CN103752583B - Halo POPs waste treatment system - Google Patents
Halo POPs waste treatment system Download PDFInfo
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- CN103752583B CN103752583B CN201410012452.1A CN201410012452A CN103752583B CN 103752583 B CN103752583 B CN 103752583B CN 201410012452 A CN201410012452 A CN 201410012452A CN 103752583 B CN103752583 B CN 103752583B
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- pops
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- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 92
- 239000002699 waste material Substances 0.000 title claims abstract description 48
- 125000001475 halogen functional group Chemical group 0.000 title claims abstract 17
- 238000000034 method Methods 0.000 claims abstract description 72
- 238000010438 heat treatment Methods 0.000 claims abstract description 71
- 239000003054 catalyst Substances 0.000 claims abstract description 57
- 230000008569 process Effects 0.000 claims abstract description 55
- 238000001816 cooling Methods 0.000 claims abstract description 45
- 238000005695 dehalogenation reaction Methods 0.000 claims abstract description 37
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims abstract description 10
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract description 10
- 230000007613 environmental effect Effects 0.000 claims abstract description 8
- 230000002950 deficient Effects 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 47
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000007599 discharging Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 10
- 238000012216 screening Methods 0.000 claims description 8
- 239000000835 fiber Substances 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 235000000396 iron Nutrition 0.000 claims description 5
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002826 coolant Substances 0.000 claims description 2
- 230000009970 fire resistant effect Effects 0.000 claims description 2
- 238000012545 processing Methods 0.000 abstract description 13
- 125000005843 halogen group Chemical group 0.000 description 57
- 238000006298 dechlorination reaction Methods 0.000 description 42
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 42
- 230000000694 effects Effects 0.000 description 37
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 34
- 239000000292 calcium oxide Substances 0.000 description 34
- 238000007792 addition Methods 0.000 description 22
- 238000010586 diagram Methods 0.000 description 14
- 230000004044 response Effects 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 235000010290 biphenyl Nutrition 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- GGMPTLAAIUQMIE-UHFFFAOYSA-N 2,3,4,5,6-pentachlorobiphenyl Chemical group ClC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=CC=CC=C1 GGMPTLAAIUQMIE-UHFFFAOYSA-N 0.000 description 3
- HLQDGCWIOSOMDP-UHFFFAOYSA-N 2,3,4,5-tetrachlorobiphenyl Chemical group ClC1=C(Cl)C(Cl)=CC(C=2C=CC=CC=2)=C1Cl HLQDGCWIOSOMDP-UHFFFAOYSA-N 0.000 description 3
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 3
- 125000006414 CCl Chemical group ClC* 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 206010021143 Hypoxia Diseases 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- VGVRPFIJEJYOFN-UHFFFAOYSA-N 2,3,4,6-tetrachlorophenol Chemical class OC1=C(Cl)C=C(Cl)C(Cl)=C1Cl VGVRPFIJEJYOFN-UHFFFAOYSA-N 0.000 description 2
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- -1 PBDE Chemical compound 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 150000008422 chlorobenzenes Chemical class 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 230000001146 hypoxic effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical class OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- BTAGRXWGMYTPBY-UHFFFAOYSA-N 1,2,3-trichloro-4-(2,3,4-trichlorophenyl)benzene Chemical compound ClC1=C(Cl)C(Cl)=CC=C1C1=CC=C(Cl)C(Cl)=C1Cl BTAGRXWGMYTPBY-UHFFFAOYSA-N 0.000 description 1
- ALDJIKXAHSDLLB-UHFFFAOYSA-N 1,2-dichloro-3-(2,5-dichlorophenyl)benzene Chemical group ClC1=CC=C(Cl)C(C=2C(=C(Cl)C=CC=2)Cl)=C1 ALDJIKXAHSDLLB-UHFFFAOYSA-N 0.000 description 1
- RKLLTEAEZIJBAU-UHFFFAOYSA-N 1,2-dichloro-4-(2,4-dichlorophenyl)benzene Chemical group ClC1=CC(Cl)=CC=C1C1=CC=C(Cl)C(Cl)=C1 RKLLTEAEZIJBAU-UHFFFAOYSA-N 0.000 description 1
- IUTPYMGCWINGEY-UHFFFAOYSA-N 2,3',4,4',5-Pentachlorobiphenyl Chemical compound C1=C(Cl)C(Cl)=CC=C1C1=CC(Cl)=C(Cl)C=C1Cl IUTPYMGCWINGEY-UHFFFAOYSA-N 0.000 description 1
- IUYHQGMDSZOPDZ-UHFFFAOYSA-N 2,3,4-trichlorobiphenyl Chemical group ClC1=C(Cl)C(Cl)=CC=C1C1=CC=CC=C1 IUYHQGMDSZOPDZ-UHFFFAOYSA-N 0.000 description 1
- LAXBNTIAOJWAOP-UHFFFAOYSA-N 2-chlorobiphenyl Chemical group ClC1=CC=CC=C1C1=CC=CC=C1 LAXBNTIAOJWAOP-UHFFFAOYSA-N 0.000 description 1
- UQMGJOKDKOLIDP-UHFFFAOYSA-N 3,3',4,4'-tetrachlorobiphenyl Chemical group C1=C(Cl)C(Cl)=CC=C1C1=CC=C(Cl)C(Cl)=C1 UQMGJOKDKOLIDP-UHFFFAOYSA-N 0.000 description 1
- OKISUZLXOYGIFP-UHFFFAOYSA-N 4,4'-dichlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=C(Cl)C=C1 OKISUZLXOYGIFP-UHFFFAOYSA-N 0.000 description 1
- 206010002660 Anoxia Diseases 0.000 description 1
- 241000976983 Anoxia Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000007953 anoxia Effects 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000003032 molecular docking Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 244000045947 parasite Species 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- Processing Of Solid Wastes (AREA)
Abstract
The present invention provides a kind of halo POPs waste treatment system, it is for realizing the halo POPs treatment of wastes produced method in turn included the following steps: (1) adds catalyst in halo POPs refuse, mass ratio between described catalyst and described halo POPs refuse is 10%, and described catalyst is alkali metal oxide and/or alkaline earth oxide；(2) under the temperature conditions of 400 DEG C, environmental oxygen levels be less than or equal to 1% atmospheric condition under, carry out the dehalogenation reaction 4 hours；And (3) are under the conditions of oxygen deficient atmospheres, refuse after the dehalogenation reaction processes is carried out cooling process, refuse is cooled to less than 150 DEG C, completing treatment of wastes produced, this halo POPs waste treatment system includes feed arrangement, preheats body of heater, reacting by heating device and chiller.The present invention effectively can carry out dehalogenation process to halo POPs refuse, has good treatment efficiency, and processing procedure is easily controlled, feature with low cost, can be widely applied to industrialized halo POPs refuse and processes.
