CN106902853A - Catalyst and its preparation method and application suitable for one-step method glycerine propionic aldehyde - Google Patents
Catalyst and its preparation method and application suitable for one-step method glycerine propionic aldehyde Download PDFInfo
- Publication number
- CN106902853A CN106902853A CN201710203202.XA CN201710203202A CN106902853A CN 106902853 A CN106902853 A CN 106902853A CN 201710203202 A CN201710203202 A CN 201710203202A CN 106902853 A CN106902853 A CN 106902853A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- propionic aldehyde
- chloride
- glycerine
- basic zirconium
- 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.)
- Pending
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- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 title claims abstract description 168
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 164
- 239000003054 catalyst Substances 0.000 title claims abstract description 99
- 238000000034 method Methods 0.000 title claims abstract description 75
- 235000011187 glycerol Nutrition 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 52
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims abstract description 43
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims abstract description 43
- 239000002184 metal Substances 0.000 claims abstract description 42
- 239000003610 charcoal Substances 0.000 claims abstract description 26
- 108091007643 Phosphate carriers Proteins 0.000 claims abstract description 23
- 239000002250 absorbent Substances 0.000 claims abstract description 22
- 230000002745 absorbent Effects 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 7
- 229910052723 transition metal Inorganic materials 0.000 claims abstract 2
- 150000003624 transition metals Chemical group 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000001257 hydrogen Substances 0.000 claims description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical group [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 21
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- 239000012266 salt solution Substances 0.000 claims description 13
- 229910019142 PO4 Inorganic materials 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 12
- 239000010452 phosphate Substances 0.000 claims description 12
- 239000000376 reactant Substances 0.000 claims description 9
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 150000003754 zirconium Chemical class 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 238000005660 chlorination reaction Methods 0.000 claims description 4
- 229910052702 rhenium Inorganic materials 0.000 claims description 4
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 238000001802 infusion Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- RWRDJVNMSZYMDV-UHFFFAOYSA-L radium chloride Chemical compound [Cl-].[Cl-].[Ra+2] RWRDJVNMSZYMDV-UHFFFAOYSA-L 0.000 claims description 2
- 229910001630 radium chloride Inorganic materials 0.000 claims description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 2
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 24
- 230000008569 process Effects 0.000 description 18
- 239000000725 suspension Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000012153 distilled water Substances 0.000 description 14
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Chinese gallotannin Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 13
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 239000011148 porous material Substances 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 235000021317 phosphate Nutrition 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 8
- 238000013019 agitation Methods 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 6
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000007037 hydroformylation reaction Methods 0.000 description 3
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 description 3
- WJIBZZVTNMAURL-UHFFFAOYSA-N phosphane;rhodium Chemical compound P.[Rh] WJIBZZVTNMAURL-UHFFFAOYSA-N 0.000 description 3
- -1 rare earth pyrophosphate Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000000205 computational method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000003317 industrial substance Substances 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- AHADSRNLHOHMQK-UHFFFAOYSA-N methylidenecopper Chemical compound [Cu].[C] AHADSRNLHOHMQK-UHFFFAOYSA-N 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- SZMNOLSLNRNAJC-UHFFFAOYSA-N formaldehyde;propane-1,2,3-triol Chemical compound O=C.OCC(O)CO SZMNOLSLNRNAJC-UHFFFAOYSA-N 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
-
- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1817—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with copper, silver or gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
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Abstract
The present invention relates to organic chemicals synthesis technical field, and in particular to prepare catalyst and its preparation method and the application of propionic aldehyde suitable for one-step method glycerine；Catalyst includes basic zirconium phosphate carrier and metallic absorbent charcoal loaded article；Wherein, basic zirconium phosphate carrier mass fraction >=70% and ＜ 100% in the catalyst, metallic absorbent charcoal loaded article mass fraction in the catalyst is ＞ 0 and≤30%；Wherein, by being obtained after activated carbon supported metal, metallic element is selected from transition metal to metallic absorbent charcoal loaded article.The present invention also provides the method that one-step method glycerine prepares propionic aldehyde, and propionic aldehyde selectivity is high, and catalyst activity is high, long lifespan, is with a wide range of applications.
Description
Technical field
The present invention relates to organic chemicals synthesis technical field, propionic aldehyde synthesis technical field is related generally to, and in particular to suitable
Catalyst and its preparation method and the application of propionic aldehyde are prepared for one-step method glycerine.
