CN1185440C - Method and industrial apparatus for treating organic halides by plasma combustion - Google Patents
Method and industrial apparatus for treating organic halides by plasma combustion Download PDFInfo
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- CN1185440C CN1185440C CN 00128708 CN00128708A CN1185440C CN 1185440 C CN1185440 C CN 1185440C CN 00128708 CN00128708 CN 00128708 CN 00128708 A CN00128708 A CN 00128708A CN 1185440 C CN1185440 C CN 1185440C
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Abstract
The present invention relates to a method and an industrial device for treating organic halides by plasma combustion. The method comprises a plasma arc generating step, a step for preheating and gasifying (atomizing) organic halides, a cracking oxidation step, a neutralizing and quick cooling step, etc. Finally, the organic halides are changed into CO2, hydrogen halide and a small amount of CO, and no poison material and solid particle carbon are generated. The reaction conditions are specifically given by an instruction. The present invention has the advantages of reliable technology, thorough reaction and high work efficiency, and is an ideal environmental protection energy saving method and a device. The present invention is especially suitable for treating halogen containing organic waste gas and waste liquid, such as fluorochlorohudrocarbon, halogen containing residual liquid with a high boiling point, polychlorinated biphenyl, etc.
Description
Technical field
The present invention relates to a kind of plasma burning disposal organohalogen compounds and especially handle fluorochlorohydrocarbon, Halogen height the boil method and the commercial plant of Halogen organic exhaust gas such as raffinate, Polychlorinated biphenyls, waste liquid.
Background technology
Traditional burning process is handled organohalogen compounds can produce new extremely toxic substance, dislikes because of, fluorophosgene, phosgene, perfluoroisobutylene, BaP etc. as two.Therefore, adopting harmless processing method of effective organohalogen compounds and device, is international top-priority ecological, environmental protective problem.
At present, in method (EP469727,1992 of disclosed several plasma burning disposal chemical wastes; US4438076,1984; US4644877,1987; RU2105928,1998) in, Russ P RU2105928 has overcome the deficiency of other several patented methods, get rid of the corrosion of cracking product article on plasma heater electrode, the time of staying that reduces reactor size and work therein, the realization neutralized system is pressed loop work, will not enter sewer with the nertralizer of crossing.
The method of Russ P RU2105928 is:
The Halogen debirs are heated in advance the temperature that is no more than its heat endurance, atomize with thermal oxide medium (as air), mixture is delivered in the plasma jet, carry out cracking here, temperature is no less than 1500 ℃, time of staying 2-50 millisecond, carbon is by complete oxidation in the refuse, halogen is generting element halogen or hydrogen halides then, and then pyrolysis product neutralize with nonexpondable alkali lye, regularly toward wherein add alkali with recover original concentration with remove in the time generation the halogen hydrogen salt.
Preheat temperature should not surpass the thermally-stabilised limit of the refuse of handling, otherwise the result in the cracking of charging system medium and low temperature can form relatively large carbon black and corrosion activity material (F, Cl, HF, HCl and other), this can cause that current cross section and charging system stop work.
Reactor outlet is in that the temperature of cracking product should be less than 1500 ℃ before the chilling, with guarantee in waste gas, there is not fluorophosgene, chlorine phosgene, benzene pyrene, two dislike because of and other extremely toxic substance produce.
Flow-rate ratio when Halogen debirs and thermal oxide medium (air etc.) add reactor is determined by the content that carbon in the refuse is completely oxidized to the carbon dioxide requisite oxygen, to guarantee not having hard carbon to produce, neutralization bases can recycle in loop, regularly add alkali remove in and the salt that generates during hydrogen halides, salt is reused or buries.
The weak point of said method is:
1, use air oxidant, the percentage by weight of oxygen has only 23% in the air, make the refuse complete oxidation, just very big weight flow must be arranged, and heating load is too high, and it is not enough to be completed into the required H atomic quantity of HF and HCl.
2, with general nitrogen during as plasma gas, wherein a small amount of O
2And H
2The existence of O, there is corrosiveness on the heated hot operation of article on plasma electrode surface.
3, difficulty is cleaned in the easy coking of electric heater used of preheating.
4, reactor and electric heater be because temperature is too high, easily with material in the high activity Cl, the F that decomposite react, particularly there is serious corrosion phenomenon in cracking temperature greater than 1500 ℃ reactor.
5, because experiment is to carry out on table apparatus, disposal ability is less, when being applied to industrialized unit, F atom total amount increases more in the refuse, easily form more crystals such as NaF, bad in the alkali lye cyclic process as if salting out technic index control, easily cause spray nozzle clogging.
6, the coolant temperature fluctuation device parts dewfall that induces reaction reduces the electrical insulating property between each point, can burn out the plasma device when serious.
