CN111203241A - Organic chlorine-containing waste gas treatment catalyst and preparation method thereof - Google Patents
Organic chlorine-containing waste gas treatment catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN111203241A CN111203241A CN202010094772.1A CN202010094772A CN111203241A CN 111203241 A CN111203241 A CN 111203241A CN 202010094772 A CN202010094772 A CN 202010094772A CN 111203241 A CN111203241 A CN 111203241A
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- China
- Prior art keywords
- calcium sulfate
- catalyst
- anhydrous calcium
- fibrous
- acid
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 107
- 239000000460 chlorine Substances 0.000 title claims abstract description 68
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 67
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000002912 waste gas Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 97
- 229940095564 anhydrous calcium sulfate Drugs 0.000 claims abstract description 92
- 238000000034 method Methods 0.000 claims abstract description 57
- 230000008569 process Effects 0.000 claims abstract description 32
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 26
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 9
- 239000011572 manganese Substances 0.000 claims abstract description 9
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 7
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 6
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 97
- 239000000463 material Substances 0.000 claims description 80
- 239000002253 acid Substances 0.000 claims description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- 229940095672 calcium sulfate Drugs 0.000 claims description 44
- 239000000835 fiber Substances 0.000 claims description 37
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 31
- 238000001035 drying Methods 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000012065 filter cake Substances 0.000 claims description 24
- 238000007598 dipping method Methods 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 21
- 238000004898 kneading Methods 0.000 claims description 21
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 19
- 238000004537 pulping Methods 0.000 claims description 19
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 19
- 238000001125 extrusion Methods 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 17
- 239000000084 colloidal system Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 13
- 239000011593 sulfur Substances 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 11
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 10
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000292 calcium oxide Substances 0.000 claims description 10
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 10
- 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 10
- 239000000126 substance Substances 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 238000007664 blowing Methods 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 229910052925 anhydrite Inorganic materials 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 5
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- JZRJULCEDCRLMD-UHFFFAOYSA-N cerium(3+) manganese(2+) dinitrate Chemical compound [N+](=O)([O-])[O-].[Ce+3].[N+](=O)([O-])[O-].[Mn+2] JZRJULCEDCRLMD-UHFFFAOYSA-N 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 238000002386 leaching Methods 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 16
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract description 16
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 15
- 238000002485 combustion reaction Methods 0.000 abstract description 7
- 239000007795 chemical reaction product Substances 0.000 abstract description 4
- 230000007062 hydrolysis Effects 0.000 abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 4
- 230000007774 longterm Effects 0.000 abstract description 3
- 235000011132 calcium sulphate Nutrition 0.000 description 44
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 28
- 229910052802 copper Inorganic materials 0.000 description 28
- 239000010949 copper Substances 0.000 description 28
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 26
- 239000007788 liquid Substances 0.000 description 23
- 230000001965 increasing effect Effects 0.000 description 19
- 238000005070 sampling Methods 0.000 description 17
- 230000003287 optical effect Effects 0.000 description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 239000003365 glass fiber Substances 0.000 description 12
- 241001391944 Commicarpus scandens Species 0.000 description 11
- -1 meta-titanic acid Chemical compound 0.000 description 11
- 230000007797 corrosion Effects 0.000 description 10
- 238000005260 corrosion Methods 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 10
- 238000002791 soaking Methods 0.000 description 10
- 239000011521 glass Substances 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 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 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 8
- 239000001569 carbon dioxide Substances 0.000 description 7
- 238000007084 catalytic combustion reaction Methods 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 230000003014 reinforcing effect Effects 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- DQTJHJVUOOYAMD-UHFFFAOYSA-N oxotitanium(2+) dinitrate Chemical compound [O-][N+](=O)O[Ti](=O)O[N+]([O-])=O DQTJHJVUOOYAMD-UHFFFAOYSA-N 0.000 description 6
- GBDZXPJXOMHESU-UHFFFAOYSA-N 1,2,3,4-tetrachlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1Cl GBDZXPJXOMHESU-UHFFFAOYSA-N 0.000 description 5
- 150000001555 benzenes Chemical class 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- OHZZTXYKLXZFSZ-UHFFFAOYSA-I manganese(3+) 5,10,15-tris(1-methylpyridin-1-ium-4-yl)-20-(1-methylpyridin-4-ylidene)porphyrin-22-ide pentachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mn+3].C1=CN(C)C=CC1=C1C(C=C2)=NC2=C(C=2C=C[N+](C)=CC=2)C([N-]2)=CC=C2C(C=2C=C[N+](C)=CC=2)=C(C=C2)N=C2C(C=2C=C[N+](C)=CC=2)=C2N=C1C=C2 OHZZTXYKLXZFSZ-UHFFFAOYSA-I 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect 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
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- QSUZZOMTZFGYHO-UHFFFAOYSA-L barium(2+) dichloride hydrochloride Chemical compound Cl.[Cl-].[Ba+2].[Cl-] QSUZZOMTZFGYHO-UHFFFAOYSA-L 0.000 description 2
- 239000001175 calcium sulphate Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000000382 dechlorinating effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 229910052905 tridymite 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
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 229910000431 copper oxide Inorganic materials 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
- 229940057307 dihydrate calcium sulfate Drugs 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
- 239000002657 fibrous material Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229940057306 hemihydrate calcium sulfate Drugs 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
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- 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
- 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
- 239000000203 mixture Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 150000004045 organic chlorine compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 231100000614 poison Toxicity 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
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910009112 xH2O Inorganic materials 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
- 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
- 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
- B01D53/8659—Removing halogens or halogen compounds
- B01D53/8662—Organic halogen compounds
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- B01J35/30—
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- B01J35/58—
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- B01J35/615—
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- B01J35/633—
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- 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
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- 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
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- 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
Abstract
The invention provides an organic chlorine-containing waste gas treatment catalyst and a preparation method thereof, wherein the catalyst comprises a fibrous anhydrous calcium sulfate reinforced titanium dioxide carrier and oxide components of manganese and cerium loaded in the carrier; the carrier comprises 10-30% of fibrous anhydrous calcium sulfate calcined at the temperature of 700-750 ℃ and more than 65% of titanium dioxide by mass, wherein more than 90% of the fibrous anhydrous calcium sulfate is monodisperse; the manganese-containing oxide of the catalyst is calculated by mass portion as MCalculated by nO, 5 to 15 percent, and cerium oxide is CeO22-5 percent. The catalyst has high organic chlorine hydrolysis activity and combustion activity, and can be used at the temperature of below 350 ℃. The preparation process of the catalyst is easy to master and can be stably repeated; the mechanical strength is high, and 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.
Description
Technical Field
The invention belongs to the technical field of organic chlorine-containing waste gas treatment, and particularly relates to an organic chlorine-containing waste gas treatment catalyst and a preparation method thereof.
Background
Chlorine-containing organic matters, also called organic chlorine, are important industrial raw materials or products, such as chlorine-containing alkane and chlorine-containing aromatic hydrocarbon, and are widely used as raw materials and solvents for chemical reactions or as addition components of a plurality of processing aids and processing processes; because of its volatility, difficult degradability and toxicity, organic chlorine in waste gas, waste liquor and waste material can be properly treated, converted and removed, and can be discharged, treated or buried; the treatment of the organic chlorine in the waste gas is the most important technical field, and the organic chlorine in the waste liquid and the waste material is driven into the waste gas through gas stripping and thermal volatilization for treatment, so that the treatment is often convenient and easy to carry out.