Background technology
Propionic aldehyde is a kind of important chemical products and industrial chemicals, is also used to production propyl alcohol, propionic acid, trimethylolethane
Deng chemical intermediate, there is extensive purposes in the field such as agricultural and feed, medicine, food, light textile, wide market.I
The propionic aldehyde production of state is still in the starting stage, the need for yield far can not meet domestic production, while also limit downstream product
The development of product propyl alcohol, propionic acid etc..Take the lead in being closed using ethene hydroformylation method from the U.S. combinating carbide company seventies in last century
Into propionic aldehyde, the method is increasingly becoming universal production method.It is divided into high-pressure process and low-pressure process again, wherein low-pressure process using rhodium phosphine as
Catalyst, activity is high, and reaction condition is gentle, and product purity is high, and isomer-free is produced.Chinese patent (CN102115433A) is just public
A kind of method that ethene low pressure carbonylation synthesis produce propionic aldehyde is opened.With ethene, carbon monoxide and hydrogen as raw material, using rhodium phosphine network
Mixture catalyst system, propionic aldehyde is synthesized by ethene hydroformylation.Feed stock conversion >=90% in terms of ethene.Propionic aldehyde is produced
Product content >=99.5%.Chinese patent (CN103373910A) describes one kind directly using ethene and hydrogen in oil refinery dry gas,
With the method that reaction of carbon monoxide prepares propionic aldehyde.Hydroformylation reaction is carried out by with that need not be separated to component, concentrated
Prepare the advantage of propionic aldehyde.Chinese patent (CN1434015) also reports a kind of dilute ethene legal system propionic aldehyde, i.e., in water-soluble rhodium phosphine network
In the water phase that compound composite catalyst is present, dilute ethene and carbon monoxide and hydrogen are reacted, prepare propionic aldehyde.Contain in reaction system
There is additional water-soluble phosphate and/or phosphite.The method generates the selectivity of propionic aldehyde more than 98%, and with separation
The process is simple of propionic aldehyde is collected, the advantages of the loss of rhodium catalyst is small.Other prepare propionic aldehyde and also have propyl alcohol oxidizing process, oxirane
Isomerization process, methacrylaldehyde hydrogenation method etc..But the above method is mostly homogeneous catalysis process, product separation is inevitably present
Problem, therefore exploitation heterogeneous catalysis technique be always people pursue target.In addition, the raw material of existing production technology is mainly
The ethene that petrochemical industry is produced, from from the point of view of environmental protection and sustainable development, people are more desirable to exploitation based on biomass
Resource is the propionic aldehyde production technology of raw material.
Glycerine is a kind of small molecule of high functionalization, by USDOE be defined as most important 12 kinds it is biomass-based flat
One of platform molecule, is also the byproduct for producing biodiesel.Due to a large amount of productions of biomass energy in recent years, its is subsidiary thick
If glycerine is all refined, then global glycerol market is necessarily disturbed.In fact, the price of refined glycerine have dropped 50%.
So, glycerine is transformed into the industrial chemicals of higher value, such as 1,2-PD, 1,3-PD, third by series reaction
Olefine aldehydr, 1- propyl alcohol etc. also turn into a hot issue.And correlative study is also had by glycerine propionic aldehyde and is reported, Laura Malek
The technique for synthesizing propionic aldehyde by glycerine using two-step method is reported, i.e., passes through WO first3/ZrO2Catalyst dehydration is obtained methacrylaldehyde, then
Hydrogenation obtains propionic aldehyde (Malek, Laura. " Simulation of propionaldehyde on Pd catalyst
production from glycerol."(2012).).Be divided into what two steps were carried out by glycerine generation propionic aldehyde at present, i.e., the
One step dehydration generation methacrylaldehyde, second step hydrogenation.
Dehydrating glycerin generation methacrylaldehyde has the catalyst that many documents have probed into some more efficients both at home and abroad.Glycerine liquid phase
The catalyst of dehydration generation methacrylaldehyde mainly has inorganic acid and its salt, metal oxide, heteropoly acid, rare earth pyrophosphate, molecule
Sieve etc..Gas phase preparing acrolein by dehydrating glycerin is mainly carried out in fixed bed, and catalyst is roughly divided into 3 kinds, be respectively molecular sieve,
Heteropllyacids and oxide-based.As Chinese patent (CN105837420A) discloses a kind of bimetallic oxide dehydrating glycerin with catalyst
The method of acrolein.Chinese patent (CN105348054A) is reported comprising oxygen, phosphorus and at least one selected from vanadium, boron or aluminium
Antigravity system, acrolein selectivity higher can be obtained.
The content of the invention
Present invention solves the technical problem that being：The technique that current glycerine prepares propionic aldehyde is all that two-step method is completed, economy
Have much room for improvement with efficiency.The present inventor after research by having found：The key of one-step glycerol method synthesis propionic aldehyde chemical process is exploitation
Efficient catalyst.Glycerine is first dehydrated generation methacrylaldehyde, then by being hydrogenated to propionic aldehyde, this process needs appropriate acidity
Position and metal position collective effect could be completed.
The purpose of the present invention is：One-step glycerol method is provided and prepares new, efficient catalyst of propionic aldehyde and preparation method thereof,
Specifically, catalyst is prepared using the method for phosphate composition metal hydrogenation position, for one-step method from glycerol production propionic aldehyde,
And then the intermediate link of two-step method is reduced, good economy performance is in hgher efficiency.
In order to solve the above technical problems, the invention provides the weight percent that a kind of one-step method glycerine synthesizes propionic aldehyde catalyst
It is than composition：Metal 0-2%, activated carbon ＞ 0 ,≤28%, basic zirconium phosphate carrier >=70, ＜ 100%.Wherein, metal includes element
The periodic table period 4-period 6 transition elements.The present invention is using multi-pore channel, cheap phosphate as synthesis third
The carrier of aldehyde, the catalyst of preparation has that long lifespan, glycerol conversion yield be high, propionic aldehyde good selective.