Description
Technical field
The present invention relates to organic pollution treatment technology, particularly relate to a kind of halo POPs refuse and process system
System.
Background technology
Persistence organic pollutant (Persistent Organic Pollutants, POPs) is that a class has
Extended residual, bioaccumulation and the organic pollution of height property, it can pass through various surrounding mediums,
The long-distance migrations such as the biggest gas and water, biology, cause serious harm to human health and environment.Its
In, Polychlorinated biphenyls (polychlorinated biphenyls, PCBs) be exactly a class synthetic
Representative POPs, is widely used as the transmission medium of the insulating oil of power capacitor, hydraulic system
Deng, during human social development, cause the existence of a large amount of PCBs；Additionally, other halo POPs
Exist the most in a large number, such as containing Perfluorooctane sulfonates and salt thereof, dioxin, Polychlorinated biphenyls, chlorobenzene class,
Chlorophenols, PBDE, tetrabromobisphenol A, Insecticides (tech) & Herbicides (tech) etc., these are all containing halogen
The organic pollution of element, generally also can be described as halo POPs, and wherein with chloro POPs and bromo
POPs is relatively conventional.
Due to the POPs hazardness to environmental and human health impacts, at post industrial state, these things
The manufacture of matter and use have obtained effective restriction, but, the artificial POPs produced of left over by history
Existing the most in a large number, the POPs by-product that production process is not intended to produce is not effectively controlled yet, and not
Disconnected have new chemical substance to be put into POPs register, and therefore POPs process is a sustainable existence
Problem.For the developing countries such as China, owing to early stage usage amount is too much, Yi Jihou
Phase deposits the reasons such as these pollutant are improper, causes the refuse containing POPs, such as soil, mud etc.
It is widely present, it is provided that a kind for the treatment of effect is preferable, and POPs waste treatment method economic again just becomes
Extremely important.Wherein, to halo POPs treatment of wastes produced, it is simply that by halo organic contamination therein
Thing carries out degradation treatment, and halo POPs is converted into low toxicity or nontoxic material.
At present, halo POPs refuse is processed and the mainstream technology of industrial applications is high-temperature heat treatment
Method, i.e. by melted, burning etc. to POPs process.PCBs refuse is being carried out burning method
During process, high askarel therein can be decomposed into small-molecule substance, to realize pollutant
Process.But, in this processing method, owing to the chloride ion in pollutant is ubiquitous, right
While POPs refuse burns, low-temperature space after combustion, chloride ion may be with other pollutant
Or Organic substance combines and generates organic chloride, and then generate dioxin or other halo POPs, this
During burning disposal, it is difficult to control and manage.High-temperature heat treatment investment in machinery and equipment is big, power consumption height,
Operating cost is high, is difficult to popularization and application on a large scale in China.
Summary of the invention
In consideration of it, the present invention provides a kind of halo POPs waste treatment system, it can be urged by increase
Agent realizes the dehalogenation of cold environmental conditions and processes.
The halo POPs waste treatment system of the present invention is for realizing the halo in turn included the following steps
POPs treatment of wastes produced method: (1) first step: add catalyst, institute in halo POPs refuse
The mass ratio stated between catalyst and described halo POPs refuse is 10%, and wherein said catalyst is alkali
Metal-oxide and/or alkaline earth oxide, carried out described catalyst before adding described catalyst
Screening Treatment so that the granularity of the described catalyst after screening is less than or equal to 200 mesh；(2) second
Step: under the temperature conditions of 400 DEG C, is the atmospheric condition less than or equal to 1% at environmental oxygen levels
Under, carry out the dehalogenation reaction 4 hours；And (3) third step: under the conditions of oxygen deficient atmospheres, to process
Refuse after the dehalogenation reaction processes carries out cooling process, and refuse is cooled to less than 150 DEG C, completes useless
The process of thing,
Wherein, this halo POPs waste treatment system includes feed arrangement, preheats body of heater, heating instead
Answer device and chiller,
Described feed arrangement includes that feeding warehouse and conveyer, described conveyer are electric pushrod charger, uses
The material added in by described feeding warehouse preheats body of heater described in being delivered to；
The described body of heater that preheats is arranged on the delivery port of described conveyer and the charging of described reacting by heating device
Between Kou, for the material transmitted from described conveyer is preheated, described in preheat entering of body of heater
The delivery port of material mouth and described conveyer and described in preheat the discharging opening of body of heater and described reacting by heating
All it is tightly connected between the charging aperture of device；
Described feeding warehouse is set at the described charging aperture preheating body of heater, sets in the bottom of described feeding warehouse
Put described conveyer, described conveyer off and on the material putting into described feeding warehouse is sent into described pre-add
Hot body of heater；
Described reacting by heating device includes body of heater, and is the heater of described body of heater heating；
The outer layer of described body of heater is ceramic fibre lightweight thermal insulation layer, and internal heating part uses by fire-resistant fibre
The combination semicircle module of dimension vacuum pouring, forms spherical hearth；
Described heater is that ferrum irons aluminum heater strip, and this ferrum irons aluminum heater strip and is partly embedded in the inwall of described body of heater；
Feed end and discharge end at described body of heater are provided with vibrator, between material is carried out by this vibrator
Have a rest vibration, it is to avoid materials from bonding is at described inboard wall of furnace body；
Discharge end at described reacting by heating device arranges discharge bucket, the thing will discharged by described discharge bucket
Described chiller sent into by material, arranges observation port to observe discharging situation, thus come at described discharge bucket
Control charging rate and heating-up temperature；
Described chiller includes cooling down storehouse, described cooling storehouse use water or air as coolant, described in add
It is tightly connected between discharging opening and the charging aperture in described cooling storehouse of thermal reaction apparatus；
Described cooling storehouse is cooling boiler tube, and this cooling boiler tube is obliquely installed with the angle of 0-1 degree, described cold
But the height of the charging aperture of boiler tube is less than the height of the discharging opening of described cooling boiler tube；
It is respectively provided with stirring transmitting device, in described cooling in described reacting by heating device and described cooling storehouse
The stirring transmitting device arranged in boiler tube is spiral stock guide, and this spiral stock guide drives material from described
The discharging opening of cooling boiler tube is discharged；
Described reacting by heating device and described chiller are respectively connected with air supply system, be used for be described in add
Thermal reaction apparatus and chiller provide pre-set gas, so that described reacting by heating device and chiller
Work under default atmospheric condition.
