CN110961153A - Ozone catalytic oxidation catalyst, preparation method thereof and method for treating toluene-containing waste gas by using ozone catalytic oxidation catalyst - Google Patents
Ozone catalytic oxidation catalyst, preparation method thereof and method for treating toluene-containing waste gas by using ozone catalytic oxidation catalyst Download PDFInfo
- Publication number
- CN110961153A CN110961153A CN201911210135.XA CN201911210135A CN110961153A CN 110961153 A CN110961153 A CN 110961153A CN 201911210135 A CN201911210135 A CN 201911210135A CN 110961153 A CN110961153 A CN 110961153A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- carrier
- toluene
- waste gas
- catalytic oxidation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 title claims abstract description 149
- 239000003054 catalyst Substances 0.000 title claims abstract description 99
- 239000002912 waste gas Substances 0.000 title claims abstract description 44
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 28
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 24
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 22
- 230000003647 oxidation Effects 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 26
- 239000000126 substance Substances 0.000 claims abstract description 18
- 230000004048 modification Effects 0.000 claims abstract description 15
- 238000012986 modification Methods 0.000 claims abstract description 15
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 38
- 238000005470 impregnation Methods 0.000 claims description 37
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 21
- 229910052684 Cerium Inorganic materials 0.000 claims description 20
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 20
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000010936 titanium Substances 0.000 claims description 20
- 229910052719 titanium Inorganic materials 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 19
- 229910052759 nickel Inorganic materials 0.000 claims description 19
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 18
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 18
- 229910052726 zirconium Inorganic materials 0.000 claims description 18
- 229910001868 water Inorganic materials 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 claims description 4
- 150000000703 Cerium Chemical class 0.000 claims description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 3
- 150000002696 manganese Chemical class 0.000 claims description 3
- 150000002815 nickel Chemical class 0.000 claims description 3
- 150000003608 titanium Chemical class 0.000 claims description 3
- 150000003754 zirconium Chemical class 0.000 claims description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 abstract description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 230000009965 odorless effect Effects 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract 1
- 238000009832 plasma treatment Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 47
- 239000007864 aqueous solution Substances 0.000 description 44
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 34
- 239000007788 liquid Substances 0.000 description 30
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 21
- 235000019441 ethanol Nutrition 0.000 description 15
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 14
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 14
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 4
- 238000010170 biological method Methods 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 230000033444 hydroxylation Effects 0.000 description 4
- 238000005805 hydroxylation reaction Methods 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000002715 modification method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 238000006396 nitration reaction Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000009489 vacuum treatment Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- -1 500 mesh Substances 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241000518994 Conta Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910002567 K2S2O8 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000000640 hydroxylating effect Effects 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- CMQCNTNASCDNGR-UHFFFAOYSA-N toluene;hydrate Chemical compound O.CC1=CC=CC=C1 CMQCNTNASCDNGR-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B01J35/618—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/10—Oxidants
- B01D2251/104—Ozone
Abstract
The invention discloses an ozone catalytic oxidation catalyst, a preparation method thereof and a method for treating toluene-containing waste gas by using the ozone catalytic oxidation catalyst. The carrier of the catalyst is a mixture of graphene oxide and TDI tar particles, and is preferably subjected to chemical surface modification and/or plasma treatment. The loaded active metal component is applied to the treatment of toluene-containing waste gas generated by acrylic acid wastewater. The catalyst has the advantages of stable performance, long service life and high efficiency, has good adsorption and catalysis effects on harmful substances in waste gas, can treat the waste gas until the waste gas is odorless, and cannot cause pollution.
Description
Technical Field
The invention relates to the technical field of waste gas treatment, in particular to an ozone catalytic oxidation catalyst and a preparation method thereof, and a method for treating toluene-containing waste gas.
Technical Field
The biological method for treating the wastewater is one of the main means of the current wastewater treatment, but the odor generated in the current biological method treatment process seriously harms the health and the environment of human beings, the biochemical waste gas mainly comes from the volatilization of organic matters in the wastewater, the main components of the biochemical waste gas are alkane organic matters, benzene series matters, ammonia, hydrogen sulfide and other substances, and the biochemical waste gas has the characteristics of large gas quantity, low concentration, large influence by seasons, low odor threshold value and strong irritation, and has great harm to the ecological environment and the health of personnel.
The common treatment means of biochemical waste gas include incineration method, absorption method, adsorption method, biological method and other methods, wherein the incineration cost is high, a large amount of fuel needs to be supplemented, and even the processes of desulfurization, denitration and the like need to be matched; the absorption method has low efficiency, is difficult to treat without odor, and the absorbed waste liquid can generate secondary pollution; the adsorption material is limited by the adsorption capacity of the adsorption material, and needs to be regenerated or replaced periodically; biological methods are weak in anti-interference capability and require the preparation of special strains to treat specific pollutants.
Ozone has extremely strong capability of decomposing pollutants, and has wide application in the fields of industrial wastewater treatment, refuse dump water seepage treatment and the like, but the ozone is only used for oxidizing and treating waste gas, the pollutants in the waste gas are difficult to be fully oxidized into pollution-free micromolecules, and in contrast, a high-grade oxidation mode is adopted, and the catalytic action of a catalyst is utilized to form a large amount of hydroxyl free radicals (& OH), so that organic matters in the waste gas are oxidized and decomposed into carbon dioxide and water, ammonia substances and the like are oxidized into nitrogen, sulfides such as methyl mercaptan and the like are oxidized into sulfate radicals, and the method has the advantages of high removal efficiency, no secondary pollution and the like.
The different catalysts have different treatment effects and costs. Therefore, the development of a high-efficiency catalyst is one of effective ways to improve the treatment effect.
CN101406831A discloses a preparation method of a manganese dioxide supported catalyst, which comprises using one or more of activated carbon, silica gel, zeolite or diatomite as a carrier, soaking in manganese acetate solution, evaporating, drying, and calcining to obtain the manganese dioxide supported catalyst.
