CN111203242B - Catalytic combustion treatment catalyst for gas flow containing organic chlorine and preparation method and application thereof - Google Patents
Catalytic combustion treatment catalyst for gas flow containing organic chlorine and preparation method and application thereof Download PDFInfo
- Publication number
- CN111203242B CN111203242B CN202010173394.6A CN202010173394A CN111203242B CN 111203242 B CN111203242 B CN 111203242B CN 202010173394 A CN202010173394 A CN 202010173394A CN 111203242 B CN111203242 B CN 111203242B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- calcium sulfate
- carrier
- organochlorine
- anhydrous calcium
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 117
- 238000007084 catalytic combustion reaction Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000460 chlorine Substances 0.000 title claims description 76
- 229910052801 chlorine Inorganic materials 0.000 title claims description 70
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims description 66
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 102
- 229940095564 anhydrous calcium sulfate Drugs 0.000 claims abstract description 71
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 26
- 239000010955 niobium Substances 0.000 claims abstract description 18
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000013078 crystal Substances 0.000 claims abstract description 12
- 229910052925 anhydrite Inorganic materials 0.000 claims abstract description 9
- 229910001935 vanadium oxide Inorganic materials 0.000 claims abstract description 4
- 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 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 49
- 239000000463 material Substances 0.000 claims description 48
- 239000002253 acid Substances 0.000 claims description 41
- 239000007789 gas Substances 0.000 claims description 33
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 29
- 239000002002 slurry Substances 0.000 claims description 27
- 230000008569 process Effects 0.000 claims description 24
- 239000006185 dispersion Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 16
- 238000001125 extrusion Methods 0.000 claims description 15
- YVGGHNCTFXOJCH-UHFFFAOYSA-N DDT Chemical compound C1=CC(Cl)=CC=C1C(C(Cl)(Cl)Cl)C1=CC=C(Cl)C=C1 YVGGHNCTFXOJCH-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 229910052720 vanadium Inorganic materials 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 13
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000000575 pesticide Substances 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 10
- 239000002912 waste gas Substances 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 229910052758 niobium Inorganic materials 0.000 claims description 9
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 9
- 239000003993 organochlorine pesticide Substances 0.000 claims description 9
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 9
- BIWJNBZANLAXMG-YQELWRJZSA-N chloordaan Chemical compound ClC1=C(Cl)[C@@]2(Cl)C3CC(Cl)C(Cl)C3[C@]1(Cl)C2(Cl)Cl BIWJNBZANLAXMG-YQELWRJZSA-N 0.000 claims description 8
- 239000012065 filter cake Substances 0.000 claims description 8
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 7
- 238000010008 shearing Methods 0.000 claims description 7
- 239000002689 soil Substances 0.000 claims description 7
- JLYXXMFPNIAWKQ-GNIYUCBRSA-N gamma-hexachlorocyclohexane Chemical group Cl[C@H]1[C@H](Cl)[C@@H](Cl)[C@@H](Cl)[C@H](Cl)[C@H]1Cl JLYXXMFPNIAWKQ-GNIYUCBRSA-N 0.000 claims description 6
- 229960002809 lindane Drugs 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- CRPUJAZIXJMDBK-UHFFFAOYSA-N Toxaphene Natural products C1CC2C(=C)C(C)(C)C1C2 CRPUJAZIXJMDBK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- OEJNXTAZZBRGDN-UHFFFAOYSA-N toxaphene Chemical compound ClC1C(Cl)C2(Cl)C(CCl)(CCl)C(=C)C1(Cl)C2(Cl)Cl OEJNXTAZZBRGDN-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- UKEBGKGQMPCEKM-UHFFFAOYSA-D niobium(5+) oxalate oxalic acid Chemical compound [Nb+5].C(C(=O)O)(=O)O.C(C(=O)[O-])(=O)[O-].C(C(=O)[O-])(=O)[O-].C(C(=O)[O-])(=O)[O-].C(C(=O)[O-])(=O)[O-].C(C(=O)[O-])(=O)[O-].[Nb+5] UKEBGKGQMPCEKM-UHFFFAOYSA-D 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 238000005067 remediation Methods 0.000 claims description 2
- 239000004576 sand Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 15
- 238000002485 combustion reaction Methods 0.000 abstract description 8
- 230000007062 hydrolysis Effects 0.000 abstract description 8
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 8
- 150000004045 organic chlorine compounds Chemical class 0.000 abstract description 2
- 229910000484 niobium oxide Inorganic materials 0.000 abstract 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 abstract 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 81
- 239000000835 fiber Substances 0.000 description 40
- 229940095672 calcium sulfate Drugs 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 30
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 21
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 17
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 17
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 17
- 239000007788 liquid Substances 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 239000003365 glass fiber Substances 0.000 description 14
- 239000000084 colloidal system Substances 0.000 description 13
- -1 methane alkane Chemical class 0.000 description 13
- 230000003287 optical effect Effects 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 239000001569 carbon dioxide Substances 0.000 description 10
- 238000005070 sampling Methods 0.000 description 10
- 238000001354 calcination Methods 0.000 description 9
- 238000007789 sealing Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 8
- 235000012255 calcium oxide Nutrition 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000000292 calcium oxide Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 238000004898 kneading Methods 0.000 description 7
- 230000003014 reinforcing effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 150000001555 benzenes Chemical class 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 235000006408 oxalic acid Nutrition 0.000 description 6
- 238000004537 pulping Methods 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 231100000331 toxic Toxicity 0.000 description 5
- 230000002588 toxic effect Effects 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003892 spreading Methods 0.000 description 4
- 230000007480 spreading Effects 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-BJUDXGSMSA-N carbon-11 Chemical compound [11C] OKTJSMMVPCPJKN-BJUDXGSMSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 2
- FMMWHPNWAFZXNH-UHFFFAOYSA-N Benz[a]pyrene Chemical compound C1=C2C3=CC=CC=C3C=C(C=C3)C2=C2C3=CC=CC2=C1 FMMWHPNWAFZXNH-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- TXVHTIQJNYSSKO-UHFFFAOYSA-N benzo[e]pyrene Chemical class C1=CC=C2C3=CC=CC=C3C3=CC=CC4=CC=C1C2=C34 TXVHTIQJNYSSKO-UHFFFAOYSA-N 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000000382 dechlorinating effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 150000002013 dioxins Chemical class 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
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- 238000010298 pulverizing process Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910009112 xH2O Inorganic materials 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical group CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- FKVDRABNRUKTDK-UHFFFAOYSA-N 4-chloro-3,3-dimethyl-2-methylidenebicyclo[2.2.1]heptane Chemical compound C1CC2(Cl)C(C)(C)C(=C)C1C2 FKVDRABNRUKTDK-UHFFFAOYSA-N 0.000 description 1
- GUNJMGBINSGRSZ-UHFFFAOYSA-N ClCCl.C1C2=CC=CC=C2C=C1.Cl.Cl.Cl.Cl.Cl.Cl.Cl.Cl Chemical compound ClCCl.C1C2=CC=CC=C2C=C1.Cl.Cl.Cl.Cl.Cl.Cl.Cl.Cl GUNJMGBINSGRSZ-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001007 puffing effect Effects 0.000 description 1
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- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- F23G2209/00—Specific waste
- F23G2209/14—Gaseous waste or fumes
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2209/00—Specific waste
- F23G2209/14—Gaseous waste or fumes
- F23G2209/142—Halogen gases, e.g. silane
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention provides a catalytic combustion treatment catalyst for organochlorine-containing gas flow, a preparation method and application thereof, wherein the catalyst has higher organochlorine hydrolysis activity and organic component combustion activity, can realize catalytic combustion of organochlorine compounds at the temperature below 350 ℃, and comprises a fibrous anhydrous calcium sulfate-enhanced titanium dioxide carrier and vanadium and niobium oxide components loaded in the carrier; the catalyst contains 1-5% of vanadium oxide calculated by MnO and Nb oxide calculated by mass2O50.1-0.3% of the total weight; the carrier comprises 10-30% of fibrous anhydrous calcium sulfate calcined at the temperature of 700-750 ℃ and more than 65% of titanium dioxide, wherein more than 80% of the fibrous anhydrous calcium sulfate is monodisperse; the fibrous anhydrous calcium sulfate is columnar crystal, the length is 15-75 μm, the average diameter is 1-4 μm, the length-diameter ratio is more than 10, and the CaSO4The content is more than or equal to 98 percent.
