CN110186063A - A kind of purifying treatment method and system of the volatile organic compounds containing chlorine - Google Patents
A kind of purifying treatment method and system of the volatile organic compounds containing chlorine Download PDFInfo
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- CN110186063A CN110186063A CN201910303193.0A CN201910303193A CN110186063A CN 110186063 A CN110186063 A CN 110186063A CN 201910303193 A CN201910303193 A CN 201910303193A CN 110186063 A CN110186063 A CN 110186063A
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000000460 chlorine Substances 0.000 title claims abstract description 102
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 102
- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 34
- 239000007789 gas Substances 0.000 claims abstract description 411
- 238000007084 catalytic combustion reaction Methods 0.000 claims abstract description 158
- 239000007788 liquid Substances 0.000 claims abstract description 103
- 239000003054 catalyst Substances 0.000 claims abstract description 95
- 239000002912 waste gas Substances 0.000 claims abstract description 80
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000005416 organic matter Substances 0.000 claims abstract description 49
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 44
- 239000010439 graphite Substances 0.000 claims abstract description 44
- 238000002485 combustion reaction Methods 0.000 claims abstract description 43
- 239000003513 alkali Substances 0.000 claims abstract description 37
- 238000004140 cleaning Methods 0.000 claims abstract description 37
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims description 80
- 238000000926 separation method Methods 0.000 claims description 37
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 29
- 229910052760 oxygen Inorganic materials 0.000 claims description 29
- 239000001301 oxygen Substances 0.000 claims description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 26
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 24
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 24
- 238000001514 detection method Methods 0.000 claims description 23
- 238000006555 catalytic reaction Methods 0.000 claims description 22
- 239000003915 liquefied petroleum gas Substances 0.000 claims description 21
- 239000002808 molecular sieve Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 16
- 239000000498 cooling water Substances 0.000 claims description 15
- 230000003647 oxidation Effects 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 10
- 239000003208 petroleum Substances 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 6
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 6
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005751 Copper oxide Substances 0.000 claims description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- 229910000431 copper oxide Inorganic materials 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims description 3
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 4
- 239000008246 gaseous mixture Substances 0.000 abstract description 3
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 26
- 229940073608 benzyl chloride Drugs 0.000 description 26
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 26
- YMWUJEATGCHHMB-UHFFFAOYSA-N dichloromethane Natural products ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 23
- 239000000463 material Substances 0.000 description 16
- 229930195733 hydrocarbon Natural products 0.000 description 14
- 150000002430 hydrocarbons Chemical class 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 11
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 10
- 238000005260 corrosion Methods 0.000 description 10
- 230000007797 corrosion Effects 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 8
- 239000000112 cooling gas Substances 0.000 description 8
- 238000007689 inspection Methods 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical compound ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 0.000 description 7
- 206010044565 Tremor Diseases 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 6
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 150000002894 organic compounds Chemical class 0.000 description 6
- 230000001172 regenerating effect Effects 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 239000003546 flue gas Substances 0.000 description 4
- 230000003694 hair properties Effects 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 239000010815 organic waste Substances 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005338 heat storage Methods 0.000 description 3
- 238000001802 infusion Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical compound C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-UHFFFAOYSA-N 0.000 description 2
- CAHQGWAXKLQREW-UHFFFAOYSA-N Benzal chloride Chemical compound ClC(Cl)C1=CC=CC=C1 CAHQGWAXKLQREW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000003009 desulfurizing effect Effects 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 210000000952 spleen Anatomy 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- QVLAWKAXOMEXPM-UHFFFAOYSA-N 1,1,1,2-tetrachloroethane Chemical class ClCC(Cl)(Cl)Cl QVLAWKAXOMEXPM-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical class CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- OSOUNOBYRMOXQQ-UHFFFAOYSA-N 1-chloro-3-methylbenzene Chemical compound CC1=CC=CC(Cl)=C1 OSOUNOBYRMOXQQ-UHFFFAOYSA-N 0.000 description 1
- 125000001340 2-chloroethyl group Chemical class [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- SRWILAKSARHZPR-UHFFFAOYSA-N 3-chlorobenzaldehyde Chemical compound ClC1=CC=CC(C=O)=C1 SRWILAKSARHZPR-UHFFFAOYSA-N 0.000 description 1
- 125000003852 3-chlorobenzyl group Chemical group [H]C1=C([H])C(=C([H])C(Cl)=C1[H])C([H])([H])* 0.000 description 1
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 description 1
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- MVPPADPHJFYWMZ-IDEBNGHGSA-N chlorobenzene Chemical group Cl[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 MVPPADPHJFYWMZ-IDEBNGHGSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- -1 dichloromethane Alkane Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- BNIXVQGCZULYKV-UHFFFAOYSA-N pentachloroethane Chemical compound ClC(Cl)C(Cl)(Cl)Cl BNIXVQGCZULYKV-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2206/00—Waste heat recuperation
- F23G2206/10—Waste heat recuperation reintroducing the heat in the same process, e.g. for predrying
Landscapes
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention discloses a kind of purifying treatment methods of volatile organic compounds containing chlorine, comprising the following steps: (1) by catalyst warm-up；(2) concentration of volatile organic matter containing chlorine is 1000-100000mg/Nm at room temperature3Exhaust gas and air gaseous mixture carry out adiabatic catalytic combustion reaction, obtain high-temperature tail gas, the part high-temperature tail gas formed after reaction is recycled to high-temperature blower entrance, the suction for being directly over resisting blower with gaseous mixture mixes, after the temperature of initial combustion for reaching CVOCs, into reactor in carry out adiabatic catalytic combustion reaction；(3) it after rest part high-temperature tail gas exchanges heat cooling in graphite heat exchanger, is directly emptied after gas-liquid separator, alkali cleaning.The present invention uses cheap resisting blower, and the heat generated to CVOCs waste gas catalytic combustion makes full use of, and so that system is can achieve heat balance, significantly reduces equipment investment and operating cost.It can direct qualified discharge without further processing by system of the present invention treated purified gas.
Description
Technical field
The invention belongs to the field of purification of the volatile organic compounds containing chlorine in chemical emission, and in particular to one kind is waved containing chlorine
The purifying treatment method and system of hair property organic compounds.
Background technique
Be more than according to statistics 60% pesticide in used containing chlorine or in process of production containing chloromethylated intermediate, in its production
The big volatile organic matter containing chlorine (CVOCs) of a large amount of complicated components, processing difficulty will certainly be generated in the process.CVOCs exhaust gas is general
All over incineration method is used, organic matter is set to resolve into HCl, CO using high temperature (1000 DEG C)2、H2The inorganic molecules substance such as O is burned and is produced
Raw heat can be recycled for heat supply or power generation etc..
Exhaust gas containing organic molecule is after catalysis burning, since molecular scission can release largely in organic compound
Heat, catalysis burning after gas carry more heat, can be used as heat source and be used.Patent CN206215024U,
The heat that CN106247354A utilizes organic waste gas catalytic combustion to generate, organic exhaust gas enters after indirect heating in heat exchanger urges
Change and reacted in combustion reactor, organic molecule is changed into qualified discharge after carbon dioxide and water.Patent
Absorption/regeneration of organic matter in Activated Carbon toward VOCs-Containing Exhausts and the catalysis of organic exhaust gas burning are integrated in one by CN206613318U
In a system, the organic exhaust gas that generation is desorbed after activated carbon adsorption is passed through in catalytic combustion reactor, in the effect of catalyst
It is lower that organic molecule is changed into carbon dioxide and water, desorption of the heat that catalysis burning releases by indirect heat exchange for charcoal of living
Regeneration, solves the problems, such as regenerating active carbon origin of heat, reduces equipment operating cost.Patent CN107435937A utilizes more
VOCs is catalyzed burning and generates thermal reservoir in heat storage by grade heat storage, is then carried out exhaust gas by heat exchanger tube indirectly more
Grade heating and cooling, to achieve the purpose that heat makes full use of.A kind of catalysis combustion heat supplying disclosed in patent CN107327856A
In system, the heat released using catalysis burning is by finned coil heat exchange pipe indirect heating unstripped gas, after heating
Unstripped gas mixed with a part of catalyst combustion reaction gas after enter reactor in the reaction was continued.
Patent CN106731562A utilizes regenerative oxidation reactor for treatment high concentration organic exhaust gas containing chlorine, after regenerative oxidation
To high-temperature flue gas remove for maintaining Self-heat-storage reaction energy balance external, rest part heat is for stirling generator hair
Electricity, the flue gas of discharge are sent into the sour gas in lye absorption tower removing flue gas, absorb waste liquid and are sent into the regeneration of electrochemical regeneration device
Lye；The device can make full use of reaction heat, recycle absorbing liquid, achieve the purpose that reduce energy consumption and material consumption；But the dress
Setting and being only used for processing chlorinated organics concentration is 7000~15000mg/Nm3Exhaust gas, and regenerative oxidation formula reactor operate when
There is also the risks of explosion.
Patent CN106731563A discloses a kind of processing method and processing device of organic exhaust gas containing chlorine, and is used for handling
Total hydrocarbon concentration is 2000-9000mg/Nm3Organic exhaust gas containing chlorobenzene；This method is storing the setting of the catalytic oxidation of hydrogen chloride bed
Between hott bed layer, regenerative oxidation bed carries out oxidation processes to chlorine organic exhaust gas, and oxidation product enters catalytic bed and carries out chlorination
The catalysis oxidation of hydrogen；Then in fume desulfurizing tower, the exhaust gas for the treatment of reactor discharge is absorbed using sodium alkali；Finally by useless suction
It receives liquid oxidation tower to be used to useless absorbing liquid not oxidized in fume desulfurizing tower carrying out deep oxidation, to enable useless absorbing liquid
Qualified discharge.This method has not only purified tail gas, but also significantly improves oxidation efficiency.
For volatile organic compounds containing chlorine, after handling using Production by Catalytic Combustion Process, the height to reactor exit is needed
Heat in warm tail gas carries out recycling and reusing.Since heat utilization herein belongs to high-temperature gas heating cryogenic gas, gas
Heat-transfer capability between gas is usually all poor, and therefore, it is necessary to the use biggish metallic recuperators of overall heat-transfer coefficient, however
In high-temperature tail gas other than the harmless carbon dioxide and water that reaction generates, also containing with extremely strong corrosive hydrogen chloride gas
Body, therefore, the material of heat exchanger must select corrosion resistant noble metal (such as nickel material).When by reactor outlet high-temperature gas expensive
When being cooled down in the heat exchanger of metal material, the steam in tail gas once reaches dew-point temperature, these hydrogen chloride gas molecules
Will the concentrated hydrochloric acid soluble in water that strong corrosive be formed, serious corrosion will be generated to metallic recuperator.And for noble metal
Heat exchanger, such as nickel material heat exchanger, equipment investment up to a million is a kind of great for enterprise once being corroded easily
Loss, will increase dramatically equipment investment cost.
Summary of the invention
Equipment investment cost is higher in order to solve, and the low problem of the utilization efficiency of heat of reaction, the present invention is waved to containing chlorine
When hair property organic compounds are catalyzed the high-temperature tail gas heat utilization after burning, it is extremely low to additionally use the investment compared with nickel material heat exchanger
The place that is exchanged as heat of resisting blower, high-temperature tail gas is directly mixed in resisting blower with low temperature feedstock gas,
So that the heat of tail gas is fully used, while reactor outlet gas temperature and air intlet flow be subjected to interlocked operation,
Keep reactor operation more steady.
It is of the present invention:
Low temperature feedstock gas: for the volatile organic matter containing chlorine at room temperature exhaust gas mix with air after obtain.
High-temperature tail gas: being the low temperature feedstock gas that is passed through of reaction initial stage and/or process steady state operation phase wait react
Mix waste gas carries out tail gas obtained by adiabatic catalytic combustion reaction, and volatile organic content containing chlorine therein is 5~25mg/
Nm3。
High temperature circulation gas: for a part in high-temperature tail gas, the heat carried using it is subsequent be passed through it is low
Warm unstripped gas.
Wait react mix waste gas: being obtained after being mixed for high temperature circulation gas with the subsequent low temperature feedstock gas being passed through.