When the content of organic chloride in the waste gas is high, the separation and utilization of the organic chloride are a treatment way; the organic chlorine with proper concentration is subjected to hydrogenation treatment, the generated hydrogen chloride which is easy to remove is more effectively converted, and the byproduct is nontoxic or utilizable hydrocarbon. However, in many cases, the concentration of organic chlorine in the exhaust gas is low, and therefore it is inconvenient to treat and utilize the organic chlorine by a separation method, or the low-concentration gas obtained after most of the organic chlorine is separated is treated by catalytic combustion, and therefore, the method is sometimes economically effective. The catalytic combustion process, which includes the steps of hydrolyzing organic chlorine to produce hydrogen chloride which is easily removed, and catalytically combusting and oxidizing chlorine-free intermediate organic species to produce carbon dioxide and water, is generally carried out at a suitable temperature, such as 250 ℃ to 400 ℃ and with a catalyst having suitable properties, wherein the hydrogen chloride is also partially oxidized to produce a small amount of chlorine.
For chlorine, e.g. 1000mg/m3Or the following common organic chlorine-containing waste gas is subjected to catalytic combustion treatment at the temperature of 400 ℃ and under the oxygen-containing condition by adopting a catalyst of active ingredients such as iron oxide, manganese oxide, copper oxide, cobalt oxide, chromium oxide, vanadium oxide, tungsten oxide, titanium oxide, rare earth oxide, ruthenium oxide and the like to convert organic chlorine into hydrogen chloride which is easy to remove, carbon dioxide and waterHydrogen chloride generated in the gas flow is removed by other methods, including absorption by alkali liquor or treatment by calcium carbonate/calcium oxide-containing dechlorinating agent, which is convenient and easy to operate in many cases; however, since the generated hydrogen chloride is highly corrosive under the reaction temperature condition, the problem is whether the mechanical strength of the dechlorination combustion catalyst can be maintained during the use process; some organic chlorine is relatively complex and difficult in hydrolysis process when being treated by catalytic combustion due to structural stability, and requires relatively high active ingredient loading capacity and relatively high pore volume and specific surface area of a 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 catalyst containing copper is liable to generate organic chlorine which is difficult to handle or organic chlorine with higher toxicity, and chromium is liable to cause the waste catalyst difficult to handle due to the toxicity.
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 hydrolytic conversion and combustion of organic chlorine besides playing a role in the framework of the catalyst. However, the titania support has a disadvantage that it is not easy to obtain a 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 an organochlorine-containing waste gas treatment catalyst and a preparation method thereof, the catalyst takes titanium oxide as a carrier, is reinforced by calcium sulfate fibers and loads oxides of manganese and cerium, active ingredients comprise oxides of titanium, manganese and cerium, the catalyst has higher organochlorine hydrolysis activity and organic ingredient combustion activity, can hydrolyze and combust organochlorine compounds at the temperature below 350 ℃, and can achieve standard discharge after hydrogen chloride and a small amount of chlorine are treated by alkali liquor absorption or a dechlorinating agent containing calcium carbonate/calcium oxide. 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, is not easy to generate organic chlorine with higher chlorine content or increase the complexity of the organic chlorine, does not contain toxic chromium, and is easier to scrap and treat the waste catalyst; the used raw materials are cheap and easily available, and the catalyst is low in cost.
The organochlorine waste gas treatment catalyst comprises a fibrous anhydrous calcium sulfate reinforced titanium dioxide carrier and oxide components of manganese and cerium loaded in the carrier; the carrier comprises 10-30% of fibrous anhydrous calcium sulfate calcined at the temperature of 700-750 ℃ and more than 65% of titanium dioxide by mass, wherein more than 90% of the fibrous anhydrous calcium sulfate is monodisperse; in parts by mass, the manganese-containing oxide of the catalyst accounts for 5-15% of MnO, and the cerium oxide accounts for CeO22-5 percent.
The preparation method of the organic chlorine waste gas treatment catalyst comprises the following steps:
A. adding 250 portions and 400 portions of water into a reaction vessel by mass portion, starting stirring, adding orthotitanic acid and/or metatitanic acid containing less than 0.3 percent of sulfur by mass portion to form TiO270-90 parts by weight, pulping, adding 10-30 parts by weight of fibrous anhydrous calcium sulfate roasted at 750 ℃ in 700-750 ℃, pulping until the monodispersion degree of the anhydrous calcium sulfate fiber is higher than 90%, pulping until orthotitanic acid and/or metatitanic acid and the fibrous anhydrous calcium sulfate are uniformly dispersed, filtering, blowing off water by using compressed air and/or blowing, airing and drying until the solid content of the filter cake is 40-55% after drying at 120 ℃, thus obtaining the fibrous anhydrous sulfurA wet cake of calcium and metatitanic acid;
B. crushing the wet filter cake containing fibrous anhydrous calcium sulfate and metatitanic acid, putting into a kneader, adding 10-20 parts of nitric acid aqueous solution with the mass concentration of 35-50%, kneading uniformly, standing for 5-20hr, and extruding; drying the extruded strips, and roasting at 400-450 deg.C in air for 2-4hr to obtain carrier;
C. dipping the carrier for 1-2 times by adopting a dipping method by using a manganese nitrate-cerium nitrate aqueous solution with required concentration, drying and roasting a primary dipping strip at the temperature of 300-350 ℃ during twice dipping, and then carrying out twice dipping;
D. drying the impregnated strip, and calcining at 420-450 deg.C in air for 2-4hr to obtain the catalyst.
The second preparation method of the organic chlorine waste gas treatment catalyst comprises the following steps:
A. adding 400 portions of water 250-one into a reaction vessel by mass portion, starting stirring, adding H containing sulfur2SO42-6% of metatitanic acid calculated as TiO270-90 parts by weight, pulping, adding calcium carbonate powder and/or calcium oxide powder with the amount of sulfur substances contained in metatitanic acid being 1.2-1.5 times of the amount of the sulfur substances contained in metatitanic acid, reacting at normal temperature for 2-10hr, gradually adding sulfuric acid, ammonium sulfate or solution thereof, reacting for 1-5hr until the residual calcium carbonate and/or calcium oxide is completely converted into calcium sulfate, adding 15-30 parts of fibrous anhydrous calcium sulfate calcined at the temperature of 700-750 ℃, pulping until the monodispersion degree of the anhydrous calcium sulfate fiber is higher than 90% and uniformly dispersing in the slurry; filtering the slurry, blowing water by using compressed air and/or blowing, airing and drying the slurry until the solid content of the filter cake is 40-55% after drying at 120 ℃ to prepare a wet filter cake containing fibrous anhydrous calcium sulfate and metatitanic acid;
B. crushing the wet filter cake containing fibrous anhydrous calcium sulfate and metatitanic acid, putting into a kneader, adding 10-20 parts of nitric acid aqueous solution with the mass concentration of 35-50%, kneading uniformly, standing for 5-20hr, and extruding; drying the extruded strips, and roasting at 400-450 deg.C in air for 2-4hr to obtain carrier;
C. dipping the carrier for 1-2 times by adopting a dipping method by using a manganese nitrate-cerium nitrate aqueous solution with required concentration, drying and roasting a primary dipping strip at the temperature of 300-350 ℃ during twice dipping, and then carrying out twice dipping;
D. drying the impregnated strip, and calcining at 420-450 deg.C in air for 2-4hr to obtain the catalyst.
The fibrous anhydrous calcium sulfate contained in the carrier and the catalyst of the invention, and the fibrous anhydrous calcium sulfate calcined at the temperature of 700-750 ℃ used in the preparation method, also called anhydrous calcium sulfate whisker, are columnar crystals, the length of which is 30-200 mu m, the average diameter of which is 1-4 mu m, the length-diameter ratio of which is 20-100, and CaSO4The 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 carrier and the catalyst is preferably a product calcined by fibrous calcium sulfate hemihydrate (also called calcium sulfate hemihydrate whisker) at 750 ℃ of 730-; the fibrous anhydrous calcium sulfate roasted at the temperature below 680 ℃ is found to have a slightly poor reinforcing effect, the cracking degree in the kneading machine process is high, and the strength is slightly low mainly due to insufficient recrystallization degree; the 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 of the strip, probably because of internal defects and reduced strength caused by trace decomposition of calcium sulfate. The fibrous anhydrous calcium sulfate is generally obtained by roasting fibrous hemihydrate calcium sulfate or fibrous dihydrate calcium sulfate 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-.
