CN114054056A - Hydroisomerization bifunctional catalyst, and preparation method and application thereof - Google Patents
Hydroisomerization bifunctional catalyst, and preparation method and application thereof Download PDFInfo
- Publication number
- CN114054056A CN114054056A CN202010753303.6A CN202010753303A CN114054056A CN 114054056 A CN114054056 A CN 114054056A CN 202010753303 A CN202010753303 A CN 202010753303A CN 114054056 A CN114054056 A CN 114054056A
- Authority
- CN
- China
- Prior art keywords
- noble metal
- hydroisomerization
- niobium
- zirconium
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 86
- ZHYBKPCYWAZTHU-UHFFFAOYSA-E niobium(5+) zirconium(4+) triphosphate Chemical compound [Zr+4].P(=O)([O-])([O-])[O-].[Nb+5].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-] ZHYBKPCYWAZTHU-UHFFFAOYSA-E 0.000 claims abstract description 40
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- 150000001336 alkenes Chemical class 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 64
- 239000000243 solution Substances 0.000 claims description 29
- 239000002243 precursor Substances 0.000 claims description 28
- 229910052763 palladium Inorganic materials 0.000 claims description 27
- 229910052697 platinum Inorganic materials 0.000 claims description 27
- 229920005862 polyol Polymers 0.000 claims description 25
- 150000003077 polyols Chemical class 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 22
- 229910052726 zirconium Inorganic materials 0.000 claims description 22
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 20
- 239000010955 niobium Substances 0.000 claims description 18
- 150000007942 carboxylates Chemical class 0.000 claims description 17
- 238000005470 impregnation Methods 0.000 claims description 17
- 229910052758 niobium Inorganic materials 0.000 claims description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims description 15
- 239000011574 phosphorus Substances 0.000 claims description 15
- LPSXSORODABQKT-FIRGSJFUSA-N exo-trimethylenenorbornane Chemical compound C([C@@H]1C2)C[C@@H]2[C@@H]2[C@H]1CCC2 LPSXSORODABQKT-FIRGSJFUSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 7
- 239000011343 solid material Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000002955 isolation Methods 0.000 claims description 5
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 3
- ZFQCFWRSIBGRFL-UHFFFAOYSA-B 2-hydroxypropane-1,2,3-tricarboxylate;zirconium(4+) Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O ZFQCFWRSIBGRFL-UHFFFAOYSA-B 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- UFDQEJWXJCPYSX-UHFFFAOYSA-I S(=O)(=O)([O-])[O-].[NH4+].[Nb+5].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-] Chemical compound S(=O)(=O)([O-])[O-].[NH4+].[Nb+5].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-] UFDQEJWXJCPYSX-UHFFFAOYSA-I 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 2
- KUJRRRAEVBRSIW-UHFFFAOYSA-N niobium(5+) pentanitrate Chemical compound [Nb+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUJRRRAEVBRSIW-UHFFFAOYSA-N 0.000 claims description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 2
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 2
- TVCBSVKTTHLKQC-UHFFFAOYSA-M propanoate;zirconium(4+) Chemical compound [Zr+4].CCC([O-])=O TVCBSVKTTHLKQC-UHFFFAOYSA-M 0.000 claims description 2
- 238000003980 solgel method Methods 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 150000001734 carboxylic acid salts Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 25
- 238000006317 isomerization reaction Methods 0.000 abstract description 14
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 38
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 36
- 229910021126 PdPt Inorganic materials 0.000 description 13
- 239000002253 acid Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000011068 loading method Methods 0.000 description 12
- LPSXSORODABQKT-UHFFFAOYSA-N tetrahydrodicyclopentadiene Chemical compound C1C2CCC1C1C2CCC1 LPSXSORODABQKT-UHFFFAOYSA-N 0.000 description 12
- CNHRNMLCYGFITG-UHFFFAOYSA-A niobium(5+);pentaphosphate Chemical compound [Nb+5].[Nb+5].[Nb+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O CNHRNMLCYGFITG-UHFFFAOYSA-A 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000003921 oil Substances 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 7
- 238000010304 firing Methods 0.000 description 7
- 239000000446 fuel Substances 0.000 description 7
- 230000001965 increasing effect Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 6
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 101000805129 Homo sapiens Protein DPCD Proteins 0.000 description 5
- 102100037836 Protein DPCD Human genes 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000001177 diphosphate Substances 0.000 description 4
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 4
- 235000011180 diphosphates Nutrition 0.000 description 4
- -1 for example Chemical compound 0.000 description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000001632 sodium acetate Substances 0.000 description 4
- 235000017281 sodium acetate Nutrition 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- LPSXSORODABQKT-YNFQOJQRSA-N (3ar,4r,7s,7as)-rel-octahydro-1h-4,7-methanoindene Chemical compound C([C@H]1C2)C[C@H]2[C@@H]2[C@H]1CCC2 LPSXSORODABQKT-YNFQOJQRSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052762 osmium Inorganic materials 0.000 description 3
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 108091007643 Phosphate carriers Proteins 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- CTUFHBVSYAEMLM-UHFFFAOYSA-N acetic acid;platinum Chemical compound [Pt].CC(O)=O.CC(O)=O CTUFHBVSYAEMLM-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000010813 internal standard method Methods 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 2
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 2
- 238000004917 polyol method Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 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 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- 229910003158 γ-Al2O3 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
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
-
- B01J35/60—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/13—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation with simultaneous isomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/09—Geometrical isomers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/14—Phosphorus; Compounds thereof
- C07C2527/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2527/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/58—Ring systems containing bridged rings containing three rings
- C07C2603/60—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members
- C07C2603/66—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members containing five-membered rings
- C07C2603/68—Dicyclopentadienes; Hydrogenated dicyclopentadienes
Abstract
The invention relates to the field of olefin hydroisomerization catalysts, and discloses a hydroisomerization bifunctional catalyst, and a preparation method and application thereof. The catalyst comprises a carrier and a metal active component loaded on the carrier; wherein the carrier is mesoporous niobium zirconium phosphate, and the metal active component is noble metal. The hydroisomerization bifunctional catalyst provided by the invention has the functions of hydrogenation and isomerization, can be used for further hydroisomerization of olefin, and has the characteristics of high raw material conversion rate, high product selectivity, high yield and high purity when being used for hydroisomerization of dicyclopentadiene, and in addition, the temperature of the hydroisomerization reaction is mild.