7, the arc initiation device decay is serious, and the starting the arc is difficult.
8, continuous arc current height.
9, electric arc easily drops on the inwall of reactor feed section, causes inwall to burn.
10, the chilling temperature is too high, and acid is difficult to capture fully.
Summary of the invention
Purpose of the present invention is exactly to solve existing weak point in the method for present existing processing organohalogen compounds.For achieving the goal, provide in the invention:
A kind of improved method for treating organic halides by plasma combustion, its reaction equation is as follows:
Fig. 1 is the technological process block-diagram of this method.Halogen organic exhaust gas and oxide isolation enter electric heater 1,3 separately through Flow-rate adjustment, mix vaporization (or atomizing) with the waste liquid that enters electric heater 2 after the intensification preheating, enter reactor 5.Protective gas enters plasma device 4 and produces plasma gas, and plasma gas enters reactor 5 to be mixed with off-gas.In reactor 5, the Halogen debirs burn cracking, and combine the simple material of generation molecular structure with oxidation promoter, in the bottom of reactor 5, through aqueous slkali spray chilling, neutralization, isolate the gas-liquid phase materials by knockout drum 6.Gaseous phase materials is respectively through cooling, separation and the purification of condenser 8, separator 9, clarifier 10, deacidifies to enter atmosphere after up to standard.Liquid phase material then send the fluorine containing waste water treating apparatus to handle through lye tank (vat) 7.
The process conditions that realize above-mentioned technical process are:
1, oxide isolation can be air, nitrogen, hydrogen, methyl alcohol, formaldehyde, water, natural gas, carbon monoxide, carbon dioxide etc., the material that preferably contains hydrogen and oxygen element, for example methyl alcohol, formaldehyde, next is a water, to realize lower oxide isolation flow, make the oxidation of Halogen debirs complete, reduce the existence of highly active halogen element in the course of reaction.
2, use nitrogen and argon gas as the protective gas that produces plasma gas, preferably high purity nitrogen, this has greatly improved the working life of electrode.
3, the plasma gas that is produced by the plasma device, temperature is between 2000～6000 ℃.
4, the cracking reaction temperature of reactor is 800～2000 ℃, preferably 1200～2000 ℃, and especially 1200～1500 ℃.Residence time of material is 0.5～100 millisecond, preferably 5～50 milliseconds.
5, the aqueous slkali spray is chilled to 100 ℃, preferably below 80 ℃, so that remove hydrogen halides etc. better.
6, the method for separating out halide salt in the neutralizer adopts automatic continuous control concentration of lye, part neutralizer to send the fluorine containing waste water treating apparatus to handle, and has solved halide salt crystallization blockage problem, prolongs the cycle of operation, and more economical.
7, control coolant temperature automatically according to air dew point.
The commercial plant of realizing said method comprises shown in the structure diagram of Fig. 2:
1, is installed in the plasma device 1 on reactor top, is used to produce plasma gas.
2, the continuous-current plant that adapts with the plasma oscillation device adopts hollow transformation coil apparatus, effectively improves the handling capacity and the continuous arc ability of high frequency electric source, and continuous arc current lower limit reaches 50 amperes.
3, in plasma device bottom the Lorentz force striking is set, reaches the anode surface thermally equivalent, prolong the purpose of the cycle of operation.Arc initiation device is set to the production scene, has solved striking energy attenuation problem, and the fiery device of setting up an office, solved the problem of starting the arc difficulty.
4, plasma gas mixes the reactor that carries out cracking reaction with off-gas, between the front portion 3 of reactor and the rear portion 4 of reactor dielectric spacer layer 2 is arranged.
5, between reactor and other structure dielectric spacer layer 2 is arranged, continuity and the electric arc of avoiding whole reactor to become plasma device anode may drop on the inwall of reactor feed section, cause that inwall burns.
6, be installed in chilling, the neutral zone 5 of reactor lower part, with cracking go out, product sprays chilling, neutralization with aqueous slkali.
7, be installed in the knockout drum of isolating the gas-liquid phase materials 6 of chilling, neutral zone bottom.
Technology of the present invention is reliable, and reaction is thorough, and high efficiency is desirable environmental protection and energy saving method and device.
Description of drawings
Fig. 1: technological process block-diagram, wherein:
1,2,3: electric heater
4: the plasma device
5: reactor
6: knockout drum
7: lye tank (vat)
8: condenser
9: separator
10: clarifier
Fig. 2: the structure diagram of commercial plant, wherein:
1: the plasma device
2: dielectric spacer layer
3: the front portion of reactor
4: the rear portion of reactor
5: chilling, neutral zone
6: knockout drum
The specific embodiment
Embodiment 1
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 waste water storage tank through pipeline, flow is that 10kg/h enters electric heater (preheat temperature is 300 ℃), high purity nitrogen enters the plasma device and produces plasma gas, plasma-arc district temperature is 4500～5000 ℃, the flow of oxide isolation-methyl alcohol and water vapour is 13.1kg/h, after the intensification preheating with preheating after the height raffinate that boils mix vaporization (or atomizing), enter reactor, 1400 ℃ of cracking reaction temperature, reaction time 10 seconds.The pyrolysis product of gained sprays chilling, neutralization with the 5%KOH aqueous solution, and 5%KOH aqueous solution circular flow is 1.1m
3/ h.The results are shown in Table one.