Specifically, in view of the shortcomings of the prior art, the invention provides following technical scheme：
A kind of catalyst suitable for one-step method glycerine propionic aldehyde, it is characterised in that lived including basic zirconium phosphate carrier and metal
Property charcoal loaded article；Wherein, basic zirconium phosphate carrier mass fraction >=70% and ＜ 100% in the catalyst, the metal is lived
Property charcoal loaded article mass fraction in the catalyst be ＞ 0 and≤30%；
Wherein, by being obtained after activated carbon supported metal, the metallic element is selected from transition to the metallic absorbent charcoal loaded article
Metallic element.
Preferably, in above-mentioned catalyst, the metallic absorbent charcoal loaded article is immersed in metal salt solution by by activated carbon
Obtain.
Preferably, in above-mentioned catalyst, the metallic absorbent charcoal loaded article accounts for the 10-30% of basic zirconium phosphate carrier quality, excellent
Elect 15-30% as.
Preferably, in above-mentioned catalyst, the specific surface area of the basic zirconium phosphate carrier is 40-120m2/ g, preferably 50-
80m2/g。
Preferably, in above-mentioned catalyst, the pore volume of the basic zirconium phosphate carrier is 0.1-0.2cm3/ g, average pore size isPreferably
Preferably, in above-mentioned catalyst, metallic element accounts for the 0-2wt% of basic zirconium phosphate carrier quality, preferably 0.5%-
2%, more preferably 0.75-1.5%.
Preferably, in above-mentioned catalyst, mass fraction of the metallic element in metallic absorbent charcoal loaded article is 2-
7%.
Preferably, in above-mentioned catalyst, the metallic element be selected from titanium, chromium, manganese, cobalt, nickel, copper, zinc, molybdenum, ruthenium, rhodium, palladium,
Tungsten, rhenium or platinum, preferably palladium, copper, ruthenium or platinum.
Preferably, in above-mentioned catalyst, the specific surface area of the activated carbon is 500-1000m2/g。
The present invention also provides a kind of preparation method of the catalyst suitable for one-step method propionic aldehyde, it is characterised in that including
Following step：
(1) by activated carbon and metal salt solution hybrid infusion, the activated carbon of metal has been loaded；
(2) after the activated carbon of carried metal is mixed as metallic absorbent charcoal loaded article with zirconium salt solution, phosphate is added
Solution, is calcined at 250-450 DEG C, obtains the catalyst.
Preferably, in above-mentioned preparation method, the phosphate is selected from ammonium dihydrogen phosphate, and the zirconates is selected from basic zirconium chloride,
The slaine is selected from titanium chloride, chromium chloride, manganese chloride, cobalt chloride, nickel chloride, copper chloride, zinc chloride, molybdenum chloride, tri-chlorination
Ruthenium, radium chloride, palladium bichloride, tungsten chloride, chlorination rhenium or chloroplatinic acid.
Preferably, in above-mentioned preparation method, the mol ratio of the phosphate and zirconates is (4-6)：3.
Preferably, in above-mentioned preparation method, the metallic absorbent charcoal loaded article is (0.02-0.1) with the mass ratio of zirconates：
1。
Preferably, in above-mentioned preparation method, addition of the slaine in activated carbon is 0-2wt%, preferably
0.5%-2%, more preferably 0.75-1.5%.
The present invention also provides a kind of catalyst suitable for one-step method glycerine propionic aldehyde, it is characterised in that by above-mentioned preparation
Method is prepared.
The present invention also provides the method that one-step method glycerine prepares propionic aldehyde, it is characterised in that using above-mentioned catalyst, including under
State step：
Catalyst is placed in reactor, reactant glycerine and hydrogen is passed through, starts reaction until reaction terminates；
Wherein, for every gram of catalyst, glycerol concentration is 1-30wt%, and glycerine flow is 0.01-0.1ml/min, hydrogen
Flow is 40-80ml/min, preferably 55-65ml/min.
Preferably, in the above method, the reaction temperature is 200-300 DEG C, and preferably 240-280 DEG C, reaction pressure is
1.0-3.0MPa, preferably 1.8-2.2MPa.
Preferably, in the above method, the glycerol concentration is 1-30wt%, preferably 5-20wt%.
Preferably, in the above method, the glycerine flow is 0.02-0.06ml/min.
The present invention also provides a kind of propionic aldehyde, it is characterised in that prepared by the above method.
The present invention also provides above-mentioned catalyst, or above-mentioned propionic aldehyde in the application of chemical field.
The beneficial effects of the invention are as follows：With stable chemical nature, specific surface area is big, cheap and good heat-transfer phosphorus
Used as carrier, the catalyst of preparation has the advantages that catalysis activity is high, propionic aldehyde selectively good and catalyst life is long to sour zirconium.
Specific embodiment
In view of process economy and efficiency that current two-step method glycerine prepares propionic aldehyde all have much room for improvement, the present invention provides a kind of
Catalyst and its preparation method and the application of propionic aldehyde are prepared suitable for one-step method glycerine.