Description
Technical Field
The invention belongs to the technical field of catalytic combustion treatment of organic chlorine, and particularly relates to a catalytic combustion treatment catalyst for an organic chlorine-containing gas flow, and a preparation method and application thereof.
Background
Chlorine-containing organic matters, also called organic chlorine, are important industrial raw materials or products, and part of the chlorine-containing organic matters are used as raw materials, solvents or processing aids of various chemical reactions, and the other part of the chlorine-containing organic matters are used as pesticides and are widely used as pesticides for insect killing, sterilization and virus treatment in agricultural planting and breeding. Organic chlorine is generally volatile or volatile, difficult to degrade and toxic, so that the organic chlorine in waste gas, waste liquid and waste material can be discharged, disposed or buried after being properly treated, converted and removed; the treatment of organic chlorine in waste gas is an important technical field, and the treatment of organic chlorine in waste liquid and waste material by gas stripping, thermal volatilization, catalytic combustion and the like is often convenient and easy to implement.
The organic chlorine pesticide, such as hexachloro cyclohexane, DDT, toxaphene, chlordane and pentachlorophenol, which are commonly used in the past and at present, has higher residual quantity in a plurality of soils, and the residual quantity in the contaminated soils after certain pesticide production plants and storage repositories are movedThe content of the organic chlorine can reach 0.1-2%. The restoration treatment method of the organochlorine pesticide contaminated soil comprises a chemical method, a biological method and a photolysis method which are implemented in situ and a cement kiln synergistic treatment method which is implemented in different places, wherein the chemical method, the biological method and the photolysis method can be completed for many years generally, the speed is low, the cement kiln synergistic treatment method is often inconvenient to implement due to long distance, and the volatilization pollution to the atmosphere is difficult to avoid in the treatment processes; the organochlorine pesticide polluted soil is subjected to gas stripping and heating volatilization at the original site or nearby, organochlorine pesticide components are driven into airflow and then are subjected to catalytic combustion, and the method is possibly suitable for restoring certain organochlorine pesticide heavily-polluted soil. Hexachloro cyclohexane of formula C 6H6Cl5(ii) a DDT, also known as bis-p-chlorophenyl trichloroethane, of formula C14H9Cl6(ii) a Toxaphene, also known as chlorocamphene, formula C10H10Cl8(ii) a Chlordane, also known as dichloromethane indene octachloride, of the formula C10H6Cl8(ii) a Pentachlorophenol of the formula C6HOCl5。
In the catalytic combustion process, organic chlorine is firstly subjected to catalytic hydrolysis, generally, the organic chlorine is hydrolyzed to generate hydrogen chloride which is easy to remove, and a byproduct of chlorine-free organic matter which can be catalytically combusted is further oxidized to generate carbon dioxide and water, wherein the two processes can be completed step by step or synchronously realized, and generally need to be realized under the conditions of proper temperature such as 250-400 ℃ and a catalyst with proper performance. The generated hydrogen chloride can be absorbed by alkali liquor or removed by dechlorinating agent containing calcium carbonate/calcium oxide.
The problem is that the mechanical strength of the dechlorination combustion catalyst can be maintained in the using process because the hydrogen chloride generated by the catalytic combustion of the organic chlorine has strong corrosivity under the reaction temperature condition; and the organic chlorine, especially the organic chlorine pesticide, has more complex and difficult hydrolysis process when being treated by catalytic combustion due to the structural stability, needs higher active ingredient loading capacity and has higher requirement on the mechanical strength of the carrier. The catalyst is more active when higher catalytic combustion reaction temperature is adopted, but the catalyst is easy to generate more difficult-to-handle organic chlorine or more toxic organic chlorine, including organic chlorine with higher chlorine or organic chlorine with more complex structure, so the catalytic combustion temperature is suitably low. In addition, the copper-containing catalyst tends to produce organic chlorine that is more difficult to handle or more toxic.
The performance, service life, mechanical strength and the like of the combustion treatment catalyst containing the organic chlorine waste gas are greatly influenced by the carrier. The common catalyst carrier which is relatively resistant to hydrogen chloride corrosion under the temperature condition of 250-400 ℃ comprises a silicon oxide carrier and a titanium oxide carrier, wherein the titanium oxide carrier can play a great role in the hydrolysis conversion and combustion of organic chlorine besides playing a role in the skeleton of the catalyst. However, the titania support has a disadvantage that it is not easy to obtain balance between mechanical strength and indexes such as specific surface area and pore volume; the low carrier strength can cause the surface dusting or powdering problem of the prepared catalyst in the using process, the low pore volume of the carrier can cause the difficulty in loading high-content active components by an impregnation method and the low activity of the prepared catalyst, and the low specific surface area of the carrier can cause the low dispersion degree of the active components, thereby causing the low activity problem of the prepared catalyst.
Disclosure of Invention
In order to solve the technical problems, the invention provides a catalytic combustion treatment catalyst for an organic chlorine-containing gas flow, and a preparation method and application thereof, wherein the catalyst takes titanium oxide as a carrier, is reinforced by calcium sulfate fibers and loads oxides of vanadium and niobium, active ingredients comprise the oxides of titanium, vanadium and niobium, and have higher organochlorine hydrolysis activity and organic ingredient combustion activity, the hydrolysis of organochlorine compounds can be realized at the temperature below 350 ℃ to generate hydrogen chloride, the byproduct chlorine-free organic ingredients or less chlorine-containing organic ingredients are subjected to catalytic combustion, and the hydrogen chloride can be further absorbed by alkali liquor or treated by a calcium carbonate/calcium oxide-containing dechlorinating agent to reach the standard and be discharged. The preparation process of the carrier and the catalyst is easy to master and can be stably repeated; the mechanical strength is high, the side pressure strength is higher than 120N/cm, the discreteness is small, the catalyst is not easy to be corroded by reaction product hydrogen chloride in the long-term use process, the catalyst is not easy to be pulverized, and the strength is not easy to be reduced; the problems that the catalyst is easy to pulverize and the strength is reduced and the like because the catalyst is easy to be corroded by hydrogen chloride which is a reaction product when alumina is used as a carrier are solved; the catalyst does not contain copper, so that organic chlorine with higher chlorine content is not easy to generate or the complexity of organic chlorine is not easy to increase; the raw materials are cheap and easily available, and the catalyst is low in cost.
The invention contains an organic chlorine gas flow catalytic combustion treatment catalyst, which comprises a fibrous anhydrous calcium sulfate reinforced titanium dioxide carrier and oxide components of vanadium and niobium loaded in the carrier; the catalyst contains vanadium oxide V in parts by mass2O51-5% in terms of Nb oxide2O50.1-0.3% of the total weight; the carrier comprises 10-30% of fibrous anhydrous calcium sulfate calcined at the temperature of 700-750 ℃ and more than 65% of titanium dioxide, wherein more than 80% of the fibrous anhydrous calcium sulfate is monodisperse; the fibrous anhydrous calcium sulfate is columnar crystal, the length is 15-75 μm, the average diameter is 1-4 μm, the length-diameter ratio is more than 10, and the CaSO4The content is more than or equal to 98 percent.
The fibrous calcium sulfate anhydrite is preferably the product of the calcination of fibrous calcium sulfate hemihydrate at 730-750 ℃.
