CN101101124A - Method for treating organic halides by plasma combustion - Google Patents

Method for treating organic halides by plasma combustion Download PDF

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Publication number
CN101101124A
CN101101124A CNA2006100895958A CN200610089595A CN101101124A CN 101101124 A CN101101124 A CN 101101124A CN A2006100895958 A CNA2006100895958 A CN A2006100895958A CN 200610089595 A CN200610089595 A CN 200610089595A CN 101101124 A CN101101124 A CN 101101124A
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plasma
incinerator
temperature
raffinate
chilling
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CN100504170C (en
Inventor
樊有三
张在利
曾子敏
刘忠文
曾本忠
喻崇权
徐美燚
吕太恒
李剑
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Zhonghao Chenguang Research Institute of Chemical Industry Co Ltd
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Zhonghao Chenguang Research Institute of Chemical Industry Co Ltd
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Abstract

The invention relates to a method of plasma burning down processing organic halide, including through the pipeline puts the boil residue into the horizontal-type structure incinerator to pre-heater by the preheating device, and enters to the electric arc area of the incinerator plasma with the oxidized medium air which preheated, with the decomposition oxidation, uses the industry water or the recycle acid to spray the sharp quenching, the recycle acid closed circuit absorbs, after the first-level acid recovery tower, the second-level acid recovery tower, alkali neutralizer, directs to the chimney and lets to the upper air. The merits of the method are that burning temperature is high; the process load is big in the unit interval, the complete combustion full, eliminated the toxic substance which possibly occurred to release in the processing system, the low maintenance, the low energy consumption, and has no two pollution, the long life.