It is a kind of preferred embodiment in, the present invention is under certain condition by activated carbon supported noble metal loading in height
In specific surface area basic zirconium phosphate duct, i.e. can obtain glycerine prepares propionic aldehyde catalyst after roasting.Evaluating catalyst experiment is solid
Completed on fixed bed reactor, the qualitative and quantitative result of gas component is completed by gas-chromatography.
In present embodiment, catalyst weight percent composition is：
Metal 0-2% activated carbons ＞ 0 ,≤28%, high-specific surface area basic zirconium phosphate carrier >=70, ＜ 100%.
In present embodiment, method for preparing catalyst is：
(1) by metal salt solution and activated carbon hybrid infusion, the activated carbon of metal, wherein metal quality hundred have been loaded
Divide than being 5%；
(2) activated carbon that will load metal mixes under agitation as metallic absorbent charcoal loaded article with zirconium salt solution
The suspension of system, wherein metallic absorbent charcoal load mass percentage are 0-30%；
(3) under agitation to phosphate solution is added dropwise in step (2) gained suspension, until precipitation is abundant；
(4) gained precipitation is stood overnight, is dried 12 hours at 100 DEG C using baking oven, be put into Muffle furnace with 250 DEG C of roastings
Burn 2 hours.Take out broken compressing tablet sieving, you can glycerine propionic aldehyde catalyst is obtained.
As described above, the metal includes the periodic table of elements period 4 to the period 6, the 3rd subgroup to the second subgroup.
The use condition of catalyst of the present invention is 240-280 DEG C of reaction temperature, reaction pressure 1.0-3.0MPa, hydrogen flowing quantity
It is 40-80ml/min.
In another preferred embodiment, the present invention provides a kind of glycerine propionic aldehyde catalyst, it is characterised in that urge
Agent percentage by weight is：
Metal 0-1.5%；Its preferred scope is：Metal 1-1.5%；
Preferably, above-mentioned metal includes the transition elements of four to period 6.
Preferably, above-mentioned basic zirconium phosphate carrier is high-specific surface area basic zirconium phosphate.
Preferably, comprise the following steps when high-specific surface area basic zirconium phosphate is as carrier：
Phosphate solution and zirconium salt solution are prepared, phosphate solution is dropwise added drop-wise in zirconium salt solution with dropping funel.
After precipitation is complete, stand overnight.Suction filtration is washed again, drying in baking oven is put into, and is subsequently placed into Muffle kiln roasting, you can obtain height
Specific surface area basic zirconium phosphate.Metal salt solution, steeped overnight are added in gained basic zirconium phosphate.Muffle kiln roasting is put into afterwards, i.e.,
Can obtain the glycerine propionic aldehyde catalyst that content of metal is 0-30%.
The use condition of above-mentioned glycerine propionic aldehyde catalyst be 240-280 DEG C of reaction temperature, reaction pressure 1.0-3.0MPa,
Hydrogen flowing quantity is 40-80ml/min.
The catalysis suitable for one-step method glycerine formaldehyde of the present invention is further illustrated below by specific embodiment
Agent and its preparation method and application.
In the following embodiments, agents useful for same and facility information are as follows：
The experiment material of table 1 and reagent
Laboratory apparatus used by the embodiment of table 2
Embodiment one is applied to the preparation of the catalyst of one-step method glycerine propionic aldehyde
Embodiment 1.1
Take 7.36g ammonium dihydrogen phosphates to be dissolved in 64ml distilled water, be configured to 1mol/L ammonium dihydrogen phosphates；Claim
10.31g basic zirconium chlorides are dissolved in 32ml distilled water, are configured to 1mol/L zirconium oxychloride solutions.5g activated carbons and 250mL are taken,
The palladium chloride solution of 1g/L is mixed with suspension.80 DEG C of drying overnight, obtain palladium carbon.Claim the palladium carbon dissolving that 0.399g is prepared
Unit for uniform suspension is prepared under agitation in 23ml zirconium oxychloride solutions.Again will with the speed of per second one drop with dropping funel
64ml ammonium dihydrogen phosphates are dropwise added drop-wise in palladium carbon suspension.Stood overnight after precipitation is complete.It is put into baking oven with 100 DEG C
Drying 12 hours, is placed into Muffle furnace and is calcined 2 hours with 250 DEG C, you can palladium load capacity 0.75%, basic zirconium phosphate carrier matter is obtained
Amount percentage is 85% glycerine propionic aldehyde catalyst.Because metallic absorbent charcoal loaded article accounts for obtained basic zirconium phosphate quality
15%, and activated carbon supported metal accounts for the 5% of its quality.So content of metal is 0.75wt%.
The gained catalyst of embodiment 1.1 is examined in a nitrogen environment at -195.8 DEG C with BET specific surface area tester
Survey, testing result is：The specific surface area of the basic zirconium phosphate is 52.0249m2/ g, pore volume is 0.1336cm3/ g, aperture is
Embodiment 1.2
Take 7.36g ammonium dihydrogen phosphates to be dissolved in 64ml distilled water, be configured to 1mol/L ammonium dihydrogen phosphates；Claim
10.31g basic zirconium chlorides are dissolved in 32ml distilled water, are configured to 1mol/L zirconium oxychloride solutions.5g activated carbons and 250mL are taken,
The palladium chloride solution of 1g/L is mixed with suspension.80 DEG C of drying overnight, obtain palladium carbon.Claim the palladium carbon dissolving that 0.798g is prepared
Unit for uniform suspension is prepared under agitation in 32ml zirconium oxychloride solutions.Again will with the speed of per second one drop with dropping funel
64ml ammonium dihydrogen phosphates are dropwise added drop-wise in palladium carbon suspension.Stood overnight after precipitation is complete.It is put into baking oven with 100 DEG C
Drying 12 hours, is placed into Muffle furnace and is calcined 2 hours with 250 DEG C, you can palladium load capacity 1.5%, basic zirconium phosphate carrier matter is obtained
Amount percentage is 70% glycerine propionic aldehyde catalyst.Because metallic absorbent charcoal loaded article accounts for obtained basic zirconium phosphate quality
30%, and activated carbon supported metal accounts for the 5% of its quality.So content of metal is 1.5wt%.
The gained catalyst of embodiment 1.1 is examined in a nitrogen environment at -195.8 DEG C with BET specific surface area tester
Survey, testing result is：The specific surface area of the basic zirconium phosphate is 54.1019m2/ g, pore volume is 0.1459cm3/ g, aperture is
Embodiment 1.3
Take 7.36g ammonium dihydrogen phosphates to be dissolved in 64ml distilled water, be configured to 1mol/L ammonium dihydrogen phosphates；Claim
10.31g basic zirconium chlorides are dissolved in 32ml distilled water, are configured to 1mol/L zirconium oxychloride solutions.5g activated carbons and 250mL are taken,
The solution of ruthenium trichloride of 1g/L is mixed with suspension.80 DEG C of drying overnight, obtain ruthenium carbon.The ruthenium carbon for claiming 0.798g to prepare is molten
Solution prepares unit for uniform suspension under agitation in 32ml zirconium oxychloride solutions.Again with dropping funel with the speed of per second one drop
64ml ammonium dihydrogen phosphates are dropwise added drop-wise in ruthenium carbon suspension liquid.Stood overnight after precipitation is complete.It is put into baking oven with 100
DEG C drying 12 hours, is placed into Muffle furnace and is calcined 2 hours with 350 DEG C, you can ruthenium load capacity 1.5%, basic zirconium phosphate carrier is obtained
Mass percent is 70% glycerine propionic aldehyde catalyst.Because metallic absorbent charcoal loaded article accounts for obtained basic zirconium phosphate quality
30%, and activated carbon supported metal accounts for the 5% of its quality.So content of metal is 1.5wt%.
The gained catalyst of embodiment 1.1 is examined in a nitrogen environment at -195.8 DEG C with BET specific surface area tester
Survey, testing result is：The specific surface area of the basic zirconium phosphate is 58.3765m2/ g, pore volume is 0.1143cm3/ g, aperture is
Embodiment 1.4
Take 7.36g ammonium dihydrogen phosphates to be dissolved in 64ml distilled water, be configured to 1mol/L ammonium dihydrogen phosphates；Claim
10.31g basic zirconium chlorides are dissolved in 32ml distilled water, are configured to 1mol/L zirconium oxychloride solutions.5g activated carbons and 250mL are taken,
The platinum acid chloride solution of 1g/L is mixed with suspension.80 DEG C of drying overnight, obtain platinum carbon.Claim the platinum carbon dissolving that 0.266g is prepared
Unit for uniform suspension is prepared under agitation in 32ml zirconium oxychloride solutions.Again will with the speed of per second one drop with dropping funel
64ml ammonium dihydrogen phosphates are dropwise added drop-wise in platinum carbon suspension.Stood overnight after precipitation is complete.It is put into baking oven with 100 DEG C
Drying 12 hours, is placed into Muffle furnace and is calcined 2 hours with 450 DEG C, you can platinum load capacity 0.5%, basic zirconium phosphate carrier matter is obtained
Amount percentage is 90% glycerine propionic aldehyde catalyst.Because metallic absorbent charcoal loaded article accounts for obtained basic zirconium phosphate quality
10%, and activated carbon supported metal accounts for the 5% of its quality.So content of metal is 0.5wt%.
The gained catalyst of embodiment 1.1 is examined in a nitrogen environment at -195.8 DEG C with BET specific surface area tester
Survey, testing result is：The specific surface area of the basic zirconium phosphate is 50.2893m2/ g, pore volume is 0.1544cm3/ g, aperture is
Embodiment 1.5
Take 7.36g ammonium dihydrogen phosphates to be dissolved in 64ml distilled water, be configured to 1mol/L ammonium dihydrogen phosphates；Claim
10.31g basic zirconium chlorides are dissolved in 32ml distilled water, are configured to 1mol/L zirconium oxychloride solutions.5g activated carbons and 250mL are taken,
The copper chloride solution of 1g/L is mixed with suspension.80 DEG C of drying overnight, obtain copper carbon.The copper carbon dissolution for claiming 0.266g to prepare
Unit for uniform suspension is prepared under agitation in 32ml zirconium oxychloride solutions.Again will with the speed of per second one drop with dropping funel
64ml ammonium dihydrogen phosphates are dropwise added drop-wise in platinum carbon suspension.Stood overnight after precipitation is complete.It is put into baking oven with 100 DEG C
Drying 12 hours, is placed into Muffle furnace and is calcined 2 hours with 450 DEG C, you can copper load capacity 0.5%, basic zirconium phosphate carrier matter is obtained
Amount percentage is 90% glycerine propionic aldehyde catalyst.Because metallic absorbent charcoal loaded article accounts for obtained basic zirconium phosphate quality
10%, and activated carbon supported metal accounts for the 5% of its quality.So content of metal is 0.5wt%.
The gained catalyst of embodiment 1.1 is examined in a nitrogen environment at -195.8 DEG C with BET specific surface area tester
Survey, testing result is：The specific surface area of the basic zirconium phosphate is 48.1520m2/ g, pore volume is 0.1329cm3/ g, aperture is
Embodiment 1.6
Claim 7.36g ammonium dihydrogen phosphates to be dissolved in 64ml distilled water, be configured to 1mol/L ammonium dihydrogen phosphates；Claim
10.31g basic zirconium chlorides are dissolved in 32ml distilled water, are configured to 1mol/L zirconium oxychloride solutions.With dropping funel by di(2-ethylhexyl)phosphate
Hydrogen ammonium salt solution is dropwise added drop-wise in zirconium oxychloride solution with the speed of per second one drop, and opens stirring.After precipitation is complete, it is heavy to stand
Form sediment overnight.Suction filtration is washed again, is put into baking oven and is dried 12 hours with 100 DEG C, add the activated carbon that mass fraction is 10%.Put again
Enter in Muffle furnace and be calcined 2 hours with 250 DEG C, you can it is 0% to obtain content of metal, and basic zirconium phosphate carrier quality percentage is
100% glycerine propionic aldehyde catalyst.
The gained catalyst of embodiment 1.1, detection knot are detected under -195.8 DEG C of nitrogen environments with BET specific surface area tester
It is really：The specific surface area of the basic zirconium phosphate is 70.0273m2/ g, pore volume is 0.1472cm3/ g, aperture is
Embodiment 1.7
Claim 7.36g ammonium dihydrogen phosphates to be dissolved in 64ml distilled water, be configured to 1mol/L ammonium dihydrogen phosphates；Claim
10.31g basic zirconium chlorides are dissolved in 32ml distilled water, are configured to 1mol/L zirconium oxychloride solutions.With dropping funel by di(2-ethylhexyl)phosphate
Hydrogen ammonium salt solution is dropwise added drop-wise in zirconium oxychloride solution with the speed of per second one drop, and opens stirring.After precipitation is complete, it is heavy to stand
Form sediment overnight.Suction filtration is washed again, is put into baking oven and is dried 12 hours with 100 DEG C, place into Muffle furnace and be calcined 2 hours with 250 DEG C,
Can obtain high-specific surface area basic zirconium phosphate.26ml1g/L chloroplatinic acids are added in basic zirconium phosphate obtained by 2.66g, was impregnated at 45 DEG C
Night.It is put into afterwards in Muffle furnace and is calcined 2 hours with 250 DEG C, you can obtains the glycerine propionic aldehyde that platinum load capacity is 1wt% and be catalyzed
Agent.It is the 1% of gained basic zirconium phosphate carrier quality 2.66g because the quality for adding metal salt solution is 0.026g, so metal is negative
Carrying capacity is 1wt%.
The gained catalyst of embodiment 1.1 is examined in a nitrogen environment at -195.8 DEG C with BET specific surface area tester
Survey, testing result is：The specific surface area of the basic zirconium phosphate is 40.9498m2/ g, pore volume is 0.1106cm3/ g, aperture is
The one-step method glycerine of embodiment two prepares propionic aldehyde
Embodiment 2.1
Using catalyst obtained in embodiment 1.1, propionic aldehyde is prepared with one-step method, detailed process is as follows：
(1) 1.0g catalyst is put into reactor, is passed through glycerite and hydrogen, use quality fraction is 15wt%'s
Glycerite, the flow of reactant glycerine is 0.04ml/min, and hydrogen flowing quantity is 60ml/min.2 are reacted at 2MPa, 260 DEG C
Hour.
(2) products therefrom is detected that it is 90.99% to obtain glycerol conversion yield, and propionic aldehyde is received using Agilent gas-chromatography
Rate is 67.47%.
Wherein, the detection method of glycerol conversion yield and propionic aldehyde yield is：
(1) propionic aldehyde yield
Detection process：Reacted liquid product is collected using beaker, after filtering, 1 microlitre is extracted in gas phase with sample introduction needle
Detected in chromatogram, the data such as record appearance time, peak area.
Computational methods：Propionic aldehyde selectivity=[(propionic aldehyde molal quantity)/(all product molar numbers)] * 100%
(2) glycerol conversion yield
Detection process：Reacted liquid product is collected using beaker, after filtering, 1 microlitre is extracted in gas phase with sample introduction needle
Detected in chromatogram, the data such as record appearance time, peak area.
Computational methods：Glycerol conversion yield=[(enter reactor amounts of glycerol-go out reactor amounts of glycerol)/enter reactor glycerine
Amount] * 100%
Embodiment 2.2
Using catalyst obtained in embodiment 1.2, propionic aldehyde is prepared with one-step method, detailed process is as follows：
(1) 1.0g catalyst is put into reactor, is passed through glycerite and hydrogen, use quality fraction is 5wt%'s
Glycerite, reactant flow is 0.04ml/min, and hydrogen flowing quantity is 55ml/min.Reacted 2 hours at 2MPa, 250 DEG C.
(2) products therefrom is detected that it is 84.23% to obtain glycerol conversion yield, and propionic aldehyde is received using Agilent gas-chromatography
Rate is 73.54%.
Embodiment 2.3
Using catalyst obtained in embodiment 1.3, propionic aldehyde is prepared with one-step method, detailed process is as follows：
(1) 1.0g catalyst is put into reactor, is passed through glycerite and hydrogen, use quality fraction is 15wt%'s
Glycerite, reactant flow is 0.04ml/min, and hydrogen flowing quantity is 60ml/min.Reacted 2 hours at 2MPa, 260 DEG C.
(2) products therefrom is detected that it is 68.12% to obtain glycerol conversion yield, and propionic aldehyde is received using Agilent gas-chromatography
Rate is 57.33%.
Embodiment 2.4
Using catalyst obtained in embodiment 1.4, propionic aldehyde is prepared with one-step method, detailed process is as follows：
(1) 1.0g catalyst is put into reactor, is passed through glycerite and hydrogen, use quality fraction is 15wt%'s
Glycerite, reactant flow is 0.04ml/min, and hydrogen flowing quantity is 60ml/min.Reacted 2 hours at 2MPa, 260 DEG C.
(2) products therefrom is detected that it is 60.48% to obtain glycerol conversion yield, and propionic aldehyde is received using Agilent gas-chromatography
Rate is 52.20%.
Embodiment 2.5
Using catalyst obtained in embodiment 1.5, propionic aldehyde is prepared with one-step method, detailed process is as follows：
(1) 1.0g catalyst is put into reactor, is passed through glycerite and hydrogen, use quality fraction is 15wt%'s
Glycerite, reactant flow is 0.04ml/min, and hydrogen flowing quantity is 60ml/min.Reacted 2 hours at 2MPa, 260 DEG C.
(2) products therefrom is detected that it is 51.85% to obtain glycerol conversion yield, and propionic aldehyde is received using Agilent gas-chromatography
Rate is 45.28%.
Embodiment 2.6
Using catalyst obtained in embodiment 1.6, propionic aldehyde is prepared with one-step method, detailed process is as follows：
(1) 1.0g catalyst is put into reactor, is passed through glycerite and hydrogen, concentration be 15% glycerine it is molten
Liquid, reactant flow is 0.04ml/min, and hydrogen flowing quantity is 60ml/min.Reacted 2 hours at 2MPa, 260 DEG C.
(2) products therefrom is detected that it is 97.77% to obtain glycerol conversion yield, and propionic aldehyde is received using Agilent gas-chromatography
Rate is 5.34%.
Embodiment 2.7
Using catalyst obtained in embodiment 1.7, propionic aldehyde is prepared with one-step method, detailed process is as follows：
(1) 1.0g catalyst is put into reactor, is passed through glycerite and hydrogen, use quality fraction is 15wt%'s
Glycerite, reactant flow is 0.04ml/min, and hydrogen flowing quantity is 60ml/min.Reacted 2 hours at 2MPa, 260 DEG C.
(2) products therefrom is detected that it is 50.09% to obtain glycerol conversion yield, and propionic aldehyde is received using Agilent gas-chromatography
Rate is 41.33%.
Comparative example 1
The comparative example 1 is similar with embodiment 1.1, differs only in, and metallic absorbent charcoal loaded article addition is 1.33g,
Account for the 50% of gained basic zirconium phosphate carrier quality.
The identical method of gained catalyst embodiment 2.1 is prepared into propionic aldehyde, gained glycerol conversion yield is 37.04%, third
Aldehyde yield is 14.82%.
Comparative example 2
The comparative example 2 is similar with embodiment 1.1, differs only in, and the sintering temperature in Muffle furnace is 600 DEG C.Will
The identical method of gained catalyst embodiment 2.1 prepares propionic aldehyde, and gained glycerol conversion yield is 30.81%, and propionic aldehyde yield is
7.51%.
In sum, catalyst of the present invention is applied to the synthesis technique that one-step method glycerine prepares propionic aldehyde, and catalyst is urged
Change activity height, long lifespan, propionic aldehyde is selectively good, is with a wide range of applications.
Claims (15)
1. a kind of catalyst suitable for one-step method glycerine propionic aldehyde, it is characterised in that including basic zirconium phosphate carrier and metal active
Charcoal loaded article；Wherein, basic zirconium phosphate carrier mass fraction >=70% and ＜ 100% in the catalyst, the metal active
Charcoal loaded article mass fraction in the catalyst is ＞ 0 and≤30%；
Wherein, by being obtained after activated carbon supported metal, the metallic element is selected from transition metal to the metallic absorbent charcoal loaded article
Element.
2. catalyst according to claim 1, wherein, the metallic absorbent charcoal loaded article accounts for the 10- of basic zirconium phosphate carrier quality
30%, preferably 15-30%.
3. catalyst according to claim 1 or claim 2, wherein, the specific surface area of the basic zirconium phosphate is 40-120m2/ g, preferably
50-80m2/g。
4. the catalyst according to right any one of 1-3, wherein, the metallic element accounts for the 0-2wt% of basic zirconium phosphate carrier quality,
Preferably 0.5%-2%, more preferably 0.75-1.5%.
5. the catalyst according to claim any one of 1-4, wherein, the metallic element is in metallic absorbent charcoal loaded article
Mass fraction is 2-7%.
6. the catalyst according to claim any one of 1-5, wherein, the metallic element be selected from titanium, chromium, manganese, cobalt, nickel, copper,
Zinc, molybdenum, ruthenium, rhodium, palladium, tungsten, rhenium or platinum, preferably palladium, copper, ruthenium or platinum.
7. the preparation method of a kind of catalyst suitable for one-step method propionic aldehyde, it is characterised in that comprise the steps：
(1) by activated carbon and metal salt solution hybrid infusion, the activated carbon of metal has been loaded；
(2) will load metal activated carbon mix with zirconium salt solution as metallic absorbent charcoal loaded article after, add phosphate it is molten
Liquid, is calcined at 250-450 DEG C, obtains the catalyst.
8. preparation method according to claim 7, wherein, the phosphate is selected from ammonium dihydrogen phosphate, and the zirconates is selected from
Basic zirconium chloride, the slaine is selected from titanium chloride, chromium chloride, manganese chloride, cobalt chloride, nickel chloride, copper chloride, zinc chloride, chlorination
Molybdenum, ruthenium trichloride, radium chloride, palladium bichloride, tungsten chloride, chlorination rhenium or chloroplatinic acid.
9. the preparation method according to claim 7 or 8, wherein, the mol ratio of the phosphate and zirconates is (4-6)：3.
10. the preparation method according to claim any one of 7-9, wherein, the metallic absorbent charcoal loaded article and zirconates
Mass ratio is (0.02-0.1)：1.
11. preparation method according to claim any one of 7-10, wherein, addition of the slaine in activated carbon
It is 0-2wt%, preferably 0.5%-2%, more preferably 0.75-1.5%.
The method that 12. one-step method glycerine prepare propionic aldehyde, it is characterised in that catalyst, bag described in usage right requirement any one of 1-6
Include following step：
Catalyst is placed in reactor, reactant glycerine and hydrogen is passed through, starts reaction until reaction terminates；
Wherein, for every gram of catalyst, glycerol concentration is 1-30wt%, and glycerine flow is 0.01-0.1ml/min, hydrogen flowing quantity
It is 40-80ml/min.
13. methods according to claim 12, wherein, the reaction temperature is 200-300 DEG C, and reaction pressure is 1.0-
3.0MPa。
14. a kind of propionic aldehyde, it is characterised in that prepared by the methods described of claim 12 or 13.
Catalyst described in 15. claim any one of 1-6, or propionic aldehyde described in claim 14 is in the application of chemical field.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108855158A (en) * | 2018-05-31 | 2018-11-23 | 华东理工大学 | A kind of preparation method and application of cobalt-ruthenium bimetallic heterogeneous catalyst |
| CN109261179A (en) * | 2018-10-09 | 2019-01-25 | 宁波蒙曼生物科技有限公司 | A kind of methanol gasoline catalyst and its preparation method and application |
| CN116943710A (en) * | 2023-09-19 | 2023-10-27 | 山东新和成药业有限公司 | Metal supported catalyst, preparation method and application thereof in Diels-Alder reaction |
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| CN104368368A (en) * | 2014-09-25 | 2015-02-25 | 华东理工大学 | Zirconium phosphate catalyst and its application in preparation of acrolein through glycerin dehydration |
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| CN104368368A (en) * | 2014-09-25 | 2015-02-25 | 华东理工大学 | Zirconium phosphate catalyst and its application in preparation of acrolein through glycerin dehydration |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108855158A (en) * | 2018-05-31 | 2018-11-23 | 华东理工大学 | A kind of preparation method and application of cobalt-ruthenium bimetallic heterogeneous catalyst |
| CN108855158B (en) * | 2018-05-31 | 2021-02-12 | 华东理工大学 | Preparation method and application of cobalt-ruthenium bimetallic heterogeneous catalyst |
| CN109261179A (en) * | 2018-10-09 | 2019-01-25 | 宁波蒙曼生物科技有限公司 | A kind of methanol gasoline catalyst and its preparation method and application |
| CN116943710A (en) * | 2023-09-19 | 2023-10-27 | 山东新和成药业有限公司 | Metal supported catalyst, preparation method and application thereof in Diels-Alder reaction |
| CN116943710B (en) * | 2023-09-19 | 2023-12-05 | 山东新和成药业有限公司 | Metal supported catalyst, preparation method and application thereof in Diels-Alder reaction |
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