Further, in the halo POPs waste treatment system of the present invention, described body of heater is swinging
Body of heater, described swinging furnace interior is provided with the continuous helical shape guide as described stirring transmitting device
Plate, described swinging body of heater connects motor.
Further, in the halo POPs waste treatment system of the present invention, described body of heater is fixed
Body of heater, described fixed furnace interior is provided with the stirring as described stirring transmitting device and advances oar, institute
Stating stirring advances oar connection to have motor.
Further, in the halo POPs waste treatment system of the present invention, described catalyst is Na2O、
K2One or more in O, MgO, CaO.
The halo POPs waste treatment system that the present invention provides, can be by adding in halo POPs refuse
Alkali metal oxide and/or alkaline earth oxide are as catalyst, and take off under lower temperature conditions
Halogen reacts, and can effectively remove the halo POPs in refuse, it is achieved to treatment of wastes produced, processed whole
Cheng Zhong, can be carried out under lower temperature conditions, and the process that controls is simple, reliable, has preferably place simultaneously
Reason effect, processing cost is relatively low, is applicable in the commercial Application that a large amount of refuse processes.
Accompanying drawing explanation
The schematic diagram of the halo POPs waste treatment method that Fig. 1 provides for the embodiment of the present invention；
Fig. 2 is under 400 DEG C of reaction conditions, under the differential responses time in refuse PCBs dechlorination rate with CaO
The schematic diagram of the change of addition；
Fig. 3 is the 4h response time, under different temperatures in refuse PCBs dechlorination rate with the change of CaO addition
The schematic diagram changed；
Fig. 4 is that CaO addition reacts the homologue of PCBs in refuse after 4h when being 10% under different temperatures
Composition schematic diagram；
Fig. 5 be corresponding diagram 4 processes before and after the GC/MS atlas analysis schematic diagram of PCBs in refuse；
The structural representation of the halo POPs waste treatment system that Fig. 6 provides for the embodiment of the present invention.
Detailed description of the invention
Carrying out processing existing problem for halo POPs refuse in prior art, the present invention proposes
A kind of technology that can carry out dehalogenation process under cryogenic, can make the place of halo POPs refuse
Reason is carried out under lower temperature conditions, have can manage, controlled, and the advantage of lower cost, simultaneously
Also will not produce secondary pollution, can be effectively used for halo POPs treatment of wastes produced, it is simple to halo POPs
The commercial introduction of refuse process and application.Wherein, cryogenic conditions described here, refer to that temperature is 700
Below DEG C, specifically refer to the temperature conditions of 250 DEG C-600 DEG C.
The waste treatment method that the present embodiment provides, specifically comprises the steps that in halo POPs refuse, adds
Adding catalyst, wherein said catalyst is alkali metal oxide and/or alkaline earth oxide；At 250 DEG C
Under the temperature conditions of-600 DEG C, environmental oxygen levels be less than or equal to 1% atmospheric condition under, carry out
The dehalogenation reaction 0.5 hour-5 hours；Under the conditions of oxygen deficient atmospheres, to giving up after the dehalogenation reaction processes
Thing carries out cooling process, refuse is cooled to less than 150 DEG C, completes treatment of wastes produced.The present embodiment
In, can by halo POPs refuse, by increase the alkali metal oxide as catalyst and/or
Alkaline earth oxide, and the dehalogenation reaction can be carried out, it is achieved right under cryogenic with under anoxia condition
Halo POPs treatment of wastes produced.
The schematic diagram of the halo POPs waste treatment method that Fig. 1 provides for the embodiment of the present invention.Such as Fig. 1
Shown in, this processing method specifically can comprise the steps:
Step 101, in halo POPs refuse, add catalyst, wherein said catalyst is alkali metal
Oxide and/or alkaline earth oxide, the mass ratio between catalyst and refuse is 5%-60%.
Wherein, the occurrence of the mass ratio between described catalyst and refuse, can be according to halo in refuse
The content of POPs is rationally arranged, typically, in halo POPs refuse, and such as soil, dirt
In the refuses such as mud, the amount of halo POPs is less than less than 0.2%, such as, and the halo in treated waste
When the content of POPs is less, the amount of catalyst just can be less, and the content of corresponding halo POPs is more
Time, the amount of catalyst just can be some more.But in practical application in industry, in the case of 5%-60% addition,
Generally individually can realize the dehalogenation treatment effect to halo POPs refuse.Therefore, the most right in the present embodiment
Halo POPs refuse adds the amount of catalyst and is particularly limited in processing, generally just can meet at 5%-60%
To halo POPs treatment of wastes produced.