B, extruding the strips by using a screw rod 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 is 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 material is similar to a liquid injector, but the discharging part is a pore plate, the fibrous anhydrous calcium sulfate contained in the material is cut less in the strip extrusion process, and the breaking degree is much lower than that of the strip extrusion machine with 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 second preparation method, 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, 3.5-5m% of sulfuric acid with sulfur and 78-83% of titanium dioxide are generally burnt at 1150 ℃, and non-fibrous calcium sulfate generated by the reaction of the contained sulfuric acid and the added excessive calcium carbonate powder and/or calcium oxide has little reinforcing effect on a carrier but still has the effect of a binder.
In the first preparation method, the ortho-titanic acid or metatitanic acid added in the step A can be prepared by reacting a titanium tetrachloride solution with an alkaline solution such as a sodium carbonate solution and ammonia water, preferably, a metatitanic acid intermediate material in the production process of titanium dioxide by a sulfuric acid method is adopted, the price is low, and the contained sulfuric acid can be removed by ammonia water immersion. The use of orthotitanic or metatitanic acid which is free or substantially free of sulphuric acid has the advantage that step a does not require the addition of calcium carbonate and/or calcium oxide, but avoids the presence of non-fibrous, non-inert calcium sulphate in the support or catalyst which has little effect on increasing its mechanical strength and is useless or even harmful for its reactivity.
In the two preparation methods, water, orthotitanic acid and metatitanic acid are added into a reaction container in the step A and are beaten to form slurry, and the average particle size of the orthotitanic acid and metatitanic acid is less than one sixth of the length of anhydrous calcium sulfate fibers in an extruded strip or a prepared carrier or a catalyst; preferably, the slurry is treated by a colloid mill to reduce the average particle size of the metatitanic acid to below 2 microns, more preferably to reduce the average particle size to 0.5-1.5 microns, so that the particle size is less than one tenth of the length of anhydrous calcium sulfate fibers in an extruded strip or a prepared carrier or catalyst, and then the fibrous anhydrous calcium sulfate is added and mixed uniformly to play the reinforcing effect and 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 carrier or the catalyst prepared by the invention is 15-75 mu m, and is basically the same as the length of the anhydrous calcium sulfate fiber in the extruded strip.
Step B, adding HNO into the wet filter cake3The reaction of titanyl nitrate produced by the reaction with orthotitanic acid and/or metatitanic acid, which is substantially not reacted with fibrous anhydrous calcium sulfate, was carried out from example 2-1The test of example 5-1 judged that the hydration of titanyl nitrate to form TiO continued mainly during the continuous standing of the wet mass after kneading and standing for a short period of time, e.g., 1hr2*xH2The O colloid and the released nitric acid react with the titanyl nitrate generated by the reaction of the orthotitanic acid and/or the metatitanic acid, or the orthotitanic acid and/or the metatitanic acid are continuously hydrated to form TiO under the action of the titanyl nitrate2*xH2O colloid, make said TiO2*xH2The O colloid can be continuously formed and stabilized, particles of the orthotitanic acid and/or the metatitanic acid and the fibrous anhydrous calcium sulfate are really bonded, the internal viscosity and the toughness of the kneaded wet material block are gradually improved in the placing process, and finally the wet material block can be extruded and molded; ortho-titanic acid, meta-titanic acid, titanyl nitrate, TiO in extruded bars2*xH2And the 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 B.
It has also been found that if the fibrous anhydrous calcium sulfate is replaced by other temperature and acid 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 water solubility, namely the surface of the used anhydrous calcium sulfate fiber still has certain activity, and the fibrous calcium sulfate hemihydrate or the fibrous calcium sulfate dihydrate is prepared by mixing the orthotitanic acid, metatitanic acid and TiO with the water-soluble material2*xH2The porous titanium oxide particles formed by roasting the O colloid have high connection strength. When the quartz glass fiber with roughened surface is added, the preparationThis phenomenon can be explained by the improvement in the mechanical strength of the carrier, which is still lower than that when fibrous calcium sulfate anhydride is added, as compared with the case of the production methods of comparative examples 11 to 13 and the side pressure strength of the obtained carrier. 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 small 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, the preparation method can be stably repeated, and the cost is low. The side pressure strength of the step D catalyst may generally be more than 5% higher than the support.
The catalyst of the invention has the temperature of 350 ℃ and the space velocity of 200-2000hr-1For example, containing chlorine, e.g. 3000mg/m3In the following treatment process of the waste gas containing chlorine alkane and chlorine arene, the waste gas containing chlorine alkane and chlorine arene has stronger hydrolytic capacity and catalytic combustion capacity, and reaction products are HCl and CO2、H2O; the combustion step reduces the inhibition on the organic chlorine hydrolysis step, and the synergistic effect of the two steps is an important factor for realizing the high-efficiency conversion and removal of the chlorine-containing alkane and the chlorine-containing aromatic hydrocarbon; the non-methane alkane may be less than 25mg/m3The benzene series organic matter can be less than 10mg/m3Generally, organic chlorine with higher chlorine content is not generated or the complexity of the organic chlorine is increased, and highly toxic chlorine-containing organic matters such as phosgene, dioxin and the like and benzopyrene are not generated. The catalyst has stable reaction performance and mechanical strength, is not easy to pulverize, has long service life and is easy to discharge after use. The catalyst of the invention also has certain combustion removal capacity for chlorine-free organic matters in the waste gas, and depends on the activity of the organic matters.
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 temperature of the catalyst bed layer is determined by the inlet temperature of the waste gas and the content of organic matters in the waste gas, including organic chlorine and chlorine-free organic matters; the exhaust gas should contain a suitable content of oxygen, for example above 5% by volume, and water vapour, for example 2-5% by volume.
The organic chlorine waste gas treatment catalyst is characterized in that before the catalyst is used for discharging the agent, the waste gas is closed, air is introduced for purging for 0.5-1hr, organic chlorine and other chlorine-containing organic matters and chlorine-free organic matters in a catalyst bed layer and a container can be completely treated, and the discharged waste agent is basically free of peculiar smell after cooling.
Detailed Description
The technical solution of the present invention will be specifically described and illustrated with reference to the following examples, but the present invention is not limited thereto.
In the following examples and comparative examples, the fineness of the metatitanic acid powder is-325 meshes, 4.2m% sulfuric acid with sulfur broken and 80.3m% titanium dioxide are sintered at 1150 ℃; 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.
Sampling 30g of each roasted material, adding 150ml of water, soaking for 12hr at room temperature, stirring once per hour, filtering the leachate, evaporating to dryness, calculating the dissolution amount of calcium sulfate according to the mass of the residue, and finding that the residue amount is 0.09-0.18g, which indicates that the dissolution ratio of the calcium sulfate is 0.3-0.6%. 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 30g of each roasted material, respectively, adding 150ml of nitric acid aqueous solution with the concentration of 1mol/L, soaking for 12 hours at room temperature, stirring once per hour, filtering the leaching solution, respectively evaporating to dryness, roasting the residues at 300 ℃, calculating the dissolution amount of calcium sulfate according to the mass of the residues after roasting, and finding that the dissolution amount of the calcium sulfate is 0.09-0.18g, which indicates that the dissolution ratio of the calcium sulfate is 0.3-0.6%. And (3) respectively detecting the shape and the length of the material soaked in the nitric acid aqueous solution by using an optical microscope, wherein the result has no obvious change from the result before soaking.
