chloride gas of purifying; For the purification by the byproduct hydrogen chloride gas that produces in the organic chloride production process, be CN1865127A at publication number, denomination of invention discloses a kind of solvent orange 2 A (benzene that at first adopts in the patent document of " a kind of separating and purifying method that contains chlorine and hydrogenchloride mix waste gas ", silicon tetrachloride, nonane, sulfur monochloride, tetracol phenixin, a kind of in the chlorsulfonic acid) with the chlorine absorption in hydrogenchloride and the chlorine mixed gas in liquid phase, it is separated with hydrogen chloride gas, and then utilize solvent B (cyclopentadiene, a kind of in the hexachlorobutadiene) remove the solvent orange 2 A of the gasification of carrying secretly in the hydrogen chloride gas, thus the hydrogen chloride gas that obtains purifying through concentrated hydrochloric acid washing and chemical washing again; Although the method has hydrogen chloride gas and chlorine after the chlorine that contains 2-50wt% in chlorine and the hydrogenchloride mix waste gas can being isolated, also obtaining respectively purifying, but the method adopt the solvent orange 2 A absorbing chlorine must be lower than under 15 ℃ the cold condition carry out, again through 70-75 ℃ of desorption under high temperature, isolated hydrogen chloride gas also need be sent into the secondary packing tower through solvent treatment ..., the A after the processing, B mixed solvent also need adopt distillation tower to separate; Thereby the method not only flow process and complicated operation, energy consumption are high, cost is high when containing the low byproduct hydrogen chloride gas of amount of chlorine especially for purification, thereby is difficult to use in to purify and contains the low gained byproduct hydrogen chloride gas from the organic chloride production process of amount of chlorine.
Summary of the invention
The objective of the invention is the defective for the background technology existence, research and develop a kind of method that removes contained chlorine in the hydrogen chloride gas, so as from the organic chloride production process, to remove contained chlorine wherein in the byproduct hydrogen chloride gas of gained, high purity chlorination hydrogen that the chlorine content that obtains can be used for producing the derived product such as PVC, trichlorosilane is lower than trace; Thereby reach process simplification and reduce operation control difficulty, improve purification efficiency, effectively reduce purifying cost, particularly effectively reduce the low purposes such as purification cost of gained byproduct hydrogen chloride gas from organic chloride is produced of chlorine content.
Solution of the present invention is that the volume percent content for chlorine in the conventional organic chloride production process gained byproduct hydrogen chloride gas generally all is lower than 5% (v/v), therefore adopt the solution of ferrous chloride that contains saturated hydrogenchloride as scavenging solution, in the conventional fillers tower, this type of byproduct hydrogen chloride gas of exporting from the organic chloride production process is processed, by the redox reaction of iron protochloride in the scavenging solution and chlorine remove wherein chlorine, again through removal moisture drying, thereby realize its goal of the invention.Thereby the inventive method comprises:
Steps A. countercurrent reaction is removed chlorine: will contain the solution of ferrous chloride of saturated hydrogenchloride as scavenging solution, spray in the packing layer from packing tower top, then directly introduce the byproduct hydrogen chloride gas of from the organic chloride production process, exporting from the packing tower bottom, byproduct hydrogen chloride gas in tower to the filling surface of upper reaches band scavenging solution and pass scavenging solution between each filling surface, after solution of ferrous chloride in the byproduct hydrogen chloride gas in contained chlorine and the scavenging solution carries out reduction reaction, chlorine is reduced into chlorion and enters scavenging solution and by discharging at the bottom of the tower, and the hydrogen chloride gas of removing behind the chlorine is then exported by cat head;
Step B. lyophilize is processed: with the hydrogen chloride gas after steps A is removed chlorine by cat head be input to freeze drying plant, to remove the water vapour in the hydrogen chloride gas, namely get the object hydrogen chloride gas.
The above-mentioned solution of ferrous chloride that contains saturated hydrogenchloride is as scavenging solution, and (weight percent) concentration of iron protochloride is 0.1-20wt% in this scavenging solution.Solution of ferrous chloride in the described byproduct hydrogen chloride gas in contained chlorine and the scavenging solution carries out reduction reaction, wherein: the flow velocity of byproduct hydrogen chloride gas is that 0.2-1.0m/s, temperature are the gained byproduct hydrogen chloride gas without the artificial temperature of processing, and the scavenging solution temperature is chamber (often) temperature.Described freeze drying plant is that shell and tube lyophilize (dehumidifying) device, lyophilize temperature are subzero 10 ℃ to subzero 5 ℃.
