CN114618578A - Catalyst for preparing vinyl chloride by cracking 1, 2-dichloroethane, preparation method and regeneration method - Google Patents
Catalyst for preparing vinyl chloride by cracking 1, 2-dichloroethane, preparation method and regeneration method Download PDFInfo
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- CN114618578A CN114618578A CN202011458294.4A CN202011458294A CN114618578A CN 114618578 A CN114618578 A CN 114618578A CN 202011458294 A CN202011458294 A CN 202011458294A CN 114618578 A CN114618578 A CN 114618578A
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- Prior art keywords
- ammonium
- catalyst
- nitrogen
- dichloroethane
- sapo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 102
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000005336 cracking Methods 0.000 title claims abstract description 27
- 238000011069 regeneration method Methods 0.000 title claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 32
- 239000002808 molecular sieve Substances 0.000 claims abstract description 30
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 30
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 25
- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical compound [AlH3].[P] URRHWTYOQNLUKY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 238000011068 loading method Methods 0.000 claims abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 48
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 32
- 239000007789 gas Substances 0.000 claims description 31
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 22
- 239000001301 oxygen Substances 0.000 claims description 22
- 229910052760 oxygen Inorganic materials 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- -1 silicon-phosphorus-aluminum Chemical compound 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 7
- ILRKKHJEINIICQ-OOFFSTKBSA-N Monoammonium glycyrrhizinate Chemical compound N.O([C@@H]1[C@@H](O)[C@H](O)[C@H](O[C@@H]1O[C@H]1CC[C@]2(C)[C@H]3C(=O)C=C4[C@@H]5C[C@](C)(CC[C@@]5(CC[C@@]4(C)[C@]3(C)CC[C@H]2C1(C)C)C)C(O)=O)C(O)=O)[C@@H]1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@H]1O ILRKKHJEINIICQ-OOFFSTKBSA-N 0.000 claims description 7
- 239000001099 ammonium carbonate Substances 0.000 claims description 7
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 7
- 238000005342 ion exchange Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 6
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 5
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 5
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 claims description 5
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 5
- 229940010552 ammonium molybdate Drugs 0.000 claims description 5
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 5
- 239000011609 ammonium molybdate Substances 0.000 claims description 5
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 4
- 239000005695 Ammonium acetate Substances 0.000 claims description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- 229940043376 ammonium acetate Drugs 0.000 claims description 4
- 235000019257 ammonium acetate Nutrition 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- YVBOZGOAVJZITM-UHFFFAOYSA-P ammonium phosphomolybdate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])=O.[O-][Mo]([O-])(=O)=O YVBOZGOAVJZITM-UHFFFAOYSA-P 0.000 claims description 4
- 229940088990 ammonium stearate Drugs 0.000 claims description 4
- YCNIBOIOWCTRCL-UHFFFAOYSA-N azane;2,2,2-trifluoroacetic acid Chemical compound [NH4+].[O-]C(=O)C(F)(F)F YCNIBOIOWCTRCL-UHFFFAOYSA-N 0.000 claims description 4
- JPNZKPRONVOMLL-UHFFFAOYSA-N azane;octadecanoic acid Chemical compound [NH4+].CCCCCCCCCCCCCCCCCC([O-])=O JPNZKPRONVOMLL-UHFFFAOYSA-N 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004251 Ammonium lactate Substances 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 229940059265 ammonium lactate Drugs 0.000 claims description 3
- 235000019286 ammonium lactate Nutrition 0.000 claims description 3
- 229920005550 ammonium lignosulfonate Polymers 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- NHJPVZLSLOHJDM-UHFFFAOYSA-N azane;butanedioic acid Chemical compound [NH4+].[NH4+].[O-]C(=O)CCC([O-])=O NHJPVZLSLOHJDM-UHFFFAOYSA-N 0.000 claims description 3
- RZOBLYBZQXQGFY-HSHFZTNMSA-N azanium;(2r)-2-hydroxypropanoate Chemical compound [NH4+].C[C@@H](O)C([O-])=O RZOBLYBZQXQGFY-HSHFZTNMSA-N 0.000 claims description 3
- CUXQLKLUPGTTKL-UHFFFAOYSA-M microcosmic salt Chemical compound [NH4+].[Na+].OP([O-])([O-])=O CUXQLKLUPGTTKL-UHFFFAOYSA-M 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 230000008929 regeneration Effects 0.000 claims description 3
- ZXQVPEBHZMCRMC-UHFFFAOYSA-R tetraazanium;iron(2+);hexacyanide Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] ZXQVPEBHZMCRMC-UHFFFAOYSA-R 0.000 claims description 3
- ZEYKLMDPUOVUCR-UHFFFAOYSA-N 2-chloro-5-(trifluoromethyl)benzenesulfonyl chloride Chemical compound FC(F)(F)C1=CC=C(Cl)C(S(Cl)(=O)=O)=C1 ZEYKLMDPUOVUCR-UHFFFAOYSA-N 0.000 claims description 2
- PMJNEQWWZRSFCE-UHFFFAOYSA-N 3-ethoxy-3-oxo-2-(thiophen-2-ylmethyl)propanoic acid Chemical compound CCOC(=O)C(C(O)=O)CC1=CC=CS1 PMJNEQWWZRSFCE-UHFFFAOYSA-N 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- GEHMBYLTCISYNY-UHFFFAOYSA-N Ammonium sulfamate Chemical compound [NH4+].NS([O-])(=O)=O GEHMBYLTCISYNY-UHFFFAOYSA-N 0.000 claims description 2
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 claims description 2
- DBAKFASWICGISY-BTJKTKAUSA-N Chlorpheniramine maleate Chemical compound OC(=O)\C=C/C(O)=O.C=1C=CC=NC=1C(CCN(C)C)C1=CC=C(Cl)C=C1 DBAKFASWICGISY-BTJKTKAUSA-N 0.000 claims description 2
- YDHJLJIJUCHSBV-UHFFFAOYSA-M Cl[Os+3].N Chemical compound Cl[Os+3].N YDHJLJIJUCHSBV-UHFFFAOYSA-M 0.000 claims description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- GRKXSKURFIUBAK-UHFFFAOYSA-N OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N Chemical compound OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N GRKXSKURFIUBAK-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 2
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims description 2
- RZOBLYBZQXQGFY-UHFFFAOYSA-N ammonium lactate Chemical compound [NH4+].CC(O)C([O-])=O RZOBLYBZQXQGFY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 229940000489 arsenate Drugs 0.000 claims description 2
- UQPRVFDDBUGZLW-UHFFFAOYSA-N azane hydroxylamine hydrochloride Chemical compound N.NO.Cl UQPRVFDDBUGZLW-UHFFFAOYSA-N 0.000 claims description 2
- XUFUCDNVOXXQQC-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)molybdenio)oxy-dioxomolybdenum Chemical compound N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 claims description 2
- ZRDJERPXCFOFCP-UHFFFAOYSA-N azane;iodic acid Chemical compound [NH4+].[O-]I(=O)=O ZRDJERPXCFOFCP-UHFFFAOYSA-N 0.000 claims description 2
- CHCFOMQHQIQBLZ-UHFFFAOYSA-N azane;phthalic acid Chemical compound N.N.OC(=O)C1=CC=CC=C1C(O)=O CHCFOMQHQIQBLZ-UHFFFAOYSA-N 0.000 claims description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- WPEJSSRSFRWYJB-UHFFFAOYSA-K azanium;tetrachlorogold(1-) Chemical compound [NH4+].[Cl-].[Cl-].[Cl-].[Cl-].[Au+3] WPEJSSRSFRWYJB-UHFFFAOYSA-K 0.000 claims description 2
- 229960003291 chlorphenamine Drugs 0.000 claims description 2
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 2
- SPPIIOPGDLITJE-VLQRKCJKSA-N diazanium;(2s,3s,4s,5r,6s)-6-[[(3s,4ar,6ar,6bs,8as,11s,12ar,14ar,14bs)-11-carboxylato-4,4,6a,6b,8a,11,14b-heptamethyl-14-oxo-2,3,4a,5,6,7,8,9,10,12,12a,14a-dodecahydro-1h-picen-3-yl]oxy]-5-[(2r,3r,4s,5s,6s)-6-carboxy-3,4,5-trihydroxyoxan-2-yl]oxy-3,4-dihy Chemical compound N.N.O([C@@H]1[C@@H](O)[C@H](O)[C@H](O[C@@H]1O[C@H]1CC[C@]2(C)[C@H]3C(=O)C=C4[C@@H]5C[C@](C)(CC[C@@]5(CC[C@@]4(C)[C@]3(C)CC[C@H]2C1(C)C)C)C(O)=O)C(O)=O)[C@@H]1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@H]1O SPPIIOPGDLITJE-VLQRKCJKSA-N 0.000 claims description 2
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 claims description 2
- MRSOZKFBMQILFT-UHFFFAOYSA-L diazanium;oxalate;titanium(2+) Chemical compound [NH4+].[NH4+].[Ti+2].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O MRSOZKFBMQILFT-UHFFFAOYSA-L 0.000 claims description 2
- DRGYXGZFRXFMHF-UHFFFAOYSA-N diazanium;tellurate Chemical compound [NH4+].[NH4+].[O-][Te]([O-])(=O)=O DRGYXGZFRXFMHF-UHFFFAOYSA-N 0.000 claims description 2
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 230000001172 regenerating effect Effects 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- BYBVAYUUISIXJJ-UHFFFAOYSA-N azane;hexahydrate Chemical compound N.O.O.O.O.O.O BYBVAYUUISIXJJ-UHFFFAOYSA-N 0.000 claims 1
- ILZWGESBVHGTRX-UHFFFAOYSA-O azanium;iron(2+);iron(3+);hexacyanide Chemical compound [NH4+].[Fe+2].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] ILZWGESBVHGTRX-UHFFFAOYSA-O 0.000 claims 1
- 230000009849 deactivation Effects 0.000 claims 1
- YLDMEZNZYLWNNL-UHFFFAOYSA-J diazanium;hexabromoplatinum(2-) Chemical compound [NH4+].[NH4+].[Br-].[Br-].[Br-].[Br-].[Br-].[Br-].[Pt+4] YLDMEZNZYLWNNL-UHFFFAOYSA-J 0.000 claims 1
- 238000007598 dipping method Methods 0.000 claims 1
- 238000001994 activation Methods 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000004227 thermal cracking Methods 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 230000004913 activation Effects 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 20
- 239000000243 solution Substances 0.000 description 19
- 238000001035 drying Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- 239000005997 Calcium carbide Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 2
- VJPICIAGVDFWEO-UHFFFAOYSA-N 2-chloro-6,7-dihydro-5h-pyrrolo[3,4-d]pyrimidine Chemical compound ClC1=NC=C2CNCC2=N1 VJPICIAGVDFWEO-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- BMWDUGHMODRTLU-UHFFFAOYSA-N azanium;trifluoromethanesulfonate Chemical compound [NH4+].[O-]S(=O)(=O)C(F)(F)F BMWDUGHMODRTLU-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- GPSSXLLMLQWNDH-UHFFFAOYSA-N triazanium phosphate hexahydrate Chemical compound [NH4+].[NH4+].[NH4+].O.O.O.O.O.O.[O-]P([O-])([O-])=O GPSSXLLMLQWNDH-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a catalyst for preparing vinyl chloride by cracking 1, 2-dichloroethane, a preparation method and a regeneration method. The catalyst is a supported phosphorus-aluminum molecular sieve catalyst, and is a catalyst which takes a nitrogen-containing material as a catalyst active component and is loaded on the surface of a phosphorus-aluminum molecular sieve. The preparation method of the catalyst comprises the steps of loading a nitrogen-containing material on a phosphorus-aluminum molecular sieve, and then calcining and pyrolyzing the phosphorus-aluminum molecular sieve at high temperature for activation. The regeneration method of the catalyst comprises the steps of roasting the catalyst with carbon deposit inactivated in an oxidizing atmosphere to remove all carbon parts on the surface, and then repeating the preparation process of the catalyst. Compared with the existing thermal cracking technology, the catalyst is simple to prepare; the reaction temperature can be reduced, the yield of the chloroethylene is high, and the stability of the whole reaction process is good; the catalyst is cheap and renewable, has long service life and is beneficial to reducing industrial cost.
Description
Technical Field
The invention relates to a catalyst for preparing chloroethylene by cracking 1, 2-dichloroethane, in particular to a supported phosphorus-aluminum molecular sieve catalyst, a preparation method and a regeneration method; belongs to the technical field of vinyl chloride monomer preparation.
Background
Vinyl chloride is an important polymeric monomer applied to polymer chemical industry, and the current industrial vinyl chloride production processes mainly comprise an ethylene method and an acetylene method. The mercury chloride catalyst generally adopted in the production of polyvinyl chloride by the acetylene method of calcium carbide can not only produce a large amount of calcium carbide slag and waste water and increase the investment cost, but also cause pollution to the environment and harm to the health of human bodies. The ethylene method mainly comprises three processes, wherein the first step is to crack light diesel oil or chemical light oil in crude oil to obtain ethylene, the second step is to directly chlorinate or oxychlorination the ethylene to generate 1, 2-dichloroethane, and the third step is to crack the 1, 2-dichloroethane in a high-temperature tubular cracking furnace to prepare chloroethylene. Therefore, the cracking of 1, 2-dichloroethane is a crucial step of ethylene process, and the industrial reaction temperature is usually 500-600 ℃ for thermal cracking, and the conversion rate of 1, 2-dichloroethane is controlled at about 50%. As the high-temperature thermal cracking reaction temperature is higher, the energy consumption is high, coking is easy to occur, the cracking furnace and the subsequent separation process equipment are blocked by coking particles, frequent coke cleaning is needed, the production period is short, and the like.
From the catalysts reported at present, the common catalyst for producing vinyl chloride by catalytic cracking of 1, 2-dichloroethane mainly uses a carbon material as a main body, and uses other supported species as an active center for catalytically cracking 1, 2-dichloroethane to produce vinyl chloride, but the processes for producing vinyl chloride by cracking 1, 2-dichloroethane by using a carbon material as a catalyst have the disadvantages of high cost, short service life, difficult regeneration and the like, and do not accord with the sustainable development strategy, so that the industrial application cannot be realized.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a catalyst for catalyzing the cracking of 1,2 dichloroethane to prepare vinyl chloride. The catalyst is applied to the reaction of preparing chloroethylene by cracking 1, 2-dichloroethane, and has the advantages of high conversion rate of 1, 2-dichloroethane, high yield of chloroethylene and good stability. And after the molecular sieve is inactivated in the using process, the carbonaceous part on the surface of the carrier can be removed by roasting, and the active component is re-loaded, so that the activity of the catalyst is recovered. And the molecular sieve can be regenerated and reused, thereby greatly reducing the cost of the catalyst and ensuring that the catalyst has great industrial application prospect.
According to one aspect of the application, a catalyst for preparing vinyl chloride by cracking 1, 2-dichloroethane is provided, wherein the catalyst is a supported catalyst and comprises a nitrogen-containing active component and a carrier; the carrier is selected from at least one of a silicon-phosphorus-aluminum molecular sieve or a phosphorus-aluminum molecular sieve; the nitrogen-containing active component is obtained by loading a nitrogen source on the carrier and carrying out heat treatment in an oxygen-containing atmosphere or a nitrogen-containing atmosphere.
The skilled person can select a suitable nitrogen source as the case may be. Optionally, the nitrogen source is at least one selected from organic substances containing nitrogen element and ammonium salts.
Preferably, the nitrogen source is selected from the group consisting of ammonia (including ammonia and ammonia), hydrazine, acetonitrile, cyanamide, pyridine, pyrrole, ethylenediamine, methylamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ammonium chloride, ammonium persulfate, ammonium dimolybdate, ammonium lactate, ferric ammonium oxalate, ammonium heptamolybdate, ammonium chloroplatinate, ammonium ureanate, ammonium chloroplatinate, ammonium chromate, ammonium fluoroborate, ammonium metavanadate, ammonium formate, ammonium sulfamate, ammonium tetrachloroaurate, ammonium hexabromate, water-soluble ammonium polyphosphate, ammonium phosphomolybdate, ammonium oxalate, ammonium dihydrogen arsenate, ferrous ammonium sulfate, ammonium phosphate hexahydrate, ammonium phosphomolybdate, ammonium fluorotitanate, sodium ammonium phosphate, ammonium glycyrrhizinate, ammonium bicarbonate, ammonium stearate, ammonium dichromate, ammonium tellurate, ammonium octamolybdate, ammonium palladium chloride, ammonium lignosulfonate, ammonium trifluoroacetate, phthalic acid, ammonium bis (ammonium) phosphate, ammonium fluotitanate, ammonium phosphate, ammonium mono (ammonium) phosphate, ammonium hydrogen carbonate, ammonium stearate, ammonium dichromate, ammonium octamolybdate, ammonium chloride, ammonium triflate, ammonium trifluoroacetate, ammonium phthalate, Ammonium hexafluorogermanate, ammonium paratungstate, ammonium chloroiridate, ammonium chloroosmium, ammonium chlororuthenate, ammonium carbonate, diammonium arsenate, ammonium polyacrylate, ammonium sulfate, ammonium tetrathiomolybdate, ammonium succinate, ammonium iodate, ammonium perrhenate, ammonium ferrocyanide hydrate, ammonium molybdate, ammonium titanyl oxalate, ammonium phosphotungstate, ammonium nitrate, ammonium chlororhodate, ammonium oxalate, diammonium glycyrrhizinate, ammonium hexachloroiridate, ammonium oxalate, ammonium chlorotaurinate, ammonium dodecaborate, ammonium sebacate tetrahydrate, ammonium polyphosphate, chlorphenamine phosphate, ammonium tetramolybdate, ammonium polyphosphate, ammonium tetrathiotungstate, ammonium violate, food grade ammonium acetate, ammonium molybdate solution, monoammonium glycyrrhizinate, ammonium hydrogen lactate, ammonium bicecanate, ammonium phosphotungstate, ammonium acetate, or ammonium hydroxylammonium hydrochloride, or at least one nitrogen-containing substance of any of the foregoing nitrogen-containing substance derivatives.
Optionally, the support is selected from at least one of SAPO-5, SAPO-11, SAPO-18, SAPO-31, SAPO-34, SAPO-35, SAPO-37, SAPO-39, SAPO-41, SAPO-47, MgAPSO-31, MnAPSO-11, CoAPO-50, ZnAPSO-39, CoAPSO-47, AlPO-5, AlPO-11, AlPO-14, AlPO-16, and AlPO-20.
Optionally, in the supported catalyst, the mass percentage of the active component to the carrier is 0.01-100%.
It is another object of the present invention to provide a method for preparing a supported catalyst, comprising the steps of: firstly, loading a nitrogen source on a carrier, and then carrying out heat treatment in a nitrogen-containing atmosphere or an oxygen-containing atmosphere; thus obtaining the supported catalyst; the heat treatment temperature is 200-1000 ℃, and the heat treatment time is 2-48 hours.
Alternatively, the loading means is direct impregnation, ion exchange or spraying of the liquid nitrogen-containing material or a solution of the nitrogen-containing material onto the support.
Optionally, the pyrolysis temperature is 600-850 ℃; the time is 3-20 hours.
Alternatively, the nitrogen-containing compound atmosphere refers to a nitrogen-containing gas or a mixed gas of a nitrogen-containing gas and an inert atmosphere gas. The nitrogen-containing gas is at least one of ammonia gas, nitrogen gas and organic amine gas.
Optionally, the oxygen-containing atmosphere is an oxygen-containing gas or a mixture of an oxygen-containing gas and nitrogen or an inert gas. The oxygen-containing compound atmosphere is selected from air and oxygen.
Optionally, the inert atmosphere gas is one or a mixture of more than two of argon gas and helium gas; if a mixed gas of nitrogen-containing gas and inert gas is adopted, the mass content of the nitrogen-containing gas in the mixed gas is more than or equal to 0.1 percent and less than 100 percent; if a mixed gas of oxygen-containing gas and inert gas is adopted, the mass content of the oxygen-containing gas in the mixed gas is more than or equal to 0.1 percent and less than 100 percent.
Optionally, the nitrogen source is dissolved in a solution and loaded on the carrier, wherein the solvent in the solution is one or two of water, hydrocarbon with 1 to 18 carbon atoms, halogenated hydrocarbon, alcohol, ether, ester, ketone, amine, acid, phenol, nitrile, furan, pyridine or pyrrole.
It is still another object of the present application to provide a method for regenerating a supported catalyst, which is deactivated in the reaction for preparing vinyl chloride by cracking 1, 2-dichloroethane to obtain a deactivated catalyst; the deactivated supported catalyst is roasted in oxidizing atmosphere to eliminate carbon of inorganic porous material and used as carrier for preparing regenerated catalyst.
Optionally, the oxidizing atmosphere is oxygen, a mixed gas of oxygen and nitrogen or inert atmosphere gas, or air; the inert atmosphere gas is one or more than two of argon or helium; the mass content of oxygen in the oxidizing atmosphere is 1-100%.
Optionally, the roasting temperature is 300-1000 ℃; the treatment time is 2-48 hours.
The application also aims to provide the application of the supported catalyst in catalyzing the cracking of 1, 2-dichloroethane to prepare vinyl chloride. Specifically, 1, 2-dichloroethane is vaporized and then is introduced into a reactor filled with the catalyst, wherein the mass space velocity (WHSV) of the reaction is 0.01-100h-1The cracking temperature is 200-450 ℃.
The beneficial effects of the application include but are not limited to:
(1) the catalyst provided by the application has the advantages of simple preparation steps and good regeneration effect;
(2) the catalyst prepared by the method is used for preparing chloroethylene by cracking dichloroethane, the yield of chloroethylene is high, and the stability of the whole reaction process is good;
(3) the catalyst prepared by the method is cheap and renewable, and has long service life; the whole reaction process has low energy consumption, is beneficial to reducing the industrial cost, and has good industrial application prospect.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples. The following examples are only some of the preferred embodiments of the present invention, and the present invention is not limited to the contents of the examples. It will be apparent to those skilled in the art that various changes and modifications can be made within the spirit of the invention, and any changes and modifications made are within the scope of the invention.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
The conversion and selectivity calculations for one hour of reaction in the examples of this application are as follows:
example 1
Spraying the mixture into 15mL SAPO-34 in 40mL 10% acetonitrile solution at room temperature, heating to 120 ℃, and drying. And (3) putting the dried SAPO-34 into a quartz tube, heating to 450 ℃ under the protection of nitrogen in the tube furnace, keeping the temperature for 3 hours, switching to an ammonia atmosphere, heating to 700 ℃ at a speed of 10 ℃/min, keeping the temperature for 3 hours, and carrying out an activation process to obtain the catalyst.
The application of the catalyst comprises the step of filling a fixed bed reactor of the 1, 2-dichloroethane cracking catalyst prepared in the embodiment with 1, 2-dichloroethane liquid in a pumping mode, wherein the temperature of the reactor is 450 ℃, and the space velocity is 80h-1。
The inactivated catalyst is roasted for 3 hours at 750 ℃ in the air, the obtained phosphorus-aluminum molecular sieve is used as a carrier and is regenerated according to the preparation process of the catalyst for use, and the activity is not reduced.
Example 2
Adding 20g of ammonium nitrate into 40mL of aqueous solution at room temperature under stirring, adding 60mL of CoAPO-50 into a beaker after dissolution for ion exchange for 6 hours, washing to remove redundant liquid, and heating to 100 ℃ for drying. And (3) putting the dried CoAPO-50 into a muffle furnace, heating to 750 ℃ in the atmosphere of air in the muffle furnace, and keeping the temperature for 6 hours to perform an activation process to obtain the catalyst.
Use of a catalyst comprising a fixed-bed reaction of 1, 2-dichloroethane with saturated steam of dichloroethane carried by nitrogen into a 1, 2-dichloroethane cracking catalystReactor, reactor temperature 220 ℃, space velocity 0.1h-1。
The deactivated catalyst is roasted for 32 hours at 400 ℃ in the air, and the obtained phosphorus-aluminum molecular sieve is used as a carrier and is regenerated according to the preparation process of the catalyst for use, so that the activity is not reduced.
Example 3
Adding 20g ammonium oxalate into 50mL aqueous solution at room temperature under stirring, dissolving, soaking into 10mL AIPO-5, filtering, washing to remove excessive liquid, heating to 110 deg.C, and oven drying. And (3) putting the dried AIPO-5 into a muffle furnace, heating to 850 ℃ in the muffle furnace under the nitrogen atmosphere, and keeping the temperature for 3 hours to perform an activation process to obtain the catalyst.
The application of the catalyst comprises the steps of taking 1, 2-dichloroethane into a fixed bed reactor of a 1, 2-dichloroethane cracking catalyst in a mode that the 1, 2-dichloroethane carries saturated steam with helium, wherein the temperature of the reactor is 300 ℃, and the space velocity is 40h-1。
The deactivated catalyst is roasted for 8 hours at 550 ℃ in the air, and the obtained phosphorus-aluminum molecular sieve is used as a carrier and is regenerated according to the preparation process of the catalyst for use, so that the activity is not reduced.
Example 4
Spraying 40mL of 25% tetramethylammonium hydroxide into 40mL of SAPO-47, and heating to 140 ℃ for drying. And (3) putting the dried SAPO-47 into a quartz tube, heating to 650 ℃ under the protection of nitrogen in the tube furnace, keeping the temperature for 7 hours, heating to 700 ℃ at the speed of 10 ℃/min, keeping the temperature for 8 hours, and performing an activation process to obtain the catalyst.
The application process is the same as that of example 1, except that the reactor temperature is 350 ℃ and the space velocity is 0.5h-1。
The deactivated catalyst is roasted for 16 hours at 800 ℃ in the air, and the obtained phosphorus-aluminum molecular sieve is used as a carrier and is regenerated for use according to the preparation process of the catalyst, so that the activity is not reduced.
Example 5
Preparing 30mL of 25% monoammonium glycyrrhizinate solution, and carrying out ion exchange to 22mL of AlPO4And 11, washing, filtering and removing redundant liquid, and heating to 130 ℃ for drying. Drying AlPO4-11, put into a quartz tubeAnd heating to 550 ℃ under the protection of nitrogen in the tubular furnace, keeping the temperature constant for 3 hours, switching to an ammonia atmosphere, heating to 800 ℃ at the speed of 20 ℃/min, keeping the temperature constant for 4 hours, and carrying out an activation process to obtain the catalyst. .
The application process is the same as that of example 2, except that the reactor temperature is 350 ℃ and the space velocity is 50h-1。
The deactivated catalyst is roasted for 9 hours at the temperature of 600 ℃ in the air, and the obtained phosphorus-aluminum molecular sieve is used as a carrier and is regenerated for use according to the preparation process of the catalyst, so that the activity is not reduced.
Example 6
10mL of 25% hydroxylamine hydrochloride aqueous solution is prepared, ions are soaked into 50mL of ZnAPSO-39, redundant liquid is removed by filtration, and the temperature is raised to 110 ℃ for drying. And (3) putting the dried ZnAPSO-39 into a muffle furnace, heating to 450 ℃ in the atmosphere of air in the muffle furnace, and keeping the temperature for 3.5 hours to carry out an activation process to obtain the catalyst.
The application process is the same as that of example 3, except that the reactor temperature is 250 ℃ and the space velocity is 15h-1。
The deactivated catalyst is roasted for 40 hours at 300 ℃ in the air, and the obtained phosphorus-aluminum molecular sieve is used as a carrier and is regenerated for use according to the preparation process of the catalyst, so that the activity is not reduced.
Example 7
10mL of 15% ammonium chloroiridate is prepared and sprayed into 40mL of SAPO-5, and the mixture is heated to 140 ℃ and dried. And (3) putting the dried SAPO-5 into a muffle furnace, heating to 350 ℃ in the muffle furnace under the nitrogen atmosphere, and keeping the temperature for 3 hours to perform an activation process to obtain the catalyst.
The application process is the same as that of example 1, except that the reactor temperature is 350 ℃ and the space velocity is 0.5h-1。
The deactivated catalyst is roasted for 16 hours at 800 ℃ in the air, and the obtained phosphorus-aluminum molecular sieve is used as a carrier and is regenerated for use according to the preparation process of the catalyst, so that the activity is not reduced.
Example 8
Preparing 30mL of 25% ammonium cyanurate solution, carrying out ion exchange on the ammonium cyanurate solution in 22mL of SAPO-11, heating to 110 ℃, and drying. And (3) putting the dried SAPO-11 into a quartz tube, heating to 550 ℃ under the protection of nitrogen in the tube furnace, keeping the temperature for 3 hours, switching to an ammonia atmosphere, heating to 800 ℃ at a speed of 30 ℃/min, keeping the temperature for 3 hours, and performing an activation process to obtain the catalyst.
The application process is the same as that of example 2, except that the reactor temperature is 360 ℃ and the space velocity is 43h-1。
The deactivated catalyst is roasted for 18 hours at 440 ℃ in the air, and the obtained phosphorus-aluminum molecular sieve is used as a carrier and is regenerated for use according to the preparation process of the catalyst, so that the activity is not reduced.
Example 9
Preparing 40mL of 25% ammonium sulfate solution, spraying into 40mL of AIPO-14, heating to 100 ℃, and drying. And (3) putting the dried AIPO-14 into a quartz tube, heating to 350 ℃ under the protection of nitrogen in the tube furnace, keeping the temperature for 4 hours, heating to 500 ℃ at the speed of 1 ℃/min, keeping the temperature for 6 hours, and carrying out an activation process to obtain the catalyst.
The application process is the same as that of example 3, except that the reactor temperature is 370 ℃, and the space velocity is 45h-1。
The inactivated catalyst is roasted for 12 hours at 750 ℃ in the air, and the obtained phosphorus-aluminum molecular sieve is used as a carrier and is regenerated according to the preparation process of the catalyst for use, so that the activity is not reduced.
Example 10
Preparing 33mL of 25% pyrrole solution, carrying out ion exchange in 22mL of SAPO-35, heating to 110 ℃, and drying. And (3) putting the dried SAPO-35 into a quartz tube, heating to 650 ℃ under the protection of nitrogen in the tube furnace, keeping the temperature for 4 hours, switching to an ammonia atmosphere, heating to 500 ℃ at a speed of 3 ℃/min, keeping the temperature for 10 hours, and performing an activation process to obtain the catalyst.
The application process is the same as that of example 1, except that the reactor temperature is 400 ℃ and the space velocity is 86h-1。
The deactivated catalyst is roasted for 8 hours at the temperature of 600 ℃ in the air, and the obtained phosphorus-aluminum molecular sieve is used as a carrier and is regenerated for use according to the preparation process of the catalyst, so that the activity is not reduced.
Example 11
The preparation was the same as in example 1, except that 58mL of 25% sodium ammonium phosphate solution was sprayed onto 40mL of SAPO-18.
The process was carried out as in example 2, except that the reactor temperature was 245 ℃ and the space velocity was 77h-1。
The deactivated catalyst is roasted for 12 hours at 400 ℃ in the air, and the obtained phosphorus-aluminum molecular sieve is used as a carrier and is regenerated according to the preparation process of the catalyst for use, so that the activity is not reduced.
Example 12
47mL of 25% ammonium lactate solution was prepared, and ion-exchanged into 22mL of SAPO-31, according to the same method as in example 2.
The application process is the same as that of example 3, except that the reactor temperature is 270 ℃ and the space velocity is 83h-1。
The deactivated catalyst is roasted in air at 300 deg.c for 10 hr to obtain P-Al molecular sieve as carrier, and the P-Al molecular sieve is regenerated for use without lowering activity.
Example 13
The preparation was the same as in example 3, except that 18mL of 25% ammonium dichromate solution was sprayed onto 40mL of SAPO-37.
The application process is the same as that of example 1, except that the reactor temperature is 290 ℃, and the space velocity is 30h-1。
The deactivated catalyst is roasted for 11 hours at 450 ℃ in the air, and the obtained phosphorus-aluminum molecular sieve is used as a carrier and is regenerated according to the preparation process of the catalyst for use, so that the activity is not reduced.
Example 14
13mL of 25% ammonium bicarbonate solution was prepared and ion-exchanged into 22mL of MgAPSO-31, the preparation method was the same as in example 4.
The application process is the same as that of example 2, except that the reactor temperature is 270 ℃ and the space velocity is 4h-1。
The deactivated catalyst is roasted for 8 hours at 700 ℃ in the air, and the obtained phosphorus-aluminum molecular sieve is used as a carrier and is regenerated for use according to the preparation process of the catalyst, so that the activity is not reduced.
Example 15
The preparation was the same as in example 5 except that 40mL of 8% ammonium octamolybdate solution was sprayed onto 40mL of AIPO-16.
The application process is the same as that of example 3, except that the reactor temperature is 260 ℃ and the space velocity is 1.5h-1。
The inactivated catalyst is roasted for 16 hours at 350 ℃ in the air, the obtained phosphorus-aluminum molecular sieve is used as a carrier and is regenerated according to the preparation process of the catalyst for use, and the activity is not reduced.
Example 16
10mL of 27% monoammonium glycyrrhizinate solution was prepared, and ion-exchanged into 22mL of AlPO-20, which was prepared in the same manner as in example 6.
The process was the same as in example 1 except that the reactor temperature was 310 ℃ and the space velocity was 6h-1。
The deactivated catalyst is roasted for 9 hours at 650 ℃ in the air, and the obtained phosphorus-aluminum molecular sieve is used as a carrier and is regenerated according to the preparation process of the catalyst for use, so that the activity is not reduced.
Example 17
The preparation was the same as in example 7 except that 23mL of a 33% ammonium ferrocyanide hydrate solution was sprayed onto 40mL of MnAPSO-11.
The application process is the same as that of example 2, except that the reactor temperature is 320 ℃ and the space velocity is 0.9h-1。
The deactivated catalyst is roasted for 5 hours at 550 ℃ in the air, and the obtained phosphorus-aluminum molecular sieve is used as a carrier and is regenerated according to the preparation process of the catalyst for use, so that the activity is not reduced.
Example 18
Prepare 34mL of 5% ammonium succinate solution, ion exchange into 22mL of SAPO-39, and prepare the same as example 8.
The application process is the same as that of example 3, except that the reactor temperature is 220 ℃, and the space velocity is 17h-1。
The inactivated catalyst is roasted for 2 hours at 800 ℃ in the air, and the obtained phosphorus-aluminum molecular sieve is used as a carrier and is regenerated according to the preparation process of the catalyst for use, so that the activity is not reduced.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. The catalyst for preparing vinyl chloride by cracking 1, 2-dichloroethane is characterized in that the catalyst is a supported catalyst and comprises a nitrogen-containing active component and a carrier;
the carrier is selected from at least one of a silicon-phosphorus-aluminum molecular sieve or a phosphorus-aluminum molecular sieve;
the nitrogen-containing active component is obtained by loading a nitrogen source on the carrier and carrying out heat treatment in an oxygen-containing atmosphere or a nitrogen-containing atmosphere.
2. The catalyst for cracking 1, 2-dichloroethane to produce vinyl chloride according to claim 1, characterized in that said nitrogen source is at least one selected from the group consisting of organic substances containing nitrogen elements and ammonium salts;
preferably, the nitrogen source is selected from the group consisting of ammonia, hydrazine, acetonitrile, cyanamide, pyridine, pyrrole, ethylenediamine, methylamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ammonium chloride, ammonium persulfate, ammonium dimolybdate, ammonium lactate, ferric ammonium oxalate, ammonium heptamolybdate, ammonium chloroplatinate, ammonium ureanate, ammonium chloroplatinate, ammonium chromate, ammonium fluoroborate, ammonium metavanadate, ammonium formate, ammonium sulfamate, ammonium tetrachloroaurate, ammonium hexabromoplatinate, water-soluble ammonium polyphosphate, ammonium phosphomolybdate, ammonium oxalate, ammonium dihydrogenate, ferric ammonium ferrocyanide sulfate, ammonium hexahydrate, ammonium phosphomolybdate, ammonium fluorotitanate, sodium ammonium phosphate, monoammonium glycyrrhizinate, ammonium bicarbonate, ammonium stearate, ammonium dichromate, ammonium tellurate, ammonium octamolybdate, ammonium palladate, ammonium lignosulfonate, ammonium trifluoroacetate, ammonium orthophthalate, ammonium phosphate, ammonium hydrogen phosphate, ammonium fluotitanate, ammonium hydrogen phosphate, ammonium glycyrrhizinate, ammonium hydrogen carbonate, ammonium stearate, ammonium dichromate, ammonium molybdate, ammonium octamolybdate, ammonium chloride, ammonium lignosulfonate, ammonium trifluoroacetate, ammonium phthalate, Ammonium hexafluorogermanate, ammonium paratungstate, ammonium chloroiridate, ammonium chloroosmium, ammonium chlororuthenate, ammonium carbonate, diammonium arsenate, ammonium polyacrylate, ammonium tetrathiomolybdate, ammonium succinate, ammonium iodate, ammonium perrhenate, ammonium ferrocyanide hydrate, ammonium molybdate, ammonium sulfate, ammonium titanyl oxalate, ammonium phosphotungstate, ammonium nitrate, ammonium chlororhodate, ammonium oxalate, diammonium glycyrrhizinate, ammonium hexachloroiridate, ammonium oxalate, ammonium chlorotaurinate, ammonium dodecaborate, ammonium sebacate tetrahydrate, ammonium polyphosphate, chlorphenamine phosphate, ammonium tetramolybdate, ammonium polyphosphate, ammonium tetrathiotungstate, ammonium violate, food grade ammonium acetate, ammonium molybdate solution, monoammonium glycyrrhizinate, ammonium hydrogen lactate, ammonium bicecanate, ammonium phosphotungstate, ammonium acetate, or ammonium hydroxylammonium hydrochloride, or at least one nitrogen-containing substance of any of the foregoing nitrogen-containing substance derivatives.
3. The catalyst for preparing vinyl chloride by cracking 1, 2-dichloroethane according to claim 1, wherein the carrier is at least one selected from the group consisting of SAPO-5, SAPO-11, SAPO-18, SAPO-31, SAPO-34, SAPO-35, SAPO-37, SAPO-39, SAPO-41, SAPO-47, MgAPSO-31, MnAPSO-11, CoAPO-50, ZnAPSO-39, CoAPSO-47, AlPO-5, AlPO-11, AlPO-14, AlPO-16 and AlPO-20.
4. A process for preparing a catalyst for vinyl chloride production by cracking 1, 2-dichloroethane according to any one of claims 1 to 3, comprising the steps of:
firstly, loading a nitrogen source on a carrier, and then carrying out heat treatment in a nitrogen-containing atmosphere or an oxygen-containing atmosphere; thus obtaining the supported catalyst;
the heat treatment temperature is 200-1000 ℃, and the heat treatment time is 2-48 hours.
5. The method according to claim 4, wherein the supporting is carried out by dipping, ion exchange or spraying.
6. The method according to claim 4, wherein the oxygen-containing atmosphere is an oxygen-containing gas or a mixture of an oxygen-containing gas and nitrogen or an inert gas; the oxygen-containing gas is selected from air and oxygen;
the nitrogen-containing atmosphere is a nitrogen-containing gas or a mixture of a nitrogen-containing gas and an inert gas; the nitrogen-containing gas is at least one of ammonia gas, nitrogen gas and organic amine gas.
7. The process for regenerating a catalyst for the preparation of vinyl chloride by cracking 1, 2-dichloroethane according to any one of claims 1 to 3, wherein the catalyst is used to obtain a deactivated catalyst after deactivation of the reaction for preparing vinyl chloride by cracking 1, 2-dichloroethane;
the deactivated catalyst is calcined in an oxidizing atmosphere and used as a carrier to prepare a regenerated catalyst according to the method of any one of claims 4 to 6.
8. The regeneration process according to claim 7, wherein the oxidizing atmosphere is oxygen, a mixture of oxygen and nitrogen or an inert atmosphere gas, or air; the inert atmosphere gas is one or more than two of argon or helium; the oxygen content in the oxidizing atmosphere is 1-100% by mass.
9. The regeneration method according to claim 7, wherein the roasting temperature is 300 ℃ to 1000 ℃; the treatment time is 2-48 hours.
10. Use of the catalyst for the cracking of 1, 2-dichloroethane to produce vinyl chloride according to any one of claims 1 to 3 for catalyzing the cracking of 1, 2-dichloroethane to produce vinyl chloride.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1485449A (en) * | 1966-07-05 | 1967-06-16 | Pullman Inc | Catalyst used in dehydrohalogenation processes |
| CN102249844A (en) * | 2011-05-20 | 2011-11-23 | 天津大沽化工股份有限公司 | Method for preparing vinyl chloride from 1,2-dichloroethane |
| CN105833892A (en) * | 2016-04-22 | 2016-08-10 | 辽宁石油化工大学 | Catalyst for preparing vinyl chloride by cracking 1,2-dichloroethane as well as preparation method and application of catalyst |
| US20180118643A1 (en) * | 2015-05-27 | 2018-05-03 | Johnson Matthey Public Limited Company | Process for the preparation of vinyl chloride |
| CN109926081A (en) * | 2017-12-15 | 2019-06-25 | 中国科学院大连化学物理研究所 | A kind of catalyst, preparation and regeneration method for 1,2- dichloroethanes cracking preparing chloroethylene |
-
2020
- 2020-12-10 CN CN202011458294.4A patent/CN114618578A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1485449A (en) * | 1966-07-05 | 1967-06-16 | Pullman Inc | Catalyst used in dehydrohalogenation processes |
| CN102249844A (en) * | 2011-05-20 | 2011-11-23 | 天津大沽化工股份有限公司 | Method for preparing vinyl chloride from 1,2-dichloroethane |
| US20180118643A1 (en) * | 2015-05-27 | 2018-05-03 | Johnson Matthey Public Limited Company | Process for the preparation of vinyl chloride |
| CN105833892A (en) * | 2016-04-22 | 2016-08-10 | 辽宁石油化工大学 | Catalyst for preparing vinyl chloride by cracking 1,2-dichloroethane as well as preparation method and application of catalyst |
| CN109926081A (en) * | 2017-12-15 | 2019-06-25 | 中国科学院大连化学物理研究所 | A kind of catalyst, preparation and regeneration method for 1,2- dichloroethanes cracking preparing chloroethylene |
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