Example 2
The catalyst was prepared as follows:
adding 3000g of water into an A.5L reaction kettle, starting stirring, adding 1059g of metatitanic acid (containing 850g of titanium dioxide), pulping, and recording the liquid level of the pulp at the moment as a liquid level Z; adding 15% diluted ammonia water 130g, soaking for 3hr to remove sulfuric acid contained in metatitanic acid, washing for 8 times within 2hr by settling and water exchange method until no SO is detected by adding barium chloride-hydrochloric acid sample into the washing solution4 2-Detecting the volume average particle size (outer diameter) of metatitanic acid in the slurry to be 4.3 mu m by using a laser particle sizer, replenishing water to a liquid level Z, adding 150g of fibrous anhydrous calcium sulfate calcined at 730 ℃ in the embodiment 1, pulping for 30min to detect the monodispersion degree of the anhydrous calcium sulfate fiber by using an optical microscope, uniformly dispersing the monodisperse degree of the anhydrous calcium sulfate fiber and the metatitanic acid, filtering, airing and air-drying a filter cake to 2300g of the filter cake (the dried solid content at 120 ℃ is 50 percent), and preparing a wet filter cake containing the fibrous anhydrous calcium sulfate and the metatitanic acid;
B. crushing the wet filter cake containing fibrous anhydrous calcium sulfate and metatitanic acid to below 5mm, putting into a kneader, adding 150g of nitric acid aqueous solution with the mass concentration of 50%, kneading for 30min until uniform, standing for 10hr, extruding into cylindrical strips with the outer diameter of 3.5mm by a push plunger extruder, and the surface is basically smooth; drying the extruded strips at 130 deg.C for 3hr, sampling about 400g, and calcining at 420 deg.C in a muffle furnace under air condition for 3hr to obtain calcium sulfate fiber-reinforced titanium oxide carrier;
C. putting 200g of a carrier into a 1000ml beaker, dipping 120ml of aqueous solution containing 3.2mol/L of manganese nitrate and 0.4mol/L of cerium nitrate for 2 times, wherein the first dipping is gradually dropwise added with 70ml of the solution in stirring within 15min according to 0.35ml/g of water absorption of the carrier, the beaker is covered and placed for 6hr until no liquid exists on the surface of the carrier, and the solution is uniformly stirred every 30min during the placement; drying the impregnated strip at 140 deg.C for 3hr, calcining at 320 deg.C for 2hr for second impregnation according to water absorption rate of 0.30ml/g, gradually dripping 50ml of the solution while stirring within 15min, covering the beaker, standing for 8hr until no liquid is on the surface of the carrier, and stirring once every 30min during the standing period;
D. drying the impregnated strip at 140 deg.C for 3hr, and calcining at 420 deg.C in air for 3hr to obtain the catalyst.
And D, respectively sampling 20g of the wet material block and the extruded strip before strip extrusion in the step B, 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 72 mu m and the average length is 60 mu m respectively.
And step A, 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 mu m respectively. The main criteria of the support prepared in step B are given in Table 1.
D, calculating the mass content of the main components in the catalyst prepared in the step D, wherein the calculated result is that the manganese oxide is 12.4 percent calculated by MnO, and the cerium oxide is CeO23.8 percent, 71.2 percent of titanium dioxide and 12.6 percent of fibrous anhydrous calcium sulfate.
Example 3
A calcium sulfate fiber-reinforced titania carrier was prepared essentially as in steps A-B of example 2, except that the kneaded mass in step B 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 D, respectively sampling 20g of the wet material block and the extruded strip before strip extrusion in the step B, 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 78 micrometers and 30 micrometers respectively.
The main criteria of the support prepared in step B are given in Table 1.
Example 4
A calcium sulfate fiber reinforced titania support was prepared essentially as in example 2, steps a-B, except that the aqueous ammonia rinse and washed slurry of step a was treated with a colloid mill to reduce the volume average particle size of metatitanic acid to 1.3 μm, followed by addition of fibrous anhydrous calcium sulfate. The surface of the extruded bar was slightly smoother than that of example 2.
And D, respectively sampling 20g of the wet material block and the extruded strip before strip extrusion in the step B, 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 lengths of the anhydrous calcium sulfate fibers in the dispersion by using an optical microscope, wherein the average lengths are 78 micrometers and 65 micrometers respectively.
The main criteria of the support prepared in step B are given in Table 1.
Example 5
Preparing a calcium sulfate fiber-reinforced titanium oxide carrier by basically using the method of the steps A-B of the embodiment 3, wherein the difference is that the slurry obtained after the ammonia water immersion washing and the washing in the step A is treated by a colloid mill, the volume average particle size of metatitanic acid is reduced to 0.9 mu m, and then fibrous anhydrous calcium sulfate is added; the catalyst was then prepared generally as in example 2, steps C-D.
The specific operation steps are as follows:
adding 3000g of water into an A.5L reaction kettle, starting stirring, adding 1059g of metatitanic acid (containing 850g of titanium dioxide), pulping, and recording the liquid level of the pulp at the moment as a liquid level Z; adding 15% diluted ammonia water 130g, soaking for 3hr to remove sulfuric acid contained in metatitanic acid, washing for 8 times within 2hr by settling and water exchange method until no SO is detected by adding barium chloride-hydrochloric acid sample into the washing solution4 2-Adding water to a liquid level Z, pulping, treating the pulp by using a colloid mill, reducing the volume average particle size of metatitanic acid to 0.9 mu m, adding 150g of fibrous anhydrous calcium sulfate calcined at 730 ℃ in the embodiment 1, pulping for 30min until the monodispersion degree of the anhydrous calcium sulfate fiber is detected by an optical microscope and is uniformly dispersed with the metatitanic acid, filtering, airing and air-drying the filter cake until 2300g of the filter cake is obtained (the dried solid content at 120 ℃ is 50 percent), and preparing a wet filter cake containing the fibrous anhydrous calcium sulfate and the metatitanic acid;
B. crushing the wet filter cake containing fibrous anhydrous calcium sulfate and metatitanic acid to below 5mm, putting into a kneader, adding 150g of nitric acid aqueous solution with the mass concentration of 50%, kneading for 30min until uniform, standing for 10hr, extruding into cylindrical strips with the outer diameter of 3.5mm by a push plunger extruder, and the surface is basically smooth; drying the extruded strips at 130 deg.C for 3hr, sampling about 600g, and calcining at 420 deg.C in a muffle furnace under air condition for 3hr to obtain calcium sulfate fiber-reinforced titanium oxide carrier;
C. putting 200g of carrier into a 1000ml beaker, soaking 66ml of aqueous solution containing 3.2mol/L of manganese nitrate and 0.4mol/L of cerium nitrate, gradually dropwise adding the solution while stirring within 15min, covering the beaker, standing for 6hr until no liquid exists on the surface of the carrier, and uniformly stirring once every 30min during standing;
D. drying the impregnated strip at 140 deg.C for 3hr, and calcining at 420 deg.C in air for 3hr to obtain the catalyst.
The surface of the extruded bar was slightly smoother than that of example 3.
And B, respectively sampling 20g of the wet material block and the extruded strip before strip extrusion in the step B, 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 85 micrometers and the average length is 37 micrometers respectively.
The main criteria of the support prepared in step B are given in Table 1.
D, calculating the mass content of the main components in the catalyst prepared in the step D, wherein the calculated result is that the oxide of the manganese accounts for 6.8 percent of MnO, and the oxide of the cerium accounts for CeO22.1 percent, 77.4 percent of titanium dioxide and 13.7 percent of fibrous anhydrous calcium sulfate.