Paratetrafluoroethylene (TFE) process units treatment of waste gas
The waste gas of tetrafluoroethene (TFE) process units is delivered to the waste gas storage tank through pipeline, to certain liquid level it is carried out burning disposal, operating procedure is with embodiment 1.Wherein exhaust gas flow is 13m
3/ h, methyl alcohol flow are 5kg/h, and steam rates is 5kg/h, and preheat temperature is 250 ℃, and plasma-arc district temperature is 4500～5000 ℃, 1350 ℃ of cracking reaction temperature, reaction time 10 seconds.The pyrolysis product of gained sprays chilling, neutralization with the 5%KOH aqueous solution, and 5%KOH aqueous solution circular flow is 0.8m
3/ h.The results are shown in Table one.
The processing of raffinate, exhaust-gas mixture
Boil raffinate, waste gas of the height of tetrafluoroethene (TFE) process units is delivered to waste liquid, waste gas storage tank through pipeline, simultaneously it carried out burning disposal to certain liquid level, operating procedure is with embodiment 1.The wherein high raffinate flow that boils is 8kg/h, and exhaust gas flow is 13m
3/ h, methyl alcohol flow are 7kg/h, and steam rates is 8kg/h, and preheat temperature is 250 ℃, and plasma-arc district temperature is 4500～5000 ℃, 1400 ℃ of cracking reaction temperature, reaction time 10 seconds.The pyrolysis product of gained sprays chilling, neutralization with the 5%KOH aqueous solution, and 5%KOH aqueous solution circular flow is 1.1m
3/ h.The results are shown in Table one.
To the boil processing of raffinate of the height of Polychlorinated biphenyls (PCB) process units
The boil burning disposal of raffinate of the height of Polychlorinated biphenyls (PCB) process units, oxide isolation methyl alcohol, other operating procedure is with embodiment 1.The wherein high raffinate flow that boils is 16.7kg/h, and the methyl alcohol flow is 15.5kg/h, and preheat temperature is 670 ℃, and plasma-arc district temperature is 4500～5000 ℃, 1500 ℃ of cracking reaction temperature, reaction time 15 seconds.The pyrolysis product of gained sprays chilling, neutralization with the 15%NaOH aqueous solution, and 15%NaOH aqueous solution circular flow is 1.1m
3/ h.The results are shown in Table one.
Table one
| Major parameter | The TFE device height raffinate that boils | TFE device discharging waste gas | Raffinate, exhaust-gas mixture | Pentachlorodiphenyl |
| Plasma device power, kw | 80 | 60 | 120 | 116 |
| The nitrogen flow of plasma device, m 3/h | Negative electrode: 8.5 anodes: 16.7 | Negative electrode: 8.5 anodes: 16.7 | Negative electrode: 8.5 anodes: 16.7 | Negative electrode: 8.5 anodes: 16.7 |
| Advance the methyl alcohol and the steam flow of reactor, kg/h | 13.1 | 10 | 15 | 15.5 |
| The refuse flow | 10kg/h | 13m 3/h | 10kg/h+13m 3/h | 16.7kg/h |
| Preheat temperature ℃ | 300 | 250 | 250 | 670 |
| The pyrolysis product temperature, ℃ | 1400 | 1350 | 1400 | 1500 |
| Reaction time, | 10 | 10 | 10 | 15 |
| Composition in chilling, the neutralization back waste gas, volume % | ||||
| O2 | 2.7 | 0.7 | 1.8 | 0.1 |
| CO2 | 18.7 | 9.3 | 14.5 | 18.8 |
| CO | 0.2 | 0.1 | 0.1 | 0.2 |
| Organohalogen compounds | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 |
| HCl，mg/m3 | 42 | 21 | 71 | 25 |
| HF，mg/m3 | ＜3 | ＜1 | ＜5 | 0 |
| N2 | 77.4 | 89.6 | 82.7 | 62.7 |
Claims (10)
1. method for treating organic halides by plasma combustion, comprise plasma striking, organohalogen compounds preheating gasification or atomizing, pyrolysis oxidization, in and four steps of chilling, organohalogen compounds finally all change CO into
2, hydrogen halides and a small amount of CO, do not have noxious material and solid particle carbon to produce, it is characterized in that:
(1) oxide isolation is the material that contains hydrogen and oxygen element;
(2) use nitrogen and argon gas as the protective gas that produces plasma gas;
(3) plasma gas that produces by the plasma device, temperature is between 2000～6000 ℃;
(4) the cracking reaction temperature of reactor is 800～2000 ℃, and residence time of material is 0.5～100 millisecond;
(5) the aqueous slkali spray is chilled to 100 ℃ and following;
(6) method of separating out halide salt in the neutralizer adopts automatic continuous control concentration of lye, part neutralizer to send the fluorine containing waste water treating apparatus to handle;
(7) control coolant temperature automatically according to air dew point.