Description
Technical Field
The invention relates to the field of olefin hydroisomerization catalysts, in particular to a hydroisomerization bifunctional catalyst, a preparation method of the hydroisomerization bifunctional catalyst, the hydroisomerization bifunctional catalyst prepared by the preparation method, application of the hydroisomerization bifunctional catalyst in olefin hydroisomerization reaction, and a preparation method of hanging type tetrahydro dicyclopentadiene.
Background
The hanging type tetrahydrodicyclopentadiene (exo-TCD) has higher volumetric heat value and very excellent low-temperature performance, and is an ideal fuel for modern novel hypersonic aircrafts. Since the raw material for producing cyclopentadiene is derived from C5 fraction cyclopentadiene produced in the ethylene cracking process, and it exists in a dimer form in a normal state, the research on the application of cyclopentadiene has focused on the application of dimer dicyclopentadiene (DCPD). At present, the fuel is synthesized into high-density liquid hydrocarbon fuel with the largest dosage, the widest application, better comprehensive performance and lower cost. In the 80's of the 20 th century, it was discovered that exo-TCD had good low temperature properties and could be used either as a fuel alone or as a diluent for high density fuels of high viscosity and high freezing point. At present, the JP-10 fuel widely applied to various missiles is a pure compound exo-TCD, and JP-10 fuel is used for axe sea-based cruise missiles, whale-fork anti-ship missiles and air-launched cruise missiles which are well known in the United states. Exo-TCD can be used as a diluent and a solvent for paint, agricultural chemicals, surfactants, semiconductor cleaning agents and the like, and can also be used as lubricating oil for lubricating and cleaning during cutting and impacting.
A route for preparing endo-TCD from DCPD is also a method adopted in the existing industrial production, namely DCPD is taken as a raw material, endo-tetrahydrodicyclopentadiene (endo-TCD) is firstly prepared by selective hydrogenation, then exo-TCD is obtained by Lewis acid catalytic isomerization, and pure exo-TCD is obtained by separation and purification. The selective hydrogenation of DCPD to obtain tetrahydrodicyclopentadiene mainly adopts metal catalysts, and how to obtain the tetrahydrodicyclopentadiene with high selectivity is one of the keys. Meanwhile, the method is strong for isomerization reaction
Acids such as sulfuric acid, phosphoric acid, polyphosphoric acid, and hydrofluoric acid are active; and for Lewis acids, anhydrous AlCl3The performance is better. The preparation of the exo-tetrahydrodicyclopentadiene by the traditional method needs two production processes of hydrogenation and isomerization.
Chinese patent application CN1101215218, which discloses a method for synthesizing exo-TCD by a gas-phase continuous flow one-step method, designs a two-section coupled tubular continuous flow hydrogenation-isomerization tandem process, wherein a hydrogenation-isomerization catalyst is Ni/gamma-Al2O3The isomerization catalyst is Ni/H beta, the technological parameters are optimized, the DCPD conversion rate reaches 100 percent, and the yield of exo-TCD is more than 70 percent. The method connects the hydrogenation process and the isomerization process in series, but two production processes are still needed, the process is immature, no industrial application exists, and the yield of exo-TCD is yet to be further improved.
Chinese patent application CN107417485 discloses a method for directly preparing exo-tetrahydrodicyclopentadiene from dicyclopentadiene, which adopts a bifunctional catalyst consisting of layered double metal hydroxide and inorganic solid acid to realize the coupling of dicyclopentadiene hydrogenation reaction and isomerization reaction, and continuously prepares exo-tetrahydrodicyclopentadiene by one-step method, but the method still needs to use two catalysts for coupling, and the hydrogenation temperature is high (above 100 ℃).
Disclosure of Invention
The present invention aims to overcome the problems of the prior art and provide a hydroisomerization bifunctional catalyst, a preparation method of the hydroisomerization bifunctional catalyst, the hydroisomerization bifunctional catalyst prepared by the preparation method, the application of the hydroisomerization bifunctional catalyst in the olefin hydroisomerization reaction, and a preparation method of exo-type tetrahydrodicyclopentadiene. The hydroisomerization bifunctional catalyst provided by the invention has the functions of hydrogenation and isomerization, can be used for further hydroisomerization of olefin, and has the characteristics of high raw material conversion rate, high product selectivity, high yield and high purity when being used for hydroisomerization of dicyclopentadiene, and in addition, the temperature of the hydroisomerization reaction is mild.
In order to achieve the above object, the present invention provides, in one aspect, a hydroisomerization bifunctional catalyst comprising a carrier and a metal active component supported on the carrier;
wherein the carrier is mesoporous niobium zirconium phosphate, and the metal active component is noble metal.