Example 6
Calcium sulfate fiber reinforced titania support was prepared essentially as in example 5, steps a-B, except that the extruded strip of step B was then co-extruded 2 times through a twin screw extruder 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 26 mu m and 18 mu m through optical microscope detection.
Example 7
The remaining dried strands from step B of example 5 were calcined in a muffle furnace at 450 deg.C in air for 2hr to produce calcium sulfate fiber reinforced titania supports.
The mass content of the main component of the calcium sulfate fiber reinforced titanium oxide carrier prepared in the step B of each embodiment is 85% of titanium dioxide, and the mass content of the fibrous anhydrous calcium sulfate calcined at the temperature of 700 ℃ and 750 ℃ is 15%.
Example 2-1
Basically, the operation is carried out according to the steps A-B of the example 2, the internal viscosity and the toughness of the wet material block in the placing process after the kneading for 30min in the step B are examined, and the internal viscosity and the toughness of the wet material block after the placing start are found to be increased rapidly in the first 5hr, slowly increased in the first 5-10hr and hardly increased in the first 10-20 hr; comparing the water dispersibility of the wet material block at different standing times after 30min kneading, by sampling the wet material block for 20g, adding 200g of water, stirring lightly with a glass rod, and recording the time consumption of the material block for completely dispersing in water, so that the wet material block needs to be stirred for 11sec when standing for 0hr, the wet material blocks need to be stirred for 38sec and 55sec when standing for 1hr and 3hr, and the wet material blocks need to be stirred for 67sec, 76sec and 80sec when standing for 5hr, 10hr and 15hr, respectively; the method comprises the steps of sampling the wet material block by 10g, compacting the wet material block into small blocks, inserting two pieces of copper sheets which are boiled, washed, degreased and cleaned to be dry by alkali liquor, placing for 1-5min according to the corrosion degree, and checking the corrosion condition of the surface of the copper sheets after being washed by water, so that the wet material block can be placed for 0hr to quickly cause the obvious corrosion on the surface of the copper sheets to be stronger, the corrosion on the copper sheets is obviously weakened after the wet material block is placed for 1hr, and the wet material block has corrosion on the copper sheets when placed for 3hr, 5hr, 10hr and 15hr but has no visible difference. The wet block is placed for 1hr, 4hr, 5hr, 10hr, and 15hr, respectively 200g is taken, and is extruded into cylindrical bar with outer diameter of 3.5mm by pushing plunger extruder, so that the wet block is easy to break and rough surface after being placed for 1hr, the wet block is not easy to break but still smooth surface after being placed for 4hr, the wet block is continuous and basically smooth surface after being placed for 5hr, and the wet block is continuous and smooth surface after being placed for 10hr and 15 hr.
Example 5-1
Basically, the procedure of example 5, Steps A-B, was followed, and by examining the internal tackiness and toughness of the wet mass during the standing process after kneading for 30min in step B according to the test methods of examples 2-1, and it was found that the internal tackiness and toughness of the wet mass after starting the standing process increased rapidly in the first 5hr, increased slowly in the first 5-10hr, and hardly increased in the first 10-20 hr; comparing the water dispersibility of the wet mass at different standing times after 30min, wherein the wet mass is stirred for 15sec when standing for 0hr, the wet mass is stirred for 46sec and 60sec when standing for 1hr and 3hr, and the wet mass is stirred for 72sec, 78sec and 81sec when standing for 5hr, 10hr and 15 hr; the corrosivity of the wet material block on the copper sheet at different standing times after the wet material block is kneaded for 30min is compared, and the result is that the wet material block can quickly cause that the obvious corrosion on the surface of the copper sheet is stronger in corrosivity on the copper sheet when the wet material block is placed for 0hr, the corrosivity on the copper sheet is obviously weaker after the wet material block is placed for 1hr, and the corrosivity on the copper sheet is realized when the wet material block is placed for 3hr, 5hr, 10hr and 15hr, but no difference is visible. The wet block is placed for 1hr, 4hr, 5hr, 10hr, and 15hr, respectively 200g is taken, and is extruded into cylindrical bar with outer diameter of 3.5mm by pushing plunger extruder, so that the wet block is easy to break and rough surface after being placed for 1hr, the wet block is not easy to break but still smooth surface after being placed for 4hr, the wet block is continuous and basically smooth surface after being placed for 5hr, and the wet block is continuous and smooth surface after being placed for 10hr and 15 hr.
Example 8
The catalyst was prepared as follows:
adding 3000g of water into an A.5L reaction kettle, starting stirring, adding 1059g of metatitanic acid (containing 850g of titanium dioxide), pulping, and recording the liquid level of the pulp at the moment as a liquid level Z; treating the slurry by using a colloid mill, reducing the volume average particle size of metatitanic acid to 1.0 mu m, adding 56g of light calcium carbonate powder, reacting at normal temperature for 5hr to convert sulfuric acid contained in metatitanic acid into calcium sulfate, adding 11g of 98% sulfuric acid to convert the remaining calcium carbonate into calcium sulfate, adding 150g of fibrous anhydrous calcium sulfate calcined at 750 ℃ in the embodiment 1, pulping for 30min until the monodispersion degree of the anhydrous calcium sulfate fiber is 94% detected by an optical microscope and the fibrous anhydrous calcium sulfate fiber is uniformly dispersed with metatitanic acid, filtering, airing and drying a filter cake until 2365g of the filter cake is dried (the dried solid content at 120 ℃ is 50%), and preparing a wet filter cake containing the fibrous anhydrous calcium sulfate, the non-fibrous calcium sulfate and the metatitanic;
B. crushing the wet filter cake containing fibrous anhydrous calcium sulfate, non-fibrous calcium sulfate and metatitanic acid to below 5mm, putting into a kneader, adding 180g of nitric acid aqueous solution with the mass concentration of 50%, kneading for 30min until the mixture is uniform, standing for 10hr, and extruding into a cylindrical strip with the outer diameter of 3.5mm by using a double-screw extruder, wherein the surface is smooth; drying the extruded strips at 130 deg.C for 3hr, sampling about 300g, and calcining at 450 deg.C in muffle furnace under air condition for 2hr to obtain calcium sulfate fiber reinforced titanium oxide carrier;
C. putting 200g of carrier into a 1000ml beaker, soaking 60ml of aqueous solution containing 3.2mol/L of manganese nitrate and 0.6mol/L of cerium nitrate, gradually dropwise adding the solution while stirring within 15min, covering the beaker, standing for 6hr until no liquid exists on the surface of the carrier, and uniformly stirring once every 30min during standing;
D. drying the impregnated strip at 140 deg.C for 3hr, and calcining at 420 deg.C in air for 3hr to obtain the catalyst.
And B, pulping for 30min, sampling the slurry before filtering, and detecting the average length of the anhydrous calcium sulfate fibers by using an optical microscope to be 110 mu m.
And B, respectively sampling 20g of the kneaded material block and the extruded strip before extruding the strip in the step B, adding 200g of water, 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 65 micrometers and the average length is 24 micrometers.
The main criteria of the support prepared in step B are given in Table 1.
In this example 8, the mass content of the main component of the calcium sulfate fiber-reinforced titanium oxide carrier prepared in step B is 79.0% of titanium dioxide, 13.9% of fibrous anhydrous calcium sulfate calcined at 700 ℃ and 750 ℃, and 7.1% of non-fibrous calcium sulfate.
D, calculating the mass content of the main components in the catalyst prepared in the step D, wherein the calculated result is that the manganese oxide is 6.2 percent calculated by MnO, and the cerium oxide is CeO22.8 percent, 71.9 percent of titanium dioxide, 12.6 percent of fibrous anhydrous calcium sulfate and 6.5 percent of non-fibrous calcium sulfate.