CN106475120A discloses a method for preparing an ozone catalyst, which comprises the steps of respectively soaking zeolite or activated carbon in aqueous solutions of sodium sulfate, aluminum sulfate, potassium sulfate, calcium sulfate and magnesium sulfate and carrying out secondary baking, wherein the surface layer and the inner film are combined more firmly due to the adoption of the secondary baking method.
CN107456978A takes activated carbon as a carrier and copper, manganese, iron and ruthenium as active ingredients, and the catalyst loaded with a plurality of effective components is prepared.
CN107744806A takes expanded graphene as a carrier and supported cerium and manganese as active ingredients to prepare a catalyst loaded with various effective components.
CN108686673A takes activated carbon and incinerator ash as carriers and loads manganese, titanium and the like as active ingredients.
CN109806743A adopts photocatalysis to treat toluene waste gas, the reaction time is 10min, and the gas-liquid contact time is too long.
CN105170152A adopts iron ion exchange titanium ion pillared montmorillonite catalyst to catalyze toluene waste gas at 375 ℃ with over-high reaction temperature.
The above catalyst has a certain effect in treating organic substances in exhaust gas, but the treatment effect at room temperature is desired to be improved for exhaust gas containing toluene. Particularly, for the treatment of the dealdehyding waste gas with high toluene content in the acrylic acid plant, the emission requirement cannot be met, and a catalyst with higher efficiency needs to be developed.
Disclosure of Invention
The invention aims to provide an ozone catalytic oxidation catalyst which has the advantages of stable performance, long service life and high efficiency. Also provides a preparation method of the catalyst, which is simple and easy to implement and has low cost. The catalyst is used for treating toluene-containing waste gas, has high treatment efficiency, low cost and high stability, can treat biochemical waste gas up to the standard, and does not produce secondary pollution.
In order to solve the technical problems, the invention provides the following technical scheme:
an ozone catalytic oxidation catalyst, the catalyst comprises a carrier and active components, wherein the carrier comprises graphene oxide and TDI tar particles, and the active components comprise titanium, nickel, manganese, zirconium and cerium which exist in oxide forms; the active component comprises the following components in percentage by weight of the carrier:
0.5 to 5.0 wt% of titanium, preferably 2.0 to 3.0 wt%;
1.0-6.5 wt% of nickel, preferably 1.8-3.5 wt%;
1.0-3.0 wt% of manganese, preferably 1.8-2.5 wt%;
1.5-2.5 wt% of zirconium, preferably 1.5-2.0 wt%;
cerium is 1.0 to 6.5 wt%, preferably 2.0 to 5.0 wt%.
The graphene oxide is mainly prepared by a hummer method known in the art, and the specific surface area is preferably 2500-3200m2/g。
The TDI tar particles are from the byproduct of TDI (toluene diisocyanate) production, and the specific surface area is 200-400m2Per g, preferably 250-400m2/g。
The preparation process of TDI is well known, and the TDI tar particles provided by the invention are derived from the following sources: the TDI device is characterized in that a toluene nitration product and a hydrogenation product are mixed with a solvent o-dichlorobenzene in a mixer and then enter a phosgenation reactor together with phosgene for phosgenation reaction, unreacted phosgene and the solvent o-dichlorobenzene are separated out by rectification, the obtained crude TDI is rectified to respectively obtain TDI products, the TDI products are sent to downstream procedures for packaging, and the generated tar is processed by a dryer to prepare TDI tar particles; the TDI tar pellets contained the following:
a method of preparing the vector of the present invention, comprising the steps of: and uniformly mixing the graphene oxide, TDI tar particles and the peptizing agent, and then molding, drying and roasting to obtain the carrier.
The mass ratio of the graphene oxide to the TDI tar particles is 1: 1-6, preferably 1: 1-5.
In the method for preparing the carrier, the peptizing agent is selected from one or more of citric acid, acrylic acid and phosphoric acid.
In the method for preparing the carrier, the mass of the peptizing agent accounts for 15-40%, preferably 25-35% of the mass sum of the graphene oxide and the TDI tar particles.
In the method for preparing the carrier, the drying temperature is 70-110 ℃, the drying time is 2-8h, preferably the drying temperature is 80-110 ℃, and the drying time is 3-5 h.
In the method for preparing the carrier, the roasting temperature is 150-.
The catalyst carrier of the invention is preferably cylindrical in shape, with a diameter of 2-4mm and a length of 3-6mm, preferably a diameter of 2-3mm and a length of 3-5 mm.
The specific surface area of the carrier is 400-1700m2G, preferably 500-1700m2/g。
As a preferable technical scheme, the carrier is subjected to chemical surface modification, so that the number and concentration of functional groups on the surface of the carrier can be further increased, the adsorption effect is enhanced, the service life is prolonged, and the catalytic oxidation removal effect of ozone is improved.
The chemical surface modification method comprises the following steps: the carrier and the hydroxylation reagent are reacted firstly, and then dried to obtain the carrier with the chemically modified surface.
In the chemical surface modification method of the invention, the reaction conditions are as follows: 1) adding the carrier into the hydroxylation reagent at 40-60 ℃, preferably 50-60 ℃, and carrying out ultrasonic treatment for 15-30min, preferably 20-25 min; 2) putting the mixed solution obtained in the step 1) into a forced air drying oven, reacting for 1-3h, preferably 2-3h at 80-100 ℃, preferably 90-100 ℃, and cleaning the obtained carrier with ethanol to obtain the chemically surface-modified carrier.
The hydroxylating agent of the present invention includes, but is not limited to, one or more of ammonia, ethylenediamine, ammonium nitrate, 1-6-hexanediamine, 1-8-octanediamine, dodecylamine (DDA), Octadecylamine (OTDA), preferably DDA and/or OTDA.