The preparation method of the catalyst for catalytic combustion treatment of the gas flow containing the organic chlorine comprises the following steps:
A. based on the mass portion, the sulfur is expressed as H2SO42-6% of metatitanic acid wet filter cake calculated as TiO25-10 parts by weight of water is added into the TiO in the slurry25-10% of mass content, treating the slurry or the filtrate thereof in a shearing dispersion machine or a sand mill until the viscosity of the slurry or the filtrate thereof is higher than 15mPa.s, and preparing peptized slurry;
B. b, transferring the peptized slurry prepared in the step A into a stirrer, adding 10-30 parts of fibrous anhydrous calcium sulfate roasted at the temperature of 700-750 ℃, pulping until the monodispersion degree of the anhydrous calcium sulfate fibers is higher than 90% and the fibers are uniformly dispersed in the slurry, adding calcium oxide powder to adjust the pH value of the slurry to be 4.5-5.5, and preparing the peptized slurry containing the anhydrous calcium sulfate fibers;
C. Based on the mass portion, the powder of the orthotitanic acid and/or metatitanic acid containing sulfuric acid with the sulfur fracture content of less than 0.3 percent is mixed with TiO260 to 85 portions are added into a kneader, and the anhydrous sulfur prepared in the step B is addedMixing and kneading the peptized slurry of the calcium carbonate fiber until the peptized slurry is uniform, and extruding strips; drying the extruded strip, and roasting at 400-450 ℃ and air for 2-4hr to obtain a carrier;
D. the carrier is impregnated by ammonium metavanadate-ammonium niobium oxalate-oxalic acid aqueous solution with required concentration by adopting an impregnation method, an impregnation strip is dried, and then the catalyst is prepared by roasting for 2-4 hours under the conditions of 420-450 ℃ and air.
The fibrous anhydrous calcium sulfate contained in the catalyst and the fibrous anhydrous calcium sulfate calcined at the temperature of 700-750 ℃ used in the preparation method are columnar crystals with the length of 30-200 mu m, the average diameter of 1-4 mu m, the length-diameter ratio of 20-100 and the CaSO ratio of4The content is more than or equal to 98 percent, is an anhydrous calcium sulfate single crystal form needle-shaped object, has uniform cross section, complete appearance, complete internal structure, high strength, high modulus, high toughness, high temperature resistance, acid and alkali corrosion resistance, no toxicity and the like, has the functions of reinforcing fiber and superfine inorganic filler, the preparation method is easy to realize monodispersity without crystal transformation and extremely low dissolving amount in water or aqueous solution, and the preparation method is easy to realize monodispersity without crystal transformation and extremely low dissolving amount in the operation process, has higher reinforcing effect on the prepared carrier and the catalyst, obviously improves the mechanical strength and the wear resistance of the carrier and the catalyst, can not be subjected to crystal transformation in the subsequent preparation process of further loading other active ingredients as the carrier, has extremely low dissolution, the catalyst further prepared has higher reinforcing effect, so that the catalyst has higher mechanical strength, wear resistance and pulverization resistance; can not be crystallized, not corroded, basically presents chemical inertness and has no influence on the reaction performance of the catalyst during the long-term application of the catalyst in the treatment of the waste gas with the product containing HCl as an acidic component. The fibrous calcium sulfate anhydrite is capable of significant reinforcement because the size of other components, such as titanium oxide particles, is much lower than the length of the fibrous calcium sulfate.
It has also been found that fibrous anhydrous calcium sulfate can increase the inner pore volume of the carrier to some extent, probably due to the larger length-diameter ratio and higher degree of monodispersion, and the uniform dispersion among titanium oxide particles of orthotitanic acid, metatitanic acid or roasted titanium oxide, so that the fibrous anhydrous calcium sulfate has bridging and puffing effects, the porosity among titanium oxide particles of orthotitanic acid, metatitanic acid or roasted titanium oxide and among fibrous anhydrous calcium sulfate is increased, especially the volume of macropores with a diameter of more than 50nm is remarkably increased, the inner pore volume of the carrier is increased, the internal diffusion of reaction material components in the catalyst strip, especially the internal diffusion of macromolecular substances is easier, and the micropores on the surface layer of the catalyst are not easy to block.
The fibrous anhydrous calcium sulfate used for preparing the catalyst is preferably a product calcined by fibrous calcium sulfate hemihydrate (also called calcium sulfate hemihydrate whisker) at 730-750 ℃, has better reinforcing and pore-forming effects on the carrier and the catalyst when the average diameter is 2-3 mu m and the length is 50-150 mu m, has moderate price and is easy to purchase; the fibrous anhydrous calcium sulfate calcined at the temperature below 680 ℃ is found to have a slightly poor reinforcing effect, the cracking degree in the kneading machine strip process is high, and the strength is slightly low due to insufficient recrystallization degree; fibrous anhydrous calcium sulfate calcined at temperatures above 780 ℃ also has a slightly poor use effect, and also has a high degree of breakage during the kneading process, probably because of internal defects and strength reduction caused by trace decomposition of calcium sulfate. The fibrous anhydrous calcium sulfate is generally obtained by roasting fibrous calcium sulfate hemihydrate or fibrous calcium sulfate dihydrate at a temperature of more than 650 ℃, dehydrating and recrystallizing; it was found that the reinforcing effect of the product calcined at 750 ℃ and 730-. The fibrous calcium sulfate hemihydrate or fibrous calcium sulfate dihydrate is prepared by growing calcium sulfate in a spiral dislocation mode at a proper temperature and/or under the condition of a crystal form control agent.
In the preparation method of the catalyst, the metatitanic acid added in the step A is preferably an intermediate material in the production process of titanium dioxide by a sulfuric acid method; the metatitanic acid used in the step C is preferably prepared by removing sulfuric acid contained in metatitanic acid intermediate material by ammonia water immersion washing in the production process of titanium dioxide by a sulfuric acid method; the metatitanic acid intermediate material is easy to purchase and low in price.
C, extruding the strips by using a screw rod strip extruding machine, wherein the materials have a strong shearing and mixing process in a screw rod and a cavity, a large part of fibrous anhydrous calcium sulfate contained in the materials can be cut off or broken to be shortened, and a discharging part is a pore plate; more preferably, the plunger pressure extrusion mode is adopted, the material does not have a shearing and mixing process in the plunger chamber, the liquid injector is similar to the material, but the discharging part is a pore plate, the fibrous anhydrous calcium sulfate contained in the material is less cut off in the strip extrusion process, and the breaking degree is much lower than that of the strip extrusion machine by using a screw, so that the average length of the fibrous anhydrous calcium sulfate in the carrier or the catalyst is larger, the reinforcing effect is larger, the mechanical strength of the carrier or the catalyst is higher, or the content of the fibrous anhydrous calcium sulfate can be slightly lower.
In the preparation method of the catalyst, the step A contains H2SO4Adding water into wet filter cake of 2-6% metatitanic acid, pulping, and gradually refining metatitanic acid to form partial metatitanic acid colloid or TiO2*xH2O colloid to gradually increase the viscosity of the slurry, H contained in metatitanic acid2SO4Has a key effect on the formation of colloid. The metatitanic acid colloid or TiO after concentration2*xH2C, binding particles of orthotitanic acid and/or metatitanic acid and fibrous anhydrous calcium sulfate by the O colloid in the kneading process in the step C, so that the uniformly kneaded wet material block has proper internal viscosity and toughness, finally the wet material block can be extruded and molded, the extruded strip has strength and surface finish meeting the requirements, and the carrier with higher strength and surface finish can be prepared by further drying and roasting; orthotitanic acid, metatitanic acid colloids or TiO in extruded strips2*xH2The O colloid is converted into porous titanium oxide particles in the roasting process of the carrier at the temperature of 400-450 ℃ in the step C.
If step A is said to contain H2SO4The metatitanic acid wet filter cake is added with water and the slurry is not subjected to shearing dispersion or sanding treatment, so that metatitanic acid colloid or TiO is not formed basically2*xH2O colloid, the slurry viscosity is lower than 2mPa.s, and anhydrous sulfuric acid is added in the step B And C, after the calcium fibers are pulped and dispersed, the calcium fibers are used in the step C, the internal viscosity and the toughness of the wet material block after uniform mixing and kneading are very low, a molding strip with proper strength and surface smoothness cannot be extruded, and the strip obtained by further drying and roasting has very low strength and unsmooth surface.