Heretofore described volatile organic compounds containing chlorine refer to and contain chlorinated organics in exhaust gas, and these contain
Chlorine organic typically refers to chlorinated aromatic hydrocarbons and chlorinated aliphatic hydrocarbon, such as monochlor-benzene, dichlorobenzene, trichloro-benzene, benzyl chloride, dichloro
Change benzyl, tri-chlorination benzyl, ortho-chlorotolu'ene, p-chlorotoluene, m-chlorotoluene, adjacent one benzyl chloride of chlorine, to one benzyl chloride of chlorine, one benzyl chloride of m-chloro, neighbour
Chlorine benzyl dichloride, to chlorine benzyl dichloride, m-chloro benzyl dichloride, o-chlorobenzaldehyde, p-chlorobenzaldehyde, m chlorobenzaldehyde, chloromethanes, dichloromethane
Alkane, chloroform, chloroethanes, dichloroethanes, trichloroethanes, tetrachloroethanes, pentachloroethane.
Specific technical solution of the present invention is as follows:
The first purpose of the invention is to provide a kind of purifying treatment method of volatile organic compounds containing chlorine, the sides
Method includes:
(1) it preheats: catalyst needed for preheating catalyst combustion reaction using hot-air；
(2) reaction heat recycles: the present invention mixes exhaust gas with air in advance before entering catalytic combustion reactor,
Catalysis burning initial reaction temperature can be reached when entering reaction, then directly carry out catalytic organism burning in the reactor
Reaction.The low temperature feedstock gas obtained after the exhaust gas of the volatile organic matter containing chlorine is mixed with air is passed through through step (1) preheating
Catalyst carries out adiabatic catalytic combustion reaction, obtains high-temperature tail gas after reaction；By the resulting portion of adiabatic catalytic combustion reaction
Divide high-temperature tail gas to mix as high temperature circulation gas with the subsequent low temperature feedstock gas being passed through, utilizes what is carried in high temperature circulation gas
The subsequent low temperature feedstock gas being passed through of heat, obtain temperature reach the volatile organic matter containing chlorine temperature of initial combustion to
React mix waste gas；It is anti-that adiabatic catalytic burning is carried out under the conditions of resulting mix waste gas to be reacted is continued existing for the catalyst
It answers, obtains high-temperature tail gas；It is urged by adjusting wait react the organic concentration in mix waste gas, maintaining mix waste gas to be reacted to be insulated
Change the temperature of the resulting high-temperature tail gas of combustion reaction；By adjusting the high-temperature tail gas amount for being recycled back to resisting blower, maintain to anti-
Answer the temperature of mix waste gas；
(3) high-temperature tail gas is handled: step (2) resulting high-temperature tail gas, in addition to part is as high temperature circulation gas, remaining part
Isolated gas and liquid after the high-temperature tail gas divided is cooling, gained liquid enters biochemistry pool purification, separation after gas-liquid separation
Gained gas carries out alkali cleaning using the sodium hydroxide solution that mass fraction is 2~5wt%, and gas obtained by alkali cleaning is expelled directly out.
Further, step (1) hot air temperature is 350~500 DEG C；Catalysis needed for the catalyst combustion reaction
Agent is preheated to 200~250 DEG C.
Further, catalyst needed for step (1) described catalyst combustion reaction be with aluminium oxide, silica, silicon carbide,
One of molecular sieve, rare-earth Y molecular sieve, H beta-molecular sieve, ZSM-5 molecular sieve, MCM-41 molecular sieve, MCM-42 molecular sieve
Or two kinds are carrier, with transition metal oxide titanium oxide, vanadium oxide, chromium oxide, manganese oxide, iron oxide, cobalt oxide, oxidation
Nickel, copper oxide, zinc oxide, one or both of lanthana, cerium oxide, praseodymium oxide, neodymia oxide is active component, living
Property component load capacity be 1~20%, catalyst particle size is 20~80 mesh, and the loadings of catalyst reactor are being urged by gas
Changing total air speed in combustion reactor is 10~500m3/ (kgcath) is calculated.
Further, in volatile organic compounds containing chlorine described in step (2), the concentration of volatile organic matter containing chlorine is 1000
~100000mg/Nm3；
The low temperature feedstock gas is by the air speed metering in adiabatic catalytic combustion reactor, wherein volatile organic matter containing chlorine
The air speed of exhaust gas is 5~50m3/ (kgcath), the total air speed of air are 1~100m3/ (kgcath), volatility containing chlorine are organic
The molar flow of object exhaust gas and air proportion is chemical according to the catalytic oxidation of oxygen in the amount and air of organic matter in exhaust gas
Metering ratio is calculated, and the volume flow ratio of volatile organic compounds containing chlorine and air is 0.1~10；
Further, adiabatic catalytic combustion reaction pressure described in step (2) be 0.1~0.25MPa (absolute pressure), temperature
Degree is 350~500 DEG C.The temperature for the high-temperature tail gas that adiabatic catalytic combustion reaction obtains is 350~500 DEG C, therein to contain
Chlorine volatile organic content is 5~25mg/Nm3。
Further, step (2) the high temperature circulation gas and catalytic combustion reactor outlet high-temperature tail gas ratio maintain
0.3~0.8, high temperature circulation gas is mixed with the subsequent low temperature feedstock gas being passed through, by obtained mix waste gas to be reacted
In organic concentration be diluted to 6000~12000mg/Nm3, high temperature circulation gas and the subsequent low temperature feedstock gas being passed through are mixed
Closing obtained mix waste gas temperature to be reacted is 200~250 DEG C；
Further, the concrete operations of step (2) temperature for maintaining high-temperature tail gas are as follows:
When the temperature of high-temperature tail gas is higher than 500 DEG C, increase air intake to reduce wait react in mix waste gas containing chlorine
The concentration of the exhaust gas of volatile organic matter makes catalytic combustion reactor inlet organic concentration be no more than 12000mg/Nm3, with
Reduce the temperature of high-temperature tail gas；
When the temperature of high-temperature tail gas is lower than 350 DEG C, liquefied petroleum gas is passed through to catalytic combustion reactor inlet or is subtracted
Few air intake has catalytic combustion reactor inlet to improve the organic concentration of catalytic combustion reactor inlet
Machine object concentration is not less than 6000mg/Nm3, improve the temperature of high-temperature tail gas.It is passed through liquefied petroleum gas or reduces air intake
In selection: since initial reaction phase air is mixed with organic compounds according to catalysis reaction ratio, this stage does not start tail
Gas circulation, but if this stage exhaust temperature is not achieved 350 DEG C, then shows that organic concentration is too low in low temperature feedstock gas, insufficient
To maintain circulation technology, so when can only increase the organic object amount entered by being passed through liquefied petroleum gas and guarantee circulation technology
Heat balance；Or in handled exhaust gas, due to the type of volatile organic matter containing chlorine itself or concentration etc., catalysis combustion
Burning reaction heat is lower, and the volatile organic matter containing chlorine for increasing same concentrations can not make reaction system temperature maintain normal level,
The stable operation of reaction system can only be then maintained by being passed through liquefied petroleum gas；And after process steady-state operation, such as wait react mixed
It closes in exhaust gas that the concentration of volatile organic matter containing chlorine is too low, then reduces air capacity or to be passed through liquefied petroleum gas two ways optional
With improving wait react the organic concentration in mix waste gas, and then improve the temperature of high-temperature tail gas.Preferably, when use is passed through
When the mode of liquefied petroleum gas improves organic concentration, to guarantee that liquefied petroleum gas converts completely, it can increase accordingly into catalysis
The amount of oxygen of combustion reactor guarantees that the oil gas for entering system can be totally converted.
Further, the concrete operations of step (2) temperature for maintaining mix waste gas to be reacted are as follows: when wait react mixing
When exhaust gas temperature is higher than 250 DEG C, the high-temperature tail gas amount for being recycled back to resisting blower is turned down, to reduce mix waste gas temperature to be reacted
Degree；When reacting mix waste gas temperature lower than 200 DEG C, tune up the high-temperature tail gas amount for being recycled back to resisting blower, with improve to
React mix waste gas temperature.
Further, the method specifically includes the following steps:
(1) it preheats: closing the first control valve 1, third control valve 3, the 4th control valve 4 and the 5th control valve 5, open the
Two control valves 2, resisting blower 6, the 6th control valve 20, preheater 8 and the first temperature controller 9；Air passes through air pipe line
18 and resisting blower 6 enter preheater 8 in preheat, hot-air by the 4th branch line 21 enter catalytic combustion reactor 7
In, the hot air temperature of catalytic combustion reactor inlet is detected by the first temperature controller 9, and controlling preheater will be empty
Gas is preheated to 350-500 DEG C, in the heat preheating catalytic combustion reactor 7 carried using hot-air needed for catalyst combustion reaction
Catalyst makes the temperature of catalyst reach 200~250 DEG C.
(2) reaction heat recycles: after the temperature of catalyst reaches 200~250 DEG C in catalytic combustion reactor 7, opening
Second control valve 2, third control valve 3, the 4th control valve 4, the 5th control valve 5, resisting blower 6, the first temperature controller 9 and
Second temperature controller 10, closes preheater 8 and the 6th control valve 20, and the exhaust gas of the volatile organic matter containing chlorine is useless by CVOCs
Air pipe 17 obtains low temperature feedstock gas after air enters the mixing of resisting blower 6 by air pipe line 18；The low temperature feedstock
Gas is entered in catalytic combustion reactor 7 by third branch line 16, carries out adiabatic catalytic combustion with the catalyst preheated through step 1
Burn reaction, the high-temperature tail gas that 7 exit of catalytic combustion reactor obtains after reaction；
When second temperature controller 10 detects that high-temperature tail gas temperature is more than 500 DEG C, pass through second temperature controller 10
The aperture for increasing the second control valve 2 is adjusted, increases air intake, to reduce the volatile organic matter containing chlorine in low temperature feedstock gas
The concentration of exhaust gas makes wait react the organic concentration in mix waste gas no more than 12000mg/Nm3, to be lowered into catalysis burning
The concentration of the volatile organic matter containing chlorine, reduces the temperature of high-temperature tail gas in the gas of reactor bed；
When second temperature controller 10 detects high-temperature tail gas temperature lower than 350 DEG C, pass through second temperature controller 10
The aperture for reducing the second control valve 2 is adjusted, reduces the air capacity for entering system, or adjust first by second temperature controller 10
The aperture of control valve 1, the organic object amount increased into system are made with improving the organic concentration in low temperature feedstock gas wait react
Organic concentration in mix waste gas maintains 6000mg/Nm3More than, improve the temperature of high-temperature tail gas；Preferably, when using logical
The aperture that second temperature controller 10 adjusts the first control valve 1 is crossed, when being passed through the mode of liquefied petroleum gas and improving organic concentration,
For guarantee liquefied petroleum gas convert completely, can suitably tune up the second control valve 2 by second temperature controller 10, increase accordingly into
Enter the amount of oxygen of reactor, guarantees that the oil gas for entering system can be totally converted.
The resulting part high-temperature tail gas of adiabatic catalytic combustion reaction passes through the first temperature controller as high temperature circulation gas
9 adjust the aperture of third control valve 3, make high temperature circulation gas by the first branch line 14 and subsequently through CVOCs flue gas leading
The exhaust gas for the volatile organic matter containing chlorine that road 17 is passed through, the low temperature feedstock gas being mixed to get by the air that air pipe line 18 is passed through
It mixes at resisting blower 6, using the heat low temperature feedstock gas carried in high temperature circulation gas, obtains wait react mixing
Exhaust gas；The mix waste gas temperature to be reacted is 200~250 DEG C；
Resulting mix waste gas to be reacted is entered in catalytic combustion reactor 7 by third branch line 16 and is insulated
Catalyst combustion reaction obtains high-temperature tail gas；
By temperature controller 9 to the temperature detection of 6 exit of resisting blower mix waste gas to be reacted, when high temperature resistant wind
It when being higher than 250 DEG C wait react mix waste gas temperature of 6 exit of machine, turns the aperture of third control valve 3 down, turns down and be recycled back to resistance to height
The high-temperature tail gas amount of warm blower, to reduce mix waste gas temperature to be reacted；When reacting mix waste gas temperature lower than 200 DEG C,
The aperture for tuning up third control valve 3 tunes up the high-temperature tail gas amount for being recycled back to resisting blower, to improve mix waste gas temperature to be reacted
Degree.
(3) high-temperature tail gas is handled: in step (2), combustion reaction terminates that resulting height is discharged in catalytic combustion reactor
For warm tail gas other than part is recycled to 6 entrance of resisting blower as high temperature circulation gas, the high-temperature tail gas of rest part is logical
It crosses second branched pipe road 15 and enters graphite heat exchanger 11, after the heat exchange cooling of graphite heat exchanger 11, pass through 12 gas of gas-liquid separator
Liquid separation, the gas that gas-liquid separation obtains directly is vented after alkali cleaning removal hydrogen chloride gas in alkali cleaning kettle 13, after gas-liquid separation
Obtained liquid goes biochemistry pool to handle.