The mass ratio of the carrier to the hydroxylation reagent is 1: (0.5-12), preferably 1: (1-10).
The hydroxylation reagent is preferably provided in the form of an aqueous solution, and the concentration is preferably 5-10 wt%.
As a preferable technical scheme, the carrier is subjected to plasma modification to obtain a plasma modified carrier, so that the number of surface hydroxyl groups is increased, and the catalytic activity is improved.
As a preferable technical scheme, the carrier with the modified chemical surface is subjected to plasma modification to obtain the carrier with the modified chemical surface and the plasma, so that the number of surface hydroxyl groups is further increased, and the catalytic activity is improved.
The plasma modification method comprises the following steps: treating the carrier or the chemically surface-modified carrier with plasma at a discharge voltage of 10-15kV, preferably 12-15kV, a discharge frequency of 30-110Hz, preferably 50-110Hz, a reaction time of 20-40min, preferably 25-35min, washing with pure water after the reaction, and drying.
A preparation method of an ozone catalytic oxidation catalyst comprises the following steps: adding a solution containing titanium salt, nickel salt, manganese salt, zirconium salt and cerium salt into the carrier or the chemically surface-modified carrier or the plasma-modified carrier or the chemically surface-and plasma-modified carrier according to the proportion, and performing equal-volume impregnation for 3-5h, preferably 3.5-5 h; and then roasting the obtained solid, wherein the roasting temperature is 200-350 ℃, the roasting time is 2-4h, preferably the roasting temperature is 300-350 ℃, and the roasting time is 2.5-4 h.
Preferably, the titanium salt, nickel salt, manganese salt, zirconium salt and cerium salt are respectively derived from one or more of nitrate, acetate and phosphate containing corresponding metal elements, preferably nitrate.
A treatment method of toluene-containing waste gas comprises the following steps: catalysis prepared by the inventionThe agent treatment of the toluene-containing waste gas can be carried out in any reactor known in the field, preferably a packed tower, and the toluene-containing waste gas and ozone are introduced into a catalytic reaction tower at the reaction temperature of 10-45 ℃, preferably 25-45 ℃; the space velocity of the mixed gas containing toluene waste gas and ozone is 400-1200h-1Preferably 600--1；O3(mg/Nm3): toluene (mg/Nm)3) 0.12-0.35, preferably 0.18-0.3.
The ozone is from an ozone generator, oxygen is used as a gas source, and the concentration of the generated ozone is 6-10 wt%, preferably 7-10 wt%.
The toluene-containing waste gas of the present invention preferably satisfies the following conditions: toluene is more than 0 and less than or equal to 200mg/Nm3Preferably 100 to 150mg/Nm3(ii) a Methyl acrylate is less than or equal to 10mg/Nm3Preferably 2 to 8mg/Nm3(ii) a N-butanol is less than or equal to 10mg/Nm3Preferably 2 to 8mg/Nm3(ii) a N-heptane less than or equal to 30mg/Nm3Preferably 10 to 25mg/Nm3(ii) a Hydrogen sulfide less than or equal to 15mg/Nm3Preferably 3 to 10mg/Nm3(ii) a The water content in the waste gas is 0.6-3.5 v%, preferably 0.6-3.0 v%, based on the volume of the toluene-containing waste gas.
By using the catalyst of the invention to treat the toluene-containing waste gas, the removal rate of VOCs in the waste gas reaches more than 95%, and the removal rate of toluene is more than 90%, thus basically realizing the odorless emission of the waste gas.
The invention has the beneficial effects that:
(1) the TDI tar particle carrier provided by the invention is a byproduct in the three-waste treatment process, is simple and easy to obtain, is low in cost, and realizes recycling of waste.
(2) The degradation of pollutants by adsorption on the catalyst surface is a prerequisite for oxidation, since the oxidation reaction takes place on the surface of the catalyst and not in the exhaust gas. The tar in the catalyst is mainly formed by polymerizing organic matters mainly containing benzene rings, has strong adsorption performance on the organic matters in the waste gas, can adsorb the organic matters to be oxidized on the surface of the catalyst, and is more favorable for the catalytic action of the catalyst.
(3) The benzene ring structure in the tar can effectively prevent water from being adsorbed on the surface of the catalyst, so that the service life of the catalyst is prolonged;
(4) the graphene oxide has a certain catalytic effect on ozone; contains developed network-shaped void structure, and can ensure that the effective metal elements are loaded on the catalyst to the maximum extent.
(5) The graphene oxide is effectively combined with tar, organic matters are efficiently adsorbed on the surface of the catalyst, and metal elements and the graphene oxide in the catalyst efficiently catalyze adsorbed organic matter molecules, so that the removal rate of toluene in waste gas is effectively improved.
(6) The composite of various oxides of titanium, nickel, iron, manganese, cerium and the like forms various centers for exciting ozone to be converted into hydroxyl radicals, and the porous channel structure, the multi-catalytic center and the synergistic effect with adsorption enable the catalyst to be fully contacted with ozone, so that the treatment efficiency is high.
(7) The ozone catalyst used in the invention improves the adsorption effect on harmful substances in the waste gas, simultaneously, under the action of the catalyst, the ozone can be quickly converted into a large amount of OH, biochemical waste gas is treated to be nearly odorless, and simultaneously, the ozone catalyst can completely decompose the reacted ozone, so that secondary pollution is avoided.
Detailed Description
The technical solution and the effects of the present invention are further described by the following specific examples. The following examples are merely illustrative of the present invention and are not intended to limit the scope of the present invention. Simple modifications of the invention applying the inventive concept are within the scope of the invention as claimed.