Example 9
The remaining dried strands from step B of example 8 were calcined in a muffle furnace at 450 deg.C in air for 2hr to produce calcium sulfate fiber reinforced titania supports.
In the above examples, the main chemical reaction in the wet mass during the kneading and leaving in step B was the reaction of metatitanic acid with nitric acid to form titanyl nitrate, and it was judged from the test phenomena in examples 2-1 and 5-1 that the main reaction occurred during the leavingBefore 1 hr; the wet mass also has a partial conversion of metatitanic acid to TiO under the action of titanyl nitrate2*xH2The process of O colloid, the released nitric acid reacts with ortho-titanic acid and/or metatitanic acid to generate titanyl nitrate, so that the TiO2*xH2The continuous formation and stabilization of O colloid can be realized, the internal viscosity and toughness of the kneaded wet material block in the placing process are gradually improved, and finally the wet material block can be extruded and molded, wherein the TiO colloid is2*xH2The O-colloid is a component that actually binds the fine particles of the raw material of orthotitanic acid and/or metatitanic acid and fibrous anhydrous calcium sulfate. The titanium dioxide carrier with higher mechanical strength can be obtained by adopting lower extrusion pressure in each strip extrusion process, the requirement on the strip extrusion pressure is lower, the surface smoothness of the extruded strip or the carrier can be adjusted to reach a better level by controlling the fineness and/or the kneading of metatitanic acid, the material mixing and the shearing degree in the extrusion process, and the main reason is that the produced TiO is also characterized in that2*xH2The combined action and combination effect of the O colloid and the fibrous anhydrous calcium sulfate.
Comparative example 1
Calcium sulfate fiber reinforced titania support, prepared as step B of example 5, was used as the catalyst for this comparative example.
Comparative example 2
Placing 100g of the calcium sulfate fiber reinforced titanium oxide carrier prepared in the step B of the embodiment 5 in a 1000ml beaker, soaking 33ml of aqueous solution containing 3.2mol/L of manganese nitrate, gradually dripping the solution while stirring within 15min, covering the beaker, placing for 6hr until no liquid exists on the surface of the carrier, and uniformly stirring once every 30min during the placing; drying the impregnated strip 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 prepared catalyst is calculated as 7.0 percent of manganese oxide calculated by MnO, 79.1 percent of titanium dioxide and 14.0 percent of fibrous anhydrous calcium sulfate.
Comparative example 3
Taking 100g of the calcium sulfate fiber reinforced titanium oxide carrier prepared in the step B of the embodiment 5, placing the carrier in a 1000ml beaker, soaking 33ml of aqueous solution containing 0.4mol/L of cerium nitrate, gradually dropwise adding the solution while stirring within 15min, covering the beaker, placing the beaker for 6hr until no liquid exists on the surface of the carrier, and uniformly stirring once every 30min during the placing; drying the impregnated strip 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 component in the prepared catalyst is calculated as that the cerium oxide is CeO22.2 percent, 83.1 percent of titanium dioxide and 14.7 percent of fibrous anhydrous calcium sulfate.
Comparative example 2-1
The procedure is essentially as in example 2, steps A-B, except that fibrous anhydrous calcium sulfate is not added in step A. When the internal viscosity and toughness of the wet block in the standing process after the kneading of the step B for 30min are examined according to the method of example 2-1, the internal viscosity and toughness of the wet block after the start of the standing process are obviously increased in the first 5hr, slowly increased in the range of 5-10hr and hardly increased in the range of 10-20hr, but are significantly lower than those of the wet block in the standing process for the same time after the kneading of the step B for 30min in example 2-1; comparing the water dispersibility of the wet mass at different standing times after 30min, wherein the wet mass is required to be stirred for 4sec when standing for 0hr, 16sec and 28sec when standing for 1hr and 3hr, and 39sec, 47sec and 50sec when standing for 5hr, 10hr and 15 hr; the corrosivity of the wet material block on the copper sheet at different standing times after the mixed kneading for 30min is tested, and the result shows that the wet material block can quickly cause the obvious corrosion on the surface of the copper sheet to be stronger when the wet material block is placed for 0hr, the corrosivity of the wet material block on the copper sheet is obviously weaker after the wet material block is placed for 1hr, the wet material block has corrosivity on the copper sheet when the wet material block is placed for 3hr, 5hr, 10hr and 15hr but has no visible difference, and the corrosivity condition of each copper sheet is basically consistent with the corrosivity condition of the copper sheet when the wet material block in the step B of the embodiment 2-1 is placed for the same time. The wet block is left for 1hr, 4hr, 5hr, 10hr, and 15hr, respectively, and is taken about 200g, and extruded into cylindrical bar with outer diameter of 3.5mm by pushing plunger extruder, so that the bar is easy to break and has rough surface after being left for 1hr, the bar is easy to break and has still unsmooth surface after being left for 4hr, the bar is easy to break and has basically smooth surface after being left for 5hr, and the bar is easy to break and has smoother surface after being left for 10hr and 15 hr.
Comparative example 5-1
The procedure is essentially as in example 5-1, steps A-B, except that fibrous calcium sulfate anhydrate is not added in step A. When the internal viscosity and toughness of the wet block during the standing process after the kneading in step B for 30min are examined by the method in example 5-1, the internal viscosity and toughness of the wet block after the start of the standing process are also obviously increased in the first 5hr, slowly increased in 5-10hr, and hardly increased in 10-20hr, but are significantly lower than those of the wet block during the same standing time after the kneading in step B in example 5-1 for 30 min; comparing the water dispersibility of the wet mass at different standing times after 30min, wherein the wet mass is required to be stirred for 7sec when standing for 0hr, 21sec and 33sec when standing for 1hr and 3hr, and 42sec, 49sec and 55sec when standing for 5hr, 10hr and 15 hr; the corrosivity of the wet material block on the copper sheet at different standing times after the mixed kneading for 30min is tested, and the result shows that the wet material block can quickly cause the obvious corrosion on the surface of the copper sheet to be stronger when the wet material block is placed for 0hr, the corrosivity of the wet material block on the copper sheet is obviously weaker after the wet material block is placed for 1hr, the wet material block has corrosivity on the copper sheet when the wet material block is placed for 3hr, 5hr, 10hr and 15hr but has no visible difference, and the corrosivity condition of each copper sheet is basically consistent with the corrosivity condition of the copper sheet when the wet material block in the step B of the embodiment 5-1 is placed for the same time. The wet material block is placed for 1hr, 4hr, 5hr, 10hr, and 15hr, respectively, and 200g is taken out, and extruded into cylindrical bar with outer diameter of 3.5mm by pushing plunger extruder, so that the wet material block is easy to break and rough in surface after being placed for 1hr, easy to break but basically smooth in surface after being placed for 4hr and 5hr, and easy to break but smooth in surface after being placed for 10hr and 15 hr.
Comparative examples 2 to 2
The procedure was essentially as in example 2, steps A-B, except that nitric acid was not added in step B, the wet cake containing fibrous anhydrous calcium sulfate and metatitanic acid was directly crushed to a size below 5mm, put into a kneader, 150g of water was added, kneaded for 30min until uniform and then placed, and it was found that the wet cake was loose after the start of placement, had very low internal viscosity and toughness and did not increase, and it was not possible to extrude the strip because the internal viscosity and toughness were too low; standing for 2hr, 5hr, 10hr, and 15hr to disperse the wet material block for no more than 5 sec; the wet block which is left for 2hr, 5hr, 10hr and 15hr is tested for the corrosivity to the copper sheet, and the result shows that the copper sheet is not corroded.