A second object of the present invention is to provide a kind of cleaning treatment system of volatile organic compounds containing chlorine, the systems
System includes the first control valve 1, the second control valve 2, third control valve 3, the 4th control valve 4, the 5th control valve 5, resisting blower
6, catalytic combustion reactor 7, preheater 8, the first temperature controller 9, second temperature controller 10, graphite heat exchanger 11, gas-liquid
Separator 12, alkali cleaning kettle 13, the first branch line 14, second branched pipe road 15, third branch line 16, CVOCs exhaust pipe
17, air pipe line 18, liquefied petroleum air pipe 19, the 6th control valve 20, the 4th branch line 21；
First control valve 1 is set on the liquefied petroleum air pipe 19, the second control valve 2 is set on air pipe line 18, the
Third control valve 3 is set on one branch line 14, the 5th control valve 5 is set on CVOCs exhaust pipe 17；
Resisting blower entrance is arranged in described 6 one end of resisting blower, and the other end is arranged resisting blower and exports, catalysis combustion
7 one end of reactor setting catalytic combustion reactor entrance, the outlet of other end setting catalytic combustion reactor are burnt, the CVOCs is useless
Air pipe 17, air pipe line 18, liquefied petroleum air pipe 19, the first branch line 14 one end respectively with resisting blower entrance
It is connected；The third branch line 16, the 4th branch line 21 one end respectively with resisting blower export connect；The catalysis
Combustion reactor entrance be arranged the first temperature controller 9, third branch line 16, the 4th branch line 21 the other end lead to respectively
It crosses the first temperature controller 9 to connect with catalytic combustion reactor entrance, the 4th control valve is set on the third branch line 16
4；Prolong airflow direction on 4th branch line and sets gradually the 6th control valve 20 and preheater 8；
The catalytic combustion reactor outlet setting second temperature controller 10,14, second points of first branch line
One end of bye-pass 15 passes through second temperature controller 10 respectively and connects catalytic combustion reactor outlet, first branch line
14 other end connects resisting blower entrance；
Graphite heat exchanger gas access is set at the top of the graphite heat exchanger 11, bottom setting graphite heat exchanger gas goes out
Mouthful, lower sidewall setting cooling water inlet, another side wall upper part be arranged cooling water outlet, the second branched pipe road 15 it is another
End is connected with graphite heat exchanger gas access；
Gas-liquid separator gas access is set at the top of the gas-liquid separator 12, and gas-liquid separator gas is arranged in side wall upper part
Gas-liquid separator liquid outlet is arranged in outlet, bottom, and the graphite heat exchanger gas vent and gas-liquid separator gas access connect
It connects, the gas-liquid separator gas vent connects alkali cleaning kettle 13, and the gas-liquid separator liquid outlet connects biochemistry pool.
Further, the catalytic combustion reactor 7 is insulation fix bed catalytic combustion reactor.
Technical solution of the present invention is compared with the existing technology:
The present invention uses cheap resisting blower, by the high-temperature tail gas and low temperature original after organic waste gas catalytic combustion containing chlorine
Material gas is directly sufficiently mixed, and is detected by second temperature controller 10 to adiabatic catalytic combustion reactor outlet temperature,
And the aperture of the first control valve 1 or the second control valve 2 is adjusted by second temperature controller 10, thus adjust liquefied petroleum gas or
The intake of air；First temperature controller 9 detects adiabatic catalytic combustion reactor inlet temperature, and by adjusting the
The aperture of three control valves 3, to adjust high temperature circulation gas flow；Reaction system is set to can achieve heat balance, while also greatly
Ground reduces equipment investment and device operating cost.
It is 1000~100000mg/Nm that the system, which can handle organic concentration,3Volatile organic matter containing chlorine (CVOCs)
Exhaust gas；Under actual working conditions, the organic concentration in exhaust gas is less able to keep stable for a long time, and this system has in exhaust gas
When machine object concentration fluctuates, it can lead to by second temperature controller 10, according to temperature variations in system into system
Enter liquefied petroleum gas or increase air feed amount, with this come guarantee whole system temperature stablize within a preset range.
By system of the present invention treated organic exhaust gas containing chlorine, all kinds of organic concentrations reach GB16297-
" chemical industry volatility is organic with Jiangsu Province provincial standard DB32/3151-2016 for 1996 " discharge standard of air pollutants "
Object discharge standard " it requires, non-methane total hydrocarbons content is lower than 80mg/Nm3, therefore purified gas is without being further processed and can directly arrange
It puts.
Detailed description of the invention
Fig. 1 is that the adiabatic catalytic of volatile organic compounds containing chlorine of the present invention is burnt and heat utilization system signal is simple
Figure；
1, the first control valve, the 2, second control valve, 3, third control valve, the 4, the 4th control valve, the 5, the 5th control valve, 6, resistance to
High-temperature blower, 7, catalytic combustion reactor, 8, preheater, the 9, first temperature controller, 10, second temperature controller, 11, graphite
Heat exchanger, 12, gas-liquid separator, 13, alkali cleaning kettle, the 14, first branch line, 15, second branched pipe road, 16, third branched pipe
Road, 17, CVOCs exhaust pipe, 18, air pipe line, 19, liquefied petroleum air pipe, the 20, the 6th control valve, 21 the 4th branched pipes
Road.
Fig. 2 is the system simplified schematic diagram of organic waste gas catalytic combustion containing chlorine described in comparative example 1.
1, the first control valve, the 2, second control valve, 3, third control valve, the 4, the 4th control valve, 5, heat exchanger, 6, graphite changes
Hot device, 7, catalytic combustion reactor, 8, gas-liquid separator, 9, alkali cleaning kettle.
Specific embodiment
As shown in Figure 1, a kind of organic waste gas catalytic combustion containing chlorine and heat utilization system, including the first control valve 1, second
Control valve 2, third control valve 3, the 4th control valve 4, the 5th control valve 5, resisting blower 6, catalytic combustion reactor 7, preheating
Device 8, the first temperature controller 9, second temperature controller 10, graphite heat exchanger 11, gas-liquid separator 12, alkali cleaning kettle 13, first
Branch line 14, second branched pipe road 15, third branch line 16, CVOCs exhaust pipe 17, air pipe line 18, liquefied petroleum
Air pipe 19, the 6th control valve 20, the 4th branch line 21；
First control valve 1 is set on the liquefied petroleum air pipe 19, the second control valve 2 is set on air pipe line 18, the
Third control valve 3 is set on one branch line 14, the 5th control valve 5 is set on CVOCs exhaust pipe 17；
Resisting blower entrance is arranged in described 6 one end of resisting blower, and the other end is arranged resisting blower and exports, catalysis combustion
7 one end of reactor setting catalytic combustion reactor entrance, the outlet of other end setting catalytic combustion reactor are burnt, the CVOCs is useless
Air pipe 17, air pipe line 18, liquefied petroleum air pipe 19, the first branch line 14 one end respectively with resisting blower entrance
It is connected；The third branch line 16, the 4th branch line 21 one end respectively with resisting blower export connect；The catalysis
Combustion reactor entrance be arranged the first temperature controller 9, third branch line 16, the 4th branch line 21 the other end lead to respectively
It crosses the first temperature controller 9 to connect with catalytic combustion reactor entrance, the 4th control valve is set on the third branch line 16
4；Prolong airflow direction on 4th branch line and sets gradually the 6th control valve 20 and preheater 8；
The catalytic combustion reactor outlet setting second temperature controller 10,14, second points of first branch line
One end of bye-pass 15 passes through second temperature controller 10 respectively and connects catalytic combustion reactor outlet, first branch line
14 other end connects resisting blower entrance；
Graphite heat exchanger gas access is set at the top of the graphite heat exchanger 11, bottom setting graphite heat exchanger gas goes out
Mouthful, lower sidewall setting cooling water inlet, another side wall upper part be arranged cooling water outlet, the second branched pipe road 15 it is another
End is connected with graphite heat exchanger gas access；
Gas-liquid separator gas access is set at the top of the gas-liquid separator 12, and gas-liquid separator gas is arranged in side wall upper part
Gas-liquid separator liquid outlet is arranged in outlet, bottom, and the graphite heat exchanger gas vent and gas-liquid separator gas access connect
It connects, the gas-liquid separator gas vent connects alkali cleaning kettle 13, and the gas-liquid separator liquid outlet connects biochemistry pool.
The catalytic combustion reactor 7 uses insulation fix bed catalytic combustion reactor.
Concrete operations include:
(1) using the catalyst in hot-air preheating catalytic combustion reactor before reaction.
It (2) will the concentration of volatile organic matter containing chlorine be at room temperature first 1000~100000mg/Nm when reaction starting3It is useless
The low temperature feedstock gas that gas obtains after mixing with air is passed through progress adiabatic catalytic combustion reaction in catalytic combustion reactor, reaction
After obtain high-temperature tail gas, the temperature of high-temperature tail gas is controlled at 350~500 DEG C.When reaction heat recycles, catalysis is fired
The part high-temperature tail gas of reactor discharge is burnt as high temperature circulation gas, is aspirated by resisting blower and low temperature feedstock gas mixed
It closes, 200~250 DEG C of temperature of initial combustion of the mix waste gas to be reacted for the CVOCs that heats up to reach, into catalyst combustion reaction
Adiabatic catalytic burning is carried out in device.When the temperature of high-temperature tail gas is higher than 500 DEG C, increase air intake to reduce wait react mixed
The concentration for closing the exhaust gas of the volatile organic matter containing chlorine in exhaust gas makes organic concentration at reactor inlet be no more than 12000mg/
Nm3, to reduce the temperature of high-temperature tail gas；When the temperature of high-temperature tail gas be lower than 350 DEG C when, to reactor inlet at be passed through liquefaction stone
Oil gas reduces air intake and to improve the organic concentration at reactor inlet makes organic concentration at reactor inlet
Not less than 6000mg/Nm3, improve the temperature of high-temperature tail gas.When mix waste gas temperature to be reacted be higher than 250 DEG C, turn third control down
The aperture of valve (3) processed, turns the high-temperature tail gas amount for being recycled back to resisting blower down, to reduce mix waste gas temperature to be reacted；When to
When reacting mix waste gas temperature lower than 200 DEG C, the high-temperature tail gas amount for being recycled back to resisting blower is tuned up, to improve wait react mixing
Exhaust gas temperature.
(3) it after another part high-temperature gas that adiabatic catalytic combustion reaction obtains exchanges heat cooling in graphite heat exchanger, passes through
It crosses gas-liquid separator and obtains gas and liquid, gained liquid enters biochemistry pool purification after gas-liquid separation, and separating obtained gas is through alkali
It is vented after washing, all kinds of organic concentrations of gas reach GB16297-1996 " atmosphere pollution comprehensive discharge mark after purified treatment
It is quasi- " it is required with Jiangsu Province's provincial standard DB32/3151-2016 " chemical industry Volatile organic emissions standard ".
Catalytic combustion reactor 7 is insulation fix bed catalytic combustion reactor, and that loads in insulation fix bed reactor urges
Change combustion catalyst to refer to aluminium oxide, silica, silicon carbide, molecular sieve, rare-earth Y molecular sieve, H beta-molecular sieve, ZSM-5 molecule
One or both of sieve, MCM-41 molecular sieve, MCM-42 molecular sieve are carrier, with transition metal oxide titanium oxide, oxygen
Change vanadium, chromium oxide, manganese oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide, zinc oxide, lanthana, cerium oxide, praseodymium oxide, oxygen
Changing one or both of neodymium oxide is active component, and the load capacity of active component is 1~20%, catalyst particle size is 20~
80 mesh, by gas, total air speed is 10~500m to the loadings of catalyst in the reactor in catalytic combustion reactor3/(kgcat·
H) it calculates.
(CVOCs) concentration of volatile organic matter containing chlorine and organic matter total concentration use SP-6890 type gas-chromatography in gas
Instrument is analyzed.
The feed rate of organic exhaust gas containing chlorine handled in embodiment is 1000Nm3/ h, temperature are room temperature, and pressure is normal
Pressure.
Below with reference to embodiment, the present invention is described in further detail.
Embodiment 1
The present embodiment uses technique shown in FIG. 1, and reaction uses insulation fix bed reactor, reaction pressure 0.1MPa；
The catalyst loaded in reactor are as follows: CeO2/Al2O3, using mixed rolling method preparation when catalyst preparation, catalyst particle size is 2~
4mm, CeO2Load capacity is 15%, and catalyst particle size is 20~80 mesh, and the loaded catalyst in reactor is 100kg, contains chlorine
The calculating air speed of volatile organic compounds is 10.73m3/(kgcat·h)。
(1) it preheats: closing the first control valve 1, third control valve 3 and the 5th control valve 5, open the second control valve 2, resistance to
High-temperature blower 6, preheater 8, second temperature controller 9 and the 6th control valve 20, utilize 5000m3/ h air passes through air pipe line
18 and resisting blower 6 enter the 4th branch line 21 on preheater 8 in preheat, hot-air lead to the 4th branch line 21 enter
In catalytic combustion reactor 7, the hot air temperature of catalytic combustion reactor inlet is detected by the first temperature controller 9,
And preheater is controlled by air preheat to 400 DEG C, it is catalyzed and fires in the heat preheating catalytic combustion reactor 7 carried using hot-air
Catalyst needed for burning reaction, makes the temperature of catalyst reach 200~250 DEG C.
(2) reaction heat recycles: the temperature of catalyst in catalytic combustion reactor 7 being reached 200~250 in hot-air
After DEG C, preheater 8 and the 6th control valve 20 are closed, opens the second control valve 2, third control valve 3, the 4th control valve 4, the 5th control
Valve 5 processed, resisting blower 6, the first temperature controller 9 and second temperature controller 10；
From the chlorinated organics in the organic exhaust gas containing chlorine that CVOCs exhaust pipe 17 is passed through be benzyl chloride, benzyl chloride it is dense
Degree is 25413mg/Nm3.Initial air feed rate calculated with the reaction ratio of oxygen being passed through in air by benzyl chloride and
, the oxygen in air and benzyl chloride molar ratio are 8.5:1 herein, and the feed volume flow of air is 165Nm3/ h, air
Calculating air speed is 1.77m3/(kgcat·h).The low temperature that chloride containing benzyl organic exhaust gas and air are mixed to get by resisting blower 6
Unstripped gas is introduced into progress adiabatic catalytic combustion reaction, second temperature control in catalytic combustion reactor 7 by third branch line 16
Device 10 processed measures adiabatic reactor and exports 434 DEG C of high-temperature tail gas temperature.
By the first temperature controller 9 to the temperature detection of mix waste gas to be reacted at reactor inlet, third control is adjusted
The aperture of valve 3 processed, (cycling rate herein refers to that being recycled back to resisting blower by third control valve 3 enters to control loop rate to 0.5
High temperature circulation gas at mouthful accounts for the ratio of the high-temperature tail gas total amount of reactor outlet, similarly hereinafter)；High temperature circulation gas passes through first
The exhaust gas of branch line 14 and the volatile organic matter containing chlorine being passed through subsequently through CVOCs exhaust pipe 17 passes through air pipe line
The low temperature feedstock gas that 18 air being passed through are mixed to get mixes at resisting blower 6, detects through the first temperature controller 9, high
The heat carried in warm circulating air makes mixed mix waste gas temperature to be reacted maintain 229 DEG C, and reactor inlet waits reacting
Organic concentration in mix waste gas is diluted to 9968mg/Nm3。
(3) high-temperature tail gas is handled: in step (2), combustion reaction terminates that resulting height is discharged in catalytic combustion reactor
For warm tail gas in addition to being recycled to 6 entrance of resisting blower as high temperature circulation gas, part in addition passes through second branched pipe road 15
Into graphite heat exchanger 11, after the cooling water heat exchange being passed through through graphite heat exchanger 11, gas temperature is down to 50 DEG C；Gas after cooling
Body is gone successively to through 12 gas-liquid separation of gas-liquid separator, and the gas that gas-liquid separation obtains, which is sent to alkali cleaning kettle, absorbs remaining acidity
Substance hydrogen chloride is directly vented afterwards, and through detecting, the gas HCl concentration after alkali cleaning is 1.7mg/Nm3；It is obtained after gas-liquid separation
Liquid goes biochemistry pool to handle.
It is computed discovery, the removal efficiency of the volatile organic matter containing chlorine reaches 99.82%, the outlet of adiabatic catalytic combustion reactor
Benzyl chloride concentration in gas is 18mg/Nm3, non-methane total hydrocarbons concentration is lower than 20mg/Nm3.Resisting blower is run 1560 hours
After start to occur wind pressure shakiness, the phenomenon that wind pressure declines, on inspection, there is corrosion hole for draught fan impeller on piece, replace wind
System stable operation after machine blade.
Embodiment 2
The present embodiment is using process flow and process conditions similarly to Example 1, and difference place is in this present embodiment
Reactor in the catalyst that loads are as follows: Cr2O3/Al2O3, prepared using coprecipitation when catalyst preparation, catalyst particle size is
2~4mm, Cr2O3Load capacity is 18%, and catalyst particle size is 20~80 mesh, and the loaded catalyst in reactor is 100kg, is contained
The calculating air speed of chlorine volatile organic compounds is 10.73m3/(kgcat·h)。
(1) it preheats: closing the first control valve 1, third control valve 3 and the 5th control valve 5, open the second control valve 2, resistance to
High-temperature blower 6, preheater 8, second temperature controller 9 and the 6th control valve 20, utilize 5000m3/ h air passes through air pipe line
18 and resisting blower 6 enter the 4th branch line 21 on preheater 8 in preheat, hot-air lead to the 4th branch line 21 enter
In catalytic combustion reactor 7, the hot air temperature of 7 inlet of catalytic combustion reactor is detected by the first temperature controller 9,
And preheater is controlled by air preheat to 450 DEG C, it is catalyzed and fires in the heat preheating catalytic combustion reactor 7 carried using hot-air
Catalyst needed for burning reaction, makes the temperature of catalyst reach 200~250 DEG C.
(2) reaction heat recycles: the temperature of catalyst in catalytic combustion reactor 7 being reached 200~250 in hot-air
After DEG C, preheater 8 and the 6th control valve 20 are closed, opens the second control valve 2, third control valve 3, the 4th control valve 4, the 5th control
Valve 5 processed, resisting blower 6, the first temperature controller 9 and second temperature controller 10；
It is methylene chloride, methylene chloride from the chlorinated organics in the organic exhaust gas containing chlorine that CVOCs exhaust pipe 17 is passed through
Concentration be 17076mg/Nm3.Oxygen in air is matched with methylene chloride molar flow as 1:1 charging, the body of feedstock of air
Product flow is 20Nm3/h.The low temperature feedstock gas that organic exhaust gas containing methylene chloride and air are mixed to get by resisting blower 6 passes through
Third branch line 16 is introduced into progress adiabatic catalytic combustion reaction in catalytic combustion reactor 7.
By the first temperature controller 9 to the temperature detection of 6 exit high-temperature tail gas of resisting blower, third control is adjusted
The aperture of valve 3, control loop rate to 0.5；First temperature controller 9 detects that resisting blower exit is mixed wait react
The temperature of mix waste gas is lower than 200 DEG C, and second temperature controller 10 measures adiabatic reactor outlet high-temperature tail gas temperature lower than 350
℃.By carrying out analysis detection through SP-6890 type gas chromatograph, wait react the dense of the volatile organic matter containing chlorine in mix waste gas
Degree is lower than 6000mg/Nm3, the first control valve 1 is opened by second temperature controller 10, control valve aperture utilizes liquefaction stone
Oil gas increases the concentration wait react organic matter in mix waste gas, for guarantee liquefied petroleum gas convert completely, need to increase accordingly into
Enter the amount of oxygen of reactor, guarantees that the oil gas for entering system can be totally converted, tune up second by second temperature controller 10
Control valve 2 adjusts air feed amount to 121Nm3/ h, the calculating air speed of air are 1.30m3/(kgcat·h)；Through SP-6890 type
Gas chromatograph carries out analysis detection, and the organic concentration of catalytic combustion reactor entrance mix waste gas to be reacted is 10275mg/
Nm3。
Detect that reactor outlet temperature is improved to 359 DEG C by second temperature controller 10；Pass through temperature controller pair
The temperature detection of exhaust gas at fan outlet, the aperture of adjusting control valve 3, control loop rate to 0.55 are recycled back to resisting blower
Exhaust gas the temperature at fan outlet is improved again to 209 DEG C.
(3) high-temperature tail gas is handled: in step (2), combustion reaction terminates that resulting height is discharged in catalytic combustion reactor
For warm tail gas in addition to being recycled to 6 entrance of resisting blower as high temperature circulation gas, part in addition passes through second branched pipe road 15
Into graphite heat exchanger 11, the gas temperature after cooling water exchanges heat being passed through through graphite heat exchanger 11 is down to 50 DEG C；After cooling
Gas go successively to through 12 gas-liquid separation of gas-liquid separator, the gas that gas-liquid separation obtains send to alkali cleaning kettle absorb it is remaining
Acidic materials hydrogen chloride is directly vented afterwards, and through detecting, the gas HCl concentration after alkali cleaning is 1.5mg/Nm3.After gas-liquid separation
To liquid go biochemistry pool to handle.
It is computed discovery, the removal efficiency of the volatile organic matter containing chlorine reaches 99.7%, the outlet of adiabatic catalytic combustion reactor
Concentration dichloromethane is 20mg/Nm in gas3, non-methane total hydrocarbons concentration is lower than 42mg/Nm3.Resisting blower is run 2820 hours
After start to occur wind pressure shakiness, the phenomenon that wind pressure declines, on inspection, there is corrosion hole for draught fan impeller on piece, replace wind
System stable operation after machine blade.
It can be seen that the present embodiment is using same process flow, since the catalysis burning of methylene chloride is anti-
Answering hot (- 480kJ/mol) is only 1/8 or so of benzyl chloride reaction heat (- 3580kJ/mol), therefore the methylene chloride of same concentrations is useless
Gas can not make reaction system temperature maintain normal level；Fan outlet temperature is controlled by temperature controller in the present embodiment
Degree, a small amount of liquefied petroleum gas is added into system, and to maintain the stable operation of reaction system, treated, and tail gas reaches standard wants
It asks.
Embodiment 3
The present embodiment is using process flow and process conditions similarly to Example 1, and difference place is in this present embodiment
Reactor in the catalyst that loads are as follows: V2O5/TiO2, it being prepared using infusion process when catalyst preparation, catalyst particle size is 2~
4mm, V2O5Load capacity is 5%, and catalyst particle size is 20~80 mesh, and the loaded catalyst in reactor is 100kg, is waved containing chlorine
The calculating air speed of hair property organic compounds is 10.73m3/(kgcat·h)。
(1) it preheats: closing the first control valve 1, third control valve 3 and the 5th control valve 5, open the second control valve 2, resistance to
High-temperature blower 6, preheater 8 and second temperature controller 9 pass through air pipe line 18 and resisting blower using 5000m3/h air
It is preheated in 6 preheaters 8 entered on the 4th branch line 21, hot-air is led into the 4th branch line 21 into catalyst combustion reaction
In device 7, the hot air temperature of 7 inlet of catalytic combustion reactor is detected by the first temperature controller 9, and controls preheater
By air preheat to 400 DEG C, preheated in catalytic combustion reactor 7 needed for catalyst combustion reaction using the heat that hot-air carries
Catalyst makes the temperature of catalyst reach 200~250 DEG C.
(2) reaction heat recycles: the temperature of catalyst in catalytic combustion reactor 7 being reached 200~250 in hot-air
After DEG C, preheater 8 and the 6th control valve 20 are closed, opens the second control valve 2, third control valve 3, the 4th control valve 4, the 5th control
Valve 5 processed, resisting blower 6, the first temperature controller 9 and second temperature controller 10；
It is monochlor-benzene, monochlor-benzene from the chlorinated organics in the organic exhaust gas containing chlorine that CVOCs exhaust pipe 17 is passed through
Concentration be 22600mg/Nm3.Initial air feed rate is by monochlor-benzene and the reaction ratio of oxygen that is passed through in air
It calculates and obtains, the oxygen in air and benzyl chloride molar ratio are 7:1, the feed volume flow 138Nm of air herein3/ h, air
Calculating air speed be 1.48m3/(kgcat·h).What organic exhaust gas containing monochlor-benzene and air were mixed to get by resisting blower 6
Low temperature feedstock gas progress adiabatic catalytic combustion reaction is introduced into catalytic combustion reactor by third branch line 16, second is warm
Degree controller 10 measures adiabatic reactor and exports 400 DEG C of high-temperature tail gas temperature.
By the first temperature controller 9 to the temperature detection of mix waste gas to be reacted at reactor inlet, third control is adjusted
The aperture of valve 3 processed, control loop rate to 0.5；High temperature circulation gas is by the first branch line 14 and subsequently through CVOCs exhaust gas
The exhaust gas containing monochlor-benzene that pipeline 17 is passed through, the low temperature feedstock gas being mixed to get by the air that air pipe line 18 is passed through are resistance to
It mixes at high-temperature blower 6, is detected through the first temperature controller 9, the heat carried in high temperature circulation gas makes mixed to anti-
Mix waste gas temperature is answered to maintain 213 DEG C, the organic concentration in catalytic combustion reactor entrance mix waste gas to be reacted is
9613mg/Nm3。
(3) high-temperature tail gas is handled: in step (2), combustion reaction terminates that resulting height is discharged in catalytic combustion reactor
For warm tail gas in addition to being recycled to 6 entrance of resisting blower as high temperature circulation gas, part in addition passes through second branched pipe road 15
Into graphite heat exchanger 11, the gas temperature after cooling water exchanges heat being passed through through graphite heat exchanger 11 is down to 50 DEG C；After cooling
Gas go successively to through 12 gas-liquid separation of gas-liquid separator, the gas that gas-liquid separation obtains send to alkali cleaning kettle absorb it is remaining
Acidic materials hydrogen chloride is directly vented afterwards, and through detecting, the gas HCl concentration after alkali cleaning is 1.6mg/Nm3.After gas-liquid separation
To liquid go biochemistry pool to handle.
It is computed discovery, the removal efficiency of volatile organic matter containing chlorine reaches 99.8%, and adiabatic catalytic combustion reactor is worked off one's feeling vent one's spleen
The concentration of monochlor-benzene is 17mg/Nm3 in body, and non-methane total hydrocarbons concentration is lower than 19mg/Nm3.Resisting blower operation 1320 is small
When after start to occur wind pressure shakiness, the phenomenon that wind pressure declines, on inspection, there is corrosion hole for draught fan impeller on piece, replace
System stable operation after fan blade.
Embodiment 4
The present embodiment is using process flow and process conditions similarly to Example 1, and difference place is in this present embodiment
Reactor in the catalyst that loads are as follows: Cr2O3/Al2O3, prepared using coprecipitation when catalyst preparation, catalyst particle size is
2~4mm, Cr2O3Load capacity is 9.3%, and catalyst particle size is 20~80 mesh, and the loaded catalyst in reactor is 100kg,
The calculating air speed of the volatile organic compounds containing chlorine is 10.73m3/(kgcat·h)。
(1) it preheats: closing the first control valve 1, third control valve 3 and the 5th control valve 5, open the second control valve 2, resistance to
High-temperature blower 6, preheater 8 and second temperature controller 9 pass through air pipe line 18 and resisting blower using 5000m3/h air
It is preheated in 6 preheaters 8 entered on the 4th branch line 21, hot-air leads to the 4th branch line 21 and enters catalytic combustion reactor
In 7, the hot air temperature of 7 inlet of catalytic combustion reactor is detected by the first temperature controller 9, and controlling preheater will
To 450 DEG C, the heat carried using hot-air is preheated in catalytic combustion reactor 7 urges needed for catalyst combustion reaction for air preheat
Agent makes the temperature of catalyst reach 200~250 DEG C.
(2) reaction heat recycles: the temperature of catalyst in catalytic combustion reactor 7 being reached 200~250 in hot-air
After DEG C, preheater 8 and the 6th control valve 20 are closed, opens the second control valve 2, third control valve 3, the 4th control valve 4, the 5th control
Valve 5 processed, resisting blower 6, the first temperature controller 9 and second temperature controller 10；
It is monochloro methane, monochloro methane from the chlorinated organics in the organic exhaust gas containing chlorine that CVOCs exhaust pipe 17 is passed through
Concentration be 10145mg/Nm3.Oxygen in air is matched with monochloro methane molar flow as 1.5:1 charging, the charging of air
Volume flow is 30Nm3/h。
Organic exhaust gas containing monochloro methane and air pass through third by the low temperature feedstock gas that resisting blower 6 is mixed to get and divide
Bye-pass 16 is introduced into progress adiabatic catalytic combustion reaction in catalytic combustion reactor, by the first temperature controller 9 to high temperature resistant
The temperature detection of 6 exit high-temperature tail gas of blower adjusts the aperture of third control valve 3, control loop rate to 0.5；First temperature
Controller 9 detects that the temperature of the mixed mix waste gas to be reacted in resisting blower exit is lower than 200 DEG C, second temperature control
Device 10 processed measures adiabatic reactor outlet high-temperature tail gas temperature lower than 350 DEG C.By being divided through SP-6890 type gas chromatograph
Analysis detection, wait react the concentration of the volatile organic matter containing chlorine in mix waste gas lower than 6000mg/Nm3, controlled by second temperature
Device 10 opens the first control valve 1, and control valve aperture liquefied petroleum gas increases the concentration wait react organic matter in mix waste gas, is
Guarantee that liquefied petroleum gas converts completely, need to increase accordingly the amount of oxygen into reactor, guarantees the oil gas energy for entering system
It is totally converted, the second control valve 2 is tuned up by second temperature controller 10, adjust air feed amount to 131Nm3/ h, air
Calculating air speed is 1.40m3/(kgcat·h)；Analysis detection, catalytic combustion reactor are carried out through SP-6890 type gas chromatograph
The organic concentration of entrance mix waste gas to be reacted is 7972mg/Nm3。
Detect that reactor outlet temperature is improved to 376 DEG C by second temperature controller 10；It is controlled by the first temperature
Temperature detection of the device 9 to 6 exit exhaust gas of blower, the aperture of adjusting control valve 3, control loop rate to 0.52 are recycled back to resistance to height
The exhaust gas of warm blower improves the temperature at fan outlet again to 208 DEG C.
(3) high-temperature tail gas is handled: in step (2), combustion reaction terminates that resulting height is discharged in catalytic combustion reactor
For warm tail gas in addition to being recycled to 6 entrance of resisting blower as high temperature circulation gas, part in addition passes through second branched pipe road 15
Into graphite heat exchanger 11, the gas temperature after cooling water exchanges heat being passed through through graphite heat exchanger 11 is down to 50 DEG C；After cooling
Gas go successively to through 12 gas-liquid separation of gas-liquid separator, the gas that gas-liquid separation obtains send to alkali cleaning kettle absorb it is remaining
Acidic materials hydrogen chloride is directly vented afterwards, and through detecting, the gas HCl concentration after alkali cleaning is 1.5mg/Nm3.After gas-liquid separation
To liquid go biochemistry pool to handle.
It is computed discovery, the removal efficiency of volatile organic matter containing chlorine reaches 99.8%, and adiabatic catalytic combustion reactor is worked off one's feeling vent one's spleen
Monochloro methane concentration is 9mg/Nm in body3, non-methane total hydrocarbons concentration is lower than 32mg/Nm3.After resisting blower is run 2910 hours
Start the phenomenon that wind pressure shakiness, wind pressure decline occur, on inspection, corrosion hole, more ventilating fan occurs for draught fan impeller on piece
System stable operation after blade.
Embodiment 5
The present embodiment is using process flow and process conditions similarly to Example 1, and difference place is in this present embodiment
Reactor in the catalyst that loads are as follows: V2O5-MOO3/TiO2, prepared using infusion process when catalyst preparation, catalyst particle size is
2~4mm, V2O5Load capacity is 1%, MOO3Load capacity is 9%, and catalyst particle size is 20~80 mesh, the catalyst dress in reactor
The amount of filling out is 100kg, and the calculating air speed of the volatile organic compounds containing chlorine is 10.73m3/(kgcat·h)。
(1) it preheats: closing the first control valve 1, third control valve 3 and the 5th control valve 5, open the second control valve 2, resistance to
High-temperature blower 6, preheater 8 and second temperature controller 9, utilize 5000m3/ h air passes through air pipe line 18 and resisting blower
It is preheated in 6 preheaters 8 entered on the 4th branch line 21, hot-air leads to the 4th branch line 21 and enters catalytic combustion reactor
In 7, the hot air temperature of 7 inlet of catalytic combustion reactor is detected by the first temperature controller 9, and controlling preheater will
To 400 DEG C, the heat carried using hot-air is preheated in catalytic combustion reactor 7 urges needed for catalyst combustion reaction for air preheat
Agent makes the temperature of catalyst reach 200~250 DEG C.
(2) reaction heat recycles: the temperature of catalyst in catalytic combustion reactor 7 being reached 200~250 in hot-air
After DEG C, preheater 8 and the 6th control valve 20 are closed, opens the second control valve 2, third control valve 3, the 4th control valve 4, the 5th control
Valve 5 processed, resisting blower 6, the first temperature controller 9 and second temperature controller 10；
It is ortho-chlorotolu'ene, ortho-chlorotolu'ene from the chlorinated organics in the organic exhaust gas containing chlorine that CVOCs exhaust pipe 17 is passed through
Concentration be 25413mg/Nm3.Initial air feed rate is by ortho-chlorotolu'ene and the reaction ratio of oxygen that is passed through in air
It calculates and obtains, the oxygen in air and ortho-chlorotolu'ene molar ratio are 8.5:1 herein, and the feed volume flow of air is 167Nm3/
H, the calculating air speed of air are 1.80m3/(kgcat·h).Organic exhaust gas containing ortho-chlorotolu'ene is mixed with air by resisting blower 6
Obtained low temperature feedstock gas is introduced into progress adiabatic catalytic combustion reaction in catalytic combustion reactor by third branch line 16,
Second temperature controller 10 measures adiabatic reactor and exports 416 DEG C of high-temperature tail gas temperature.
By the first temperature controller 9 to the temperature detection of mix waste gas to be reacted at reactor inlet, third control is adjusted
The aperture of valve 3 processed, control loop rate to 0.5.High temperature circulation gas is by the first branch line 14 and subsequently through CVOCs exhaust gas
The exhaust gas for the volatile organic matter containing chlorine that pipeline 17 is passed through, the low temperature feedstock being mixed to get by the air that air pipe line 18 is passed through
Gas mixes at resisting blower 6, detects through the first temperature controller 9, after the heat carried in high temperature circulation gas makes mixing
Mix waste gas temperature to be reacted maintain 220 DEG C, catalytic combustion reactor entrance mix waste gas organic concentration to be reacted is
9442mg/Nm3。
(3) high-temperature tail gas is handled: in step (2), combustion reaction terminates that resulting height is discharged in catalytic combustion reactor
For warm tail gas in addition to being recycled to 6 entrance of resisting blower as high temperature circulation gas, part in addition passes through second branched pipe road 15
Into graphite heat exchanger 11, the gas temperature after cooling water exchanges heat being passed through through graphite heat exchanger 11 is down to 50 DEG C；After cooling
Gas go successively to through 12 gas-liquid separation of gas-liquid separator, the gas that gas-liquid separation obtains send to alkali cleaning kettle absorb it is remaining
Acidic materials hydrogen chloride is directly vented afterwards, and through detecting, the gas HCl concentration after alkali cleaning is 1.1mg/Nm3.After gas-liquid separation
To liquid go biochemistry pool to handle.
It is computed discovery, the removal efficiency of volatile organic compounds containing chlorine reaches 99.8%, and adiabatic catalytic combustion reactor goes out
The concentration of ortho-chlorotolu'ene is 16mg/Nm3 in gas, and non-methane total hydrocarbons concentration is lower than 18mg/Nm3.Resisting blower operation
Start the phenomenon that wind pressure shakiness, wind pressure decline occur after 1330 hours, on inspection, etch pit occurs for draught fan impeller on piece
System stable operation after fan blade is replaced in hole.
Embodiment 6
The present embodiment is using process flow and process conditions similarly to Example 1, and difference place is in this present embodiment
Reactor in the catalyst that loads are as follows: MnO2/Al2O3, it being prepared using infusion process when catalyst preparation, catalyst particle size is 2~
4mm, MnO2 load capacity are 20%, and catalyst particle size is 20~80 mesh, and the loaded catalyst in reactor is 100kg, contain chlorine
The calculating air speed of volatile organic compounds is 10.73m3/(kgcat·h)。
(1) it preheats: closing the first control valve 1, third control valve 3 and the 5th control valve 5, open the second control valve 2, resistance to
High-temperature blower 6, preheater 8 and second temperature controller 9, utilize 5000m3/ h air passes through air pipe line 18 and resisting blower
It is preheated in 6 preheaters 8 entered on the 4th branch line 21, hot-air leads to the 4th branch line 21 and enters catalytic combustion reactor
In 7, the hot air temperature of 7 inlet of catalytic combustion reactor is detected by the first temperature controller 9, and controlling preheater will
To 400 DEG C, the heat carried using hot-air is preheated in catalytic combustion reactor 7 urges needed for catalyst combustion reaction for air preheat
Agent makes the temperature of catalyst reach 200~250 DEG C.
(2) reaction heat recycles: the temperature of catalyst in catalytic combustion reactor 7 is reached 200~250 DEG C by hot-air
Afterwards, preheater 8 and the 6th control valve 20 are closed, the second control valve 2, third control valve 3, the 4th control valve 4, the 5th control are opened
Valve 5, resisting blower 6, the first temperature controller 9 and second temperature controller 10；
From the chlorinated organics in the organic exhaust gas containing chlorine that CVOCs exhaust pipe 17 is passed through be 1,2- dichloroethanes, 1,2-
The concentration of dichloroethanes is 19888mg/Nm3.By in air oxygen and 1,2- dichloroethanes molar flow match for 2.5:1 into
Material, the feed volume flow of air are 49Nm3/h.The organic exhaust gas of dichloroethanes containing 1,2- is mixed with air by resisting blower 6
Obtained low temperature feedstock gas is introduced into progress adiabatic catalytic combustion reaction in catalytic combustion reactor by third branch line 16, leads to
The first temperature controller 9 is crossed to the temperature detection of 6 exit high-temperature tail gas of resisting blower, adjusts the aperture of third control valve 3,
Control loop rate is to 0.5；First temperature controller 9 detects the mixed mix waste gas to be reacted in resisting blower exit
Temperature is lower than 200 DEG C, and second temperature controller 10 measures adiabatic reactor outlet high-temperature tail gas temperature lower than 350 DEG C.Pass through through
SP-6890 type gas chromatograph carries out analysis detection, and the concentration wait react the volatile organic matter containing chlorine in mix waste gas is lower than
6000mg/Nm3, the first control valve 1 is opened by second temperature controller 10, control valve aperture liquefied petroleum gas increases to anti-
The concentration of organic matter in mix waste gas is answered, to guarantee that liquefied petroleum gas converts completely, needs to increase accordingly the oxygen into reactor
Tolerance guarantees that the oil gas for entering system can be totally converted, tunes up the second control valve 2 by second temperature controller 10, adjusts
Air feed amount is to 150Nm3/ h, the calculating air speed of air are 1.61m3/ (kgcath), detects that catalytic combustion reactor enters
The organic concentration of mouth mix waste gas to be reacted is 11789mg/Nm3。
Detect that reactor outlet temperature is improved to 422 DEG C by second temperature controller 10；It is controlled by the first temperature
Temperature detection of the device 9 to exhaust gas at fan outlet, the aperture of adjusting control valve 3, control loop rate to 0.52 are recycled back to high temperature resistant
The exhaust gas of blower improves the temperature at fan outlet again to 233 DEG C.
(3) high-temperature tail gas is handled: in step (2), combustion reaction terminates that resulting height is discharged in catalytic combustion reactor
For warm tail gas in addition to being recycled to 6 entrance of resisting blower as high temperature circulation gas, part in addition passes through second branched pipe road 15
Into graphite heat exchanger 11, the gas temperature after cooling water exchanges heat being passed through through graphite heat exchanger 11 is down to 50 DEG C；After cooling
Gas go successively to through 12 gas-liquid separation of gas-liquid separator, the gas that gas-liquid separation obtains send to alkali cleaning kettle absorb it is remaining
Acidic materials hydrogen chloride is directly vented afterwards, and through detecting, the gas HCl concentration after alkali cleaning is 1.2mg/Nm3.After gas-liquid separation
To liquid go biochemistry pool to handle.
It is computed discovery, CVOCs removal efficiency reaches 99.9%, 1,2- dichloro in adiabatic catalytic combustion reactor exit gas
Ethane concentration is 6mg/Nm3, and non-methane total hydrocarbons concentration is lower than 25mg/Nm3.Resisting blower starts to occur after running 1710 hours
There is corrosion hole for draught fan impeller on piece, is after replacing fan blade on inspection in the phenomenon that wind pressure is unstable, and wind pressure declines
System stable operation.
Embodiment 7
The present embodiment is using process flow and process conditions similarly to Example 1, and difference place is in this present embodiment
Reactor in the catalyst that loads are as follows: CeO2/SiO2, catalyst particle size is 2~4mm, CeO2Load capacity be 15%, catalysis
Agent partial size is 20~80 mesh, and the loaded catalyst in reactor is 100kg, the calculating air speed of the volatile organic compounds containing chlorine
For 10.73m3/(kgcat·h)。
(1) it preheats: closing the first control valve 1, third control valve 3 and the 5th control valve 5, open the second control valve 2, resistance to
High-temperature blower 6, preheater 8 and second temperature controller 9, utilize 5000m3/ h air passes through air pipe line 18 and resisting blower
It is preheated in the preheater 8 of 6 the 4th branch lines 21 of entrance, hot-air leads to the 4th branch line 21 and enters catalytic combustion reactor 7
In, the hot air temperature of 7 inlet of catalytic combustion reactor is detected by the first temperature controller 9, and controlling preheater will
To 400 DEG C, the heat carried using hot-air is preheated in catalytic combustion reactor 7 urges needed for catalyst combustion reaction for air preheat
Agent makes the temperature of catalyst reach 200~250 DEG C.
(2) reaction heat recycles: the temperature of catalyst in catalytic combustion reactor 7 being reached 200~250 in hot-air
After DEG C, preheater 8 and the 6th control valve 20 are closed, opens the second control valve 2, third control valve 3, the 4th control valve 4, the 5th control
Valve 5 processed, resisting blower 6, the first temperature controller 9 and second temperature controller 10；
It is o-chlorobenzaldehyde, adjacent chlorobenzene from the chlorinated organics in the organic exhaust gas containing chlorine that CVOCs exhaust pipe 17 is passed through
The concentration of formaldehyde is 28125mg/Nm3.Initial air feed rate is anti-by o-chlorobenzaldehyde and the oxygen that is passed through in air
Calculating should be matched and obtained, the oxygen in air and o-chlorobenzaldehyde molar ratio are 7.5:1 herein, and the feed volume flow of air is
148Nm3/ h, the calculating air speed of air are 1.59m3/(kgcat·h).Organic exhaust gas containing o-chlorobenzaldehyde and air are by high temperature resistant
The low temperature feedstock gas that blower 6 is mixed to get is introduced into catalytic combustion reactor by third branch line 16 and carries out adiabatic catalytic
Combustion reaction, second temperature controller 10 measure adiabatic reactor and export 404 DEG C of high-temperature tail gas temperature.
By the first temperature controller 9 to the temperature detection of mix waste gas to be reacted at reactor inlet, third control is adjusted
The aperture of valve 3 processed, control loop rate to 0.5；High temperature circulation gas is by the first branch line 14 and subsequently through CVOCs exhaust gas
Pipeline 17 be passed through containing the exhaust gas containing o-chlorobenzaldehyde, the low temperature feedstock gas that is mixed to get by the air that air pipe line 18 is passed through
It mixes at resisting blower 6, is detected through the first temperature controller 9, the heat carried in high temperature circulation gas makes mixed
Mix waste gas temperature to be reacted maintains 212 DEG C, the organic concentration in catalytic combustion reactor entrance mix waste gas to be reacted
It is diluted to 11280mg/Nm3。
(3) high-temperature tail gas is handled: in step (2), combustion reaction terminates that resulting height is discharged in catalytic combustion reactor
For warm tail gas in addition to being recycled to 6 entrance of resisting blower as high temperature circulation gas, part in addition passes through second branched pipe road 15
Into graphite heat exchanger 11, the gas temperature after cooling water exchanges heat being passed through through graphite heat exchanger 11 is down to 50 DEG C；After cooling
Gas go successively to through 12 gas-liquid separation of gas-liquid separator, the gas that gas-liquid separation obtains send to alkali cleaning kettle absorb it is remaining
Acidic materials hydrogen chloride is directly vented afterwards, and through detecting, the gas HCl concentration after alkali cleaning is 1.3mg/Nm3.After gas-liquid separation
To liquid go biochemistry pool to handle.
It is computed discovery, the removal efficiency of volatile organic matter containing chlorine reaches 99.9%, detects adiabatic catalytic combustion reactor
The concentration of o-chlorobenzaldehyde is 17mg/Nm in exit gas3, non-methane total hydrocarbons concentration is lower than 19mg/Nm3.Resisting blower operation
Start the phenomenon that wind pressure shakiness, wind pressure decline occur after 1280 hours, on inspection, etch pit occurs for draught fan impeller on piece
System stable operation after fan blade is replaced in hole.
Embodiment 8
The present embodiment is using process flow and process conditions similarly to Example 1, and difference place is in this present embodiment
The concentration of benzyl chloride changes in a certain range in organic exhaust gas, and benzyl chloride initial concentration is 84710mg/Nm3, dropped after one hour
To 42355mg/Nm3, then through one hour afterchlorinate benzyl concentration it is again decreased to 2824mg/Nm3.Catalyst packing in reactor
Amount is 100kg, and the calculating air speed of the volatile organic compounds containing chlorine is 10.73m3/(kgcat·h)；The flow of initial air by
The reaction ratio of benzyl chloride and oxygen is calculated and obtain, herein oxygen and benzyl chloride molar ratio in air are as follows: 8.5:1, air into
Stream amount is 566Nm3/ h, the calculating air speed of air are 6.07m3/(kgcat·h)。
(1) it preheats: closing the first control valve 1, third control valve 3 and the 5th control valve 5, open the second control valve 2, resistance to
High-temperature blower 6, preheater 8 and second temperature controller 9, utilize 5000m3/ h air passes through air pipe line 18 and resisting blower
It is preheated in 6 preheaters 8 entered on the 4th branch line 21, hot-air leads to the 4th branch line 21 and enters catalytic combustion reactor
In 7, the hot air temperature of 7 inlet of catalytic combustion reactor is detected by the first temperature controller 9, and controlling preheater will
To 400 DEG C, the heat carried using hot-air is preheated in catalytic combustion reactor 7 urges needed for catalyst combustion reaction for air preheat
Agent 100kg makes the temperature of catalyst reach 200~250 DEG C.
(2) reaction heat recycles: the temperature of catalyst in catalytic combustion reactor 7 being reached 200~250 in hot-air
After DEG C, preheater 8 and the 6th control valve 20 are closed, opens the second control valve 2, third control valve 3, the 4th control valve 4, the 5th control
Valve 5 processed, resisting blower 6, the first temperature controller 9 and second temperature controller 10；
From the chlorinated organics in the organic exhaust gas containing chlorine that CVOCs exhaust pipe 17 is passed through be benzyl chloride, benzyl chloride it is dense
Degree is 84710mg/Nm3.Initial air feed rate calculated with the reaction ratio of oxygen being passed through in air by benzyl chloride and
, the oxygen in air and benzyl chloride molar ratio are 8.5:1 herein, and the feed volume flow of air is 566Nm3/h.Chloride containing
Benzyl organic exhaust gas and air, which are introduced by the low temperature feedstock gas that resisting blower 6 is mixed to get by third branch line 16, to be catalyzed
Adiabatic catalytic combustion reaction is carried out in combustion reactor, by the first temperature controller 9 to 6 exit high temperature tail of resisting blower
The temperature detection of gas adjusts the aperture of third control valve 3, control loop rate to 0.5；First temperature controller 9 detects resistance to height
The temperature of mixed mix waste gas to be reacted is higher than 250 DEG C at warm fan outlet, and it is anti-that second temperature controller 10 measures insulation
Device outlet high-temperature tail gas temperature is answered to be higher than 500 DEG C.It is mixed wait react by carrying out analysis detection through SP-6890 type gas chromatograph
The concentration for closing the volatile organic matter containing chlorine in exhaust gas is higher than 12000mg/Nm3, the second control is tuned up by second temperature controller 10
2 aperture of valve processed increases air feed amount, and with Dilution air mixed gas, air feed rate is 2713Nm at this time3/ h, air
Calculating air speed be 29.12m3/(kgcat·h)；Detect the organic matter of catalytic combustion reactor entrance mix waste gas to be reacted
Concentration is 10803mg/Nm3。
Detect that reactor outlet temperature is reduced to 464 DEG C by second temperature controller 10；It is controlled by the first temperature
Temperature detection of the device 9 to exhaust gas at fan outlet, the aperture of adjusting control valve 3, control loop rate to 0.5 are recycled back to high temperature resistant
The exhaust gas of blower improves the temperature at fan outlet again to 244 DEG C.It is computed discovery, CVOCs removal efficiency reaches 99.9%,
The concentration for detecting benzyl chloride in reactor outlet gas is 15mg/Nm3, non-methane total hydrocarbons concentration is lower than 17mg/Nm3。
System detects that reactor outlet gas temperature is fast after stable operation one hour, through second temperature controller 10
Prompt drop is turned down the aperture of the second control valve 2 by temperature controller 10, gradually reduces air feed amount down to 320 DEG C, this space-time
Gas feed rate is 927Nm3/ h, the calculating air speed of air are 9.95m3/(kgcat·h)；The heat that benzyl chloride reaction is released makes
Reactor outlet gas temperature is improved again to 456 DEG C.It is examined by temperature of first temperature controller 9 to exhaust gas at fan outlet
It surveys, adjusts the aperture of third control valve 3, the cycling rate of high-temp waste gas is set as 0.5 herein, and the exhaust gas for being recycled back to resisting blower will
Temperature at fan outlet is improved to 240 DEG C.Through analysis detection, the organic concentration in reactor inlet mixed gas reaches
10555mg/Nm3；It is computed discovery, CVOCs removal efficiency at this time reaches 99.5%, detects chlorination in reactor outlet gas
The concentration of benzyl is 15mg/Nm3, non-methane total hydrocarbons concentration is lower than 17mg/Nm3。
System after stable operation one hour, detects reactor outlet gas temperature by second temperature controller 10 again
It quickly reduces, turns the aperture of the second control valve 2 down by temperature controller 10, gradually reduce air feed amount, reactor outlet
Gas temperature continues to drop to 350 DEG C；By the first temperature controller 9 to the temperature detection of exhaust gas at fan outlet, the is adjusted
The aperture of three control valves 3, control loop rate to 0.5, temperature controller detect that the temperature of resisting blower exit exhaust gas is low
In 200 DEG C；It is at this time 3107mg/Nm wait react the organic concentration in mix waste gas through detecting3, controlled by second temperature
Device 10 opens the first control valve 1, and control valve aperture liquefied petroleum gas increases the concentration wait react organic matter in mix waste gas, is
Guarantee that liquefied petroleum gas converts completely, need to increase accordingly the amount of oxygen into reactor, guarantees the oil gas energy for entering system
It is totally converted, the second control valve 2 is tuned up by second temperature controller 10, adjust air feed amount to 145Nm3/ h, air
Calculating air speed is 1.56m3/ (kgcath) detects that the organic matter of catalytic combustion reactor entrance mix waste gas to be reacted is dense
Degree is 6009mg/Nm3。
It detects that reactor outlet temperature is promoted to 405 DEG C by second temperature controller 10, is recycled back to resisting blower
High temperature circulation gas the mix waste gas temperature to be reacted at fan outlet is improved again to 215 DEG C.Through analysis detection, reaction
Organic concentration in device entrance mixed gas reaches 10555mg/Nm3；It is computed discovery, CVOCs removal efficiency reaches at this time
99.4%, detect that benzyl chloride concentration is 7mg/Nm in reactor outlet gas3, non-methane total hydrocarbons concentration is lower than 13mg/Nm3。
(3) high-temperature tail gas is handled: in step (2), combustion reaction terminates that resulting height is discharged in catalytic combustion reactor
For warm tail gas in addition to being recycled to 6 entrance of resisting blower as high temperature circulation gas, part in addition passes through second branched pipe road 15
Into graphite heat exchanger 11, the gas temperature after cooling water exchanges heat being passed through through graphite heat exchanger 11 is down to 50 DEG C；After cooling
Gas go successively to through 12 gas-liquid separation of gas-liquid separator, the gas that gas-liquid separation obtains send to alkali cleaning kettle absorb it is remaining
Acidic materials hydrogen chloride, is directly vented afterwards, and the liquid obtained after gas-liquid separation goes biochemistry pool to handle.
System passes through stable operation in three hours, in the adiabatic catalytic combustion reactor exit gas detected in three hours
Benzyl chloride concentration be consistently lower than 16mg/Nm3, non-methane total hydrocarbons concentration is below 18mg/Nm3, the removal efficiency of CVOCs is always not
Lower than 99.4%, the gas HCl concentration after alkali cleaning is below 1.7mg/Nm3。
The phenomenon that resisting blower starts wind pressure shakiness occur after running 3103 hours, wind pressure declines is on inspection blower
Occur corrosion hole on impeller blade, replaces system stable operation after fan blade.
Comparative example 1
Exhaust gas and process conditions are handled with embodiment 1, the difference is that substitute resisting blower with heat exchanger, as returning
The device of heat of reaction is received, the high-temperature tail gas of reactor outlet heats the gaseous mixture before reactor inlet, specific work
Skill flow chart is referring to fig. 2；Due to being the heat exchange between gas, to guarantee heat exchange efficiency, while slowing down high-temperature tail gas heat exchanging device
Internal corrosion, used herein is the good nickel material heat exchanger of heat transfer property.
After the low temperature feedstock gas for adjusting the system that is passed through by the second control valve 2, third control valve 3 is stablized, waved containing chlorine
The inlet amount of hair property organic compounds is 1000Nm3/ h, the calculating air speed of the volatile organic compounds containing chlorine are 10.73m3/
(kgcath), the concentration of volatile organic matter containing chlorine therein is 25413mg/Nm3, initial air feed rate is by benzyl chloride
It calculates and obtains with the reaction ratio of oxygen, herein the oxygen in air and benzyl chloride molar ratio are as follows: 8.5:1, the body of feedstock of air
Product flow is 165Nm3/ h, the calculating air speed of air are 1.77m3/(kgcat·h).Through heat exchanger 5 and have been subjected to catalysis burning instead
After the high-temperature tail gas heat exchange heating being discharged after answering, reactor inlet mixture temperature is 225 DEG C, through catalytic combustion reactor
The high-temperature tail gas temperature of 7 outlet discharges is 485 DEG C；After high-temperature tail gas and the heat exchange cooling of subsequent low temperature feedstock gas, it is passed through graphite and changes
Further cooling, the gas temperature after cooling water exchanges heat being passed through through graphite heat exchanger 6 are down to 50 DEG C to hot device 6；After cooling
Gas is gone successively to through 8 gas-liquid separation of gas-liquid separator, and the gas that gas-liquid separation obtains, which is sent to alkali cleaning kettle 9, absorbs remaining acid
Property substance hydrogen chloride, afterwards directly emptying.The liquid obtained after gas-liquid separation goes biochemistry pool to handle.Discovery is calculated, CVOCs is de- at this time
Except rate reaches 99.4%, detect that benzyl chloride concentration is 7mg/Nm in adiabatic catalytic Combustion outlet gas3, non-methane total hydrocarbons concentration
Lower than 13mg/Nm3, the gas HCl concentration after alkali cleaning is 1.8mg/Nm3。
There is hole on the tubulation for after operation in 1021 hours, there is one third in heat exchanger 5 in the system, needs
More switching heat-exchanger.For the system of comparative example compared with the system of embodiment, the main distinction of the two is the system of comparative example by resistance to height
Warm blower replaces with device of the heat exchanger as recycling heat of reaction；Through calculating, the equipment of nickel material heat exchanger and resisting blower
The ratio between cost is about 15~25 or so.
It can be seen that the system not only has corrosion equipment and shortens the risk of equipment life, and it will increase equipment
Investment cost.
Claims (10)
1. a kind of purifying treatment method of volatile organic compounds containing chlorine, which is characterized in that the described method includes:
(1) it preheats: catalyst needed for preheating catalyst combustion reaction using hot-air；
(2) reaction heat recycles: the low temperature feedstock gas obtained after the exhaust gas of the volatile organic matter containing chlorine is mixed with air, leads to
Enter the catalyst preheated through step (1), carry out adiabatic catalytic combustion reaction, obtains high-temperature tail gas after reaction, it will part height
Warm tail gas is mixed as high temperature circulation gas with low temperature feedstock gas, former using the heat low temperature carried in high temperature circulation gas
Expect gas, obtain mix waste gas to be reacted, the temperature of the mix waste gas to be reacted reaches the starting combustion of the volatile organic matter containing chlorine
Burn temperature；Resulting mix waste gas to be reacted is subjected to adiabatic catalytic combustion reaction, obtains high-temperature tail gas；By adjusting wait react
Organic concentration in mix waste gas maintains the temperature of high-temperature tail gas；By adjusting the high temperature circulation for being recycled back to resisting blower
Gas flow maintains the temperature of mix waste gas to be reacted；
(3) high-temperature tail gas is handled: step (2) resulting high-temperature tail gas, in addition to part is as high temperature circulation gas, rest part
Isolated gas and liquid after high-temperature tail gas is cooling, gained liquid enters biochemistry pool purification after gas-liquid separation, separating obtained
Gas carries out alkali cleaning using the sodium hydroxide solution of 2~5wt%, and gas obtained by alkali cleaning directly empties.
2. the purifying treatment method of the volatile organic compounds according to claim 1 containing chlorine, which is characterized in that step
(1) hot air temperature is 350~500 DEG C；The catalyst warm-up is to 200~250 DEG C.
3. the purifying treatment method of the volatile organic compounds according to claim 1 containing chlorine, which is characterized in that step
(1) catalyst is with aluminium oxide, silica, silicon carbide, molecular sieve, rare-earth Y molecular sieve, H beta-molecular sieve, ZSM-5 molecule
One or both of sieve, MCM-41 molecular sieve, MCM-42 molecular sieve are carrier, with transition metal oxide titanium oxide, oxygen
Change vanadium, chromium oxide, manganese oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide, zinc oxide, lanthana, cerium oxide, praseodymium oxide, oxygen
Changing one or both of neodymium oxide is active component, and the load capacity of active component is 1~20%, catalyst particle size is 20~
80 mesh, by gas, total air speed in catalytic combustion reactor is 10~500m to the loadings of catalyst in catalytic combustion reactor3/
(kgcatH) it calculates.
4. the purifying treatment method of the volatile organic compounds according to claim 1 containing chlorine, it is characterised in that step (2)
In, in the exhaust gas of the volatile organic matter containing chlorine, the concentration of volatile organic matter containing chlorine is 1000~100000mg/Nm3；Containing chlorine
The air speed of volatile organic compounds is 5~50m3/(kgcatH), the total air speed of air is 1~100m3/(kgcatH), contain chlorine
The flowrate proportioning of volatile organic compounds and air is according to oxygen in the amount and air of the volatile organic matter containing chlorine in exhaust gas
The flow-rate ratio of catalytic oxidation mol ratio, volatile organic compounds containing chlorine and air is 0.1~10.
5. the purifying treatment method of the volatile organic compounds according to claim 1 containing chlorine, which is characterized in that step
(2) in, the adiabatic catalytic combustion reaction pressure is 0.1~0.25MPa (absolute pressure), reaction temperature is 350~500
℃；The temperature for the high-temperature tail gas that adiabatic catalytic combustion reaction obtains is 350~500 DEG C, and volatility containing chlorine therein is organic
Object content is 5~25mg/Nm3。
6. the purifying treatment method of the volatile organic compounds according to claim 1 containing chlorine, which is characterized in that step
(2) the high temperature circulation gas and catalytic combustion reactor outlet high-temperature tail gas ratio maintain 0.3~0.8, high temperature circulation gas
Body is mixed with low temperature feedstock gas, and the obtained organic concentration wait react in mix waste gas is diluted to 6000~12000mg/
Nm3, mix waste gas temperature to be reacted is 200~250 DEG C.
7. the purifying treatment method of the volatile organic compounds according to claim 1 containing chlorine, which is characterized in that step
(2) concrete operations of the temperature for maintaining high-temperature tail gas are as follows: when the temperature of high-temperature tail gas is higher than 500 DEG C, it is logical to increase air
Enter amount to reduce the concentration wait react the exhaust gas of the volatile organic matter containing chlorine in mix waste gas, makes catalytic combustion reactor inlet
Organic concentration is no more than 12000mg/Nm3, to reduce the temperature of high-temperature tail gas；When the temperature of high-temperature tail gas is lower than 350 DEG C,
Liquefied petroleum gas is passed through to catalytic combustion reactor inlet or reduces air intake, to improve catalytic combustion reactor entrance
The organic concentration at place makes catalytic combustion reactor inlet organic concentration not less than 6000mg/Nm3, improve high-temperature tail gas
Temperature.