In a second aspect, the present invention provides a method for preparing a hydroisomerization bifunctional catalyst, comprising:
(1) first contacting a niobium source, a zirconium source, and a phosphorus source in the presence of an alcohol to form a sol;
(2) aging the sol to form a gel;
(3) sequentially carrying out first drying and first roasting on the gel to obtain the mesoporous niobium zirconium phosphate;
(4-1) impregnating the mesoporous niobium zirconium phosphate with a solution of a precursor containing a noble metal, and sequentially performing second drying and second roasting on the impregnated solid material to obtain the hydroisomerization bifunctional catalyst; or
(4-2) in the presence of polyol and carboxylate, carrying out second contact on a precursor of a noble metal and the mesoporous niobium zirconium phosphate, and drying a contacted solid material to obtain the hydroisomerization bifunctional catalyst.
In a third aspect, the present invention provides a hydroisomerization bifunctional catalyst prepared by the process described above.
In a fourth aspect, the present invention provides the use of a hydroisomerization bifunctional catalyst, as described above, in the hydroisomerization of olefins.
The fifth aspect of the invention provides a preparation method of exo-tetrahydrodicyclopentadiene, which comprises the following steps: under the condition of dicyclopentadiene hydroisomerization, dicyclopentadiene is contacted with the hydroisomerization bifunctional catalyst to obtain the hanging-type tetrahydrodicyclopentadiene.
The invention takes mesoporous niobium zirconium phosphate as a carrier and noble metal as metal active metal to prepare the high-activity and high-stability hydroisomerization bifunctional catalyst, realizes the coupling of DCPD catalytic hydrogenation reaction and isomerization reaction, reduces the reaction temperature (below 100 ℃), improves the yield of the hanging type tetrahydrodicyclopentadiene, greatly improves the stability of the catalyst, can effectively reduce the cost of the catalyst, and has good economic benefit and industrial application prospect. In addition, the catalyst of the present invention is used in hydrogenating and isomerizing dicyclopentadiene to prepare exo-tetrahydro dicyclopentadiene, and the product has purity as high as 98% and needs no further separation and purification.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the present invention provides a hydroisomerization bifunctional catalyst comprising a carrier and a metal active component supported on said carrier; wherein the carrier is mesoporous niobium zirconium phosphate, and the metal active component is noble metal.
According to the present invention, the kind of the noble metal is not particularly limited, and may be, for example, at least one or more of gold, silver, ruthenium, rhodium, palladium, osmium, iridium, and platinum. Preferably, the noble metal is Pd and/or Pt; more preferably, the noble metals are Pd and Pt; more preferably, the molar ratio of Pd to Pt is 2 to 8:1, and may be, for example, 2:1, 2.5:1, 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1, 4.2:1, 4.4:1, 4.6:1, 4.8:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, preferably 3 to 5: 1.
According to a preferred embodiment of the invention, the noble metal is a carboxylate coordinated noble metal, preferably the amount of carboxylate will be in the range of 5 to 25mol for 1mol noble metal.
According to the present invention, the amount of the noble metal supported on the hydroisomerization bifunctional catalyst may be selected within a wide range, and preferably, the amount of the noble metal supported on the total dry weight of the catalyst is 0.1 to 5 wt%, for example, 0.1 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, and preferably, the amount of the noble metal supported is 0.5 to 1 wt%, based on the noble metal element.
According to the present invention, it is preferable that the particle size of the metal active component is 2 to 3 nm.
According to the present invention, preferably, the mesoporous niobium zirconium phosphate is prepared by a sol-gel method using a niobium source, a zirconium source and a phosphorus source as raw materials.
According to a preferred embodiment of the present invention, the method for preparing mesoporous niobium zirconium phosphate comprises:
(1) first contacting a niobium source, a zirconium source, and a phosphorus source in the presence of an alcohol to form a sol;
(2) aging the sol to form a gel;
(3) and sequentially carrying out first drying and first roasting on the gel to obtain the mesoporous niobium zirconium phosphate.
In the step (1)
Preferably, the ratio of the amount of phosphorus to the total amount of niobium and zirconium may be 1 to 3:1, for example, 1:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2:1, 2.2:1, 2.4:1, 2.6:1, 2.8:1, 3:1, preferably 1.4 to 2.5:1, on a molar basis.
Preferably, the ratio of the niobium element to the zirconium element is 1:1.2 to 2.5, for example, 1:1.2, 1:1.4, 1:1.6, 1:1.8, 1:2, 1:2.2, 1: 2.5.
Preferably, the alcohol is a C1-C5 alcohol, and may be, for example, a C1 alcohol, a C2 alcohol, a C3 alcohol, a C4 alcohol, a C5 alcohol, more preferably a C2-C4 alcohol, still more preferably ethanol, for example, absolute ethanol.
Preferably, the alcohol is used in an amount of 2 to 3L, for example, 2L, 2.2L, 2.4L, 2.6L, 2.8L, 3L, relative to 1mol of the total amount of the niobium element and the zirconium element.
Preferably, the method of first contacting comprises: an aqueous solution of a phosphorous source is added to an alcohol solution of a niobium source and a zirconium source. Among them, the rate of addition is preferably 5 to 20mL/h, and may be, for example, 5mL/h, 7mL/h, 10mL/h, 12mL/h, 15mL/h, 18mL/h, or 20mL/h, in order to enable better sol formation.
Specifically, a predetermined amount of niobium source and a predetermined amount of zirconium source are weighed and dissolved in alcohol under stirring in a greenhouse to obtain an alcohol solution of the niobium source and the zirconium source. Then weighing a predetermined amount of the phosphorus source, and dissolving the phosphorus source in deionized water to obtain an aqueous solution of the phosphorus source. And finally, adding the aqueous solution of the phosphorus source into the alcoholic solution of the niobium source and the zirconium source at the adding speed of 5-20mL/h to obtain the sol.
Preferably, the niobium source is selected from at least one of niobium pentachloride, niobium nitrate, ammonium niobium sulfate, and niobium pentoxide.
Preferably, the zirconium source is selected from at least one of zirconium oxychloride, zirconium nitrate, zirconium citrate and zirconium propionate.
Preferably, the phosphorus source is selected from at least one of ammonium dihydrogen phosphate, ammonium phosphate, phosphorus pentoxide, and phosphoric acid.
In the step (2)
According to the present invention, the aging conditions are not particularly limited as long as a gel can be obtained. Preferably, the gel can be obtained by standing and aging for 8-20h at room temperature.
In the step (3)
According to the present invention, the conditions of the first drying are not particularly limited, and a conventional drying method may be employed. Preferably, the drying is carried out at 100-200 ℃ for 10-20 hours.
According to the present invention, the conditions of the first firing are not particularly limited, and a conventional firing method may be employed. Preferably, the calcination is carried out at 300-500 ℃ for 1-6 hours. Wherein the firing may be performed in an atmosphere of air.
According to the present invention, it is also preferable to grind the first dried material before the first firing to obtain a uniform powder.
According to the present invention, preferably, the mesoporous niobium zirconium phosphate has an average pore diameter of 10 to 18 nm. Compared with the mesoporous phosphate carrier which singly uses niobium or zirconium, the mesoporous niobium zirconium phosphate provided by the invention has larger specific surface area (80-120 m)2Per g) and total pore volume (0.15-0.35 cm)3In terms of/g). This is probably because, in the structural unit of ZrNb diphosphate, the P-OH and Nb-OH functions can provide
Acid center, and coordination unsaturation of Nb5+And Zr4+Can be used as Lewis acid center. In addition, the ZrNb diphosphate sample has more
Acid sites, which should be due to the presence of abundant terminal P-OH functional groups on their surface. The mesoporous niobium zirconium phosphate provided by the invention has stronger acid performance.
Wherein the average pore diameter is determined by a nitrogen physical adsorption method.
Wherein, the specific surface area is measured by a nitrogen physical adsorption method.
Wherein, the total pore volume is measured by adopting a nitrogen physical adsorption method.
In a second aspect, the present invention provides a method for preparing a hydroisomerization bifunctional catalyst, comprising:
(1) first contacting a niobium source, a zirconium source, and a phosphorus source in the presence of an alcohol to form a sol;
(2) aging the sol to form a gel;
(3) sequentially carrying out first drying and first roasting on the gel to obtain the mesoporous niobium zirconium phosphate;
(4-1) impregnating the mesoporous niobium zirconium phosphate with a solution of a precursor containing a noble metal, and sequentially performing second drying and second roasting on the impregnated solid material to obtain the hydroisomerization bifunctional catalyst; or
(4-2) in the presence of polyol and carboxylate, carrying out second contact on a precursor of a noble metal and the mesoporous niobium zirconium phosphate, and drying a contacted solid material to obtain the hydroisomerization bifunctional catalyst.
The preparation method of the mesoporous niobium zirconium phosphate is described in detail above, and is not repeated here.
In the step (4-1)
According to the invention, the impregnation is an isovolumetric impregnation or an over-volumetric impregnation, preferably an isovolumetric impregnation.
According to the present invention, preferably, the impregnation method comprises: soaking for 5-20min under ultrasonic condition, and soaking for 20-30h under air isolation condition.
According to the present invention, the impregnation may be normal temperature impregnation.
According to a preferred embodiment of the present invention, the method of impregnation comprises: dissolving a precursor of the noble metal in water (deionized water) to prepare a solution of the precursor containing the noble metal, then dropwise adding the solution of the precursor containing the noble metal into the mesoporous niobium zirconium phosphate by adopting an isometric immersion method, carrying out ultrasonic treatment for 5-20min at room temperature, and then carrying out immersion for 20-30h under the condition of air isolation.
According to the present invention, the kind of the noble metal is not particularly limited, and may be, for example, at least one or more of gold, silver, ruthenium, rhodium, palladium, osmium, iridium, and platinum. Preferably, the noble metal is Pd and/or Pt; more preferably, the noble metal is Pd and Pt, and still more preferably, the respective contents of Pd and Pt in the solution containing the noble metal precursor are such that Pd and Pt are supported on the mesoporous niobium zirconium phosphate at a molar ratio of 2 to 8:1, and may be, for example, 2:1, 2.5:1, 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1, 4.2:1, 4.4:1, 4.6:1, 4.8:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, preferably 3 to 5: 1.
According to the present invention, the solution of the precursor containing the noble metal and the mesoporous niobium zirconium phosphate are preferably used in such amounts that the noble metal is supported at 0.1 to 5% by weight, for example, 0.1% by weight, 0.5% by weight, 1% by weight, 1.5% by weight, 2% by weight, 2.5% by weight, 3% by weight, 3.5% by weight, 4% by weight, 4.5% by weight, 5% by weight, and preferably, at 0.5 to 1% by weight, in terms of the noble metal element, based on the total dry weight of the resulting catalyst.
According to the invention, the precursor of the noble metal may be a conventional compound that can provide the noble metal element, for example, a salt of the noble metal. When the noble metal is Pd, the precursor thereof may be at least one of palladium chloride, palladium nitrate, sodium chloroplatinate, palladium acetate and palladium acetylacetonate, and when the noble metal is Pt, the precursor thereof may be at least one of chloroplatinic acid, sodium chloroplatinate, platinum acetate, platinum acetylacetonate and platinum nitrate.
According to the present invention, the conditions of the second drying are not particularly limited, and a conventional drying method may be employed. Preferably, the drying is carried out at 100-200 ℃ for 10-20 hours.
According to the present invention, the conditions of the second firing are not particularly limited, and a conventional firing method may be employed. Preferably, the calcination is carried out at 300-500 ℃ for 1-6 hours. Wherein the firing may be performed in an atmosphere of air.
According to the invention, before use, the hydroisomerization bifunctional catalyst thus prepared also needs to be subjected to a reduction treatment, which may be a conventional method, for example, a reduction treatment using hydrogen or carbon monoxide.
In the step (4-2)
According to the invention, when the polyalcohol method is used for preparing the hydroisomerization bifunctional catalyst, the polyalcohol can serve as a solvent, and can also serve as a reducing agent due to the reducibility of the contained hydroxyl group, so that the reduction treatment in the later stage of the prepared catalyst can be omitted, and the operation is simpler. And the catalyst is prepared under this process without the use of a surfactant.
According to the present invention, the polyol may be any polyol existing as a liquid at normal temperature and pressure, and may be a diol, a triol, a tetraol, a pentaol, a hexaol, and the like. According to a preferred embodiment of the present invention, the polyol is at least one of a diol, a triol and a tetraol, more preferably ethylene glycol and/or glycerol.
According to the present invention, the carboxylate may be various carboxylates such as conventional ones as long as they can provide a carboxylate. The carboxylate may act as a ligand for the noble metal element, inducing the noble metal to form a sol in the presence of the polyol. Preferably, the carboxylate is sodium carboxylate and/or potassium carboxylate.
In order to further improve the performance of the prepared catalyst, it is preferred that the molar ratio of the carboxylate to the noble metal (calculated as noble metal element) is greater than 5, preferably 5 to 10: 1.
according to the present invention, the method for preparing the sol preferably comprises: adding a carboxylate to a polyol solution containing a precursor of a noble metal and forming a black sol, specifically, may include: a predetermined amount of a precursor solution of a noble metal is weighed and dissolved in a polyol so that the concentration of the noble metal (in terms of noble metal element) is 0.01 to 0.05mol/L, and then a carboxylate is added so that the molar ratio of the carboxylate to the noble metal (in terms of noble metal element) is more than 5 to form a black sol. Wherein, the formation of the black sol can be completed by standing the system at room temperature.
According to the present invention, it is preferable that the conditions of the second contacting include: the contact time is 5-20min under the ultrasonic condition, and then the contact time is 2-3h under the air isolation condition.
Preferably, the second contact manner includes: and contacting the noble metal with mesoporous niobium zirconium phosphate in the form of sol. Wherein the sol can be prepared according to the above method. Specifically, the method may include: a predetermined amount of mesoporous niobium zirconium phosphate was added to the formed black sol to perform the second contact.
According to the present invention, after the second contact is completed, the solid material can be obtained by means of solid-liquid separation (e.g., filtration) and washing.
According to the invention, the drying is preferably carried out under an inert atmosphere. The inert gas may be a nitrogen atmosphere or an argon atmosphere.
According to the present invention, the kind of the noble metal is not particularly limited, and may be, for example, at least one or more of gold, silver, ruthenium, rhodium, palladium, osmium, iridium, and platinum. Preferably, the noble metal is Pd and/or Pt; more preferably, the noble metal is Pd and Pt, and still more preferably, the Pd and Pt are contained in amounts such that the Pd and Pt are supported on the mesoporous niobium zirconium phosphate in a molar ratio of 2 to 8:1, and may be, for example, 2:1, 2.5:1, 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1, 4.2:1, 4.4:1, 4.6:1, 4.8:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, and preferably 3 to 5: 1.
According to the present invention, the precursor of the noble metal and the mesoporous niobium zirconium phosphate are preferably used in such amounts that the noble metal is supported at 0.1 to 5% by weight, for example, 0.1% by weight, 0.5% by weight, 1% by weight, 1.5% by weight, 2% by weight, 2.5% by weight, 3% by weight, 3.5% by weight, 4% by weight, 4.5% by weight, 5% by weight, and preferably, at 0.5 to 1% by weight, in terms of the noble metal element, based on the total dry weight of the resulting catalyst.
According to the invention, the precursor of the noble metal may be a conventional compound that can provide the noble metal element, for example, a salt of the noble metal. When the noble metal is Pd, the precursor thereof may be at least one of palladium chloride, palladium nitrate, sodium chloroplatinate, palladium acetate and palladium acetylacetonate, and when the noble metal is Pt, the precursor thereof may be at least one of chloroplatinic acid, sodium chloroplatinate, platinum acetate, platinum acetylacetonate and platinum nitrate.
According to a preferred embodiment of the present invention, the noble metal is Pd and Pt, and before adding the carboxylate to the polyol solution containing the precursor of the noble metal, an alkaline substance is added to treat the Pd and Pt to form a bimetallic complex.
Wherein, the alkaline substance can be strong alkaline substances such as sodium hydroxide, potassium hydroxide and the like.
Among them, it is preferable that the basic substance is used in an amount of 2 to 10mol with respect to 1mol of the total amount of Pd and Pt.
Among them, the time for the treatment of the alkaline substance may be preferably 4 to 8 hours.
According to the present invention, the noble metal component of the catalyst prepared by the polyol process is present in the form of carboxylate-coordinated noble metal.
According to the catalyst prepared by the polyol method, the metal active component has uniform particle size, and the particle size is 2-3 nm.
In a third aspect, the present invention provides a hydroisomerization bifunctional catalyst prepared by the process described above.
In a fourth aspect, the present invention provides the use of a hydroisomerization bifunctional catalyst, as described above, in the hydroisomerization of olefins.
According to the invention, the olefin is preferably a C2-C5 olefin, for example ethylene, propylene, butene, pentene.
According to a most preferred embodiment of the invention, the olefin is propylene.
According to the present invention, preferably, the polymerization reaction is an oligomerization reaction, and for example, may be a dimerization reaction, a trimerization reaction, a tetramerization reaction, and more preferably a dimerization reaction.
In a fifth aspect, the invention provides a preparation method of exo-tetrahydrodicyclopentadiene, which comprises the following steps: under the condition of dicyclopentadiene hydroisomerization, dicyclopentadiene is contacted with the hydroisomerization bifunctional catalyst to obtain the hanging-type tetrahydrodicyclopentadiene.
According to the invention, the temperature of the dicyclopentadiene hydroisomerization can be chosen within a wide range, preferably with a feed temperature of 40 to 100 ℃ and, for example, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃ and, more preferably, with a feed temperature of 60 to 80 ℃. Compared with the feeding temperature of the prior art (CN107417485), the feeding temperature of the invention is lower, and therefore, the reaction condition is milder.
According to the invention, the hydrogen partial pressure of the dicyclopentadiene hydroisomerization can be chosen within a wide range, preferably from 2 to 6MPa, and can be, for example, 2MPa, 2.5MPa, 3MPa, 3.5MPa, 4MPa, 4.5MPa, 5MPa, 5.5MPa, 6 MPa.
According to the invention, the volume space velocity of the dicyclopentadiene hydroisomerization can be selected within a wide range, preferably, the volume space velocity is 0.5-4h-1For example, it may be 0.5h-1、1h-1、1.5h-1、2h-1、2.5h-1、3h-1、3.5h-1、4h-1More preferably, the volume space velocity is 1-3h-1。
According to the invention, the hydrogen-oil volume ratio of the dicyclopentadiene hydroisomerization can be selected in a wide range, and preferably, the hydrogen-oil volume ratio is 400-600: 1, for example, may be 400: 1. 420: 1. 440, a step of: 1. 460: 1. 480: 1. 500: 1. 520, the method comprises the following steps: 1. 540: 1. 560: 1. 580: 1. 600: 1, more preferably, the hydrogen-oil volume ratio is 500-600: 1.
according to the present invention, in order to further improve the reaction efficiency, it is preferable that dicyclopentadiene is diluted with exo-tetrahydrodicyclopentadiene before the reaction, and it is preferable that the concentration of dicyclopentadiene is 20 to 40% by volume after dissolution.
According to the present invention, the hydroisomerization of dicyclopentadiene may be carried out in conventional reactors, for example, by packing the catalyst in a fixed bed reactor. According to a preferred embodiment of the invention, the catalyst loading is 800-1250g relative to a 1L volume of the reactor.
The present invention will be described in detail below by way of examples.
Preparation example
This preparation example is used to illustrate the preparation of mesoporous niobium zirconium phosphate carrier
1.93g of zirconium oxychloride and 1.62g of NbCl were weighed out separately5Dissolved in 45mL of absolute ethanol, and stirred at room temperature for 30min until completely dissolved. 2.76g of ammonium dihydrogen phosphate was further weighed and completely dissolved in 10mL of deionized water, and the solution was added to the above ethanol solution of zirconium and niobium at an addition rate of 12mL/h to form a sol. After standing and aging for 12h, the sol gradually forms gel. Then, the gel was dried at 100 ℃ overnight, ground to homogeneity and calcined at 400 ℃ for 4h in an air atmosphere. Preparing the mesoporous zirconium niobium phosphate (ZrNbPO)4)。
And preparing the mesoporous niobium phosphate (NbPO) by the same method4) And mesoporous zirconium phosphate (ZrPO)4). Wherein, zirconium oxychloride or NbCl is used for preparing mesoporous niobium phosphate and mesoporous zirconium phosphate5The molar amount of the zirconium oxychloride and the NbCl during the preparation of the mesoporous niobium zirconium phosphate5The total molar amount of (a) is the same.
The physical structural properties of the three supports are shown in table 1. Wherein, the average pore diameter is measured by adopting a nitrogen physical adsorption method; the specific surface area is measured by adopting a nitrogen physical adsorption method; the total pore volume was measured by nitrogen physical adsorption.
TABLE 1
| Type of support | Specific surface area (m)2/g) | Average pore diameter (nm) | Total pore volume (cm)3/g) |
| NbPO4 | 30 | 7.8 | 0.08 |
| ZrNbPO4 | 52 | 9.6 | 0.14 |
| ZrPO4 | 90 | 11.0 | 0.37 |
As can be seen from table 1, the support incorporated with zirconium has a larger specific surface area and a larger total pore volume. In the structural unit of ZrNb diphosphate, P-OH and Nb-OH functional groups can provide
Acid center, and coordination unsaturation of Nb5+And Zr4+Can be used as Lewis acid center. In addition, the ZrNb diphosphate sample has more
Acid sites, due to the abundance of terminal P-OH functional groups on their surface, thus, the zirconium-doped samples exhibit a greater contrast to NbPO4Stronger acid properties of the sample.
Example 1
This example illustrates the preparation of a hydroisomerization dual function catalyst by impregnation
Weighing dried carrier powder (NbPO)4、ZrNbPO4、ZrPO4) In a 500mL sample bottle, chloroplatinic acid was weighed for a monometallic platinum catalyst, palladium chloride for a monometallic palladium catalyst, and bimetallic PdPtThe chloroplatinic acid and palladium chloride (in such amounts that Pd and Pt are supported on a carrier in a molar ratio of 4: 1) were weighed out and dissolved in an appropriate amount of deionized water, respectively. And dropwise adding the prepared metal solution into the carrier by adopting an isometric immersion method, carrying out ultrasonic dispersion for 10min, and sealing and storing for 24 h. Drying the impregnated catalyst at 110 ℃ overnight and roasting the dried catalyst at 400 ℃ for 3 hours in an air atmosphere to prepare the hydroisomerization dual-function catalyst (Pd/NbPO) with different metal loading (based on the total mass)4、Pd/ZrNbPO4、Pd/ZrPO4、Pt/NbPO4、Pt/ZrNbPO4、Pt/ZrPO4、PdPt/NbPO4、PdPt/ZrNbPO4、PdPt/ZrPO4) Wherein the dosage of each raw material is that the metal loading of each catalyst is about 0.5 wt% and 1 wt% respectively by ICP detection, namely, 18 kinds of hydrogenation isomerization dual-function catalysts are prepared. Before use H2Reducing at 400 ℃ for 2 hours in situ.
Example 2
This example illustrates the preparation of a bifunctional catalyst for hydroisomerization by the polyol sol process
(1) For single metal catalysts
Respectively dissolving chloropalladic acid and chloroplatinic acid into ethylene glycol, wherein the metal concentration is 0.03mol/L, adding a sodium acetate solution, wherein the total molar ratio of sodium acetate to metal is more than 5, and standing at room temperature for a period of time to generate black sol. Weighing appropriate amount of dried carrier powder (NbPO) according to the predetermined active metal loading4、ZrNbPO4、ZrPO4) Adding into a predetermined amount of the above solution, ultrasonically dispersing uniformly, soaking for 2h, filtering, washing, and drying in inert atmosphere to obtain stable hydroisomerization bifunctional catalyst (Pd/NbPO)4(1)、Pd/ZrNbPO4(1)、Pd/ZrPO4(1)、Pt/NbPO4(1)、Pt/ZrNbPO4(1)、Pt/ZrPO4(1)). The dosage of each raw material is respectively 0.5 wt% and 1 wt% of metal loading of each catalyst by ICP detection, namely, 12 kinds of hydrogenation isomerization dual-function catalysts are prepared. The catalyst does not need to be reduced before use.
(2) For bimetallic catalysts
Dissolving chloropalladic acid and chloroplatinic acid (the dosage is that Pd and Pt are loaded on a carrier in a molar ratio of 4: 1) into ethylene glycol, wherein the total metal concentration is 0.03mol/L, firstly adding a proper amount of sodium hydroxide to generate a bimetallic complex, then adding a sodium acetate solution, wherein the molar ratio of sodium acetate to total metal is more than 5, standing at room temperature for a period of time to generate black sol, and weighing a proper amount of dried carrier powder (NbPO) according to a preset active metal loading amount4、ZrNbPO4、ZrPO4) Adding into a predetermined amount of the above solution, ultrasonically dispersing uniformly, soaking for 2h, filtering, washing, and drying in inert atmosphere to obtain stable hydroisomerization bifunctional catalyst (PdPt/NbPO)4(1)、PdPt/ZrNbPO4(1)、PdPt/ZrPO4(1)). The dosage of each raw material is respectively 0.5 wt% and 1 wt% of metal loading of each catalyst by ICP detection, namely, 6 kinds of hydrogenation isomerization dual-function catalysts are prepared. The catalyst does not need to be reduced before use.
Test example 1
The effect of different carriers on the hydroisomerization performance of DCPD was compared.
Pd/NbPO prepared by polyol sol method and having metal loading of substantially about 1 wt% by ICP detection4(1)、Pd/ZrNbPO4(1)、Pd/ZrPO4(1)。
Reaction conditions are as follows: the DPCD concentration is 20 vol% (hanging tetrahydrodicyclopentadiene as solvent), the feeding temperature is 60 ℃, the hydrogen partial pressure is 4MPa, and the volume space velocity is 2h-1Hydrogen-oil volume ratio 600: 1 under the conditions of the following conditions.
The conversion of DPCD was determined by the gas chromatography internal standard method, and the selectivity of exo-TCD and the selectivity of by-products were determined by the gas chromatography internal standard method. The results are shown in Table 2.
TABLE 2
As can be seen from Table 2: the mesoporous niobium zirconium phosphate is used as a carrier, the best hydroisomerization effect is achieved, and the exo-TCD selectivity is greater than 97.5%.
Test with NbPO following the same method4(1) And ZrPO4(1) The catalyst is a carrier and is loaded with Pt or PdPt, the conversion rate is between 80 and 92 percent, but the selectivity of exo-TCD is not higher than 90 percent.
Test example 2
The effect of different loadings of different metals on the hydroisomerization performance of DCPD was compared.
Pd/ZrNbPO prepared by polyol sol method and having metal loading of substantially about 1 wt% by ICP detection4(1)、Pt/ZrNbPO4(1)、PdPt/ZrNbPO4(1)。
Reaction conditions and test methods: as in test example 1. The results are shown in Table 3.
TABLE 3
As can be seen from Table 3: the bimetallic PdPt is used as an active component, and the mesoporous niobium zirconium phosphate is used as a carrier, so that the best hydroisomerization effect is achieved.
The conversion and exo-TCD selectivity of a 0.5 wt% supported catalyst prepared by the polyol sol process were tested according to the same procedure and showed essentially the same behavior.
Test example 3
The influence of different preparation methods on the hydroisomerization performance of DCPD without loading is compared.
PdPt/ZrNbPO prepared by impregnation method and polyol sol method and basically supported by ICP detection metal of about 1 weight percent4、PdPt/ZrNbPO4(1)。
Reaction conditions and test methods: as in test example 1. The results are shown in Table 4.
TABLE 4
As can be seen from Table 4: prepared by polyol sol methodPdPt/ZrNbPO4(1) Has the best hydroisomerization effect and the exo-TCD selectivity of 99.5 percent. The characterization shows that the catalyst prepared by the polyol sol method has uniform metal particle size, and the metal particle size is 2-3 nm.