In the step C, the average grain diameter of the orthotitanic acid and the metatitanic acid is less than one sixth of the length of anhydrous calcium sulfate fibers in the extruded strips or the prepared carrier or catalyst; preferably, the metatitanic acid with the average particle size reduced to below 2 mu m is obtained by ultrafine grinding, more preferably, the metatitanic acid with the average particle size of 0.5-1.5 mu m is obtained, so that the particle size of the metatitanic acid is lower than one tenth of the length of anhydrous calcium sulfate fibers in an extruded strip or a prepared carrier or catalyst, and then, fibrous anhydrous calcium sulfate is added and mixed uniformly to play the reinforcing effect of the fibrous anhydrous calcium sulfate, the bridging and expanding effect of the fibrous anhydrous calcium sulfate and the effect of increasing the volume of macropores with the diameter of more than 50 nm. The length of the anhydrous calcium sulfate fiber in the prepared carrier or catalyst is 15-75 μm, the length-diameter ratio is more than 10, preferably more than 20, and the length-diameter ratio of the anhydrous calcium sulfate fiber in the prepared carrier or catalyst are basically the same as those of the anhydrous calcium sulfate fiber in the extruded strip.
It was also found that if the fibrous anhydrous calcium sulfate is replaced by other temperature and acid corrosion resistant fibrous materials, such as quartz glass fibers with an average diameter of 3.0 μm and a length of 300- 2*xH2The low strength of the bond between the porous titanium oxide particles formed by firing the O-colloid may be a major cause. The fibrous calcium sulfate hemihydrate or fibrous calcium sulfate dihydrate as the precursor of the fibrous calcium sulfate anhydrite is prepared by growing calcium sulfate in a spiral dislocation mode at a proper temperature and/or under the condition of a crystal form control agent, so that the surface of the used anhydrous calcium sulfate fiber has certain roughness, and the water solubility of the anhydrous calcium sulfate fiber still has certain activity, and the fibrous calcium sulfate hemihydrate or fibrous calcium sulfate dihydrate is prepared by mixing the orthotitanic acid, metatitanic acid colloid, TiO colloid and the like2*xH2The porous titanium oxide particles formed by roasting the O colloid have high connection strength. This phenomenon can be explained by adding the silica glass fibers having roughened surfaces, which improves the mechanical strength of the prepared carrier but is still lower than that when fibrous calcium sulfate anhydrite is added, specifically, by comparing the preparation methods of comparative examples 11 to 13 and the side pressure strength of the obtained carriers. The quartz glass fiber comprises long fiber or cellucotton, the price of the quartz glass fiber is dozens of times of that of the fibrous anhydrous calcium sulfate used in the invention, and the quartz glass fiber has low yield and is inconvenient to apply; other glass fibers include E-type alkali-free glass fibers, which are generally not resistant to attack by the strong acid component HCl.
The calcium sulfate fiber reinforced titanium oxide carrier or the further prepared catalyst has high mechanical strength, lateral pressure strength higher than 100N/cm or even 120N/cm, and less discreteness; the raw materials are easy to obtain, the preparation method is simple, reliable and easy to implement, the preparation process is easy to master, and the method can be stably repeated and has low cost. The side pressure strength of the catalyst in step D is generally more than 5% higher than that of the support.
The catalyst of the invention has the temperature of 280-350 ℃ and the space velocity of 200-3000hr-1For example, containing chlorine, e.g. 4000mg/m3The following common organic chlorine waste gas has stronger hydrolytic capability and catalytic combustion capability to organic chlorine in the treatment process of chlorine-containing alkane, chlorine-containing alkene and chlorine-containing aromatic hydrocarbon waste gas, and reaction products are HCl and CO2、H2O and a small amount of Cl2The reaction process comprises hydrolysis of organic chlorine and combustion of a byproduct of chlorine-free organic matters and a small amount of chlorine-free organic matters contained in the waste gas; the combustion step reduces the concentration of byproduct chlorine-free organic matters, reduces the inhibition on the organic chlorine hydrolysis step, and the synergistic effect of the two steps is an important factor for realizing the efficient conversion and removal of organic chlorine; the non-methane alkane may be less than 25mg/m3The benzene series organic matter can be less than 10mg/m3Because the reaction temperature is lower, organic chlorine with higher chlorine content is not generated or the complexity of the organic chlorine is increased generally, and highly toxic chlorine-containing organic matters such as dioxin and the like and benzopyrene are not generated. The activity and reaction effect of the catalyst are the result of the combined action of the oxides containing titanium, vanadium and niobium and their dispersion relation. The carrier skeleton is not influenced during the use of the catalyst The organic chlorine and other organic chlorine and the HCl as reaction products are corroded, the reaction performance and the mechanical strength are stable, the pulverization is not easy, the service life is long, and the product is easy to discharge after use.
In the using process of the catalyst, the temperature of a catalyst bed layer is controlled not to exceed 360 ℃ so as to avoid the reduction of the surface area and the activity of titanium dioxide; the catalyst bed temperature is determined by the exhaust gas inlet temperature and the content of organics in the exhaust gas, including organic chlorine and chlorine-free organics, which are also typically removed by combustion. The exhaust gas should contain a suitable amount of oxygen, e.g. above 5% by volume, and water vapour, e.g. 2-15% by volume; the catalyst of the invention allows water vapor with the volume of up to 15 percent in the process of organochlorine catalytic combustion, which is different from the characteristic that the organochlorine catalytic combustion performance of the catalyst in the prior art is obviously inhibited by water vapor with the volume of more than 10 percent.
The catalyst of the invention is also particularly suitable for catalytic combustion treatment of waste gas containing organochlorine pesticide. The organochlorine pesticide comprises the conventional and current conventional components such as hexachloro cyclohexane, DDT, toxaphene, chlordane, pentachlorophenol and the like, and can realize the conversion rate of the organochlorine pesticide components of over 95 percent and even over 98 percent. The organochlorine pesticide-containing waste gas can be generated in the process of remediation treatment of organochlorine pesticide-contaminated soil.
Detailed Description
The technical solution of the present invention will be specifically described and illustrated below with reference to examples, but the present invention is not limited thereto.
In the following examples and comparative examples, the metatitanic acid wet filter cake has 23.1% of dry basis at 130 ℃, 4.0m% of sulfuric acid with sulfur broken can be burnt out from 130 ℃ dried material at 1150 ℃, and 80.7m% of titanium dioxide; the metatitanic acid powder is prepared by adding water with 3 times of mass into metatitanic acid wet filter cakes for pulping, adding ammonia water for washing, washing for many times, filtering, drying at 130 ℃, airflow crushing into two superfine powders with volume average particle size (outer diameter) of 4.1 mu m and 1.3 mu m, and detecting that 0.2m% of sulfuric acid is burnt out at 1150 ℃ and 84.9m% of titanium dioxide; the fibrous calcium sulfate anhydrite is obtained by roasting commercially available fibrous calcium sulfate hemihydrate, namely calcium sulfate hemihydrate whiskers, at different temperatures, wherein the used fibrous calcium sulfate hemihydrate has the average diameter of 2.1 mu m, the average diameter of 125 mu m, the average length-diameter ratio of 60, the whiteness of 95 and the pH value of 5.5-6.
Example 1
And (2) taking 800g of each six parts of fibrous calcium sulfate hemihydrate, respectively roasting in a muffle furnace at 650 ℃, 680 ℃, 700 ℃, 730 ℃, 750 ℃, 780 ℃, 800 ℃ and air atmosphere for 3 hours, charging at room temperature, powering on, heating, and naturally cooling to below 80 ℃ after constant temperature is over.
The purity of the roasted material is detected by sampling at 700 ℃, and the result is CaSO4The content is 99.3%.
The roasted materials are respectively sampled, the shapes of the materials are respectively detected by an optical microscope, the results are the same as those before roasting, and the average length change is very small.
And (3) respectively sampling 28g of roasted materials, adding 150ml of water, soaking at room temperature for 12 hours, stirring once per hour, filtering the leaching solution, then respectively evaporating to dryness, calculating the dissolution amount of calcium sulfate according to the mass of residues, and finding that the residue amount is lower than 0.18g, which indicates that the dissolution ratio of the calcium sulfate is lower than 0.6%. And (3) respectively detecting the shape and the length of the material soaked in the water by using an optical microscope, wherein the result is not obviously changed from the result before soaking.
Sampling 28g of each roasted material, placing in 100ml ground bottle, capping, sealing, placing in 60 deg.C oven, preheating for 2hr, adding V at 60 deg.C used in step D2O56.0g、Nb2O570ml of vanadyl oxalate-niobium oxalate-oxalic acid aqueous solution with the weight of 0.4g and the weight of oxalic acid with the weight of 12.0g is sealed and put back into a 60 ℃ oven, the vanadyl oxalate-niobium oxalate-oxalic acid aqueous solution is removed by washing after 6 hours, the shape and the length of the material soaked in the nitric acid aqueous solution are respectively detected by an optical microscope, and the results are not obviously changed before soaking; and drying the anhydrous calcium sulfate fiber, and detecting that the contents of vanadium and niobium are respectively lower than 100ppm and 15ppm, which indicates that the anhydrous calcium sulfate fiber does not basically react with the vanadyl oxalate-niobium oxalate-oxalic acid aqueous solution.
Example 2
The catalyst was prepared as follows:
A. adding 571g of water into a shearing dispersion machine, starting stirring, adding 429g of the metatitanic acid wet filter cake (containing 80g of titanium dioxide), pulping until the pulp is completely opaque, and carrying out shearing dispersion treatment for 12 hours under the conditions of sealing, cooling water temperature control until the viscosity of the pulp is 18mPa.s to obtain semitransparent peptized pulp;
B. transferring the peptized slurry prepared in the step A into a stirrer, adding 150g of fibrous anhydrous calcium sulfate roasted at 730 ℃ in the embodiment 1, pulping for 30min until the monodispersion degree of the anhydrous calcium sulfate fibers is detected by an optical microscope and is 91 percent and uniformly dispersed, adding 2.2g of calcium oxide powder, and adjusting the pH value of the peptized slurry to be 4.5-5.5 to prepare the peptized slurry containing the anhydrous calcium sulfate fibers;
C. 907g of metatitanic acid powder (TiO content) having a volume average particle size (outer diameter) of 4.1 μm and containing 0.2% of sulfuric acid having sulfur double bond was charged into a kneader2770g) Adding the peptization slurry containing the anhydrous calcium sulfate fibers prepared in the step B, kneading for 1hr until uniform, extruding into a cylindrical strip with the outer diameter of 3.5mm by using a pushing plunger extruder, and the surface is basically smooth; drying the extruded strips at 130 deg.C for 3hr, and calcining 600g of the dried strips in a muffle furnace at 420 deg.C under air for 3hr to obtain calcium sulfate fiber-reinforced titanium oxide carrier; measuring the lateral pressure strength, the pore volume and the specific surface area of the carrier, and the lateral pressure strength, the pore volume and the specific surface area are listed in the table 1;
D. Collecting 193.6g of calcium sulfate fiber reinforced titanium oxide carrier prepared in step C, placing in 500ml ground bottle, capping, sealing, placing in 60 deg.C oven, preheating for 2hr, gradually adding V at 60 deg.C into titanium oxide carrier during 14-15min shaking2O56.0g、Nb2O50.4g of vanadyl oxalate, 12.0g of oxalic acid and 72ml of oxalic acid solution, covering a ground bottle, sealing, putting the bottle back to an oven at 60 ℃, taking out the bottle and shaking the bottle once every 5min to ensure that residual liquid at the bottom of the bottle is uniformly adhered to the surface of a carrier until no residual liquid at the bottom of the bottle and the surface of the carrier are dried, and then placing the bottle and homogenizing the bottle for 5hr to obtain a dipping strip; taking out the impregnated strip, spreading in a material tray to obtain 8-10mm thin layer, drying at 140 deg.C for 3hr, and calcining at 420 deg.C in air for 3hr to obtain the catalyst.
And C, respectively sampling 20g of the wet material block and the extruded strip before strip extrusion in the step C, adding 200g of water into the material block and the extruded strip respectively, slightly stirring the material block and the extruded strip by using a glass rod, and detecting the average length of the anhydrous calcium sulfate fibers in the dispersion liquid by using an optical microscope, wherein the average length is 64 micrometers and the average length is 55 micrometers respectively.
And B, pulping for 30min, sampling the pulp before filtering, and detecting the average length of the anhydrous calcium sulfate fibers by using an optical microscope, wherein the average length is 110 micrometers respectively.
D, calculating the mass content of the main components in the catalyst prepared in the step D, wherein the calculated result is that the vanadium-containing oxide is V 2O53.0% in terms of Nb oxide2O50.2 percent of the total weight, 81.8 percent of titanium dioxide and 14.4 percent of fibrous anhydrous calcium sulfate.
Example 3
A calcium sulfate fiber-reinforced titania carrier was prepared essentially as in steps A-C of example 2, except that the kneaded mass in step C was extruded into a cylindrical strand having an outer diameter of 3.5mm using a twin-screw extruder, and the surface of the extruded strand was slightly smoother than that of example 2.
And C, respectively sampling 20g of the wet material block and the extruded strip before strip extrusion in the step C, adding 200g of water respectively, slightly stirring by using a glass rod, respectively dispersing the material block and the extruded strip, and detecting the average length of the anhydrous calcium sulfate fiber in the dispersion liquid by using an optical microscope, wherein the average length is 62 micrometers and the average length is 28 micrometers respectively.
The main criteria of the support prepared in step C are given in Table 1.
Example 4
A calcium sulfate fiber reinforced titania support was prepared essentially as in steps A-C of example 2, except that in step C, metatitanic acid powder having a volume average particle size of 4.1 μm was replaced with metatitanic acid powder having the same mass as the above-mentioned volume average particle size of 1.3 μm, and fibrous anhydrous calcium sulfate was then added. The surface of the extruded bar was slightly smoother than that of example 2.
And C, respectively sampling 20g of the wet material block and the extruded strip before strip extrusion in the step C, adding 200g of water respectively, slightly stirring by using a glass rod, respectively dispersing the material block and the extruded strip, and detecting the average length of the anhydrous calcium sulfate fiber in the dispersion liquid by using an optical microscope, wherein the average length is 71 micrometers and the average length is 63 micrometers respectively.
The main criteria for the support prepared in step C are given in Table 1.
Example 5
Preparing a calcium sulfate fiber reinforced titanium oxide carrier by basically adopting the method of the steps A-C of the example 4, wherein the difference is that the kneaded material block in the step C is extruded into a cylindrical strip with the outer diameter of 3.5mm by a double-screw extruder, and the surface of the extruded strip is slightly smoother than that of the example 4; about 900g of the dried pellets were twice calcined at 420 ℃ in a muffle furnace under air for 3 hours, and the catalyst was further prepared by the method of example 2, step D.
And C, respectively sampling 20g of the wet material block and the extruded strip before strip extrusion in the step C, adding 200g of water respectively, slightly stirring by using a glass rod, respectively dispersing the material block and the extruded strip, and detecting the average length of the anhydrous calcium sulfate fiber in the dispersion liquid by using an optical microscope, wherein the average length is 70 micrometers and the average length is 42 micrometers respectively.
The main criteria of the support prepared in step C are given in Table 1.
The mass content of the main component in the catalyst prepared in the step D is the same as that of the catalyst in the embodiment 2, and the calculated result is also the vanadium-containing oxide V2O53.0% in terms of Nb oxide2O50.2 percent, 81.8 percent of titanium dioxide and 14.4 percent of fibrous anhydrous calcium sulfate.
The calcium sulfate fiber-reinforced titanium oxide carrier prepared by the method of steps A to C of this example was used in about 1000g for the following examples and comparative examples.
Example 6
Calcium sulfate fiber reinforced titania support was prepared essentially as in example 5, steps a-C, except that the extruded strip of step B was then co-extruded through a twin screw extruder 2 times three times.
20g of each extruded strip in the two-time extrusion and the three-time extrusion is sampled, 200g of water is added in the same way, a glass rod is used for stirring lightly, the material block and the extruded strip are respectively dispersed, and the average length of the anhydrous calcium sulfate fiber in the dispersion liquid is respectively 38 mu m and 25 mu m through optical microscope detection.
Example 7
The remaining dried strands from step C of example 5 were calcined in a muffle furnace at 450 deg.C for 2hr in air to produce a calcium sulfate fiber-reinforced titania support, and the catalyst was further prepared as in step D of example 2.
The mass content of the main components in the catalyst prepared in the step D is the same as that of the catalysts in the examples 2 and 5, and the calculated result is also the vanadium-containing oxide V2O53.0% in terms of Nb oxide2O50.2 percent, 81.8 percent of titanium dioxide and 14.4 percent of fibrous anhydrous calcium sulfate.
The mass content of the main components of the calcium sulfate fiber reinforced titanium oxide carrier prepared in the step C of the above embodiments is 84.6% of titanium dioxide, 14.9% of fibrous anhydrous calcium sulfate calcined at 700-750 ℃, and the balance of 0.5% of non-fibrous calcium sulfate generated by sulfuric acid contained in the metatitanic acid wet filter cake in the step A and the calcium oxide powder added in the step B.
Example 8
Using the calcium sulfate fiber reinforced titania support prepared by step C of example 5, the catalyst was prepared as follows in step D:
D. collecting 193.4g of the prepared calcium sulfate fiber reinforced titanium oxide carrier, placing in 500ml ground bottle, capping, sealing, placing in 60 deg.C oven, preheating for 2hr, gradually adding V at 60 deg.C into titanium oxide carrier while shaking for 14-15min2O572ml of vanadyl oxalate-niobium oxalate-oxalic acid aqueous solution with 6.0g and 12.0g of oxalic acid, capping a ground bottle, sealing, putting the bottle back into a 60 ℃ oven, taking out the bottle and shaking the bottle once every 5min to ensure that residual liquid at the bottom of the bottle is uniformly adhered to the surface of a carrier until no residual liquid at the bottom of the bottle and the surface of the carrier are dried, and then placing the bottle and homogenizing the bottle for 5hr to obtain a dipping strip; taking out the impregnated strip, spreading in a material tray to obtain 8-10mm thin layer, drying at 140 deg.C for 3hr, and calcining at 420 deg.C in air for 3hr to obtain the catalyst.
The mass content of the main components in the catalyst prepared in the step D is the same as that of the catalysts in the embodiments 2 and 5, and the calculated result is also the vanadium-containing oxide V2O53.0% in terms of Nb oxide2O50.3 percent, 81.7 percent of titanium dioxide and 14.4 percent of fibrous anhydrous calcium sulfate.
The fibrous anhydrous calcium sulfate in each of the carriers and catalysts of the above examples was monodispersed at 80% or more by optical microscopy.
Comparative example 1
The calcium sulfate fiber-reinforced titanium oxide carrier prepared in step C of example 5 was used as the catalyst of the present comparative example, and the mass content of the main components was calculated to be 84.6% of titanium dioxide, 14.9% of fibrous anhydrous calcium sulfate, and the balance was non-fibrous calcium sulfate, and oxides containing vanadium and niobium were not contained.
Comparative example 2
A calcium sulfate fiber reinforced titania support was prepared as in step C of example 5, and the catalyst was prepared as in step D, below:
D. putting 194.0g of the prepared calcium sulfate fiber reinforced titanium oxide carrier into 500ml ground bottle, capping, sealing, placing in 60 deg.C oven, preheating for 2hr, gradually adding V at 60 deg.C into titanium oxide carrier while shaking for 14-15min2O572ml of vanadyl oxalate-oxalic acid aqueous solution with 6.0g and 12.0g of oxalic acid, capping a ground bottle, sealing, putting back to a 60 ℃ oven, taking out the bottle and shaking once every 5min to ensure that residual liquid at the bottom of the bottle is uniformly adhered to the surface of a carrier until no residual liquid at the bottom of the bottle and the surface of the carrier are dried, and then standing and homogenizing for 5hr to obtain a dipping strip; taking out the impregnated strip, spreading in a material tray to obtain 8-10mm thin layer, drying at 140 deg.C for 3hr, and calcining at 420 deg.C in air for 3hr to obtain the catalyst.
D, calculating the mass content of the main component in the catalyst prepared in the step D, wherein the calculated result is that the vanadium-containing oxide is V 2O53.0 percent, 82.0 percent of titanium dioxide, 14.5 percent of fibrous anhydrous calcium sulfate and oxide containing no niobium.
Comparative example 3
The calcium sulfate fiber reinforced titania support prepared in step C of example 5 was used to prepare a catalyst according to the method of step D below:
D. 199.6g of the prepared calcium sulfate fiber reinforced titanium oxide carrier is put into a 500ml ground bottle, covered and sealed, put into a 60 ℃ oven for preheating for 2 hours, and then Nb with the temperature of 60 ℃ is gradually dripped into the titanium oxide carrier in shaking for 14-15min2O572ml niobium oxalate-oxalic acid aqueous solution of 0.4g and oxalic acid 12.0g, capping a ground bottle, sealing, putting back into a 60 ℃ oven, taking out the bottle and shaking once every 5min to ensure that residual liquid at the bottom of the bottle is uniformly adhered to the surface of the carrier until no residual liquid at the bottom of the bottle and the surface of the carrier are dried, and then standing and homogenizing for 5hr to obtain a dipping strip; taking out the impregnated strip, spreading in a material tray to obtain 8-10mm thin layer, drying at 140 deg.C for 3hr, and calcining at 420 deg.C in air for 3hr to obtain the catalyst.
D, calculating the mass content of the main component in the catalyst prepared in the step D, wherein the calculated result is that the oxide containing niobium is Nb2O50.2 percent of titanium dioxide 84.4 percent, fibrous anhydrous calcium sulfate 14.9 percent and oxide without vanadium.
Comparative example 4
300g of the dried pellets obtained in step C of example 5 were calcined in a muffle furnace at 500 ℃ in air for 2 hours to obtain a calcium sulfate fiber-reinforced titanium oxide carrier, and a catalyst was further prepared in the same manner as in step D of example 2.
The mass content of the main components in the catalyst prepared in the step D is the same as that of the catalysts in the examples 2 and 5, and the calculated result is also the vanadium-containing oxide V2O53.0% in terms of Nb oxide2O50.2 percent, 81.8 percent of titanium dioxide and 14.4 percent of fibrous anhydrous calcium sulfate.
Comparative example 5
The process is essentially carried out as in steps A-C of example 5, except that the slurry in step A is not subjected to said shear dispersion treatment and the viscosity of the slurry is less than 2 mPa.s. It was found that the wet mass in step C was relatively loose, had little increase in internal viscosity and toughness, and after kneading for 1hr, the wet mass was too low in internal viscosity and toughness to break easily during extrusion, had a rough surface, and had low strength after drying and firing, and could not be used as a carrier.
Comparative example 6
The procedure is essentially as in example 5, steps A-C, except that the slurry is shear dispersed to a viscosity of 8mPa.s in step A. The wet material block in the step C is found to have certain internal viscosity and toughness, the wet material block is extruded continuously after being kneaded for 1hr, the surface is basically smooth, but the strength after drying and roasting is not enough, and the wet material block cannot be used as a carrier.
Comparative example 7
The process is essentially as described in example 5, Steps A-C, except that in step B fibrous calcium sulfate anhydrate is obtained by calcination at 1680 ℃ for 3 hours.
And C, respectively sampling 20g of the wet material block and the extruded strip before strip extrusion in the step C, adding 200g of water respectively, slightly stirring by using a glass rod, respectively dispersing the material block and the extruded strip, and detecting the average length of the anhydrous calcium sulfate fiber in the dispersion liquid by using an optical microscope, wherein the average length is 55 micrometers and the average length is 20 micrometers respectively.
Comparative example 8
The process is essentially as described in example 5, Steps A-C, except that in step B, the fibrous anhydrous calcium sulfate is prepared by calcining at 1780 ℃ for 3 hours.
And C, respectively sampling 20g of the wet material block and the extruded strip before strip extrusion in the step C, adding 200g of water respectively, slightly stirring by using a glass rod, respectively dispersing the material block and the extruded strip, and detecting the average length of the anhydrous calcium sulfate fiber in the dispersion liquid by using an optical microscope, wherein the average length is 60 micrometers and the average length is 22 micrometers respectively.
Comparative example 9
The titania-based sulfur recovery catalyst prepared by the method of example 1 of CN109126830A was used as the catalyst of this comparative example. The proportion of the titanium dioxide is 85.8m percent and the proportion of the calcium sulfate is 14.2m percent, wherein, part of the calcium sulfate generates short fiber-shaped crystals in the preparation process, the short fiber-shaped crystals are distributed among micro-particles of the catalyst to play a role in enhancing, and the rest calcium sulfate is non-fibrous. The preparation method comprises the following steps:
A. 5.375kg of metatitanic acid powder L (with the average particle size of 0.72 mu m, 4.0m percent of sulfuric acid with sulfur broken out at 1150 ℃ and 80m percent of titanium dioxide), 0.295kg of calcium oxide powder N (-600 meshes, the purity of 99.4m percent and the magnesium oxide of 0.3m percent) are added and mixed evenly, 4.4kg of aqueous solution containing 0.412kg of ammonium sulfate is added and kneaded into a uniform wet block; the ratio of the sum of the amounts of substances of ammonium sulfate contained in the ammonium sulfate solution and substances of sulfuric acid formed by the reduction of sulfur contained in metatitanic acid to the amount of the added calcium oxide is 1: 1;
B. Putting 9.63kg of wet material blocks into a polypropylene plastic bag (the mass of the plastic bag is 65 g), compacting into a thin layer, tying a port but ventilating a small amount, putting the thin layer into a middle bracket of a 30L autoclave, injecting 3000ml of pure water below the bracket, electrically heating the bottom of the autoclave, inserting a thermocouple into the center part of the wet material blocks of the plastic bag to detect the temperature, and preserving the heat outside the autoclave; closing the autoclave, starting and controlling external electric heating at the bottom of the autoclave, discharging air in the autoclave for 5min through a pressure release valve after pure water in the autoclave boils, closing the pressure release valve, raising the central temperature of a wet material block to 90 ℃, then preserving heat for 0.5hr at 90-100 ℃, opening the pressure release valve to discharge air in the autoclave for 5min, then closing the pressure release valve, raising the temperature to 120 ℃, then keeping the temperature for 2hr, keeping the pressure in the autoclave at 200 and 205kPa (absolute pressure) in the process of keeping the temperature at 120 ℃, and keeping the pressure in the autoclave at 120 ℃ to be higher than 200kPa before keeping the temperature; cutting off power after constant temperature is over, and cooling to below 100 deg.C for 0.5 hr;
C. opening the kettle, taking out the wet material block plastic bag, weighing 9.65kg, cooling to about 50 deg.C within 0.3hr, immediately extruding through a phi 3.5mm orifice plate to obtain relatively hard and straight strips, drying at 120 deg.C in a hot air mesh belt furnace for 0.3hr, and calcining 600g of dried strips in a muffle furnace at 450 deg.C for 3hr to obtain the catalyst.
Comparative example 10
Essentially the procedure is as in example 5, Steps A-C, except that in step B, a mean diameter of 3 μm, a diameter range of 2.7-3.2 μm, a length range of 300-500 μm, a mean length of 360 μm, SiO 2150g of quartz glass fibers with a content of 99.4% replace the fibrous anhydrous calcium sulfate used. The surface of the used quartz glass fiber is not coated, the hydrophilicity is good, and the monodispersion degree in the peptizing sizing agent in the step B can reach 90 percent and the monodispersion is uniform.
As a result, the carrier produced has low mechanical strength and a rough and unsmooth surface.
Comparative example 11
The procedures of comparative example 10 were basically followed except that the amount of the quartz glass fiber used in step B was increased to 300 g.
As a result, the mechanical strength of the resulting support is still not high, and the surface is also rough and not smooth.
Comparative example 12
The procedure of comparative example 10 was essentially followed except that in step B, surface-roughened silica glass fibers were used.
As a result, the mechanical strength of the carrier prepared was higher than that of comparative example 9, and the surface was still rough and not smooth.
The surface roughening method of the quartz glass fiber comprises the following steps: and (3) putting 150g of quartz glass fiber in a 1000ml plastic cup, adding water to reach the total volume of 900ml, adding 20ml of 40% hydrofluoric acid, stirring uniformly, standing for 6 hours, stirring uniformly once per hour, changing water for washing three times, and adding the slurry in the step (B).
The average length of the silica glass fiber in each of the carriers and catalysts of comparative examples 10 to 12 was 80 μm or more and the degree of monodispersion was 70 to 80% as measured by an optical microscope.
The main physicochemical indexes of the carriers prepared in the above examples and comparative examples were tested, and some results are shown in table 1, in which the catalyst of comparative example 8 was used as a carrier to compare with the carrier of the present invention.
TABLE 1 Main index of each example and comparative example carrier
Evaluation test example
The catalysts prepared in examples 2, 5 and 8 and comparative examples 1 to 4 were tested in a laboratory evaluation apparatus, each containing 60ml of the catalyst; the gas condition is DDT 2000mg/m3About (containing chlorine 1100 mg/m)3) 5% by volume of oxygen, 8% by volume of carbon dioxide and 5-6% by volume of water vapor, the balance being nitrogen; the space velocities of the gases are all 1500hr-1The bed temperature was 320 ℃ and the test time was 30hr each.
The evaluation results included: examples 2, 5, 8 catalysts all had DDT contents in the off-gas of less than 100mg/m3The total amount of other organic chlorine is less than 40mg/m3The non-methane hydrocarbon content is less than 20mg/m3The content of benzene and benzene series organic matters is less than 10mg/m3Selectivity of carbon dioxide is higher than 96%, selectivity of HCl is higher than 98%, and Cl is added2Selectivity is lower than 1%, and other organochlorines or organic matters with nondegradable property, complexity and toxicity higher than DDT (dichloro-diphenyl-trichloroethane) are not considered to be generated; the DDT content in the off-gas of the catalysts of comparative examples 1 and 3 is higher than 600mg/m 3(ii) a Comparative example 2 catalyst having a DDT content in the offgas higher than 230mg/m3(ii) a Comparative example 4 catalyst having a DDT content in the offgas higher than 350mg/m3。
Example 5 after the completion of the 30hr test, the catalyst was evaluated for a further 30hr with 11-12% by volume of water vapor in the gas and the remaining conditions unchanged; the result is a DDT content in the off-gas of less than 100mg/m3The total amount of other organic chlorine is less than 50mg/m3The non-methane hydrocarbon content is less than 20mg/m3The content of benzene and benzene series organic matters is less than 20mg/m3Selectivity of carbon dioxide is higher than 97%, selectivity of HCl is higher than 99%, and Cl is added2The selectivity is lower than 0.8%; other organochlorines or organics such as dioxins, benzopyrenes that are considered to not produce recalcitrance, complexity, toxicity higher than DDT.
Example 5 catalyst in completing the secondAfter 30hr of testing, comparative example 2 catalyst after completion of the first 30hr of testing, gas conditions were changed to chlordane 2150mg/m3About (containing chlorine at 1500 mg/m)3) 5% by volume of oxygen, 8% by volume of carbon dioxide and 11-12% by volume of water vapor, the balance being nitrogen; continuously evaluating for 30hr under constant temperature and airspeed conditions; as a result, the content of chlordane in the catalyst off-gas of example 5 was less than 100mg/m3The total amount of other organic chlorine is less than 50mg/m 3The non-methane hydrocarbon content is less than 20mg/m3The content of benzene and benzene series organic matters is less than 10mg/m3Selectivity of carbon dioxide is higher than 97%, selectivity of HCl is higher than 99%, and Cl is added2The selectivity is lower than 1%; other organic chlorine or organic substances such as dioxin and benzopyrene with higher toxicity than chlordane are not considered to be generated due to the difficult degradability, complexity and toxicity.