BET specific surface area, the apparatus is Quadrasorb SI type specific surface area of Conta company of America;
the element composition is measured by an inductively coupled plasma atomic emission spectrometer. The instrument is an ICP-OES type inductively coupled plasma atomic emission spectrometer 700Series of Agilent company in America;
measuring the reaction product by gas chromatography with an instrument GC7890 of Agilent company in America;
the plasma device is self-made and consists of a high-voltage pulse and discharge reactor;
an ozone generator, model CF-G-2, available from Qingdao national forest environmental protection science and technology, Inc.;
the catalytic oxidation tower was purchased from yozhou longtai ozone equipment manufacturing ltd;
natural flake graphite, 500 mesh, chemical reagents of national drug group limited;
TDI tar particles, a by-product from the production of wanhua chemical TDI; the main production steps are as follows: the TDI device is characterized in that toluene nitration and hydrogenation products and solvent o-dichlorobenzene are mixed in a mixer and then enter a phosgenation reactor together with phosgene for phosgenation reaction, unreacted phosgene and solvent o-dichlorobenzene are respectively separated out by rectification, TDI products respectively obtained by rectifying crude TDI obtained are sent to downstream procedures for packaging, generated tar is processed by a dryer to prepare TDI tar particles with the specific surface area of 250-400 m-2(ii)/g; the TDI tar pellets contained the following:
example 1: preparation of the support
Graphene oxide preparation
6g of graphite powder are initially charged at 80 ℃ to 20ml of 80 wt.% H2SO4In (1). Then 5g of K2S2O8And 5g of P2O5Slowly adding into the mixed solution. Stirring was continued for 3h while maintaining 80 ℃ after which time cooling to room temperature was followed by dilution with 1.0L of deionized water. Then washing and filtering to remove residual acid, and drying a filter cake layer; adding the pretreated graphite powder into 120ml of 80 wt% sulfuric acid solution at 0 ℃, and adding 30g of KMnO at the same temperature4Slowly added to the above solution. After the addition was complete and cooled, stir for 2h, then slowly add 1L of deionized water under ice bath conditions to dilute the solution. Then 40ml of 30 wt% H were added2O2The solution was dropped into the mixed solution dropwise to carry out a reaction until the solution became golden yellow. Then 2L of 12% by weight HCl solution and extensive deionizationWashing the solution with water to remove metal ions and residual acid, centrifuging, and freeze-drying to obtain loose 3200m with specific surface area of 2500-2Per gram of graphene oxide.
Preparation of A vector
Uniformly mixing 13g of graphene oxide and 17g of TDI tar particles; adding 9g of citric acid and 3g of water into the mixed powder, uniformly mixing, and kneading for 1 min; extruding the kneaded material into a columnar shape with the diameter of 2mm and the length of 5 mm; then roasting for 4 hours at the temperature of 250 ℃ to obtain a finished product.
Preparation of vector B
Uniformly mixing 13g of graphene oxide and 17g of TDI tar particles; adding 7.5g of citric acid and 4.5g of water into the mixed powder, uniformly mixing, and kneading for 1 min; extruding the kneaded material into a columnar shape with the diameter of 2mm and the length of 5 mm; then calcined at 250 ℃ for 4 h. Adding 600ml of 5 wt% OTDA absolute ethyl alcohol solution into the carrier, carrying out ultrasonic treatment for 20min under the reaction condition of 50 ℃, and then putting the carrier into an air-blast drying oven to react for 3h under the condition of 100 ℃ to obtain the carrier after chemical surface modification.
Preparation of C Carrier
Uniformly mixing 13g of graphene oxide and 17g of TDI tar particles; adding 7.5g of citric acid and 4.5g of water into the mixed powder, uniformly mixing, and kneading for 1 min; extruding the kneaded material into a columnar shape with the diameter of 2mm and the length of 5 mm; then roasting for 3h at 250 ℃, placing the sample into 200mL of pure water after cooling, slowly pouring the sample into a plasma reactor, carrying out vacuum treatment on the reactor, and then starting a power supply to discharge, wherein the discharge voltage is 15kV, and the discharge frequency is 110 Hz. And taking out the carrier after reacting for 30min, washing with pure water, and drying to obtain the plasma modified carrier C.
Preparation of D vector
Uniformly mixing 13g of graphene oxide and 17g of TDI tar particles; adding 7.5g of citric acid and 4.5g of water into the mixed powder, uniformly mixing, and kneading for 1 min; extruding the kneaded material into a columnar shape with the diameter of 2mm and the length of 5 mm; then calcined at 250 ℃ for 3 h. Adding 600ml of 5 wt% OTDA absolute ethyl alcohol solution into the cooled carrier, carrying out ultrasonic treatment for 20min under the reaction condition of 50 ℃, and then putting the carrier into an air-blast drying oven to react for 3h under the condition of 100 ℃ to obtain the carrier subjected to chemical surface modification; and after cooling the sample, placing the sample in 200mL of pure water, slowly pouring the sample into a plasma reactor, carrying out vacuum treatment on the reactor, and then starting a power supply to discharge, wherein the discharge voltage is 15kV, and the discharge frequency is 110 Hz. And taking out the carrier after reacting for 30min, washing with pure water, and drying to obtain the carrier after surface modification and plasma modification.
Preparation of E vector
Adding 7.5g of citric acid and 4.5g of water into 30g of graphene oxide powder, uniformly mixing, and kneading for 1 min; extruding the kneaded material into strips with the diameter of 2mm and the length of 5 mm; roasting at 250 deg.c for 3 hr to obtain the carrier.
Preparation of F Carrier
Adding 7.5g of citric acid and 4.5g of water into 30g of TDI tar particles, uniformly mixing, and kneading for 1 min; extruding the kneaded material into strips with the diameter of 2mm and the length of 5 mm; then calcined at 250 ℃ for 3 h.