Description

A kind of method for treating organic halides by plasma combustion
Technical field
The present invention relates to handle the method for organohalogen compounds, specifically, relate to a kind of method for treating organic halides by plasma combustion.
Background technology
In the organic fluorine material industrial production, tetrafluoroethene and hexafluoropropene are the important source material of producing fluororesin, fluorubber.When producing tetrafluoroethene and hexafluoropropene, all generate a certain amount of, hypertoxic perfluoroisobutylene (PFIB).Perfluoroisobutylene is a kind of extremely organofluorine compound of poison, its toxicity is than surplus the phosgene big ten times, and the half lethal concentration LC50 that its acute suction is poisoned is 0.5ppm, and the toxic action band is extremely narrow, toxicity incubation period is by soakage and physique difference and difference is arranged, incubation period by 3~5 days up to 1~2 week.Because toxicity is very big, organic fluorine residual liquid definitely can not arbitrarily discharge, and condition of storage harshness, expense height, and storage for a long time is in case to leak consequence hardly imaginable.International the Organization for the Prohibition of Chemical Weapons (OPCW) has classified PFIB as subordinate list IIA compounds, and its production capacity, output and consumption figure must be declared to government by relevant manufacturing enterprise, and accepts the production facility verification of OPCW.Zhong Hao Chenguang Research Institute of Chemical Industry accepts and has passed through the inspection of OPCW in October, 1997, continuous 2 years of in September, 1998.
The producer of domestic production tetrafluoroethene and perfluoropropene is except that Zhong Hao Chenguang Research Institute of Chemical Industry, also have Shanghai three to like richness, Jiangsu plum orchid, Zhejiang three rings, hugeization of Zhejiang etc., handling raffinate at present all is to adopt the method for burning basically, mix vaporific raffinate with natural gas or coal gas etc. and burning more than 1150 ℃, again with gas high altitude discharge after absorbing neutralization.For a long time, the processing to raffinate is one of difficult problem of Organic fluoride chemical industry always.Though domestic research to the raffinate comprehensive utilization is more, most of producers can only take the way of general high temperature incineration to handle at present.
May cause occurring extrahazardous secondary compound with traditional firing method Technology for Heating Processing, as two oxines (two (oxine)), two fluorophosgenes, chlorine phosgene, octafluoroisobutene, benzene pyrene or the like.Could thermal cracking in the time of will reaching extra high temperature in addition they.As just generate when 750~900 ℃ of temperature 2,3,7,8-Tetrachlorodiphenyl-n-two oxines will destroy them and need reach 1200~1400 ℃, just its concentration just drops to safety value when temperature reaches 1350 ℃.
(GB18484-2001) stipulate that incineration temperature requires 〉=1200 ℃ according to " dangerous waste incineration pollution control criterion ", the time of staying 〉=2 second.In fact adopt burning method to be difficult to reach the time of staying of 1200 ℃ and 2 seconds.At present, domestic traditional incinerating method can not reach 1500 ℃.
Hazardous waste can be broken down into single ion and atomic structure rapidly in the plasma heating furnace of energy-intensive, as organic matter being decomposed into element and CO equimolecular structures such as carbon, hydrogen, chlorine and silicon.Metal is molten state or distillation is gaseous state.Plasma is that the plasmatorch or the beam-plasma that utilize between electrode to be produced produce high temperature, produce plasmatorch or beam-plasma and can use methods such as interchange, direct current, power frequency and high frequency, arc (bundle) heart temperature can reach more than 7000 ℃, but and moment realization high temperature.
For organic halogen compound effective and that harmless is handled in the raffinate must make temperature be not less than 1400 ℃, and the prior heat treatment method of using the combustion furnace of fuel gas is difficult to the requirement that reaches such, plasma method is easy to reach 1500 ℃, in 1500 ℃, organic matter can thoroughly decompose at 15 milliseconds.The burning disposal operating temperature is at 1200 ℃~2000 ℃, and residence time of material can guarantee thorough decomposition at 0.5~100 millisecond in this temperature.They are carried out the most promising of thermal decomposition is plasma chemistry technology.
Owing to adopt plasma method, be easy to moment to obtain ultra-high temperature.Can be in 850 ℃ to 3000 ℃ scope regulate arbitrarily, and domestic incinerator generally is difficult to reach 1200 ℃, and toxic organics is when 1500 ℃ of temperature, the longest cracking fully in 15 milliseconds, general danger wastes just can be finished at several milliseconds.
Chinese patent CN1185440C discloses a kind of method for treating organic halides by plasma combustion and commercial plant.Still there is following defective in the method for this patent disclosure:
1. there is easy coking in disclosed pre-thermal recovery electric heater heating in this patent background technology, cleans difficulty, the defective that energy consumption increases;
2. the disclosed incinerator of this patent is a vertical heater, plasma generator is installed in stove top, it is not very convenient exist plasma generator to install changing, and easily by the defective of hydrogen halide corrosion in the waste gas in the incinerator and high temperature ablation, if it is and the plasma device is installed in reactor lower part, blocked easily.
3. this patented method vent gas treatment adopts aqueous slkali spray chilling, has a large amount of fluorine containing waste water waste liquids to produce, and need send sewage-treatment plant to handle.
Summary of the invention
Purpose of the present invention aims to provide a kind of method for treating organic halides by plasma combustion.
To achieve these goals, the present invention relates to a kind of method for treating organic halides by plasma combustion, may further comprise the steps: the height raffinate that boils is delivered to raffinate metering storage tank through pipeline, keeping metering storage tank internal pressure is 0.2~0.3MPa, flow out with 10~100kg/h flow, being preheated to temperature is 50~300 ℃, and high purity nitrogen enters plasma generator and produces high-temperature plasma gas, plasma arc district temperature is 4500~5000 ℃, and the flow of oxide isolation air is 15~250Nm 3/ h, the height after the intensification preheating after the preheating raffinate that boils enters incinerator plasma arc district, 1400~1600 ℃ of cracking reaction temperature, 5~10 seconds pyrolysis oxidizations when reaction is empty, in and chilling, after the vent gas treatment behind the chilling, cause the chimney high altitude discharge.