Comparative examples 5 to 2
The procedure was essentially as in example 5, steps A-B, except that nitric acid was not added in step B, the wet cake containing fibrous anhydrous calcium sulfate and metatitanic acid was directly crushed to a size below 5mm, put into a kneader, 150g of water was added, kneaded for 30min until uniform and then placed, and it was found that the wet cake was loose after the start of placement, had very low internal viscosity and toughness and did not increase, and it was not possible to extrude the strip because the internal viscosity and toughness were too low; standing for 2hr, 5hr, 10hr, and 15hr to disperse the wet material block for no more than 5 sec; the wet block which is left for 2hr, 5hr, 10hr and 15hr is tested for the corrosivity to the copper sheet, and the result shows that the copper sheet is not corroded.
Comparative examples 5 to 3
The process is essentially as described in example 5, Steps A-B, except that in step A, the fibrous calcium sulfate anhydrate is prepared by calcination at 1680 ℃ for 3 hours.
And B, respectively sampling 20g of the wet material block and the extruded strip before strip extrusion in the step B, 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 65 micrometers and the average length is 24 micrometers respectively.
Comparative examples 5 to 4
The procedure is essentially as in example 5, Steps A-B, except that in step A, the fibrous calcium sulfate anhydrate produced by calcination at 1780℃ for 3hr is used.
And B, respectively sampling 20g of the wet material block and the extruded strip before strip extrusion in the step B, 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 28 micrometers respectively.
Comparative example 10
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 11
Essentially the procedure is as in example 5, Steps A-B, except that in step A, a mean diameter of 3.0 μm, a length range of 300-500 μm, a mean length of 360 μm, SiO2150g of quartz glass fibres with a content of 99.9% replace the fibrous anhydrous calcium sulphate used.
As a result, the carrier produced has low mechanical strength and a rough and unsmooth surface.
Comparative example 12
The procedures of comparative example 11 were substantially followed except that the amount of the quartz glass fiber used in step A 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 13
The procedure of comparative example 11 was essentially followed except that in step A, surface-roughened silica glass fibers were used.
As a result, the mechanical strength of the carrier prepared was higher than that of comparative example 8, and the surface was still rough and not smooth.
The surface roughening method of the quartz glass fiber comprises the following steps: the diameter is 3.0 μm, the length range is 300-500 μm, the average length is 360 μm, SiO2Putting 150g of quartz glass fiber with the content of 99.9 percent into a 1000ml plastic cup, adding water to reach the total volume of 900ml, adding 20ml of 40 percent hydrofluoric acid, stirring uniformly, standing for 6 hours, stirring uniformly once per hour, changing water and washing for three times, and then adding the pulp obtained in the step A.
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 10 was used as a carrier to compare with the carrier of the present invention.
TABLE 1 Main index of the carriers of the examples and comparative examples
Application example
The catalysts prepared in examples 2, 5 and 8 and comparative examples 1 to 3 were tested in a laboratory evaluation apparatus, each containing 60ml of the catalyst; the gas condition is 1,2,3, 4-tetrachlorobenzene 760mg/m3About (containing 500mg/m chlorine in turn)3) 5% by volume of oxygen, 2% by volume of carbon dioxide and 3.5-4% by volume of water vapor, the balance being nitrogen; the gas space velocity is 500hr-1The bed temperature was 300 ℃ and the test time was 30hr each.
The evaluation results included: examples 2, 5, 8 the 1,2,3, 4-tetrachlorobenzene content in the off-gas of the catalysts was less than 30mg/m3The total amount of other organic chlorine is less than 20mg/m3End of pentachloro and aboveOrganic matter of (2), non-methane hydrocarbon content lower 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 90%, and Cl is added2The selectivity is lower than 10 percent; the 1,2,3, 4-tetrachlorobenzene contents in the outlet gases of the catalysts of comparative examples 1 and 2 are all higher than 100mg/m3Generating trace pentachloride and above organic matters; comparative example 3 catalyst with an 1,2,3, 4-tetrachlorobenzene content in the offgas of more than 150mg/m3Generating a small amount of pentachloride and above organic substances, and benzene series organic substances with the content higher than 30mg/m3。
Example 5 catalyst after completion of the 30hr test, the gas space velocity was changed to 2000hr-1Evaluating at 320 deg.C for 30 hr; as a result, the content of 1,2,3, 4-tetrachlorobenzene in the off-gas was less than 30mg/m3The total amount of other organic chlorine is less than 20mg/m3Organic substances of pentachloride and above are generated, and the content of non-methane hydrocarbon is lower 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 95%, and Cl is added2The selectivity is lower than 5 percent; it is considered that no highly toxic substances such as dioxin, benzopyrene, etc. are produced.
EXAMPLE 5 after completion of the second 30hr test, the catalyst was further evaluated under another gas condition containing 700mg/m of 1, 2-dichloroethane3(contains 500mg/m of chlorine)3) 5% by volume of oxygen, 2% by volume of carbon dioxide and 3.5-4% by volume of water vapor, the balance being nitrogen; gas space velocity of 2000hr-1Evaluating at 300 deg.C for 30 hr; the result is a dichloroethane content in the off-gas of less than 10mg/m3The total amount of organic chlorine is less than 20mg/m3Without generating organic matter of trichloro or more, the non-methane hydrocarbon content is less than 20mg/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 95 percent, and Cl is generated2The selectivity is less than 5%.
Claims (10)
1. An organic chlorine-containing waste gas treatment catalyst comprises a fibrous anhydrous calcium sulfate-reinforced titanium dioxide carrier and a catalyst loaded on the carrierOxide components of manganese and cerium in the body; the carrier comprises 10-30% of fibrous anhydrous calcium sulfate calcined at the temperature of 700-750 ℃ and more than 65% of titanium dioxide by mass, wherein more than 90% of the fibrous anhydrous calcium sulfate is monodisperse; in parts by mass, the manganese-containing oxide of the catalyst accounts for 5-15% of MnO, and the cerium oxide accounts for CeO22-5 percent.
2. The organochlorine-containing exhaust gas treatment catalyst according to claim 1, wherein the fibrous anhydrous calcium sulfate is columnar crystals having a length of 30 to 200 μm, an average diameter of 1 to 4 μm, an aspect ratio of 20 to 100, and a CaSO4The content is more than or equal to 98 percent.
3. The organic chlorine-containing exhaust gas treatment catalyst according to claim 1, wherein the fibrous calcium sulfate anhydrite is a product obtained by calcining fibrous calcium sulfate hemihydrate at 750 ℃ and has an average diameter of 2 to 3 μm and a length of 50 to 150 μm.
4. A method for producing the organic chlorine-containing exhaust gas treatment catalyst according to claim 1, comprising the steps of:
A. adding 250 portions and 400 portions of water into a reaction vessel by mass portion, starting stirring, adding orthotitanic acid and/or metatitanic acid containing less than 0.3 percent of sulfur by mass portion to form TiO270-90 parts by weight, pulping, adding 10-30 parts of fibrous anhydrous calcium sulfate roasted at 750 ℃ at 700-750 ℃, pulping until the monodispersion degree of the anhydrous calcium sulfate fiber is higher than 90%, pulping until orthotitanic acid and/or metatitanic acid and the fibrous anhydrous calcium sulfate are uniformly dispersed, filtering, blowing off water by using compressed air and/or blowing, airing and drying until the solid content is 40-55% at 120 ℃ of a filter cake, and preparing a wet filter cake containing the fibrous anhydrous calcium sulfate and metatitanic acid;
B. crushing the wet filter cake containing fibrous anhydrous calcium sulfate and metatitanic acid, putting into a kneader, adding 10-20 parts of nitric acid aqueous solution with the mass concentration of 35-50%, kneading uniformly, standing for 5-20hr, and extruding; drying the extruded strips, and roasting at 400-450 deg.C in air for 2-4hr to obtain carrier;
C. dipping the carrier for 1-2 times by adopting a dipping method by using a manganese nitrate-cerium nitrate aqueous solution with required concentration, drying and roasting a primary dipping strip at the temperature of 300-350 ℃ during twice dipping, and then carrying out twice dipping;