Example 2: preparation of catalyst # 0
200g of the A carrier is taken and put into a beaker, and simultaneously 40.0mL of titanium nitrate aqueous solution containing 0.10g/mL of titanium, 40.0mL of nickel nitrate aqueous solution containing 0.15g/mL of nickel, 40.0mL of manganese nitrate aqueous solution containing 0.10g/mL of manganese, 40.0mL of zirconium nitrate aqueous solution containing 0.1g/mL of zirconium and 40.0mL of cerium nitrate aqueous solution containing 0.10g/mL of cerium are taken and added into ethanol aqueous solution with the ethanol concentration of 5 wt% to prepare impregnation liquid with the total volume of 500.0 mL. Uniformly mixing the impregnation liquid and the carrier in a beaker, keeping the temperature at 60 ℃ for impregnation for 5h, filtering the impregnation liquid, putting the carrier adsorbed with the impregnation liquid into a muffle furnace, and roasting at 350 ℃ for 4h to obtain the 0# catalyst.
In the obtained 0# catalyst, the contents of the following components are calculated by taking the weight of graphene oxide and TDI tar particles as the reference: 2.0 wt% of titanium, 3.0 wt% of nickel, 2 wt% of manganese, 2.0 wt% of zirconium and 2.0 wt% of cerium.
Example 3: preparation of catalyst # 1
200g of the B carrier is taken and put into a beaker, and simultaneously 40.0mL of titanium nitrate aqueous solution containing 0.10g/mL of titanium, 40.0mL of nickel nitrate aqueous solution containing 0.15g/mL of nickel, 40.0mL of manganese nitrate aqueous solution containing 0.10g/mL of manganese, 40.0mL of zirconium nitrate aqueous solution containing 0.1g/mL of zirconium and 40.0mL of cerium nitrate aqueous solution containing 0.10g/mL of cerium are taken and added into ethanol aqueous solution with the ethanol concentration of 5 wt% to prepare impregnation liquid with the total volume of 500.0 mL. Uniformly mixing the impregnation liquid and the carrier in a beaker, keeping the temperature at 60 ℃ for impregnation for 5h, filtering the impregnation liquid, and putting the carrier adsorbed with the impregnation liquid into a muffle furnace to be roasted for 4h at 350 ℃ to obtain the No. 1 catalyst.
In the obtained 1# catalyst, based on the weight of the graphene oxide and TDI tar particles after chemical surface modification, the contents of the following components are as follows: 2.0 wt% of titanium, 3.0 wt% of nickel, 2 wt% of manganese, 2.0 wt% of zirconium and 2.0 wt% of cerium.
Example 4: preparation of catalyst # 2
200g of the C carrier is put into a beaker, and simultaneously 40.0mL of titanium nitrate aqueous solution containing 0.10g/mL of titanium, 40.0mL of nickel nitrate aqueous solution containing 0.15g/mL of nickel, 40.0mL of manganese nitrate aqueous solution containing 0.10g/mL of manganese, 40.0mL of zirconium nitrate aqueous solution containing 0.1g/mL of zirconium and 40.0mL of cerium nitrate aqueous solution containing 0.10g/mL of cerium are added into ethanol aqueous solution with the ethanol concentration of 5 wt% to prepare impregnation liquid with the total volume of 500.0 mL. And uniformly mixing the impregnation liquid and the carrier in a beaker, keeping the temperature at 60 ℃ for impregnation for 5h, filtering the impregnation liquid, and roasting the carrier adsorbed with the impregnation liquid in a drying oven at 350 ℃ for 4h in a muffle furnace to obtain the No. 2 catalyst.
In the obtained 2# catalyst, the contents of the following components are calculated by taking the weight of the graphene oxide and TDI tar particles after plasma modification as a reference: 2.0 wt% of titanium, 3.0 wt% of nickel, 2 wt% of manganese, 2.0 wt% of zirconium and 2.0 wt% of cerium.
Example 5: preparation of No. 3 catalyst
200g of the D carrier is put into a beaker, and 40.0mL of titanium nitrate aqueous solution containing 0.10g/mL of titanium, 40.0mL of nickel nitrate aqueous solution containing 0.15g/mL of nickel, 40.0mL of manganese nitrate aqueous solution containing 0.10g/mL of manganese, 40.0mL of zirconium nitrate aqueous solution containing 0.1g/mL of zirconium and 40.0mL of cerium nitrate aqueous solution containing 0.10g/mL of cerium are added into ethanol aqueous solution with the ethanol concentration of 5 wt% to prepare impregnation liquid with the total volume of 500.0 mL. And uniformly mixing the impregnation liquid and the carrier in a beaker, keeping the temperature at 60 ℃ for impregnation for 5h, filtering the impregnation liquid, and putting the carrier adsorbed with the impregnation liquid into a muffle furnace for roasting at 350 ℃ for 4h to obtain the 3# catalyst.
In the obtained 3# catalyst, based on the weight of the graphene oxide and TDI tar particles after chemical surface modification and plasma modification, the following components are contained: 2.0 wt% of titanium, 3.0 wt% of nickel, 2 wt% of manganese, 2.0 wt% of zirconium and 2.0 wt% of cerium.
Comparative example 1: preparation of catalyst # 4
200g of the E carrier is put into a beaker, and simultaneously 40.0mL of titanium nitrate aqueous solution containing 0.15g/mL of titanium, 40.0mL of nickel nitrate aqueous solution containing 0.15g/mL of nickel, 40.0mL of manganese nitrate aqueous solution containing 0.10g/mL of manganese, 40.0mL of zirconium nitrate aqueous solution containing 0.1g/mL of zirconium and 40.0mL of cerium nitrate aqueous solution containing 0.2g/mL of cerium are added into ethanol aqueous solution with the ethanol concentration of 5 wt% to prepare impregnation liquid with the total volume of 500.0 mL. And uniformly mixing the impregnation liquid and the carrier in a beaker, keeping the temperature at 60 ℃ for impregnation for 5h, filtering the impregnation liquid, and putting the carrier adsorbed with the impregnation liquid into a muffle furnace for roasting at 350 ℃ for 4h to obtain the 4# catalyst.