2. the described method for treating organic halides by plasma combustion of claim 1, wherein, oxide isolation is air, hydrogen, methyl alcohol, formaldehyde, water, natural gas, carbon monoxide, carbon dioxide.
3. the described method for treating organic halides by plasma combustion of claim 1, wherein, oxide isolation is a methyl alcohol.
4. the described method for treating organic halides by plasma combustion of claim 1, wherein, oxide isolation is a formaldehyde.
5. the described method for treating organic halides by plasma combustion of claim 1, wherein, oxide isolation is a water.
6. the described method for treating organic halides by plasma combustion of claim 1, wherein, the protective gas that produces plasma gas is high purity nitrogen.
7. the described method for treating organic halides by plasma combustion of claim 1, wherein, the cracking reaction temperature of reactor is 1200～2000 ℃, residence time of material is 5～50 milliseconds.
8. the described method for treating organic halides by plasma combustion of claim 1, wherein, the cracking reaction temperature of reactor is 1200～1500 ℃.
9. the described method for treating organic halides by plasma combustion of claim 1, wherein, the aqueous slkali spray is chilled to below 80 ℃.
10. use each described method of claim 1～9 and custom-designed plasma burning commercial plant, comprising:
(1) is installed in the plasma device on reactor top, is used to produce plasma gas;
(2) continuous-current plant that adapts with the plasma oscillation device adopts hollow transformation coil apparatus, effectively improves the handling capacity and the continuous arc ability of high frequency electric source, and continuous arc current lower limit reaches 50 amperes;
(3) in plasma device bottom the Lorentz force striking is set, reaches the anode surface thermally equivalent, the purpose of the prolongation cycle of operation is set to the production scene with arc initiation device, has solved striking energy attenuation problem, and the fiery device of setting up an office, and has solved the problem of starting the arc difficulty;
(4) plasma gas mixes the reactor that carries out cracking reaction with off-gas, between the front portion of reactor and the rear portion of reactor dielectric spacer layer is arranged;
(5) between reactor and other structure dielectric spacer layer is arranged;
(6) be installed in chilling, the neutral zone of reactor lower part, with cracking go out, product sprays chilling, neutralization with aqueous slkali;
(7) be installed in the knockout drum of isolating the gas-liquid phase materials of chilling, neutral zone bottom.
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| CN 00128708 CN1185440C (en) | 2000-09-08 | 2000-09-08 | Method and industrial apparatus for treating organic halides by plasma combustion |
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|---|---|---|---|
| CN 00128708 CN1185440C (en) | 2000-09-08 | 2000-09-08 | Method and industrial apparatus for treating organic halides by plasma combustion |
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| CN1185440C true CN1185440C (en) | 2005-01-19 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1328186C (en) * | 2005-07-28 | 2007-07-25 | 北京红树林环保技术工程有限责任公司 | New processing method for indusrial toxic harmful waste liquid |
| CN101318065B (en) * | 2008-04-29 | 2011-01-19 | 北京航天石化技术装备工程公司 | Nuisance-free processing method for chlorine containing waste liquor and waste gas, and special apparatus thereof |
| 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 |
| CN105605591B (en) * | 2016-03-04 | 2018-08-21 | 杭州左纳实业有限公司 | The processing method of organic wastewater burner and organic wastewater |
| CN106524187A (en) * | 2016-12-13 | 2017-03-22 | 江苏帕斯玛环境科技有限公司 | Generating device for liquid waste disposal |
| CN106524188A (en) * | 2016-12-13 | 2017-03-22 | 江苏帕斯玛环境科技有限公司 | Plasma liquid waste disposal system with energy-saving preheating system |
| CN106524186A (en) * | 2016-12-13 | 2017-03-22 | 江苏帕斯玛环境科技有限公司 | Incineration tank |
| CN106482130A (en) * | 2016-12-13 | 2017-03-08 | 江苏帕斯玛环境科技有限公司 | Plasma liquid waste treatment system with efficient cooling system |
| 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 |
| CN106594759A (en) * | 2016-12-13 | 2017-04-26 | 江苏帕斯玛环境科技有限公司 | High-risk waste liquid treatment process |
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