Step 102, in the temperature conditions that temperature is 350 DEG C-550 DEG C, environmental oxygen levels for less than or etc.
Under the atmospheric condition of 1%, carry out the dehalogenation reaction 0.5 hour-5 hours.
Here temperature conditions and dehalogenation reaction time, can set the biggest according to specific circumstances
Little, if generally temperature and time arranges a suitable value, there is optimal dehalogenation effect, but
In certain limit, the scope limited such as this step, dehalogenation effect can be realized equally, simply the dehalogenation time is slightly
Length or temperature are higher, or dehalogenation effect is slightly lower, but this has no effect on the actual work of the present invention
Industry is applied.
Step 103, under anoxic conditions, carries out cooling process to the refuse after dehalogenation processes, will
Refuse is cooled to less than 150 DEG C, completes treatment of wastes produced.
Processed by cooling, in the refuse after the dehalogenation reaction can be made to process, each material stable performance, keeps away
Exempt from synthesizing halogen organic pollution again, it is ensured that dehalogenation effect.
In the present embodiment, described halo POPs refuse, be specifically as follows containing Perfluorooctane sulfonates and
Salt, dioxin, Polychlorinated biphenyls, chlorobenzene class, chlorophenols, PBDE, tetrabromobisphenol A, parasite killing
The polluting waste of one or more POPs in agent, herbicide, such as, contaminated soil, flying ash,
The refuses such as industrial solid wastes, deposit, mud, cause in the typically industrial processes of these refuses
, or cause when depositing halo POPs.In the present embodiment, halo POPs can be carried out dehalogenation,
Or transfer high halides to low halides.
In the present embodiment, described alkali metal oxide and/or alkaline earth oxide, it is specifically as follows oxygen
Change sodium Na2O, potassium oxide K2The mixing of one or more in O, magnesium oxide MgO, calcium oxide CaO
Thing.It will be understood by those skilled in the art that Na2O、K2O is alkali metal oxide, and MgO, CaO are
Alkaline earth oxide, equally applicable for otheralkali metal oxide or alkaline earth oxide.This reality
Execute in example and this is not particularly limited.
In the present embodiment, before addition of catalyst, may also include that described catalyst is carried out at screening
Reason so that the granularity of the catalyst after screening is less than or equal to 200 mesh.Same, add in refuse
Before adding catalyst, it is possible to screen refuse, the granularity after screening can be controlled in 60 mesh, so that
Refuse and catalyst can be sufficiently mixed, and improve the dehalogenation effect of the dehalogenation reaction.
In the present embodiment, due in halo POPs refuse, the content of halo POPs generally 0.2% with
Under, therefore, when adding catalyst, the mass ratio between catalyst and refuse can be controlled in 5%-60%
Between, for halo POPs refuse, catalyst is added within the range, can meet de-
Halogen processes to be needed.Certainly, in actual application, can be time in refuse, halo POPs content be many, catalyst
Amount can be added more, on the contrary, can add less, but in actual application, the addition of catalyst some more or
Less, being normally carried out of dehalogenation process can't be affected.Therefore, in the actual application of the present embodiment, not
Meeting is to the addition of catalyst and has particularly restriction with the amount of halo POPs in refuse, as long as generally
Increase a certain amount of, such as, more than 5%, the dehalogenation to halo POPs can be met and process needs, certainly
Increments is The more the better, but more than 60% after, it will usually cause the waste of catalyst, and will not be to dehalogenation
Process brings benefit.
In the present embodiment, described environmental oxygen levels is the atmospheric condition less than or equal to 1%, is specially
Vacuum protection, nitrogen protection, CO can be passed through2In protection, inert gas shielding, reducing gas protection
One or more control climate methods control to obtain.This atmospheric condition specifically can be come by special equipment
Realize, equipment is embodied in this and is not particularly limited.
In the present embodiment, described to the dehalogenation reaction process after refuse cool down, specifically can use water-cooled
Or air cooling.Water-cooled and air cooling realize simple, economical and effective.
In a kind of preferred embodiment mode, described catalyst specifically can use CaO.And catalyst
And the mass ratio between refuse is 10%.The temperature conditions of the described dehalogenation reaction is specially 400 DEG C.
The time of the described dehalogenation reaction is specially 4 hours.By a large amount of actual application, for major part halo
For POPs refuse, carry out dehalogenation treatment effect under this condition optimal.
In the embodiment of the present invention, by adding alkali metal oxide and/or alkaline earth in halo POPs refuse
Metal-oxide is as catalyst, and carries out the dehalogenation reaction under lower temperature conditions, can effectively remove useless
Organic halogen in thing, it is achieved to treatment of wastes produced, in whole processing procedure, can be in lower temperature conditions
Under carry out, the process that controls is simple, reliable, has preferable treatment effect simultaneously, and processing cost is relatively low,
It is applicable in the commercial Application of a large amount for the treatment of of wastes produced.
Above-mentioned halo POPs treatment of wastes produced is illustrated by the present invention, in order to the technology of the present invention
Halo POPs treatment of wastes produced effect is being had a better understanding, below by the place with instantiation by scheme
Reason process illustrates, and respectively by experiment by the way of to different disposal condition, and process before and after
Dehalogenation effect is analyzed.
In this example, using CaO as catalyst, to containing PCBs, namely the refuse containing chloro POPs enters
Row processes.And for the ease of in processing dechlorination treatment effect and dechlorination treatment effect under different condition
Understanding, carried out relative analysis.