In the obtained 4# catalyst, the contents of the following components are calculated by taking the weight of the graphene oxide as a reference: 3.0 wt% of titanium, 3.0 wt% of nickel, 2 wt% of manganese, 2.0 wt% of zirconium and 4.0 wt% of cerium.
Comparative example 2: preparation of No. 5 catalyst
200g of the F carrier is put into a beaker, and 40.0mL of titanium nitrate aqueous solution containing 0.15g/mL of titanium, 40.0mL of nickel nitrate aqueous solution containing 0.1g/mL of nickel, 50.0mL of manganese nitrate aqueous solution containing 0.10g/mL of manganese, 40.0mL of zirconium nitrate aqueous solution containing 0.1g/mL of zirconium and 40.0mL of ferric nitrate aqueous solution containing 0.2g/mL of cerium are added into ethanol aqueous solution with the ethanol concentration of 5 wt% to prepare impregnation liquid with the total volume of 500.0 mL. And uniformly mixing the impregnation liquid and the carrier in a beaker, keeping the temperature at 60 ℃ for impregnation for 5h, filtering the impregnation liquid, and putting the carrier adsorbed with the impregnation liquid into a muffle furnace for roasting at 350 ℃ for 4h to obtain the 5# catalyst.
In the obtained 5# catalyst, the contents of the following components are calculated by taking the weight of TDI tar particles as a reference: 3.0 wt% of titanium, 2.0 wt% of nickel, 2.5 wt% of manganese, 2.0 wt% of zirconium and 4.0 wt% of cerium.
Comparative example 3: preparation of No. 6 catalyst
200g of the A carrier is taken and put into a beaker, and simultaneously, 18.0mL of titanium nitrate aqueous solution containing 0.1g/mL of titanium, 16.0mL of nickel nitrate aqueous solution containing 0.1g/mL of nickel, 24.0mL of manganese nitrate aqueous solution containing 0.10g/mL of manganese, 20.0mL of zirconium nitrate aqueous solution containing 0.1g/mL of zirconium and 20.0mL of cerium nitrate aqueous solution containing 0.2g/mL of cerium are taken and added into ethanol aqueous solution with the ethanol concentration of 5 wt% to prepare impregnation liquid with the total volume of 500.0 mL. And uniformly mixing the impregnation liquid and the carrier in a beaker, keeping the temperature at 60 ℃ for impregnation for 5h, filtering the impregnation liquid, and putting the carrier adsorbed with the impregnation liquid into a muffle furnace for roasting at 350 ℃ for 4h to obtain the No. 6 catalyst.
In the obtained 6# catalyst, the contents of the following components are calculated by taking the weight of the graphene oxide and TDI tar particles as the reference: 0.9 wt% of titanium, 0.8 wt% of nickel, 1.2 wt% of manganese, 1.0 wt% of zirconium and 2.0 wt% of cerium. .
Comparison of exhaust gas treatment Performance of different catalysts
Toluene-containing waste gas was collected from a Wanhua chemical acrylic acid wastewater treatment system, and the composition thereof is shown in Table 1.
TABLE 1 composition of toluene-containing waste gas
Corresponding catalysts are respectively filled in an ozone catalytic oxidation tower, the waste gas shown in the table 1 and ozone are introduced into the ozone catalytic oxidation tower together, the reaction temperature is 30 ℃, and the space velocity is 1000h-1、O3(mg/Nm3): toluene (mg/Nm)3) 0.2, namely the concentration of ozone in the mixed gas is 30mg/Nm3The results are shown below:
(1) catalyst is not filled, and the toluene removal efficiency is 0.5%;
(2) CN108686673A catalyst # 3 of example 5, with a toluene removal rate of 72%, a methyl acrylate removal rate of 90%, an n-butanol removal rate of 83%, and the balance not detected;
(3) the toluene removal efficiency of the No. 0 catalyst is 92.1 percent, and the rest catalyst is not detected;
(4) the toluene removal efficiency of the No. 1 catalyst is 94.7 percent, and the rest catalyst is not detected;
(5) the toluene removal efficiency of the No. 2 catalyst is 93.8 percent, and the rest catalyst is not detected;
(6) the toluene removal efficiency of the 3# catalyst is 97.2 percent, and the rest catalyst is not detected;
(7) the toluene removal efficiency of the No. 4 catalyst is 78%, the methyl acrylate removal efficiency is 82%, the n-butanol removal efficiency is 83%, and the rest is not detected;
(8) the toluene removal efficiency of the No. 5 catalyst is 42%, the methyl acrylate removal efficiency is 70%, the n-butanol removal efficiency is 78%, and the rest is not detected;
(9) the 6# catalyst has toluene removal efficiency of 78%, methyl acrylate removal efficiency of 89%, n-butanol removal efficiency of 85%, and the balance not detected.
Catalyst stability test
The No. 0, No. 4 and No. 5 catalysts are respectively filled in the ozone catalytic oxidation tower, the waste gas shown in the table 1 and the ozone are introduced into the ozone catalytic oxidation tower together, the reaction temperature is 30 ℃, and the space velocity is 1000h-1、O3(mg/Nm3): toluene (mg/Nm)3) 0.2, namely the concentration of ozone in the mixed gas is 30mg/Nm3After 8000 consecutive hours, the efficiency of each catalyst is as follows:
(1) the toluene removal efficiency of the No. 0 catalyst is 92%, and the rest is not detected;
(2) the toluene removal efficiency of the No. 4 catalyst is 48%, the methyl acrylate removal efficiency is 52%, the n-butanol removal efficiency is 55%, and the rest is not detected;
(3) the toluene removal efficiency of the No. 5 catalyst is 41.8 percent, the methyl acrylate removal efficiency is 44 percent, the n-butanol removal efficiency is 48 percent, and the rest is not detected;
TABLE 2 high water toluene offgas composition
The No. 0, No. 4 and No. 5 catalysts are respectively filled in the ozone catalytic oxidation tower, the waste gas shown in the table 2 and the ozone are introduced into the ozone catalytic oxidation tower together, the reaction temperature is 30 ℃, and the space velocity is 1000h-1、O3(mg/Nm3): toluene (mg/Nm)3) 0.2, namely the concentration of ozone in the mixed gas is 30mg/Nm3After 8000 consecutive hours, the efficiency of each catalyst is as follows:
(1) the toluene removal efficiency of the No. 0 catalyst is 91.9 percent, and the rest catalyst is not detected;
(2) the toluene removal efficiency of the No. 4 catalyst is 32 percent, the methyl acrylate removal efficiency is 33 percent, the n-butanol removal efficiency is 48 percent, and the rest is not detected;
(3) the toluene removal efficiency of the No. 5 catalyst was 41.8%, the methyl acrylate removal efficiency was 43.2%, the n-butanol removal efficiency was 47.8%, and the balance was not detected.