Represent when reaction is empty that certain gas volume is by the time of incinerator needs under the standard state.
Wherein: when height boils raffinate when having solid or thickness sediment, regularly clean, during cleaning, industrial chloroform is pressed in the measuring tank, place after 2 hours, deliver to DC arc plasma burning zone burning disposal with nitrogen with chloroform.
The pre-thermal recovery incinerator of organohalogen compounds waste heat carries out, thereby the coking that is caused can avoid using the electric heater heating time is cleaned problems such as difficulty, and improved rate of energy; In operation, incinerator is heated to feed temperature earlier, the heat radiation of incinerator own can be used for preheating height boil raffinate and oxide isolation air, in addition, incinerator in burning process in the stove temperature very high, 1400~1600 ℃ of cracking temperatures, the heat radiation of incinerator own also are used for preheating height boil raffinate and oxide isolation air.
Negative pressure 20~80 millimeters of water in the incinerator less than extraneous normal atmosphere (An), have been eliminated the contingent noxious material of treatment system and have been leaked during pyrolysis oxidization, guarantee to handle safety.
In and chilling adopt industry water or recycle acid spray chilling, the recycle acid closed cycle absorbs, behind primary acids recovery tower, secondary acid recovery tower, caustic neutralizer column, cause the chimney high altitude discharge, handle back recovery concentration 30~40% halogen acids and sell outward, do not have discharging of waste liquid as commodity.
Described incinerator is preferably horizontal chamber furnace (oven) structure incinerator, and horizontal chamber furnace (oven) is optimized structure to design and can be protected plasma generator not by hydrogen halide corrosion in the waste gas in the stove and high temperature ablation, makes things convenient for the quick replacing of plasma generator simultaneously.
Described incinerator is preferably horizontal chamber furnace (oven) structure incinerator, specifically is configured to the disclosed commercial plant of Chinese patent CN1185440C, but profile is revised as horizontal.Plasma generator is installed in the incinerator end face, makes plasma generator easier for installation, and is difficult for by hydrogen halide corrosion in the waste gas in the incinerator and high temperature ablation.
Method for treating organic halides by plasma combustion of the present invention has that incineration temperature height, unit interval treating capacity are big, burning cmpletely, eliminated that contingent noxious material leaks in the treatment system, low maintenance, low energy consumption, non-secondary pollution, long advantage of life-span.
Description of drawings
Fig. 1 plasma burning disposal organic fluorine residual liquid general flow chart.
The specific embodiment
Following examples are used to illustrate the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
To the boil processing of raffinate of hexafluoropropene (HFP) process units height
The height of hexafluoropropene (HFP) the process units raffinate that boils is delivered to raffinate metering storage tank through pipeline, entering the incinerator preheater with the 10kg/h flow, to be preheated to temperature be 10 ℃, high purity nitrogen enters plasma generator and produces high-temperature plasma gas, plasma-arc district temperature is 4500~5000 ℃, and the flow of oxide isolation air is 15Nm 3/ h, the height after oxidation air and the preheating raffinate that boils enters reactor plasma arc district, 1400 ℃ of cracking reaction temperature, when reaction is empty 5 seconds, negative pressure 20 millimeters of water in the incinerator, oxicracking.After the pyrolysis product of gained sprays chilling with hydrofluoric acid solution, hydrofluoric acid spray chilling, the hydrofluoric acid closed cycle absorbs, in primary acids recovery tower, secondary acid recovery tower, the alkali cleaning of caustic neutralizer column limewash and after cause the chimney high altitude discharge, handle back recovery concentration 30~40% halogen acids and sell outward, do not have discharging of waste liquid as commodity.
Embodiment 2
To the boil processing of raffinate of hexafluoropropene (HFP) process units height
The height of hexafluoropropene (HFP) the process units raffinate that boils is delivered to raffinate metering storage tank through pipeline, entering the incinerator preheater with the 100kg/h flow, to be preheated to temperature be 300 ℃, high purity nitrogen enters plasma generator and produces high-temperature plasma gas, plasma-arc district temperature is 4500~5000 ℃, and the flow of oxide isolation air is 250Nm 3/ h, the height after oxidation air and the preheating raffinate that boils enters reactor plasma arc district, 1600 ℃ of cracking reaction temperature, when reaction is empty 10 seconds, negative pressure 80 millimeters of water in the incinerator, oxicracking.After the pyrolysis product of gained sprays chilling with hydrofluoric acid solution, hydrofluoric acid spray chilling, the hydrofluoric acid closed cycle absorbs, in primary acids recovery tower, secondary acid recovery tower, the alkali cleaning of caustic neutralizer column limewash and after cause the chimney high altitude discharge, handle back recovery concentration 30~40% halogen acids and sell outward, do not have discharging of waste liquid as commodity.
Embodiment 3
The boil processing of raffinate of Paratetrafluoroethylene (TFE) process units height
The height of tetrafluoroethene (TFE) the process units raffinate that boils is delivered to raffinate metering storage tank through pipeline, entering the incinerator preheater with the 55kg/h flow, to be preheated to temperature be 175 ℃, high purity nitrogen enters plasma generator and produces high-temperature plasma gas, plasma-arc district temperature is 4500~5000 ℃, and the flow of oxide isolation air is 110Nm 3/ h, the height after oxidation air and the preheating raffinate that boils enters reactor plasma arc district, 1500 ℃ of cracking reaction temperature, when reaction is empty 7 seconds, negative pressure 50 millimeters of water in the incinerator, oxicracking.After the pyrolysis product of gained sprays chilling with hydrofluoric acid solution, hydrofluoric acid spray chilling, the hydrofluoric acid closed cycle absorbs, in primary acids recovery tower, secondary acid recovery tower, the alkali cleaning of caustic neutralizer column limewash and after cause the chimney high altitude discharge, handle back recovery concentration 30~40% halogen acids and sell outward, do not have discharging of waste liquid as commodity.