First, a pretreatment is carried out to containing PCBs refuse and CaO.This sample is dangerous for taking from certain
The PCBs refuse at Waste disposal center, before processing refuse, has carried out pretreatment to refuse, including:
Natural air drying, grinds and crosses 60 mesh sieves, storage in room temperature.Meanwhile, CaO is also carried out Screening Treatment,
Cross 200 mesh sieves.
Secondly, waste component is analyzed, and is divided into many parts, with under subsequent authentication different condition
Refuse dechlorination treatment effect.Wherein, waste component analysis is used X fluorescence spectrum analytic process, to inorganic
Chlorine analysis uses the most water-soluble extraction-chromatography of ions, determines that in refuse, Cl is all with organochlorine by analysis
Form exists, and is i.e. PCBs in refuse, and the content of PCBs is 1080 μ g/g, i.e. PCBs institute accounting
Example is 0.108%.
After above-mentioned handling well, under different temperatures, different CaO addition, differential responses time conditions
(other condition is the most identical), carries out dechlorination process, and has carried out as follows to dechlorination result refuse
Contrast.
Fig. 2 is under 400 DEG C of reaction conditions, under the differential responses time in refuse PCBs dechlorination rate with CaO
The schematic diagram of the change of addition.In this Fig. 2, illustrate under 400 DEG C of temperature conditionss, during reaction
Between when being respectively 2h, 3h and 4h, in the case of different CaO additions, same refuse is taken off
The effect schematic diagram that chlorine processes, it can be seen that along with the increase of CaO addition, dechlorination rate presents and first increases
The trend reduced after big, when CaO addition is 10%, dechlorination rate is maximum, show CaO and refuse it
Between mass ratio when about 1:10, there is preferably PCBs dechlorination effect, i.e. raw by organochlorine removing
Become inorganic chlorine best results；In the case of 400 DEG C of reaction 2h, add 5%CaO refuse dechlorination rate by not
Add CaO 34.0% increases to 66.2%, and after showing to add CaO, in refuse, the dechlorination rate of PCBs has bright
Showing and increase, this is owing to the C-Cl key of CaO Yu PCBs interacts, thus weakens C-Cl key,
Reaction is made to be easier to make for；In the case of CaO addition is identical, dechlorination rate is along with the increasing in response time
Grow and increase, but the dechlorination efficiency of PCBs increases DeGrain, when CaO addition is 10%,
Dechlorination rate, at reaction 2h, respectively reaches 81.6%, 85.7% and 88.5%, illustrates along with instead after 3h, 4h
Increase PCBs dechlorination reaction rate reduction between Ying Shi.
Contrast is processed it can be seen that in temperature conditions necessarily, certain response time by figure 2 above refuse
Under, the dechlorination treatment effect of refuse increases along with catalyst and improves, but when reaching certain numerical value, will
Reach optimum, after a while for reducing.This shows, in actual applications, and can be by setting certain temperature value
And the response time, by rationally adding the amount of catalyst, optimal dechlorination treatment effect can be obtained.But
As long as from figure 2 it may also be seen that add a certain amount of catalyst in refuse, and certain temperature and
In the response time, just have than the dechlorination effect not adding catalyst and be significantly improved, therefore, in reality
In application, it is not identical owing to refuse containing the amount of PCBs, therefore, as long as containing PCBs
Refuse in increase catalyst, and under certain temperature conditions, react a period of time, it is possible to reach
The effect that dechlorination processes, therefore in actual industrial production, the addition to catalyst does not has bigger restriction.
Fig. 3 is the 4h response time, under different temperatures in refuse PCBs dechlorination rate with the change of CaO addition
The schematic diagram changed.In this Fig. 3, illustrating in the 4h response time, reaction temperature is respectively 300 DEG C,
At 350 DEG C and 400 DEG C, in the case of different CaO additions, same refuse is carried out dechlorination process
Effect schematic diagram, it can be seen that when CaO addition is 10%, the dechlorination rate of PCBs at 300 DEG C,
45.6%, 62.7%, 88.5% is respectively reached, along with reaction temperature after reacting 4h at 350 DEG C and 400 DEG C
The rising of degree, in refuse, PCBs dechlorination rate increases, and dechlorination efficiency significantly improves, and shows that temperature gets over Gao Yue
Be conducive to the fracture of C-Cl key；Under different temperatures, the mass ratio of CaO and refuse is in the case of 1:10
PCBs dechlorination rate is maximum, shows that when CaO adding proportion is 10%, inorganic chlorine generates best results, namely
Dechlorination effect is optimal.
By this Fig. 3 it can be seen that along with temperature raises, in the case of adding same catalyst, can have
There is more preferably dechlorination effect, but in actual application, apply for the ease of industrialized production so that industrialization
Practicality is more preferable, and typical temperature will not set the highest.
Fig. 4 is that CaO addition reacts the homologue of PCBs in refuse after 4h when being 10% under different temperatures
Composition schematic diagram.As seen from the figure, processing PCBs homologue in refuse is 2～5 chlorine, wherein trichloro biphenyls
Being that master accounts for 71.9%, DCBP 9.8%, tetrachloro biphenyl 17.6%, pentachlorodiphenyl only accounts for 0.6%；Along with
Temperature raises, and a chlordiphenyl growing amount is gradually increased, at 300 DEG C, 350 DEG C, react 4h at 400 DEG C after
Being followed successively by 37.2 μ g/g, 64.8 μ g/g and 75.9 μ g/g, trichloro biphenyl content is then gradually lowered, and is followed successively by
122.9 μ g/g, 36.5 μ g/g and 9.7 μ g/g, show that reaction temperature is the highest, and in refuse, PCBs is to low chloro
Biphenyl degradation is the most abundant, and namely dechlorination effect is more preferable.