8. the purifying treatment method of the volatile organic compounds according to claim 1 containing chlorine, which is characterized in that step
(2) concrete operations of the temperature for maintaining mix waste gas to be reacted are as follows: when reacting mix waste gas temperature higher than 250 DEG C,
The high-temperature tail gas amount for being recycled back to resisting blower is turned down, to reduce mix waste gas temperature to be reacted；When mix waste gas temperature to be reacted
When degree is lower than 200 DEG C, the high-temperature tail gas amount for being recycled back to resisting blower is tuned up, to improve mix waste gas temperature to be reacted.
9. the purifying treatment method of the volatile organic compounds according to claim 1 containing chlorine, which is characterized in that the side
Method specifically includes the following steps:
(1) it preheats: closing the first control valve (1), third control valve (3), the 4th control valve (4) and the 5th control valve (5), beat
Open the second control valve (2), the 6th control valve (20), resisting blower (6), preheater (8) and the first temperature controller (9)；It is empty
Gas enters preheating in preheater (8) by air pipe line (18) and resisting blower (6), and hot-air passes through the 4th branch line
(21) enter in catalytic combustion reactor (7), detect catalytic combustion reactor inlet by the first temperature controller (9)
Hot air temperature, and preheater (8) is controlled by air preheat to 350-500 DEG C, the pre- thermocatalytic of heat carried using hot-air
Catalyst needed for catalyst combustion reaction, makes the temperature of catalyst reach 200~250 DEG C in combustion reactor (7)；
(2) reaction heat recycles: after the temperature of catalytic combustion reactor (7) interior catalyst reaches 200~250 DEG C, opening the
Two control valves (2), third control valve (3), the 4th control valve (4), the 5th control valve (5), resisting blower (6), the first temperature
Controller (9) and second temperature controller (10) close preheater (8) and the 6th control valve (20), volatile organic matter containing chlorine
Exhaust gas by CVOCs exhaust pipe (17), after air enters resisting blower (6) mixing by air pipe line (18), obtain
Low temperature feedstock gas；The low temperature feedstock gas is entered in catalytic combustion reactor (7) by third branch line (16), and through step
(1) catalyst preheated carries out adiabatic catalytic combustion reaction, the height that catalytic combustion reactor (7) exit obtains after reaction
Warm tail gas；
When second temperature controller (10) detects that high-temperature tail gas temperature is more than 500 DEG C, pass through second temperature controller (10)
The aperture for increasing the second control valve (2) is adjusted, increases air intake, to reduce volatile organic matter containing chlorine in low temperature feedstock gas
Exhaust gas concentration, make wait react the organic concentration in mix waste gas no more than 12000mg/Nm3, reduce the temperature of high-temperature tail gas
Degree；
When second temperature controller (10) detects high-temperature tail gas temperature lower than 350 DEG C, pass through second temperature controller (10)
The aperture for reducing the second control valve (2) is adjusted, reduces the air capacity for entering system, or adjust by second temperature controller (10)
The aperture for increasing the first control valve (1) is passed through liquefied petroleum gas, increases the organic object amount for entering system, to improve low temperature feedstock
Organic concentration in gas makes the organic concentration wait react in mix waste gas maintain 6000mg/Nm3More than, improve high temperature
The temperature of tail gas；
The resulting part high-temperature tail gas of adiabatic catalytic combustion reaction passes through the first temperature controller (9) as high temperature circulation gas
The aperture for adjusting third control valve (3) makes high temperature circulation gas by the first branch line (14) and low temperature feedstock gas in resistance to height
It mixes at warm blower (6), using the heat low temperature feedstock gas carried in high temperature circulation gas, obtains useless wait react mixing
Gas；Resulting mix waste gas to be reacted is entered in catalytic combustion reactor (7) by third branch line (16) and is insulated
Catalyst combustion reaction obtains high-temperature tail gas；
By temperature controller (9) to the temperature detection of resisting blower (6) exit mix waste gas to be reacted, when wait react mixed
When closing exhaust gas temperature higher than 250 DEG C, turns the aperture of third control valve (3) down, turn the high-temperature tail gas for being recycled back to resisting blower down
Amount, to reduce mix waste gas temperature to be reacted；When reacting mix waste gas temperature lower than 200 DEG C, third control valve (3) are tuned up
Aperture, the high-temperature tail gas amount for being recycled back to resisting blower is tuned up, to improve mix waste gas temperature to be reacted.
(3) high-temperature tail gas is handled: step (2) resulting high-temperature tail gas is other than part is as high temperature circulation gas, remaining part
The high-temperature tail gas divided enters graphite heat exchanger (11) by second branched pipe road (15), exchanges heat and cools down through graphite heat exchanger (11)
Afterwards, by gas-liquid separator (12) gas-liquid separation, the gas that gas-liquid separation obtains removes hydrogen chloride in the interior alkali cleaning of alkali cleaning kettle (13)
It is directly vented after gas, the liquid obtained after gas-liquid separation goes biochemistry pool to handle.
10. a kind of cleaning treatment system of volatile organic compounds containing chlorine, which is characterized in that the system comprises the first controls
Valve (1), the second control valve (2), third control valve (3), the 4th control valve (4), the 5th control valve (5), resisting blower (6),
Catalytic combustion reactor (7), preheater (8), the first temperature controller (9), second temperature controller (10), graphite heat exchanger
(11), gas-liquid separator (12), alkali cleaning kettle (13), the first branch line (14), second branched pipe road (15), third branch line
(16), CVOCs exhaust pipe (17), air pipe line (18), liquefied petroleum air pipe (19), the 6th control valve (20), the 4th point
Bye-pass (21)；
It is arranged the first control valve (1) on the liquefied petroleum air pipe (19), the second control valve is arranged on (18) in air pipe line
(2), third control valve (3) are set on the first branch line (14), the 5th control valve (5) is set on CVOCs exhaust pipe (17)；
Resisting blower entrance is arranged in described resisting blower (6) one end, and the other end is arranged resisting blower and exports, catalysis burning
Catalytic combustion reactor entrance is arranged in reactor (7) one end, other end setting catalytic combustion reactor exports, and the CVOCs is useless
Air pipe (17), air pipe line (18), liquefied petroleum air pipe (19), the first branch line (14) one end respectively with high temperature resistant
Fans entrance is connected；The third branch line (16), the 4th branch line (21) one end respectively with resisting blower export
Connection；The first temperature controller (9) are arranged in the catalytic combustion reactor entrance, third branch line (16), the 4th branched pipe
The other end on road (21) passes through the first temperature controller (9) respectively and connect with catalytic combustion reactor entrance, the third branch
4th control valve (4) is set on pipeline (16)；Prolong airflow direction on 4th branch line and sets gradually the 6th control valve
(20) and preheater (8)；
Catalytic combustion reactor outlet setting second temperature controller (10), first branch line (14), second point
One end of bye-pass (15) passes through the outlet of second temperature controller (10) connection catalytic combustion reactor, first branch respectively
The other end of pipeline (14) connects resisting blower entrance；
Graphite heat exchanger gas access is arranged in graphite heat exchanger (11) top, graphite heat exchanger gas vent is arranged in bottom,
Lower sidewall be arranged cooling water inlet, another side wall upper part be arranged cooling water outlet, the second branched pipe road (15) it is another
End is connected with graphite heat exchanger gas access；
Gas-liquid separator gas access is set at the top of the gas-liquid separator (12), and side wall upper part setting gas-liquid separator gas goes out
Mouthful, gas-liquid separator liquid outlet is arranged in bottom, and the graphite heat exchanger gas vent is connect with gas-liquid separator gas access,
The gas-liquid separator gas vent connects alkali cleaning kettle (13), and the gas-liquid separator liquid outlet connects biochemistry pool；Preferably,
The catalytic combustion reactor (7) is insulation fix bed catalytic combustion reactor.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111545164A (en) * | 2020-04-27 | 2020-08-18 | 北京泷涛环境科技有限公司 | Filtering material for purifying volatile organic compounds and preparation method thereof |
| CN112268288A (en) * | 2020-10-16 | 2021-01-26 | 重庆渝久环保产业有限公司 | Waste gas detection system |
| CN113046101A (en) * | 2021-03-16 | 2021-06-29 | 山东驰盛新能源设备有限公司 | Flue waste gas circulation system for VOC (volatile organic compound) produced in coke oven treatment |
| CN113209793A (en) * | 2021-05-13 | 2021-08-06 | 湖南农业大学 | Purification system and purification process for chlorine-containing volatile organic compounds |
| CN114100621A (en) * | 2021-11-08 | 2022-03-01 | 荆楚理工学院 | Catalyst for catalytic oxidation treatment of explosive hydrogen-containing waste gas, preparation method and application thereof |
| CN114728274A (en) * | 2019-10-31 | 2022-07-08 | 地方独立行政法人东京都立产业技术研究中心 | Catalyst for VOC treatment, VOC treatment device, and VOC treatment method |
| CN117258531A (en) * | 2023-08-21 | 2023-12-22 | 宁波中瑞环保科技有限公司 | Treatment process and equipment for catalytic oxidation of ethane-containing waste gas at ignition temperature |
| CN117258531B (en) * | 2023-08-21 | 2024-05-28 | 宁波中瑞环保科技有限公司 | Treatment process and equipment for catalytic oxidation of ethane-containing waste gas at ignition temperature |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1817417A (en) * | 2005-09-22 | 2006-08-16 | 中国石油化工股份有限公司 | Waste polyester gas purification |
| JP2015206559A (en) * | 2014-04-22 | 2015-11-19 | 新日鐵住金株式会社 | Fuel control method and fuel control device of blast furnace gas boiler |
| CN106540538A (en) * | 2015-09-17 | 2017-03-29 | 北京化工大学 | A kind of apparatus and method for of wind resource assessment catalysis oxidation |
-
2019
- 2019-04-16 CN CN201910303193.0A patent/CN110186063B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1817417A (en) * | 2005-09-22 | 2006-08-16 | 中国石油化工股份有限公司 | Waste polyester gas purification |
| JP2015206559A (en) * | 2014-04-22 | 2015-11-19 | 新日鐵住金株式会社 | Fuel control method and fuel control device of blast furnace gas boiler |
| CN106540538A (en) * | 2015-09-17 | 2017-03-29 | 北京化工大学 | A kind of apparatus and method for of wind resource assessment catalysis oxidation |
Non-Patent Citations (1)
| Title |
|---|
| 刘新培: "RCO 在 ABS 工艺尾气提标改造项目中的应用", 《化学工业与工程》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114728274A (en) * | 2019-10-31 | 2022-07-08 | 地方独立行政法人东京都立产业技术研究中心 | Catalyst for VOC treatment, VOC treatment device, and VOC treatment method |
| CN111545164A (en) * | 2020-04-27 | 2020-08-18 | 北京泷涛环境科技有限公司 | Filtering material for purifying volatile organic compounds and preparation method thereof |
| CN111545164B (en) * | 2020-04-27 | 2023-05-05 | 北京泷涛环境科技有限公司 | Filtering material for purifying volatile organic compounds and preparation method thereof |
| CN112268288A (en) * | 2020-10-16 | 2021-01-26 | 重庆渝久环保产业有限公司 | Waste gas detection system |
| CN113046101A (en) * | 2021-03-16 | 2021-06-29 | 山东驰盛新能源设备有限公司 | Flue waste gas circulation system for VOC (volatile organic compound) produced in coke oven treatment |
| CN113209793A (en) * | 2021-05-13 | 2021-08-06 | 湖南农业大学 | Purification system and purification process for chlorine-containing volatile organic compounds |
| CN114100621A (en) * | 2021-11-08 | 2022-03-01 | 荆楚理工学院 | Catalyst for catalytic oxidation treatment of explosive hydrogen-containing waste gas, preparation method and application thereof |
| CN117258531A (en) * | 2023-08-21 | 2023-12-22 | 宁波中瑞环保科技有限公司 | Treatment process and equipment for catalytic oxidation of ethane-containing waste gas at ignition temperature |
| CN117258531B (en) * | 2023-08-21 | 2024-05-28 | 宁波中瑞环保科技有限公司 | Treatment process and equipment for catalytic oxidation of ethane-containing waste gas at ignition temperature |
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