Example 5 catalyst after completion of the third 30hr test, the gas conditions were changed to sixty six 1750mg/m3About (containing 1200mg/m chlorine per turn)3) 5% by volume of oxygen, 8% by volume of carbon dioxide and 11-12% by volume of water vapor, the balance being nitrogen; continuously evaluating for 30hr under the condition of unchanged temperature and airspeed; the result is that the content of hexachloro-cyclohexane in the outlet gas is less than 100mg/m3The total amount of other organic chlorine is less than 50mg/m3The non-methane hydrocarbon content is less than 20mg/m3The content of benzene and benzene series organic matters is less than 10mg/m3Selectivity of carbon dioxide is higher than 97%, selectivity of HCl is higher than 99%, and Cl is added2The selectivity is lower than 0.8%; other organochlorines or organics such as dioxins, benzopyrenes that are considered to not produce a refractory, complex, more toxic than hexachloro-hexa.
EXAMPLE 5 after completion of the fourth 30hr test, the catalyst was further evaluated under another gas condition containing 1400mg/m of 1, 2-dichloroethane 3(reaction chlorine 1000 mg/m)3) 5% by volume of oxygen, 8% by volume of carbon dioxide and 11-12% by volume of water vapor, the balance being nitrogen; gas space velocity of 2000hr-1Continuously evaluating for 30hr at bed temperature of 300 deg.C; the result is a dichloroethane content in the off-gas of less than 15mg/m3The total amount of organic chlorine is less than 30mg/m3Without generating organic matter of trichloro or higher, with a non-methane hydrocarbon content lower than20mg/m3Benzene and benzene series organic matters are not generated, the selectivity of carbon dioxide is higher than 98 percent, the selectivity of HCl is higher than 99 percent, and Cl is generated2The selectivity is less than 1%.
DDT, chlordane and hexachloro cyclohexane for evaluating and testing gas distribution are chemical pesticide reagents containing respective standard mixture ratio isomeric components.
In the catalysts of the examples and the comparative examples, air purging is changed into air purging before the post-discharging of the catalyst, so that organic chlorine, other chlorine-containing organic matters and chlorine-free organic matters in a catalyst bed layer and a container can be treated completely, the discharged waste agent after cooling is basically free from peculiar smell, the surface smoothness of the catalyst is not changed visually before evaluation, and the catalyst is pulverized and reduced in strength.
Claims (7)
1. A catalytic combustion treatment catalyst containing organic chlorine gas flow comprises a titanium dioxide carrier and oxide components of vanadium and niobium loaded in the carrier; the catalyst contains vanadium oxide V in mass fraction 2O51-5% in terms of Nb oxide2O50.1-0.3% of the total weight; the carrier is a titanium dioxide carrier enhanced by fibrous anhydrous calcium sulfate, and comprises 10-30% of fibrous anhydrous calcium sulfate and more than 65% of titanium dioxide by mass fraction, wherein more than 80% of fibrous anhydrous calcium sulfate is monodisperse; the fibrous anhydrous calcium sulfate is a product obtained by roasting fibrous calcium sulfate hemihydrate at the temperature of 730-750 ℃, is columnar crystal, has the length of 15-75 mu m, the average diameter of 1-4 mu m, the length-diameter ratio of more than 10 and CaSO4The content is more than or equal to 98 percent;
the preparation method of the catalyst for catalytic combustion treatment of the gas flow containing the organic chlorine comprises the following steps:
A. based on the mass portion, the sulfur is expressed as H2SO42-6% of metatitanic acid wet filter cake calculated as TiO25-10 parts by weight of water is added into the TiO in the slurry25-10% of mass content, treating the slurry or the filtrate thereof in a shearing dispersion machine or a sand mill until the viscosity of the slurry or the filtrate thereof is higher than 15 mPa.s, and preparing peptized slurry;
B. transferring the peptized slurry prepared in the step A into a stirrer, adding 10-30 parts of fibrous anhydrous calcium sulfate roasted at 750 ℃ and 730-;
C. Based on the mass portion, the powder of the orthotitanic acid and/or metatitanic acid containing sulfuric acid with the sulfur fracture content of less than 0.3 percent is mixed with TiO260-85 parts by weight of the mixture is added into a kneader, peptized slurry containing the fibrous anhydrous calcium sulfate prepared in the step B is added, and the mixture is kneaded to be uniform and then extruded into strips; drying the extruded strip, and roasting at 400-450 ℃ and air for 2-4hr to obtain a carrier;
D. the carrier is impregnated by ammonium metavanadate-ammonium niobium oxalate-oxalic acid aqueous solution with required concentration by adopting an impregnation method, an impregnation strip is dried, and then the catalyst is prepared by roasting for 2-4 hours under the conditions of 420-450 ℃ and air.
2. The organochlorine-containing gas stream catalytic combustion processing catalyst of claim 1, wherein the metatitanic acid added in step A is a metatitanic acid intermediate material in a titanium dioxide production process by a sulfuric acid process; and/or the metatitanic acid used in the step C is prepared by removing sulfuric acid from a metatitanic acid intermediate material in the production process of titanium dioxide by a sulfuric acid method by using ammonia water for immersion cleaning.
3. The catalyst for catalytic combustion treatment of a gaseous stream containing organic chlorine according to claim 1, wherein in step C, powders of ortho-titanic acid and/or meta-titanic acid having an average particle size of less than 2 μm are used; and/or the strip extrusion mode comprises screw rod extrusion or plunger pressure extrusion.
4. The use of the organochlorine-containing gas stream catalytic combustion treatment catalyst of claim 1 in the treatment of chlorine-containing alkanes, chlorine-containing alkenes, or chlorine-containing aromatics waste gases.
5. Use of the catalytic combustion treatment catalyst for organochlorine-containing gas streams according to claim 1 for the treatment of organochlorine-containing pesticide exhaust gases.
6. Use of the catalyst for catalytic combustion treatment of an organochlorine-containing gas stream for the treatment of an organochlorine-containing pesticide exhaust gas as defined in claim 5, wherein the organochlorine pesticide is hexachloro-cyclohexane, DDT, toxaphene, chlordane, or pentachlorophenol.
7. The use of the catalytic combustion treatment catalyst for an organochlorine-containing gas stream in the treatment of an organochlorine-containing pesticide exhaust gas as claimed in claim 5, wherein said organochlorine-containing pesticide exhaust gas is generated during a remediation treatment of organochlorine pesticide-contaminated soil.
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| CN1382072A (en) * | 1999-09-29 | 2002-11-27 | 三井化学株式会社 | Catalyst for decomposing organic hazardous material and method for decomposing organic halides using the same |
| JP2007054694A (en) * | 2005-08-22 | 2007-03-08 | Tokyo Institute Of Technology | Method for decomposing hardly decomposable chlorinated organic compound, and carbon nanotube composite material |
| CN101862593A (en) * | 2010-06-22 | 2010-10-20 | 华东理工大学 | Low-temperature catalytic combustion elimination method for chlorine-containing volatile organic compounds |
| CN109126830A (en) * | 2018-08-04 | 2019-01-04 | 山东迅达化工集团有限公司 | A kind of preparation method of titania-based catalyst for recovering sulfur |
| CN109126755A (en) * | 2018-08-04 | 2019-01-04 | 山东迅达化工集团有限公司 | The preparation method of titania-based catalyst for recovering sulfur |
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| CN1382072A (en) * | 1999-09-29 | 2002-11-27 | 三井化学株式会社 | Catalyst for decomposing organic hazardous material and method for decomposing organic halides using the same |
| JP2007054694A (en) * | 2005-08-22 | 2007-03-08 | Tokyo Institute Of Technology | Method for decomposing hardly decomposable chlorinated organic compound, and carbon nanotube composite material |
| CN101862593A (en) * | 2010-06-22 | 2010-10-20 | 华东理工大学 | Low-temperature catalytic combustion elimination method for chlorine-containing volatile organic compounds |
| CN109126830A (en) * | 2018-08-04 | 2019-01-04 | 山东迅达化工集团有限公司 | A kind of preparation method of titania-based catalyst for recovering sulfur |
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