Claims (9)
1. An ozone catalytic oxidation catalyst, the catalyst comprises a carrier and active components, wherein the carrier comprises graphene oxide and TDI tar particles, and the active components comprise titanium, nickel, manganese, zirconium and cerium which exist in oxide forms; the active component comprises the following components in percentage by weight of the carrier:
0.5 to 5.0 wt% of titanium, preferably 2.0 to 3.0 wt%;
1.0-6.5 wt% of nickel, preferably 1.8-3.5 wt%;
1.0-3.0 wt% of manganese, preferably 1.8-2.5 wt%;
1.5-2.5 wt% of zirconium, preferably 1.5-2.0 wt%;
cerium is 1.0 to 6.5 wt%, preferably 2.0 to 5.0 wt%.
2. The catalyst as claimed in claim 1, wherein the graphene oxide is prepared by hummer method, and the specific surface area is 2500-2/g。
3. The catalyst according to claim 1 or 2, wherein the TDI tar particles are derived from by-products of TDI production process and have a specific surface area of 200-400m2Per g, preferably 250-400m2/g。
4. The catalyst according to any one of claims 1 to 3, wherein the mass ratio of graphene oxide to TDI tar particles is 1 (1-6), preferably 1 (1.5-5).
5. The catalyst according to any one of claims 1 to 4, wherein the support is prepared by the following method: uniformly mixing the graphene oxide, TDI tar particles and a peptizing agent, then forming, drying and roasting to obtain the carrier, preferably, the carrier is further subjected to chemical surface modification and/or plasma modification.
6. The catalyst as claimed in claim 5, wherein the calcination temperature is 150-250 ℃, and the calcination time is 2-4h, preferably the calcination temperature is 200-250 ℃, and the calcination time is 2.5-4 h.
7. A process for preparing the catalyst of any one of claims 1-6, comprising the steps of: adding a solution containing titanium salt, nickel salt, manganese salt, zirconium salt and cerium salt into the carrier or the chemically surface-modified carrier or the plasma-modified carrier or the chemically surface-and plasma-modified carrier according to the proportion, and performing equal-volume impregnation for 3-5h, preferably 3.5-5 h; and then roasting the obtained solid, wherein the roasting temperature is 200-350 ℃, the roasting time is 2-4h, preferably the roasting temperature is 300-350 ℃, and the roasting time is 2.5-4 h.
8. A treatment method of toluene-containing waste gas comprises the following steps: treating toluene-containing waste gas with the catalyst according to any one of claims 1 to 6, introducing the toluene-containing waste gas into a catalytic reaction tower together with ozone, at a reaction temperature of 10 to 45 ℃, preferably 25 to 45 ℃; airspeed of 400--1Preferably 600--1；O3The mass ratio of the toluene to the toluene is 0.12-0.35: 1, preferably 0.18 to 0.3: 1.
9. the method according to claim 8, wherein the toluene-containing off-gas satisfies the following condition: toluene is more than 0 and less than or equal to 200mg/Nm3Preference is given to100～150mg/Nm3(ii) a Methyl acrylate is less than or equal to 10mg/Nm3Preferably 2 to 8mg/Nm3(ii) a N-butanol is less than or equal to 10mg/Nm3Preferably 2 to 8mg/Nm3(ii) a N-heptane less than or equal to 30mg/Nm3Preferably 10 to 25mg/Nm3(ii) a Hydrogen sulfide less than or equal to 15mg/Nm3Preferably 3 to 10mg/Nm3(ii) a The water content in the waste gas is 0.6-3.5 v%, preferably 0.6-3.0 v%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911210135.XA CN110961153B (en) | 2019-12-02 | 2019-12-02 | Ozone catalytic oxidation catalyst, preparation method thereof and method for treating toluene-containing waste gas by using ozone catalytic oxidation catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911210135.XA CN110961153B (en) | 2019-12-02 | 2019-12-02 | Ozone catalytic oxidation catalyst, preparation method thereof and method for treating toluene-containing waste gas by using ozone catalytic oxidation catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110961153A true CN110961153A (en) | 2020-04-07 |
| CN110961153B CN110961153B (en) | 2022-08-05 |
Family
ID=70032459
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911210135.XA Active CN110961153B (en) | 2019-12-02 | 2019-12-02 | Ozone catalytic oxidation catalyst, preparation method thereof and method for treating toluene-containing waste gas by using ozone catalytic oxidation catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110961153B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113999519A (en) * | 2021-11-16 | 2022-02-01 | 万华化学集团股份有限公司 | Polyurethane modified natural rubber and preparation method thereof |
| CN114618547A (en) * | 2020-12-11 | 2022-06-14 | 万华化学集团股份有限公司 | Dinitrotoluene hydrogenation catalyst, and preparation method and application thereof |
| CN116199567A (en) * | 2021-12-01 | 2023-06-02 | 万华化学集团股份有限公司 | Green treatment method for tar generated in preparation of benzenediol by phenol hydroxylation |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4138424A (en) * | 1977-07-13 | 1979-02-06 | Orient Chemical Industries, Ltd. | Method for removing tar from crude tolylene diisocyanate |
| WO2007090951A1 (en) * | 2006-02-06 | 2007-08-16 | Degremont | Catalytic method for purifying gases |