The present invention is owing to adopt the solution of ferrous chloride that contains saturated hydrogenchloride to contain the hydrogen chloride gas of a small amount of chlorine as scavenging solution, processing, remove chlorine contained in the hydrogen chloride gas by the redox reaction of iron protochloride in the scavenging solution and chlorine, again by lyophilize, obtain the highly purified hydrogen chloride gas of chlorine content below 1ppm.Thereby, the present invention is simple, reliable to the removal methods of contained chlorine in the byproduct hydrogen chloride gas of conventional organic chloride production process, it is fast to remove (reaction) speed, the energy consumption and the cost that purify are low, Effective Raise the using value of byproduct hydrogen chloride gas, widened the characteristics such as range of application of byproduct hydrogen chloride gas; In addition, the inventive method also can be used for chlorine content is lower than the processing that removes of chlorine in the hydrogen chloride gas of the synthesizing chlorinated hydrogen of 5% (v/v) and other Production Flow Chart by-product.
Embodiment
Embodiment 1:
Steps A. countercurrent reaction is removed chlorine: the iron protochloride concentration that will contain saturated hydrogenchloride is that the scavenging solution of 10wt% sprays in the packing layer from packing tower top, and the present embodiment filler adopts Raschig ring filler, the axial thick 150cm of packing layer; Then will adopt the hydrogen chloride gas of tetracol phenixin and methane gas production zellon institute by-product at the bottom of packing tower, to input; Contain chlorine 1.1% (v/v), gas flow rate 0.4m/s in the present embodiment byproduct hydrogen chloride gas, byproduct hydrogen chloride gas upwards fully contacts with scavenging solution in packing layer at the bottom of tower, iron protochloride in the scavenging solution and chlorine carry out redox reaction, chlorine and are reduced into chlorion and enter scavenging solution and discharge at the bottom of by tower with scavenging solution, and the hydrogen chloride gas that removes behind the chlorine is transported to the drying treatment operation through cat head; Present embodiment packing tower interior reaction temperature is about 10 ℃, pressure 1.0 * 10
5Pa;
Step B. lyophilize is processed: the hydrogen chloride gas after steps A removes chlorine is sent into the shell and tube freeze drying plant, carries out drying treatment under subzero 6 ℃ temperature, after removing the water vapour in the hydrogen chloride gas, namely get object (after the purification) hydrogen chloride gas.
Present embodiment gained hydrogen chloride gas is after testing: the result is for can't check chlorine (being that content is below 1ppm), and the removal effect of its chlorine is fabulous.
Embodiment 2:
Steps A. countercurrent reaction is removed chlorine: the iron protochloride concentration that will contain saturated hydrogenchloride is that the scavenging solution of 0.8wt% sprays in the packing layer from packing tower top, and the present embodiment filler adopts the whole filler of silicon, the axial thick 150cm of packing layer; Then the methyl alcohol method is produced the hydrogen chloride gas of methyl chloride institute by-product and at the bottom of packing tower, input, contain chlorine 1.0% (v/v), gas flow rate 0.6m/s in the hydrogen chloride gas of present embodiment by-product; Byproduct hydrogen chloride gas upwards fully contacts with scavenging solution in packing layer at the bottom of tower, iron protochloride in the scavenging solution and chlorine carry out redox reaction, chlorine and are reduced into chlorion and enter scavenging solution and discharge at the bottom of by tower with scavenging solution, and the hydrogen chloride gas that removes behind the chlorine is transported to the drying treatment operation through cat head; Scavenging solution temperature in the present embodiment imported fill tower is about 20 ℃, the packing tower interior reaction temperature is about 50 ℃, pressure 1.2 * 10
5Pa;
Step B. lyophilize is processed: the hydrogen chloride gas after steps A removes chlorine is sent into the shell and tube freeze drying plant, carries out drying treatment under subzero 10 ℃ temperature, after removing the water vapour in the hydrogen chloride gas, namely get object (after the purification) hydrogen chloride gas.
Present embodiment gained hydrogen chloride gas is after testing: the result is for can't check chlorine (being that content is below 1ppm), and the removal effect of its chlorine is also fabulous.
Claims (4)
1. method that removes contained chlorine in the hydrogen chloride gas comprises:
Steps A. countercurrent reaction is removed chlorine: will contain the solution of ferrous chloride of saturated hydrogenchloride as scavenging solution, spray in the packing layer from packing tower top, then directly introduce the byproduct hydrogen chloride gas of from the organic chloride production process, exporting from the packing tower bottom, byproduct hydrogen chloride gas in tower to the filling surface of upper reaches band scavenging solution and pass scavenging solution between each filling surface, after solution of ferrous chloride in the byproduct hydrogen chloride gas in contained chlorine and the scavenging solution carries out reduction reaction, chlorine is reduced into chlorion and enters scavenging solution and by discharging at the bottom of the tower, and the hydrogen chloride gas of removing behind the chlorine is then exported by cat head;
Step B. lyophilize is processed: with the hydrogen chloride gas after steps A is removed chlorine by cat head be input to freeze drying plant, to remove the water vapour in the hydrogen chloride gas, namely get the object hydrogen chloride gas.
2. by the described method that removes contained chlorine in the hydrogen chloride gas of claim 1, it is characterized in that the described solution of ferrous chloride that contains saturated hydrogenchloride as scavenging solution, the concentration of iron protochloride is 0.1-20wt% in this scavenging solution.
3. by the described method that removes contained chlorine in the hydrogen chloride gas of claim 1, it is characterized in that the solution of ferrous chloride in the contained chlorine and scavenging solution carries out reduction reaction in the described byproduct hydrogen chloride gas, wherein: the flow velocity of byproduct hydrogen chloride gas is that 0.2-1.0m/s, temperature are the gained byproduct hydrogen chloride gas without the artificial output temperature of processing, and the scavenging solution temperature is room temperature.
4. by the described method that removes contained chlorine in the hydrogen chloride gas of claim 1, it is characterized in that described freeze drying plant is that shell and tube freeze drying plant, lyophilize temperature are subzero 10 ℃ to subzero 5 ℃.
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| CN2012101015880A CN102849681A (en) | 2012-04-06 | 2012-04-06 | Method for removing chlorine included in hydrogen chloride gas |
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| CN2012101015880A CN102849681A (en) | 2012-04-06 | 2012-04-06 | Method for removing chlorine included in hydrogen chloride gas |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014186954A1 (en) * | 2013-05-22 | 2014-11-27 | Bayer Materialscience Ag | Process for purifying raw-material gases by fractionation |
| CN106477525A (en) * | 2016-09-26 | 2017-03-08 | 常州大学 | A kind of chlorination tail gas hydrogen chloride dechlorination gas purifying method |
| CN106518605A (en) * | 2016-08-30 | 2017-03-22 | 安徽八化工股份有限公司 | Technology for removing free chlorine from acid discharge at bottom of chlorinator |
| CN115006975A (en) * | 2022-05-07 | 2022-09-06 | 南通星球石墨股份有限公司 | Method for recycling hydrogen chloride in dichlorobenzene byproducts |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5073355A (en) * | 1989-07-05 | 1991-12-17 | Kronos (U.S.A.), Inc. | Process for the removal of chlorine from off-gases |
| CN1165110A (en) * | 1997-06-19 | 1997-11-19 | 刘建昆 | Method and equipment for preparing reagent grade hydrochloric acid |
| CN1311053A (en) * | 2000-03-03 | 2001-09-05 | 北京清华紫光英力化工技术有限责任公司 | Refining and recovering process for industrial by-product halogen hydride gas |
| CN1640813A (en) * | 2004-01-15 | 2005-07-20 | 山东滨化集团有限责任公司 | Method for producing reagent-level hydrochloric acid |
| CN101823694A (en) * | 2010-05-06 | 2010-09-08 | 杭州四面体科技有限公司 | Processing method for purifying sulfur-containing chlorine hydride |
-
2012
- 2012-04-06 CN CN2012101015880A patent/CN102849681A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5073355A (en) * | 1989-07-05 | 1991-12-17 | Kronos (U.S.A.), Inc. | Process for the removal of chlorine from off-gases |
| CN1165110A (en) * | 1997-06-19 | 1997-11-19 | 刘建昆 | Method and equipment for preparing reagent grade hydrochloric acid |
| CN1311053A (en) * | 2000-03-03 | 2001-09-05 | 北京清华紫光英力化工技术有限责任公司 | Refining and recovering process for industrial by-product halogen hydride gas |
| CN1640813A (en) * | 2004-01-15 | 2005-07-20 | 山东滨化集团有限责任公司 | Method for producing reagent-level hydrochloric acid |
| CN101823694A (en) * | 2010-05-06 | 2010-09-08 | 杭州四面体科技有限公司 | Processing method for purifying sulfur-containing chlorine hydride |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014186954A1 (en) * | 2013-05-22 | 2014-11-27 | Bayer Materialscience Ag | Process for purifying raw-material gases by fractionation |
| US9938147B2 (en) | 2013-05-22 | 2018-04-10 | Covestro Deutschland Ag | Process for purifying raw-material gases by fractionation |
| US10011484B1 (en) | 2013-05-22 | 2018-07-03 | Coverstro Deutschland Ag | Process for purifying raw-material gases by fractionation |
| CN106518605A (en) * | 2016-08-30 | 2017-03-22 | 安徽八化工股份有限公司 | Technology for removing free chlorine from acid discharge at bottom of chlorinator |
| CN106477525A (en) * | 2016-09-26 | 2017-03-08 | 常州大学 | A kind of chlorination tail gas hydrogen chloride dechlorination gas purifying method |
| CN106477525B (en) * | 2016-09-26 | 2021-04-27 | 常州大学 | Method for purifying chlorination tail gas chlorine hydride dechlorination gas |
| CN115006975A (en) * | 2022-05-07 | 2022-09-06 | 南通星球石墨股份有限公司 | Method for recycling hydrogen chloride in dichlorobenzene byproducts |
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Application publication date: 20130102 |