Fig. 5 be corresponding diagram 4 processes before and after the GC/MS atlas analysis schematic diagram of PCBs in refuse.As
Shown in Fig. 5, retention time 25.073min and 26.019min are respectively PCB105 (2,3,3 ', 4,4 '-five
Chlordiphenyl) and PCB118 (2,3 ', 4,4 ', 5-pentachlorodiphenyl), at calcium oxide addition 10%, 300 DEG C
After reaction 4h, pentachlorodiphenyl does not detects, and tetrachloro biphenyl has PCB44 (2,2 ', 3,5 '-tetrachloro biphenyl), PCB66
(2,3 ', 4,4 '-tetrachloro biphenyl) and PCB77 (3,3 ', 4,4 '-tetrachloro biphenyl), protect at 350 DEG C and 400 DEG C
The time 8.731min of staying is biphenyl, it addition, at 400 DEG C, Organic substance after three kinds of CaO addition reactions
In all detect biphenyl, show PCBs dechlorination process under the conditions of 350 DEG C and 400 DEG C there occurs dechlorination
/ hydrogenation reaction, the dechlorination completely of part PCBs.
Dechlorination effect to refuse in above-mentioned Fig. 2-Fig. 5, and the analysis of waste component, be all to pass through sample
Product analysis obtains, and existing various component analyzing method can be used to obtain, and concrete analyzing and processing process is originally
Embodiment does not limits.
From above to containing PCBs treatment of wastes produced, and to the analysis for the treatment of effect it can be seen that
(1) PCBs clearance increases along with the rising of temperature and the prolongation in response time；CaO adds
When amount is 10%, after reacting 4h at 400 DEG C, the clearance of PCBs reaches 87.7%, and dechlorination rate is
88.5%.
(2) when CaO addition is 1:10, the dechlorination rate of PCBs is the highest, after reacting 4h at 400 DEG C, useless
In thing, original tetrachloro biphenyl and pentachlorodiphenyl all do not detect, and generate with biphenyl and a chlordiphenyl, explanation
PCBs progressively there occurs dechlorination/hydrogenation reaction, has the complete dechlorination of part PCBs.
Figure 2 above-Fig. 5 is only the analysis to the treatment of wastes produced process containing PCBs and explanation, above-mentioned
The condition that various dechlorinations process, such as the selection of catalyst, the amount of catalyst, reaction temperature, response time
It is for being easy to the understanding to technical solution of the present invention to select, the dechlorination under the conditions of other is processed,
Also having similar treatment effect, the ability that simply dechlorination processes is the most different, but the present invention is also
The condition that dechlorination processes will not be done particularly restriction, the most under certain conditions, such as, select CaO
As catalyst, temperature selects at 400 DEG C, and the response time, catalyst loading was about 10% at 4h
Having preferably treatment effect, processing procedure is easy to control simultaneously.
The structural representation of the halo POPs waste treatment system that Fig. 6 provides for the embodiment of the present invention.
The embodiment of the present invention also provides for a kind of system realizing said method, and this system structure is simple, it is easy to
Realizing, specifically, as shown in Figure 6, this system can include feed arrangement 10, reacting by heating device
20 and chiller 30, feed arrangement 10 includes feeding warehouse 102 and conveyer 101, this conveyer
101 materials added in by feeding warehouse 102 are delivered to reacting by heating device 20；Reacting by heating fills
Put 20 and include body of heater, and the heater (not shown) for body of heater heating, conveyer 101
The charging aperture of material delivery port and body of heater be tightly connected；Chiller 30 includes cooling down storehouse, heating
It is tightly connected between discharging opening and the charging aperture in cooling storehouse of reaction unit 20；Reacting by heating device 20
And in cooling storehouse 30, it is respectively provided with stirring transmitting device (not shown)；Additionally, reacting by heating
Device 20, and chiller 30 is respectively connected with air supply system, for for reacting by heating device 20
Pre-set gas is provided, so that reacting by heating device 20 and chiller 30 can with chiller 30
Being operated in default atmospheric condition, this air supply system can provide the gas with default oxygen content, to reach
Atmospheric condition needed for said method.
In the present embodiment, as shown in Figure 6, the conveyer 101 of this feed arrangement 10, it is specially and uses
Rustless steel electric pushrod charger, this pusher feeding machine is that interval advances, top docking feeding warehouse 102,
Enter from feeding warehouse 102 through the POPs refuse of mixing and the material of catalyst, and by electric pushrod
Charger advances follow-up reacting by heating device 20.Specifically, in the charging of reacting by heating device 20
Mouth arranges feeding warehouse 102, and feeding warehouse 102 bottom arranges electric pushrod charger, when needs are heating
When reaction unit 20 adds material, can will be put into charging off and on by the electric pushrod of feeding warehouse bottom
Reacting by heating device 20 sent into by the material in storehouse.Meanwhile, as shown in Figure 6, the going out of electric pushrod charger
The mouth that material mouth, i.e. feeding warehouse 102 dock with the charging aperture of reacting by heating device, with reacting by heating device
Charging aperture between be tightly connected by sealing device, so, in follow-up material heating process,
Will not be by external environment influence.In actual application, material can be sent into being not required to charger as required
Time, it is possible to it is provided with switching device, such as valve at the place of being tightly connected, closes reacting by heating device
Charging aperture, it is achieved the heated sealed of reacting by heating device processes.In actual application, above-mentioned is electronic
The fltting speed of push rod is adjustable, realizes the control to charging rate by adjusting fltting speed.It is concrete
Governing speed can set as desired.
In the present embodiment, the body of heater of reacting by heating device 20 concretely swinging body of heater, swinging stove
Body is internally provided with the continuous helical shape stock guide as stirring transmitting device, and body of heater connects motor.
Additionally, described swinging body of heater is provided with helical form stock guide in being divided into multistage, every section.Heating
Heater in reaction unit 20 concretely ferrum irons aluminum heater strip, is arranged on the inwall of body of heater,
Specifically, this heater strip can partly be embedded in circular inboard wall of furnace body, has layout succinct, and the efficiency of heating surface is high
Feature.Additionally, the present embodiment system may also include preheats body of heater 40, it is arranged on conveyer 101
Delivery port and the charging aperture of reacting by heating device 20 between, for the material transmitted from conveyer
Preheat；And preheat the charging aperture R1 of body of heater 40 and the delivery port of conveyer, and pre-add
All it is tightly connected between discharging opening and the charging aperture of reacting by heating device of hot body of heater.Additionally, this heating
The body of heater of reaction unit 20 can also be fixed body of heater, and this fixed furnace interior is provided with stirring
Advance oar, stirring to advance oar to connect and have motor.
Specifically, as shown in Figure 6, reacting by heating device 20 is specially swinging body of heater, can use
316L rustless steel is special to be processed, and with as preheating apparatus preheat body of heater 40 one.
Boiler tube is divided into pre-add hot arc K, and reacting by heating section A, B, C, D, E, F, is all provided with in every section
It is equipped with heater, and each section is provided with stock guide.Body of heater is connected with motor 201, body of heater rotational band
Dynamic stock guide rotates.Owing to boiler tube inner surface is smooth, inside can be provided with continuous helical shape guide
Plate, so can make the material in entrance body of heater be heated evenly, reacts fully, advance in order.Boiler tube
Feed end and discharge end use combination sealing, both can guarantee that the good sealing property being association of activity and inertia, again can be
Life-time service under high temperature.Wherein, the stock guide in each boiler tube all can drive body of heater to rotate at motor 201
Shi Yiqi rotates, and outside uniformly overturning material, also realizes the conveying to material, will material
It is delivered to the conveying mouth of reacting by heating device 20, to enter in chiller 30.
In the present embodiment, the rotating speed of motor 201 can set according to specific needs, specifically, and can
Time according to heating setpoint etc. because being usually arranged to suitable speed, to guarantee that material is by preheating
Section K sequentially enters reacting by heating section A, B, C, D, E, F the most slowly so that material exists
After entrance preheats body of heater, can be under the drive of stock guide, Uniform Flow, the onwards transmission of upset,
And uniformly heat under the heating of heater, and finally enter from the discharging opening R2 of reacting by heating device 20
Enter the charging aperture R3 of chiller 30, during this is whole, material can thermally equivalent, improve thing
Material dehalogenation treatment effect in reacting by heating device.The dehalogenation reaction will be carried out specifically below
Bright.Meanwhile, the discharge end at reacting by heating device can arrange discharge bucket, by discharge bucket by discharge
Chiller sent into by material, can arrange observation port at this discharge bucket, to observe discharging situation, and can basis
Manual observation controls the temperature control etc. of charging rate, heating；And also may be used inside reacting by heating device
It is provided with sensor, to be detected the temperature of heating by sensor, can be as required to heating power
It is adjusted, to guarantee in the temperature range set.
In the present embodiment, chiller 30 specifically can use the type of cooling such as water-cooled, air cooling, does not does at this
Limiting especially, wherein, as shown in Figure 6, the cooling storehouse of chiller 30 specifically can use cooling boiler tube,
This cooling boiler tube is obliquely installed, angle of inclination can at 0-1 degree, and cooling boiler tube charging aperture R3 the lowest
In the height of the discharging opening R4 of cooling boiler tube, by the pipeline communication sealed between them；Wherein, cold
But it is provided with spiral stock guide in boiler tube, and the motor arranged with boiler tube end is connected, with in motor belt motor
Dynamic lower driving material to discharge from the discharging opening of cooling boiler tube, discharging opening leans on after may be provided at the end of boiler tube
The position of close end, the present embodiment is not particularly limited.Wherein, cool down boiler tube tilting gearing, can be
During driven by motor stock guide, move from lower to upper, to realize the process of the cooling to material, can
The material made can continuous print cooling boiler tube discharging opening discharge；Meanwhile, can going out at cooling boiler tube
Material one end arranges discharge bucket, and can arrange observation port at discharge bucket, in order to artificial observation discharging situation,
Can be to the rotating speed of motor, heating-up temperature, the speed of charging etc. is controlled.
In the invention described above embodiment, at the input and output material end of the body of heater of reacting by heating device, also can arrange
There is vibrator, so that, during material heating and transmitting, intermittent control shaking can be carried out, in avoiding body of heater
The wall a large amount of materials of bonding.
In the invention described above embodiment, each motor, and heater etc. all can connect and have a controller,
So that whole heating-up temperature, material transfer rate etc. are carried out centralized Control, to improve the process to material
Efficiency.Certainly, it is possible to according to the needs of actual design, it is not provided with controller, but according to design load
Motor and heater are heated and is controlled.
In the invention described above embodiment, the body of heater as reacting by heating device can use lightweight refracrory
Being made, wherein, outer layer can be ceramic fibre lightweight thermal insulation layer, and internal heating part can be selected for resistance to
Fire fiber vacuum cast combination semicircle module, to form spherical hearth, can have preferably heating and joint
Can effect.
In the invention described above embodiment, as shown in Figure 6, each device all may be provided on metal framework G,
To utilize metal framework G to support each device.
In the invention described above embodiment, reacting by heating device and chiller all can connect by air inlet and
The air supply system of gas exhaust piping composition, this gas handling system can have source of the gas set in advance, with by being
Its internal gas providing certain atmosphere, to realize the reacting by heating under the conditions of particular atmosphere and cooling
Processing, concrete set-up mode the present embodiment is not particularly limited.
In the system that the embodiment of the present invention provides, can be by feed arrangement 10 to through mixed POPs
Refuse and catalyst, send into reacting by heating device 20；Reacting by heating device 20 can be in air supply system effect
Under, maintain hypoxic atmosphere condition, i.e. oxygen content less than or equal under the atmospheric condition of 1%, simultaneously can be
Under heater effect therein, the temperature of heating setpoint, such as 350 DEG C-550 DEG C, and by controlling motor
Body of heater is driven to drive stock guide to rotate so that material can carry out the time that the dehalogenation reaction is preset, example wherein
Such as 4 hours；Material after reacting by heating device 20 can send into chiller 30, equally, cooling
Device 30 can maintain oxygen deficient atmospheres condition under air supply system effect, and oxygen deficient atmospheres specifically refers to contain here
The environment that oxygen amount is relatively low, specifically may refer to as above-mentioned hypoxic atmosphere condition, simultaneously can be at cooling system
Under system effect, it is cooled to less than 150 degree, and discharges from discharge gate, thus realize halo POPs is given up
The process of thing, it implements process and can be found in the explanation of the invention described above embodiment of the method, at this no longer
Repeat.
The system that the embodiment of the present invention provides, it is possible to achieve halo POPs refuse is carried out continuous processing,
Its simple in construction, it is achieved convenient, the temperature of process have only to again less than 600 degree carry out, there is control
Simply, low cost, the advantage that treatment effeciency is high, can be widely applied to halo POPs treatment of wastes produced
In.
Last it is noted that various embodiments above is only in order to illustrate technical scheme, rather than right
It limits；Although the present invention being described in detail with reference to foregoing embodiments, this area common
Skilled artisans appreciate that the technical scheme described in foregoing embodiments still can be modified by it,
Or the most some or all of technical characteristic is carried out equivalent；And these amendments or replacement, and
The essence not making appropriate technical solution departs from the scope of various embodiments of the present invention technical scheme.
Claims (4)
1. a halo POPs waste treatment system, it is for realizing the halo in turn included the following steps
POPs treatment of wastes produced method: (1) first step: add catalyst, institute in halo POPs refuse
The mass ratio stated between catalyst and described halo POPs refuse is 10%, and wherein said catalyst is alkali
Metal-oxide and/or alkaline earth oxide, carried out described catalyst before adding described catalyst
Screening Treatment so that the granularity of the described catalyst after screening is less than or equal to 200 mesh；(2) second
Step: under the temperature conditions of 400 DEG C, is the atmospheric condition less than or equal to 1% at environmental oxygen levels
Under, carry out the dehalogenation reaction 4 hours；And (3) third step: under the conditions of oxygen deficient atmospheres, to process
Refuse after the dehalogenation reaction processes carries out cooling process, and refuse is cooled to less than 150 DEG C, completes useless
The process of thing,
Described halo POPs waste treatment system is characterised by,
This halo POPs waste treatment system includes feed arrangement, preheats body of heater, reacting by heating device
And chiller, wherein:
Described feed arrangement includes that feeding warehouse and conveyer, described conveyer are electric pushrod charger, uses
The material added in by described feeding warehouse preheats body of heater described in being delivered to；
The described body of heater that preheats is arranged on the delivery port of described conveyer and the charging of described reacting by heating device
Between Kou, for the material transmitted from described conveyer is preheated, described in preheat entering of body of heater
The delivery port of material mouth and described conveyer and described in preheat the discharging opening of body of heater and described reacting by heating
All it is tightly connected between the charging aperture of device；
Described feeding warehouse is set at the described charging aperture preheating body of heater, sets in the bottom of described feeding warehouse
Put described conveyer, described conveyer off and on the material putting into described feeding warehouse is sent into described pre-add
Hot body of heater；
Described reacting by heating device includes body of heater, and is the heater of described body of heater heating；
The outer layer of described body of heater is ceramic fibre lightweight thermal insulation layer, and internal heating part uses by fire-resistant fibre
The combination semicircle module of dimension vacuum pouring, forms spherical hearth；
Described heater is that ferrum irons aluminum heater strip, and this ferrum irons aluminum heater strip and is partly embedded in the inwall of described body of heater；
Feed end and discharge end at described body of heater are provided with vibrator, between material is carried out by this vibrator
Have a rest vibration, it is to avoid materials from bonding is at described inboard wall of furnace body；
Discharge end at described reacting by heating device arranges discharge bucket, the thing will discharged by described discharge bucket
Described chiller sent into by material, arranges observation port to observe discharging situation, thus come at described discharge bucket
Control charging rate and heating-up temperature；
Described chiller includes cooling down storehouse, described cooling storehouse use water or air as coolant, described in add
It is tightly connected between discharging opening and the charging aperture in described cooling storehouse of thermal reaction apparatus；
Described cooling storehouse is cooling boiler tube, and this cooling boiler tube is obliquely installed with the angle of 0-1 degree, described cold
But the height of the charging aperture of boiler tube is less than the height of the discharging opening of described cooling boiler tube；
It is respectively provided with stirring transmitting device, in described cooling in described reacting by heating device and described cooling storehouse
The stirring transmitting device arranged in boiler tube is spiral stock guide, and this spiral stock guide drives material from described
The discharging opening of cooling boiler tube is discharged；
Described reacting by heating device and described chiller are respectively connected with air supply system, be used for be described in add
Thermal reaction apparatus and chiller provide pre-set gas, so that described reacting by heating device and chiller
Work under default atmospheric condition.
Halo POPs waste treatment system the most according to claim 1, it is characterised in that described
Body of heater is swinging body of heater, and described swinging furnace interior is provided with the company as described stirring transmitting device
Continuous helical form stock guide, described swinging body of heater connects motor.
Halo POPs waste treatment system the most according to claim 1, it is characterised in that described
Body of heater is fixed body of heater, and described fixed furnace interior is provided with stirring as described stirring transmitting device
Mixing propelling oar, described stirring advances oar to connect motor.
4. according to the halo POPs waste treatment system according to any one of claim 1-3, its feature
Being, described catalyst is Na2O、K2One or more in O, MgO, CaO.
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| JP2003300910A (en) * | 2002-04-12 | 2003-10-21 | Kiyoshi Otsuka | Method for treatment of organic halogen compound |
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