| CN108686673A (en) * | 2018-05-17 | 2018-10-23 | 万华化学集团股份有限公司 | A kind of ozone catalytic oxidation catalyst and preparation method thereof |
| CN109701546A (en) * | 2017-10-25 | 2019-05-03 | 万华化学集团股份有限公司 | A kind of ozone catalytic oxidation catalyst and its method for handling biochemical waste gas |
| CN109772301A (en) * | 2019-02-27 | 2019-05-21 | 知合环境（北京）有限责任公司 | Modified ozone oxidation catalyst of a kind of graphene oxide and preparation method thereof |
| CN109794260A (en) * | 2019-02-22 | 2019-05-24 | 上海电气集团股份有限公司 | A kind of preparation method and ozone oxidation catalyst of ozone oxidation catalyst |
-
2019
- 2019-12-02 CN CN201911210135.XA patent/CN110961153B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4138424A (en) * | 1977-07-13 | 1979-02-06 | Orient Chemical Industries, Ltd. | Method for removing tar from crude tolylene diisocyanate |
| WO2007090951A1 (en) * | 2006-02-06 | 2007-08-16 | Degremont | Catalytic method for purifying gases |
| CN109701546A (en) * | 2017-10-25 | 2019-05-03 | 万华化学集团股份有限公司 | A kind of ozone catalytic oxidation catalyst and its method for handling biochemical waste gas |
| CN108686673A (en) * | 2018-05-17 | 2018-10-23 | 万华化学集团股份有限公司 | A kind of ozone catalytic oxidation catalyst and preparation method thereof |
| CN109794260A (en) * | 2019-02-22 | 2019-05-24 | 上海电气集团股份有限公司 | A kind of preparation method and ozone oxidation catalyst of ozone oxidation catalyst |
| CN109772301A (en) * | 2019-02-27 | 2019-05-21 | 知合环境（北京）有限责任公司 | Modified ozone oxidation catalyst of a kind of graphene oxide and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 姚振华等: ""二氧化锰/石墨烯臭氧催化氧化甲苯反应性能"", 《广州化工》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114618547A (en) * | 2020-12-11 | 2022-06-14 | 万华化学集团股份有限公司 | Dinitrotoluene hydrogenation catalyst, and preparation method and application thereof |
| CN113999519A (en) * | 2021-11-16 | 2022-02-01 | 万华化学集团股份有限公司 | Polyurethane modified natural rubber and preparation method thereof |
| CN116199567A (en) * | 2021-12-01 | 2023-06-02 | 万华化学集团股份有限公司 | Green treatment method for tar generated in preparation of benzenediol by phenol hydroxylation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110961153B (en) | 2022-08-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110961153B (en) | Ozone catalytic oxidation catalyst, preparation method thereof and method for treating toluene-containing waste gas by using ozone catalytic oxidation catalyst | |
| Shan et al. | Preparation of microwave-activated magnetic bio-char adsorbent and study on removal of elemental mercury from flue gas | |
| CN108686673B (en) | Ozone catalytic oxidation catalyst and preparation method thereof | |
| Yang et al. | Mercury removal from flue gas by magnetic iron-copper oxide modified porous char derived from biomass materials | |
| Cheng et al. | Desulfurization and denitrification technologies of coal-fired flue gas. | |
| Tan et al. | Preparation and characterization of Fe2O3–SiO2 composite and its effect on elemental mercury removal | |
| CN102824844B (en) | Desulfurization and denitrification agent, preparation method and application thereof | |
| CN102423688B (en) | Preparation method for walnut shell active carbon adsorbent for purifying low concentration phosphine | |
| Sun et al. | Simultaneous catalytic hydrolysis of carbonyl sulfide and carbon disulfide over Al2O3-K/CAC catalyst at low temperature | |
| CN110385023B (en) | Low-temperature flue gas denitration agent and preparation method and application thereof | |
| CN102836636B (en) | Desulfurization denitration composition, preparation method and application thereof | |
| CN102580525A (en) | Method for using activated carbon load copper oxide composite catalyst to absorb nitrogenous oxide | |
| Peng et al. | Study on the mechanism of NO removal by plasma-adsorption catalytic process | |
| CN104190358B (en) | NOx adsorber | |
| CN101695651A (en) | Copper and iron-loaded modified activated carbon absorbent and method for preparing same | |
| CN109701546A (en) | A kind of ozone catalytic oxidation catalyst and its method for handling biochemical waste gas | |
| Cui et al. | Enhanced mercury removal performance of Cu-Fe binary oxide sorbents modified by non-thermal plasma | |
| CN107321148A (en) | A kind of VOCs for removing low concentration big flow method and its modified catalyst | |
| Jiang et al. | Simultaneous removal of hydrogen sulfide and ammonia in the gas phase: a review | |
| CN114057193A (en) | Nitrogen-doped activated carbon-based desulfurizer as well as preparation method and application thereof | |
| Park et al. | Catalytic oxidation of benzene with ozone over nanoporous mn/MCM-48 catalyst | |
| Wei et al. | Degradation of mixed typical odour gases via non-thermal plasma catalysis | |
| Liu et al. | Removal of gaseous elemental mercury using corn stalk biochars modified by a green oxidation technology | |
| CN111203179A (en) | Preparation method and application of renewable phenol-containing organic wastewater catalytic adsorption material | |
| CN103920454A (en) | Composite copper-based desulfurizing agent for removing sulfur-containing repugnant substances at normal temperature and preparation method of composite copper-based desulfurizing agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |