CN101274195B - Method for removing residual chlorine gas in tail gas in production processes of chloroacetic acid - Google Patents
Method for removing residual chlorine gas in tail gas in production processes of chloroacetic acid Download PDFInfo
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- CN101274195B CN101274195B CN2007100601291A CN200710060129A CN101274195B CN 101274195 B CN101274195 B CN 101274195B CN 2007100601291 A CN2007100601291 A CN 2007100601291A CN 200710060129 A CN200710060129 A CN 200710060129A CN 101274195 B CN101274195 B CN 101274195B
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Abstract
The invention discloses a method for removing residual chlorine in the tail gas during the production process of chloroactic acid. A device adopted by the method comprises a reaction absorption tower; the process of the method is that the tail gas generated in a chlorinating reactor enters the reaction absorption tower from the bottom of the absorption tower through a condenser; acetic acid which is one of the chlorinating reaction raw materials is used as absorbent which enters the absorption tower from the top part of the reaction absorption tower; the tail gas and the absorbent carry out a reflux contact reaction in the tower and the operation is circularly carried out; when the chlorine content in the tail gas achieves the standard, the tail gas is sent to a saturated hydrochloride solution washing tower; the absorbing solution at the bottom of the saturated hydrochloride solution washing tower is used as the raw materials in the next chlorinating reaction. The method of the invention has simple devices, mild operation conditions, requires no desorption operation and disposal of absorbent, thus saving the equipment expense and operation expense, also has high utilization ratio of chlorine resource and is beneficial for environmental protection.
Description
Technical field
The present invention relates to remove in a kind of production processes of chloroacetic acid the method for remaining chlorine in the tail gas, particularly a kind of in the organic chloride production process vent gas treatment technology.
Background technology
In many organic chloride processes, relate to and directly in material, feed the step that chlorine reacts, contain a large amount of byproduct hydrogen chloride gas and the unreacted chlorine of part in the tail gas that this step produces.The adiabatic absorption process of domestic most employing single hop is made with extra care hydrogen chloride and is converted into hydrochloric acid.But the chlorine in the mist enters color and concentration that absorption system will influence hydrochloric acid, and the hydrochloric acid product quality is not high, can only be used for pickling of metal, and added value is very low.Wherein the unreacted chlorine of part can not directly discharge, and also needs to use in the alkali lye and recovery, has caused waste.So, need before entering last absorption, handle tail gas, remove the chlorine in the tail gas, to improve the quality of by-product hydrochloric acid, the wasting of resources and the environmental pollution of avoiding chlorine to overflow and cause.Processing method commonly used at present has condensation method, solvent absorption, firing method etc.
United States Patent (USP) (US5126119,1992) discloses a kind of by tail gas is burnt to remove the chlorine in the hydrogen chloride with hydrogen-containing fuel gas and oxygen, and water absorbs the method that flue gas obtains hydrochloric acid again.
United States Patent (USP) (US5861049,1999) discloses a kind of method that reclaims chlorine with carbon tetrachloride from the tail gas that contains chlorine.Depress absorption chlorine adding, obtain chlorine and reenter reactor through resolving, carbon tetrachloride can be recycled.
Patent 00510025910.6 has been announced a kind of method of utilizing the solvent pairs absorption process to separate the mix waste gas that produces in the purification aromatic hydrocarbons chlorination process, solvent orange 2 A absorbs chlorine, solvent B lyosoption A does not enter into the water absorption thereby acquisition does not contain the hydrogen chloride gas of chlorine, obtains high-quality hydrochloric acid.Taking off chlorine after the suction returns chlorination system and recycles; Solvent can separate through rectifying, can be recycled.
Above method all exists technological process long, and the equipment complexity will be controlled the temperature and pressure of absorption/parse operation, and investment is too high concerning general small-sized chloridizing unit.
Summary of the invention
The object of the present invention is to provide the method that removes remaining chlorine in the tail gas in a kind of production processes of chloroacetic acid, it is simple that this method has process, the characteristics that the chlorine in the tail gas is fully utilized.
The present invention is realized by following technical proposals: the method that removes remaining chlorine in the tail gas in a kind of production processes of chloroacetic acid, the device that this method adopts comprises the reaction absorption tower, is disposed with liquid distribution trough, filler, gatherer in the reaction absorption tower to the bottom from the top.Realization removes that the process feature of remaining chlorine is in the tail gas:
The tail gas that produces from the chlorination reaction still enters the reaction absorption tower through condenser by the bottom, absorption tower, with the acetic acid of one of chlorination reaction raw material as absorbent, this absorbent enters the absorption tower from the top on reaction absorption tower, tail gas and absorbent carry out counter current contacting reaction in tower, carry out cycling normal pressure and 50 ℃～70 ℃.After chlorine content in the tail gas was up to standard, tail gas was sent into saturated salt acid solution scrubbing tower, and the absorption liquid that comes out at the bottom of the tower is as the raw material of next group chlorination reaction.
The present invention compared with prior art has following characteristics: operative installations is simple, operating condition is gentle, only need a reaction absorption tower, less demanding to absorbing temperature and pressure, do not need to take off and inhale operation and, saved installation cost and operating cost the processing of absorbent.The chlorine resource utilization is high and help environmental protection.
Description of drawings
Fig. 1 is for realizing process flow diagram of the present invention.
Among the figure: 1. chlorination reaction still, 2. condenser, 3. reaction absorption tower.
The specific embodiment
Embodiment
For the present invention is described better, now the present invention is described further for following embodiment, but embodiment is not a limitation of the present invention.
Tail gas comes out from chlorination reaction still 1 top, enters from reaction 3 bottoms, absorption tower through condenser 2, and this reaction absorption tower 3 is the enamel packed tower of DN600 * 8000, filler gripper shoe, liquid distribution trough and the liquid header of built-in polytetrafluoroethylene (PTFE) material.Filler is a 500Y ceramic wafer ripple packing.The top on autoreaction absorption tower 3, acetic acid is with 5m
3The flow velocity of/h drenches down along filling surface through the liquid distribution trough back that evenly distributes, and with the tail gas counter current contacting that rises, free chlorine and acetic acid in the tail gas react, the generation monoxone.Absorption liquid after reaction absorbs is recycled to cat head by pump and carries out the circular response absorption.The tail gas that contains low content chlorine (＜1%) after reaction absorbs is gone into next vent gas treatment workshop section from reaction absorption tower 3 jackings.Circulate after 12 hours, the absorption liquid that reaction 3 bottoms, absorption tower obtain enters as the raw material of next group chlorination reaction that chlorination reaction still 1 carries out degree of depth chlorination in the workshop.
Producing monoxone with certain factory is example, and the present invention is further specified.In acetic acid chlorination synthesis of chloroacetic acid process, the mist that contains chlorine and hydrogen chloride from chlorination reaction still 1 comes out consists of: hydrogen chloride 85%, chlorine 10%, other low-boiling-point substances 5% (being volume fraction) are through entering into reaction absorption tower 3 after the condenser 2.In reaction absorption tower 3, serve as to react absorbent to add from top of tower with acetic acid (containing the catalyst acetic acid acid anhydride), react absorption normal pressure and 50 ℃～70 ℃, be free chlorine and acetic acid generation substitution reaction generate monoxone and hydrogen chloride gas, thereby realized separating of the chlorine in the tail gas and hydrogen chloride gas.After absorption liquid (being to contain the chloroacetic reactant liquor of part behind the prechlorination) circulation a period of time of coming out in reaction 3 bottoms, absorption tower, as the raw material of the next group charging of chlorination reaction still 1.Reaction absorption tower 3 top tail gas discharged contain chlorine and are lower than 1% (volume fraction), and this tail gas enters saturated hydrogen chloride scrubbing tower and further removes impurity such as acetic acid, and the hydrogen chloride gas after making with extra care enters hydrochloric acid absorption tower.Gained technical hydrochloric acid color and luster and concentration all meet relevant criterion, and discharging tail gas meets standard.
Before this reaction absorption tower was not set, tail gas directly entered saturated hydrogen chloride scrubbing tower and water absorption tower after condensation, prepared hydrochloric acid color jaundice, and the hydrochloric acid quality is not high, can only be used for acid pickling and rust removing, and the alkali consumption of improvement tail gas chlorine is big.
In addition, the present invention also is applicable in other chlorination reaction process such as preparing chloracetyl chloride and removes remaining chlorine in the tail gas.
Producing chloracetyl chloride with certain factory is example, and the present invention is further specified.The mist that contains chlorine and hydrogen chloride that the synthetic chloracetyl chloride process of monoxone chlorination produces consists of: hydrogen chloride 80%, chlorine 16%, other low-boiling-point substances 4% (being volume content).In chlorine gas absorption tower be with the monoxone absorbent under normal pressure, 50 ℃～70 ℃ are reacted absorption.The chloride tolerance of cat head tail gas discharged enters saturated hydrogen chloride scrubbing tower afterwards and further deviates from impurity less than 2% (volume content), and the tail gas that removes behind the chlorine enters hydrochloric acid absorption tower.Gained technical hydrochloric acid color and luster and concentration all meet relevant criterion, and discharging tail gas meets standard.Absorption liquid behind the prechlorination is as the next group reaction feed of chlorination reaction still.
Claims (1)
1. remove the method for remaining chlorine in the tail gas in the production processes of chloroacetic acid, the device that this method adopts comprises the reaction absorption tower, reaction sets gradually liquid distribution trough from the top to the bottom in the absorption tower, filler, gatherer, realization removes remaining chlorine in the tail gas, it is characterized in that comprising following process: the tail gas that produces from the chlorination reaction still enters this tower through condenser by bottom, reaction absorption tower, with the acetic acid of one of chlorination reaction raw material as absorbent, this absorbent enters this tower from the top on reaction absorption tower, tail gas and absorbent carry out the counter current contacting reaction in the reaction absorption tower, carry out cycling normal pressure and 50 ℃～70 ℃, chlorine content tail gas up to standard after reaction absorbs, this tail gas is sent into saturated salt acid solution scrubbing tower, and the absorption liquid at the bottom of the reaction absorption tower is as the raw material of next group chlorination reaction.
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| CN2007100601291A CN101274195B (en) | 2007-12-24 | 2007-12-24 | Method for removing residual chlorine gas in tail gas in production processes of chloroacetic acid |
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| CN2007100601291A CN101274195B (en) | 2007-12-24 | 2007-12-24 | Method for removing residual chlorine gas in tail gas in production processes of chloroacetic acid |
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| CN101274195A CN101274195A (en) | 2008-10-01 |
| CN101274195B true CN101274195B (en) | 2010-06-30 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102675158B (en) * | 2012-05-10 | 2014-12-03 | 杭州海虹精细化工有限公司 | Method for producing ADC foaming agent by using chlorine gas-oxidized HDCA (biurea) in saturated hydrochloric acid solution |
| CN102816045B (en) * | 2012-09-05 | 2015-06-03 | 河北科技大学 | Method for synthesizing chloromethane by tail gas generated during chloroacetic acid production |
| CN105480946A (en) * | 2014-09-19 | 2016-04-13 | 上海氯碱化工股份有限公司 | Recycling method for oxygen in process of preparing chlorine from hydrogen chloride |
| CN107789966A (en) * | 2017-11-21 | 2018-03-13 | 南京钟腾化工有限公司 | The recovery system and method for tail gas in a kind of chlorination toluene production |
| CN108100996A (en) * | 2018-02-13 | 2018-06-01 | 唐山三友氯碱有限责任公司 | The processing system and method for by-product HCl in continuity method production processes of chloroacetic acid |
| CN108671747A (en) * | 2018-05-18 | 2018-10-19 | 苏州朗道节能技术有限公司 | A kind of method and system discharging recycling purification helium in exhaust gas from preform sintering furnace |
| CN108926965A (en) * | 2018-06-27 | 2018-12-04 | 青岛科技大学 | A kind of tail gas separation method of Mannheim proeess production potassium sulfate |
| CN109529545A (en) * | 2018-12-12 | 2019-03-29 | 安徽金禾实业股份有限公司 | A kind of methyl acetoacetate exhaust gas treating method and device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5861049A (en) * | 1997-01-24 | 1999-01-19 | Membrane Technology And Research, Inc. | Chlorine separation process combining condensation, membrane separation and flash evaporation |
| 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 |
| CN1865127A (en) * | 2005-05-18 | 2006-11-22 | 浙江巍华化工有限公司 | Separation and purification method of mixed waste gas containing chlorine and hydrogen chloride |
-
2007
- 2007-12-24 CN CN2007100601291A patent/CN101274195B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5861049A (en) * | 1997-01-24 | 1999-01-19 | Membrane Technology And Research, Inc. | Chlorine separation process combining condensation, membrane separation and flash evaporation |
| 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 |
| CN1865127A (en) * | 2005-05-18 | 2006-11-22 | 浙江巍华化工有限公司 | Separation and purification method of mixed waste gas containing chlorine and hydrogen chloride |
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