Claims (3)

1, a kind of method for treating organic halides by plasma combustion, comprise the steps: the height raffinate that boils is delivered to raffinate metering storage tank through pipeline, keeping metering storage tank internal pressure is 0.2~0.3MPa, flow out with 10~100kg/h flow, being preheated to temperature is 50~300 ℃, high purity nitrogen enters plasma generator and produces high-temperature plasma gas, and plasma arc district temperature is 4500~5000 ℃, and the flow of oxide isolation air is 15~250Nm 3/ h, the height after the intensification preheating after the preheating raffinate that boils enters incinerator plasma arc district, 1400~1600 ℃ of cracking reaction temperature, 5~10 seconds pyrolysis oxidizations when reaction is empty, in and chilling, after the vent gas treatment behind the chilling, cause the chimney high altitude discharge, it is characterized in that:
(1) the pre-thermal recovery incinerator of organohalogen compounds waste heat carries out;
(2) negative pressure 20~80 millimeters of water in incinerator during pyrolysis oxidization;
(3) adopt industry water or recycle acid spray chilling with chilling in, the recycle acid closed cycle absorbs, and causes the chimney high altitude discharge behind primary acids recovery tower, secondary acid recovery tower, caustic neutralizer column.
2, a kind of method for treating organic halides by plasma combustion as claimed in claim 1 is characterized in that described incinerator is a horizontal chamber furnace (oven) structure incinerator.
3, a kind of method for treating organic halides by plasma combustion as claimed in claim 1 is characterized in that described plasma generator is installed in the incinerator end face.
CNB2006100895958A 2006-07-05 2006-07-05 Method for treating organic halides by plasma combustion Active CN100504170C (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101659399B (en) * 2009-09-22 2011-06-22 中昊晨光化工研究院 Method for preparing anhydrous hydrofluoric acid
CN102337157A (en) * 2010-07-20 2012-02-01 北京光耀电力设备股份有限公司 Plasma super-turbulence pyrolysis gasifier
CN102679374A (en) * 2012-05-10 2012-09-19 中昊晨光化工研究院 Device and method for burning residual organic fluorine liquid by using plasmas
CN106745417A (en) * 2016-12-13 2017-05-31 江苏帕斯玛环境科技有限公司 Liquid waste treatment system
CN109798531A (en) * 2017-11-17 2019-05-24 中昊晨光化工研究院有限公司 A kind of device and method of plasma cracking processing organic fluorine residual liquid

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
HU184389B (en) * 1981-02-27 1984-08-28 Villamos Ipari Kutato Intezet Method and apparatus for destroying wastes by using of plasmatechnic
US4909164A (en) * 1988-04-21 1990-03-20 Shohet J Leon Hazardous waste incinerator using cyclotron resonance plasma

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101659399B (en) * 2009-09-22 2011-06-22 中昊晨光化工研究院 Method for preparing anhydrous hydrofluoric acid
CN102337157A (en) * 2010-07-20 2012-02-01 北京光耀电力设备股份有限公司 Plasma super-turbulence pyrolysis gasifier
CN102337157B (en) * 2010-07-20 2013-09-18 北京光耀能源技术股份有限公司 Plasma super-turbulence pyrolysis gasifier
CN102679374A (en) * 2012-05-10 2012-09-19 中昊晨光化工研究院 Device and method for burning residual organic fluorine liquid by using plasmas
CN102679374B (en) * 2012-05-10 2014-12-03 中昊晨光化工研究院 Device and method for burning residual organic fluorine liquid by using plasmas
CN106745417A (en) * 2016-12-13 2017-05-31 江苏帕斯玛环境科技有限公司 Liquid waste treatment system
CN109798531A (en) * 2017-11-17 2019-05-24 中昊晨光化工研究院有限公司 A kind of device and method of plasma cracking processing organic fluorine residual liquid

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Owner name: ZHONGHAO CHENGUANG RESEARCH INSTITUTE OF CHEMICAL

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Address after: 643201 Zigong County, Sichuan Province, Chenguang Road, No. 135, Fushun

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Address before: 643201 science and Technology Planning Department of Chenguang Chenguang Chemical Research Institute, Zigong, Sichuan

Patentee before: Zhonghao Chenguang Chemical Research Inst.