D. drying the impregnated strip, and calcining at 420-450 deg.C in air for 2-4hr to obtain the catalyst.
5. The second production method of the organic chlorine-containing exhaust gas treatment catalyst according to claim 1, comprising the steps of:
A. adding 400 portions of water 250-one into a reaction vessel by mass portion, starting stirring, adding H containing sulfur2SO42-6% of metatitanic acid calculated as TiO270-90 parts by weight, pulping, adding calcium carbonate powder and/or calcium oxide powder with the amount of sulfur substances contained in metatitanic acid being 1.2-1.5 times of the amount of the sulfur substances contained in metatitanic acid, reacting at normal temperature for 2-10hr, gradually adding sulfuric acid, ammonium sulfate or solution thereof, reacting for 1-5hr until the residual calcium carbonate and/or calcium oxide is completely converted into calcium sulfate, adding 15-30 parts of fibrous anhydrous calcium sulfate calcined at the temperature of 700-750 ℃, pulping until the monodispersion degree of the anhydrous calcium sulfate fiber is higher than 90% and uniformly dispersing in the slurry; filtering the slurry, blowing water by using compressed air and/or blowing, airing and drying the slurry until the solid content of the filter cake is 40-55% after drying at 120 ℃ to prepare a wet filter cake containing fibrous anhydrous calcium sulfate and metatitanic acid;
B. crushing the wet filter cake containing fibrous anhydrous calcium sulfate and metatitanic acid, putting into a kneader, adding 10-20 parts of nitric acid aqueous solution with the mass concentration of 35-50%, kneading uniformly, standing for 5-20hr, and extruding; drying the extruded strips, and roasting at 400-450 deg.C in air for 2-4hr to obtain carrier;
C. dipping the carrier for 1-2 times by adopting a dipping method by using a manganese nitrate-cerium nitrate aqueous solution with required concentration, drying and roasting a primary dipping strip at the temperature of 300-350 ℃ during twice dipping, and then carrying out twice dipping;
D. drying the impregnated strip, and calcining at 420-450 deg.C in air for 2-4hr to obtain the catalyst.
6. The process for preparing a catalyst for treating exhaust gas containing organic chloride, according to claim 4, wherein the ortho-titanic acid or meta-titanic acid added in step A is prepared by reacting a titanium tetrachloride solution with an alkaline solution, or is prepared by leaching an intermediate material of meta-titanic acid in the production process of titanium dioxide by a sulfuric acid method with ammonia water to remove sulfuric acid contained therein.
7. The method for preparing the catalyst for treating waste gas containing organic chloride according to claim 5, wherein the metatitanic acid added in the step A is an intermediate metatitanic acid in the production process of titanium dioxide by a sulfuric acid process.
8. The method for producing the organic chlorine-containing exhaust gas treatment catalyst according to claim 4 or 5, wherein the extrusion in the step B comprises an extrusion with a screw extruder or a ram pressure extrusion.
9. The process for producing a catalyst for treating an exhaust gas containing organic chlorine according to claim 4 or 5, wherein the slurry obtained by adding water, orthotitanic acid or metatitanic acid to the reaction vessel in the step A is treated with a colloid mill to reduce the average particle size of metatitanic acid to 2 μm or less, and then fibrous anhydrous calcium sulfate is added.
10. The method as claimed in claim 1, wherein the catalyst bed is at a temperature of 280-350 ℃ and a space velocity of 200-2000hr-1(ii) a And/or the waste gas contains more than 5% by volume of oxygen and 2-5% by volume of water vapor.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115970722A (en) * | 2023-03-21 | 2023-04-18 | 山东迅达化工集团有限公司 | Low-temperature combustion catalyst with organic chloride hydrolysis function and application thereof in purification treatment of steam-containing airflow |
| CN116371436A (en) * | 2023-02-08 | 2023-07-04 | 美瑞科技(河南)有限公司 | Catalyst capable of efficiently decomposing phosgene and resisting chlorobenzene poisoning, and preparation and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5260044A (en) * | 1990-09-06 | 1993-11-09 | Masakatsu Hiraoka | Method for removing organic chlorine compounds from combustion waste gas |
| CN1314206A (en) * | 2000-03-22 | 2001-09-26 | 中国科学院大连化学物理研究所 | Metal oxide catalyst for clearing halogenated aromatic through catalytic oxidation |
| CN1342522A (en) * | 2000-09-13 | 2002-04-03 | 中国科学院大连化学物理研究所 | Catalyst for eliminating haloaromatic contaminant by catalytic combustion |
| CN102698751A (en) * | 2012-06-26 | 2012-10-03 | 华东理工大学 | Catalyst for eliminating chlorine-containing volatile organic compounds by low-temperature catalytic combustion |
| CN104328480A (en) * | 2013-09-11 | 2015-02-04 | 江西峰竺新材料科技有限公司 | Preparation method of calcium sulfate whisker |
| CN106390990A (en) * | 2016-08-31 | 2017-02-15 | 国家电投集团远达环保催化剂有限公司 | Method for modifying special exhaust gas denitrification catalyst |
| 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 |
| 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 |
-
2020
- 2020-02-16 CN CN202010094772.1A patent/CN111203241B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5260044A (en) * | 1990-09-06 | 1993-11-09 | Masakatsu Hiraoka | Method for removing organic chlorine compounds from combustion waste gas |
| CN1314206A (en) * | 2000-03-22 | 2001-09-26 | 中国科学院大连化学物理研究所 | Metal oxide catalyst for clearing halogenated aromatic through catalytic oxidation |
| CN1342522A (en) * | 2000-09-13 | 2002-04-03 | 中国科学院大连化学物理研究所 | Catalyst for eliminating haloaromatic contaminant by catalytic combustion |
| CN102698751A (en) * | 2012-06-26 | 2012-10-03 | 华东理工大学 | Catalyst for eliminating chlorine-containing volatile organic compounds by low-temperature catalytic combustion |
| CN104328480A (en) * | 2013-09-11 | 2015-02-04 | 江西峰竺新材料科技有限公司 | Preparation method of calcium sulfate whisker |
| CN106390990A (en) * | 2016-08-31 | 2017-02-15 | 国家电投集团远达环保催化剂有限公司 | Method for modifying special exhaust gas denitrification catalyst |
| 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 |
| 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 |
Non-Patent Citations (3)
| Title |
|---|
| FEI HE ET AL.: "Effect of calcination temperature on the structure and performance of CeOx-MnOx/TiO2 nanoparticles for the catalytic combustion of chlorobenzene", 《J NANOPART RES》 * |
| YANPING REN ET AL.: "Low temperature catalytic combustion of o-dichlorobenzene over supported Mn-Ce oxides: effect of support and Mn/Ce ratio", 《RSC ADVANCES》 * |
| 汪潇等: "《脱硫石膏晶须制备与稳定化一体技术》", 31 October 2017, 冶金工业出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116371436A (en) * | 2023-02-08 | 2023-07-04 | 美瑞科技(河南)有限公司 | Catalyst capable of efficiently decomposing phosgene and resisting chlorobenzene poisoning, and preparation and application thereof |
| CN115970722A (en) * | 2023-03-21 | 2023-04-18 | 山东迅达化工集团有限公司 | Low-temperature combustion catalyst with organic chloride hydrolysis function and application thereof in purification treatment of steam-containing airflow |
| CN115970722B (en) * | 2023-03-21 | 2023-05-16 | 山东迅达化工集团有限公司 | Low-temperature combustion catalyst with organic chlorine hydrolysis function and application thereof in purification treatment of gas flow containing water vapor |
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