CN103877833B - The processing method of a kind of chloride Bian, chlorine and hydrogen chloride mix waste gas - Google Patents
The processing method of a kind of chloride Bian, chlorine and hydrogen chloride mix waste gas Download PDFInfo
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- CN103877833B CN103877833B CN201410056418.4A CN201410056418A CN103877833B CN 103877833 B CN103877833 B CN 103877833B CN 201410056418 A CN201410056418 A CN 201410056418A CN 103877833 B CN103877833 B CN 103877833B
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Abstract
The invention belongs to exhaust-gas treatment field, relate to the processing method of a kind of chloride Bian, chlorine and hydrogen chloride mix waste gas.The method is by mix waste gas once by Bian chlorine spray absorber, chlorine spray absorber, hydrochloric acid spray absorber, and the absorption respectively by solvent orange 2 A, B, C successfully achieves chlorine Bian, chlorine is separated with hydrogen chloride.This method have simple to operate, processing cost is low, reclaim added value of product high, the advantages such as plant investment is little.
Description
Technical field
The invention belongs to exhaust-gas treatment field, relate to the processing method of a kind of chloride Bian, chlorine and hydrogen chloride mix waste gas.
Background technology
It is a kind of important process in Chemical Manufacture that chlorination replaces, be usually used in the intermediate such as agricultural chemicals, medicine, such as, 4-chloro-benzaldehyde is as a kind of important industrial chemicals, technique conventional at present adopts parachlorotoluene after superchlorination, hydrolysis is obtained, strong and stimulating, the chlorine Bian of tearing property and inorganic chlorine and hydrogen chloride gas can be produced in this art production process, not only serious pollution is caused to environment, more have a strong impact on the resident of site operation personnel and surrounding.
At present, due to the complicated component of inorganic organic exhaust gas, intractability is large, major part enterprise adopts simple water to absorb or Alkali absorption treatment process, not only weak effect, also can produce a large amount of high slat-containing wastewaters and spent acid simultaneously, belong to hazardous waste, greatly increase the weight of environmental protection pressure and the processing cost of enterprise.Therefore avoid evaporating, emitting, dripping or leaking of liquid or gas in process of production as far as possible, disordered exhaust gas is collected to become focus on after waste gas in a organized way, the discharge of decreasing pollution thing.To the inevitable inorganic organic mixed waste gas produced, then must be purified or be recycled.
In addition, other treatment technologies, absorption process of such as burning, active carbon adsorption, compression freezing etc., in these methods, most result can only reduce pollutant, and resource rate is low, and processing cost is high, of poor benefits, not only can cause the waste of resource, more aggravate the burden of enterprise.
The key technology of process organic-inorganic mix waste gas is effectively to be isolated according to the character of each component, substep purifying.Owing to containing more organic impurities in inorganic component, the sour added value made is very low, can only be used as the industries such as acid washing phosphorization.So, in the urgent need to good separating effect, and simple to operate, the treatment process that resource purity is high, one-time investment is little, can avoid the pollution to environment on the one hand, even can bring profit for enterprise on the other hand.
Summary of the invention
The technical issues that need to address of the present invention are: for current chloride Bian, chlorine, hydrogen chloride emission treatment technology efficiency is low, cost is high, there is secondary pollution problems, and provides a kind of method that can process chloride Bian, chlorine, hydrogen chloride emission efficiently, at low cost.
A processing method containing chlorine Bian, chlorine and hydrogen chloride mix waste gas, the method comprises the following steps:
(1) be the spray absorber of absorbent by described to pass into solvent orange 2 A containing chlorine Bian, chlorine and hydrogen chloride mix waste gas, organic component chlorine Bian in mix waste gas is absorbed in the liquid phase, be separated with chlorine with the inorganic component hydrogen chloride of gas phase, absorb saturated after solvent orange 2 A again through desorb obtain be separated chlorine Bian;
(2) spray absorber that to pass into solvent B by remaining inorganic mix waste gas be absorbent, by the chlorine absorption in remaining inorganic mix waste gas in the liquid phase, with the HCl separation of gas phase, absorb saturated after solvent B obtain the free chlorine of purifying again through desorb;
(3) remaining discarded passing into solvent C is the spray absorber of absorbent, by absorbing hydrogen chloride gas in liquid phase, absorb saturated after solvent orange 2 A obtain the hydrogen chloride gas of purifying again through desorb;
Wherein, described solvent orange 2 A be selected from the sub-phosphoric triamide HMPT of hexamethyl, the sub-phosphoric triamide HEPT of Hexaethyl, sulfolane, pertroleum wax any one; Solvent B be selected from carbon tetrachloride, silicon tetrachloride, n-dodecane any one; Solvent C be selected from n-butanol, glycerine, diethyl carbonate, trimethyl phosphate any one.
Described consist of monochlor(in)ate benzyl 0.5 ~ 4wt%, benzyl dichloride 5 ~ 18wt%, chlorine 15 ~ 35wt%, hydrogen chloride 43 ~ 79.5wt% containing chlorine Bian, chlorine and hydrogen chloride mix waste gas.
Described spray absorber is packed tower, and filler material is any one in pottery, polypropylene PP, stainless steel; Sprinkle density scope is 4 ~ 8m
3/ (m
2, h).
In the inventive method, the spray temperature of solvent orange 2 A is 30 ~ 50 DEG C.
In the inventive method, absorb saturated after solvent orange 2 A heating desorption go out chlorine Bian Posterior circle use, wherein, monochlor(in)ate Bian desorption temperature is 175 ~ 185 DEG C, and dichloride Bian desorption temperature is 200 ~ 210 DEG C.Absorb saturated after solvent B heating desorption go out chlorine Posterior circle use, desorption temperature is 50 ~ 80 DEG C; The chlorine obtained absorbs through the NaOH aqueous solution that concentration is 6 ~ 15wt% prepares clorox.Absorb saturated after solvent C heating desorption go out hydrogen chloride, desorption temperature is 50 ~ 70 DEG C, and the hydrogen chloride of gained absorbs through falling liquid film water makes hydrochloric acid.
Method of the present invention, the chlorine Bian of recovery can be back to production, and hypochlorite and hydrochloric acid can be used as technical-grade hydrochloric acid.
Beneficial effect:
(1) the inventive method is comformed in multi-solvent, select again the combination of solvent orange 2 A, B, C, multistage substep is adopted to absorb chloride Bian, chlorine, hydrogen chloride emission, the method effectively can realize being separated of organic component chlorine Bian and inorganic component, and the separation between two kinds of inorganic components, exhaust-gas treatment is thorough, all can realize resource and reclaim, and organic efficiency is high.
(2) solvent for use of the present invention can recycle, non-secondary pollution, and operating cost is low.
(3) to reclaim the reagent added value obtained high in the present invention, avoids the wasting of resources, have obvious economic benefit.
(4) the invention provides one and process chloride Bian, chlorine, hydrogen chloride emission efficiently, at low cost, have simple to operate, processing cost is low, reclaim added value of product high, the advantages such as plant investment is little.
Accompanying drawing explanation
A kind of process flow figure containing chlorine Bian, chlorine and hydrogen chloride mix waste gas of Fig. 1 the present invention.
Detailed description of the invention
Following examples carry out the process containing chlorine Bian, chlorine and hydrogen chloride mix waste gas by the following method:
(1) be the spray absorber of absorbent by described to pass into solvent orange 2 A containing chlorine Bian, chlorine and hydrogen chloride mix waste gas, organic component chlorine Bian in mix waste gas is absorbed in the liquid phase, be separated with chlorine with the inorganic component hydrogen chloride of gas phase, absorb saturated after solvent orange 2 A in rectifying column through desorb obtain be separated chlorine Bian;
(2) spray absorber that to pass into solvent B by remaining inorganic mix waste gas be absorbent, by the chlorine absorption in remaining inorganic mix waste gas in the liquid phase, with the HCl separation of gas phase, absorb saturated after solvent B in rectifying column, obtain the free chlorine of purifying through desorb; The chlorine obtained absorbs through the NaOH aqueous solution that concentration is 6 ~ 15wt% prepares clorox.
(3) remaining discarded passing into solvent C is the spray absorber of absorbent, by absorbing hydrogen chloride gas in liquid phase, absorb saturated after solvent orange 2 A in stripping vessel, obtain the hydrogen chloride gas of purifying through desorb; The hydrogen chloride of gained absorbs through falling liquid film water makes hydrochloric acid.
Embodiment 1
Process is containing chlorine Bian, chlorine and hydrogen chloride mix waste gas according to the method described above.The main device that the present embodiment adopts comprises: Bian chlorine spray absorber, chlorine spray absorber, hydrochloric acid spray absorber, be stainless steel packed tower, built with ceramic packing.Sprinkle density is respectively 4m
3/ (m
2, h), 5m
3/ (m
2, h), 4m
3/ (m
2, h).
Containing consisting of of chlorine Bian, chlorine and hydrogen chloride mix waste gas: monochlor(in)ate benzyl 0.5%(mass fraction), benzyl dichloride 18%(mass fraction), chlorine 30%(mass fraction), hydrogen chloride 52.5%(mass fraction).
Solvent for use A is the sub-phosphoric triamide of HMPT(hexamethyl), its spray temperature is 40 DEG C.Solvent B is silicon tetrachloride; Solvent C is n-butanol.
Absorb saturated after solvent orange 2 A desorb in rectifying column, do not get 175 DEG C of cuts and 200 DEG C of cuts, obtaining product purity is respectively the monochlor(in)ate Bian of 95%, the dichloride Bian of 98%, and the HMPT after desorb is cycled to used in Bian chlorine spray-absorption, and monochlor(in)ate Bian and the dichloride Bian of preparation can be back to production; Absorb saturated after solvent B desorb in rectifying column, desorption temperature is 50 DEG C, and after desorb, free purity of chlorine gas feeding reaches 99%, and the absorption alkali lye selected is the NaOH solution of 6%, makes liquor natrii hypochloritis; Absorb saturated after solvent C desorb in stripping vessel, desorption temperature is 60 DEG C, adopts falling liquid film water to absorb the hydrochloric acid making 31%, its quality meet GB320 ?1993 technical requirements.Exhaust emissions after treatment meets " discharge standard of air pollutants " (GB16297 ?1996) secondary standard.
Embodiment 2
Process is containing chlorine Bian, chlorine and hydrogen chloride mix waste gas according to the method described above.The main device that the present embodiment adopts comprises: Bian chlorine spray absorber, chlorine spray absorber, hydrochloric acid spray absorber, be stainless steel packed tower, built with stainless steel helices, sprinkle density is respectively 8m
3/ (m
2, h), 6m
3/ (m
2, h), 8m
3/ (m
2, h).
Containing consisting of of chlorine Bian, chlorine and hydrogen chloride mix waste gas: monochlor(in)ate benzyl 3.5%(mass fraction), benzyl dichloride 15%(mass fraction), chlorine 35%(mass fraction), hydrogen chloride 46.5%(mass fraction).
Solvent for use A is sulfolane, and its spray temperature is 30 DEG C; Solvent B is carbon tetrachloride; Solvent C is diethyl carbonate.
Absorb saturated after solvent orange 2 A desorb in rectifying column, do not get 180 DEG C and 205 DEG C of cuts, obtaining product purity is respectively the monochlor(in)ate Bian of 97%, the dichloride Bian of 99%, and the HMPT after desorb is cycled to used in Bian chlorine spray-absorption, and monochlor(in)ate Bian and the dichloride Bian of preparation can be back to production; Absorb saturated after solvent B desorption temperature be 60 DEG C, after desorb, free purity of chlorine gas feeding reaches 99%, and the absorption alkali lye selected is the NaOH solution of 10%, makes liquor natrii hypochloritis; Absorb saturated after solvent C desorption temperature be 60 DEG C, adopt falling liquid film water to absorb the hydrochloric acid making 31%, its quality meet GB320 ?1993 technical requirements.Exhaust emissions after treatment meets " discharge standard of air pollutants " (GB16297 ?1996) secondary standard.
Embodiment 3
Process is containing chlorine Bian, chlorine and hydrogen chloride mix waste gas according to the method described above.The main device that the present embodiment adopts comprises: chlorine spray absorber, chlorine spray absorber, hydrochloric acid spray absorber, be stainless steel packed tower, built with stainless steel helices, sprinkle density is respectively 4m
3/ (m
2, h), 6m
3/ (m
2, h), 6m
3/ (m
2, h).
Containing consisting of of chlorine Bian, chlorine and hydrogen chloride mix waste gas: monochlor(in)ate benzyl 4%(mass fraction), benzyl dichloride 12%(mass fraction), chlorine 17%(mass fraction), hydrogen chloride 67%(mass fraction).
Solvent for use A is the sub-phosphoric triamide of HEPT(Hexaethyl), its spray temperature is 40 DEG C; Solvent B is n-dodecane; Solvent C is glycerine.
Absorb saturated after solvent orange 2 A desorb in rectifying column, do not get 175 DEG C and 205 DEG C of cuts, obtaining product purity is respectively the monochlor(in)ate Bian of 96%, the dichloride Bian of 99%, and the HMPT after desorb is cycled to used in Bian chlorine spray-absorption, and monochlor(in)ate Bian and the dichloride Bian of preparation can be back to production; Absorb saturated after solvent B desorption temperature be 80 DEG C, after desorb, free purity of chlorine gas feeding reaches 98%, and the absorption alkali lye selected is the NaOH solution of 8%, makes liquor natrii hypochloritis; Absorb saturated after solvent C desorption temperature be 60 DEG C, adopt falling liquid film water to absorb the hydrochloric acid making 31%, its quality meet GB320 ?1993 technical requirements.Exhaust emissions after treatment meets " discharge standard of air pollutants " (GB16297 ?1996) secondary standard.
Embodiment 4
Process is containing chlorine Bian, chlorine and hydrogen chloride mix waste gas according to the method described above.The main device that the present embodiment adopts comprises: Bian chlorine spray absorber, chlorine spray absorber, hydrochloric acid spray absorber, in-built polypropylene (PP), sprinkle density is respectively 5m
3/ (m
2, h), 7.5m
3/ (m
2, h), 7m
3/ (m
2, h).
Containing consisting of of chlorine Bian, chlorine and hydrogen chloride mix waste gas: monochlor(in)ate benzyl 0.5%(mass fraction), benzyl dichloride 5%(mass fraction), chlorine 15%(mass fraction), hydrogen chloride 79.5%(mass fraction).
Solvent for use A is pertroleum wax, and its spray temperature is 45 DEG C; Solvent B is carbon tetrachloride; Solvent C is trimethyl phosphate.
Absorb saturated after solvent orange 2 A desorb in rectifying column, do not get 180 DEG C and 200 DEG C of cuts, obtaining product purity is respectively the monochlor(in)ate Bian of 98%, the dichloride Bian of 97%, can reuse and production; Absorb saturated after solvent B desorption temperature be 60 DEG C, after desorb, free purity of chlorine gas feeding reaches 99%, and the absorption alkali lye selected is the NaOH solution of 15%, makes liquor natrii hypochloritis; Absorb saturated after solvent C desorption temperature be 70 DEG C, adopt falling liquid film water to absorb the hydrochloric acid making 31%, its quality meet GB320 ?1993 technical requirements.Exhaust emissions after treatment meets " discharge standard of air pollutants " (GB16297 ?1996) secondary standard.
Embodiment 5
Process is containing chlorine Bian, chlorine and hydrogen chloride mix waste gas according to the method described above.The main device that the present embodiment adopts comprises: Bian chlorine spray absorber, chlorine spray absorber, hydrochloric acid spray absorber, be stainless steel packed tower, in-built ceramic packing, sprinkle density is respectively 6m
3/ (m
2, h), 5m
3/ (m
2, h), 5.5m
3/ (m
2, h).
Containing consisting of of chlorine Bian, chlorine and hydrogen chloride mix waste gas: monochlor(in)ate benzyl 4%(mass fraction), benzyl dichloride 18%(mass fraction), chlorine 35%(mass fraction), hydrogen chloride 46.5%(mass fraction).
Solvent for use A is sulfolane, and its spray temperature is 30 DEG C; Solvent B is n-dodecane; Solvent C is n-butanol.
Absorb saturated after solvent orange 2 A desorb in rectifying column, do not get 185 DEG C and 210 DEG C of cuts, obtaining product purity is respectively the monochlor(in)ate Bian of 95%, the dichloride Bian of 98%, can reuse and production; Absorb saturated after solvent B desorption temperature be 80 DEG C, after desorb, free purity of chlorine gas feeding reaches 99%, and the absorption alkali lye selected is the NaOH solution of 10%, makes liquor natrii hypochloritis; Absorb saturated after solvent C desorption temperature be 60 DEG C, adopt falling liquid film water to absorb the hydrochloric acid making 31%, its quality meet GB320 ?1993 technical requirements.Exhaust emissions after treatment meets " discharge standard of air pollutants " (GB16297 ?1996) secondary standard.
Claims (7)
1. the processing method containing chlorine Bian, chlorine and hydrogen chloride mix waste gas, is characterized in that the method comprises the following steps:
(1) be the spray absorber of absorbent by described to pass into solvent orange 2 A containing chlorine Bian, chlorine and hydrogen chloride mix waste gas, organic component chlorine Bian in mix waste gas is absorbed in the liquid phase, be separated with chlorine with the inorganic component hydrogen chloride of gas phase, absorb saturated after solvent orange 2 A again through desorb obtain be separated chlorine Bian;
(2) spray absorber that to pass into solvent B by remaining inorganic mix waste gas be absorbent, by the chlorine absorption in remaining inorganic mix waste gas in the liquid phase, with the HCl separation of gas phase, absorb saturated after solvent B obtain the free chlorine of purifying again through desorb;
(3) remaining waste gas passes into solvent C is the spray absorber of absorbent, by absorbing hydrogen chloride gas in liquid phase, absorb saturated after solvent C obtain the hydrogen chloride gas of purifying again through desorb;
Wherein, described solvent orange 2 A be selected from the sub-phosphoric triamide HMPT of hexamethyl, the sub-phosphoric triamide HEPT of Hexaethyl, sulfolane, pertroleum wax any one; Solvent B be selected from carbon tetrachloride, silicon tetrachloride, n-dodecane any one; Solvent C be selected from n-butanol, glycerine, diethyl carbonate, trimethyl phosphate any one.
2. method according to claim 1, is characterized in that described consisting of monochlor(in)ate benzyl 0.5 ~ 4wt%, benzyl dichloride 5 ~ 18 wt %, chlorine 15 ~ 35 wt %, hydrogen chloride 43 ~ 79.5wt% containing chlorine Bian, chlorine and hydrogen chloride mix waste gas.
3. method according to claim 1, is characterized in that described spray absorber is packed tower, and filler material is any one in pottery, polypropylene PP, stainless steel; Sprinkle density scope is 4 ~ 8m
3/ (m
2, h).
4. method according to claim 1, is characterized in that the spray temperature of solvent orange 2 A is 30 ~ 50 DEG C.
5. method according to claim 1, it is characterized in that absorb saturated after solvent orange 2 A heating desorption go out chlorine Bian Posterior circle use, wherein, monochlor(in)ate Bian desorption temperature is 175 ~ 185 DEG C, and dichloride Bian desorption temperature is 200 ~ 210 DEG C.
6. method according to claim 1, it is characterized in that absorb saturated after solvent B heating desorption go out chlorine Posterior circle use, desorption temperature is 50 ~ 80 DEG C; The chlorine obtained absorbs through the NaOH aqueous solution that concentration is 6 ~ 15wt% prepares clorox.
7. method according to claim 1, it is characterized in that absorbing saturated after solvent C heating desorption go out hydrogen chloride, desorption temperature is 50 ~ 70 DEG C, and the hydrogen chloride of gained absorbs through falling liquid film water makes hydrochloric acid.
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| CN104478151B (en) * | 2014-12-18 | 2016-08-24 | 重庆海洲化学品有限公司 | Environment-friendly treatment method containing Caustic soda sodium hypochlorite waste liquid |
| CN106925079A (en) * | 2017-03-17 | 2017-07-07 | 烟台国邦化工机械科技有限公司 | One kind reclaims HCl and Cl2Apparatus and method |
| CN111111411A (en) * | 2019-12-31 | 2020-05-08 | 南京工大环境科技有限公司 | Treatment method of chlorotoluene rectification tail gas |
| CN111333032A (en) * | 2020-03-12 | 2020-06-26 | 江苏维尤纳特精细化工有限公司 | Environment-friendly recovery method of hydrogen chloride tail gas in chlorothalonil production |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3641049B2 (en) * | 1995-12-20 | 2005-04-20 | 鶴見曹達株式会社 | Production method of high purity hydrochloric acid |
| CN101185796A (en) * | 2007-12-11 | 2008-05-28 | 华东理工大学 | Chlorination aromatic hydrocarbon waste gases catalytic purification method |
| JP2009274906A (en) * | 2008-05-14 | 2009-11-26 | Jfe Steel Corp | Hydrochloric acid recovering apparatus and method for recovering hydrochloric acid from waste hydrochloric acid solution |
| CN202061528U (en) * | 2011-05-19 | 2011-12-07 | 蒋超 | Hydrogen chloride tail gas recovery device |
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2014
- 2014-02-19 CN CN201410056418.4A patent/CN103877833B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3641049B2 (en) * | 1995-12-20 | 2005-04-20 | 鶴見曹達株式会社 | Production method of high purity hydrochloric acid |
| CN101185796A (en) * | 2007-12-11 | 2008-05-28 | 华东理工大学 | Chlorination aromatic hydrocarbon waste gases catalytic purification method |
| JP2009274906A (en) * | 2008-05-14 | 2009-11-26 | Jfe Steel Corp | Hydrochloric acid recovering apparatus and method for recovering hydrochloric acid from waste hydrochloric acid solution |
| CN202061528U (en) * | 2011-05-19 | 2011-12-07 | 蒋超 | Hydrogen chloride tail gas recovery device |
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Effective date of registration: 20210218 Address after: 210043 Building 8, Zhicheng Park, 6 Zhida Road, Jiangbei new district, Nanjing City, Jiangsu Province Patentee after: NANJING GONGDA ENVIRONMENT TECHNOLOGY Co.,Ltd. Address before: No.30 Puzhu South Road, Pukou District, Nanjing City, Jiangsu Province 211816 Pukou campus of Nanjing University of Technology Patentee before: NANJING TECH University Patentee before: NANJING GONGDA ENVIRONMENT TECHNOLOGY Co.,Ltd. |