Other catalysts prepared by the comparative polyol sol method and the impregnation method (with the same support, supported metal and loading) were tested according to the same method, and both the conversion and exo-TCD selectivity showed substantially the same behavior.
Test example 4
The effect of different reaction conditions on the hydroisomerization performance of DCPD.
Preparation of PdPt/ZrNbPO by polyol sol method4(1) As catalyst, under the reaction conditions: the DPCD concentration is 20 vol% (hanging tetrahydrodicyclopentadiene as solvent), the feeding temperature is 60-100 ℃, the hydrogen partial pressure is 2-6MPa, and the volume airspeed is 0.5-4h-1The volume ratio of hydrogen to oil is 400-600: 1 under the condition of the reaction. The results are shown in Table 5.
TABLE 5
As can be seen from Table 5: the reaction temperature is increased, and the content of the by-product adamantane is increased; the pressure is increased, the conversion rate is increased, and the content of adamantane is slightly increased; increasing contact time, the adamantane content increases; increasing the hydrogen-to-oil ratio is beneficial to reducing the generation of byproducts. The optimal reaction conditions are as follows: the DPCD concentration is 20 volume percent, the feeding temperature is 60 ℃, the hydrogen partial pressure is 4MPa, and the volume space velocity is 2h-1Hydrogen-oil volume ratio 600: 1.
the catalyst supporting the monometallic Pd and Pt and the catalyst prepared by the impregnation method also showed substantially the same regularity.
Test example 5
To illustrate the stability of the catalyst
On the basis of test example 4, the DPCD concentration was 20% by volume, the feed temperature was 60 ℃, the hydrogen partial pressure was 4MPa, and the volume space velocity was 2h-1Hydrogen-oil volume ratio 600: 1, examine catalyst stability. The results are shown in Table 6。
TABLE 6
Experimental results of each stage of the process running for 400 hours show that PdPt/ZrNbPO4(1) prepared by a polyol sol method is used as a catalyst, a fixed bed hydroisomerization mode is adopted to carry out hydroisomerization on DCPD, the purity of the hanging type tetrahydrodicyclopentadiene is more than 98%, and the hanging type tetrahydrodicyclopentadiene can be directly sold as an industrial product. The results show that the technology of the invention has good stability and long service life of the catalyst.
The catalyst supporting the monometallic Pd and Pt and the catalyst prepared by the impregnation method also showed substantially the same regularity.
It should be noted that "substantially the same law" does not mean that substantially the same effect is obtained, but means that the law of variation of the effect is substantially the same.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (13)
1. A hydroisomerization dual-function catalyst, characterized in that, the catalyst comprises a carrier and a metal active component loaded on the carrier;
wherein the carrier is mesoporous niobium zirconium phosphate, and the metal active component is noble metal.
2. The catalyst according to claim 1, wherein the noble metal is Pd and/or Pt;
preferably, the noble metal is Pd and Pt;
more preferably, the molar ratio of Pd to Pt is 2-8: 1;
preferably, the noble metal is a carboxylate-coordinated noble metal.
3. The catalyst according to claim 1 or 2, wherein the supported amount of the noble metal is 0.1 to 5% by weight in terms of noble metal element, based on the total dry weight of the catalyst;
preferably, the particle size of the metal active component is 2 to 3 nm.
4. The catalyst according to any one of claims 1 to 3, wherein the mesoporous niobium zirconium phosphate has an average pore diameter of 10 to 18nm and a specific surface area of 80 to 120m2Per g, total pore volume of 0.15-0.35cm3/g；
Preferably, the mesoporous niobium zirconium phosphate is prepared by taking a niobium source, a zirconium source and a phosphorus source as raw materials and utilizing a sol-gel method.
5. A method for preparing a hydroisomerization bifunctional catalyst, comprising:
(1) first contacting a niobium source, a zirconium source, and a phosphorus source in the presence of an alcohol to form a sol;
(2) aging the sol to form a gel;
(3) sequentially carrying out first drying and first roasting on the gel to obtain the mesoporous niobium zirconium phosphate;
(4-1) impregnating the mesoporous niobium zirconium phosphate with a solution of a precursor containing a noble metal, and sequentially performing second drying and second roasting on the impregnated solid material to obtain the hydroisomerization bifunctional catalyst; or
(4-2) in the presence of polyol and carboxylate, carrying out second contact on a precursor of a noble metal and the mesoporous niobium zirconium phosphate, and drying a contacted solid material to obtain the hydroisomerization bifunctional catalyst.
6. The method according to claim 5, wherein in the step (1), the ratio of the amount of the phosphorus element to the total amount of the niobium element and the zirconium element is 1-3: 1;
preferably, the ratio of the niobium element to the zirconium element is 1: 1.2-2.5;
preferably, the alcohol is a C1-C5 alcohol, more preferably a C2-C4 alcohol;
preferably, the alcohol is used in an amount of 2 to 3L relative to 1mol of the total amount of the niobium element and the zirconium element;
preferably, the method of first contacting comprises: adding an aqueous solution of a phosphorus source to an alcohol solution of a niobium source and a zirconium source; the adding speed is preferably 5-20 mL/h;
preferably, the niobium source is selected from at least one of niobium pentachloride, niobium nitrate, ammonium niobium sulfate and niobium pentoxide;
preferably, the zirconium source is selected from at least one of zirconium oxychloride, zirconium nitrate, zirconium citrate, and zirconium propionate;
preferably, the phosphorus source is selected from at least one of ammonium dihydrogen phosphate, ammonium phosphate, phosphorus pentoxide, and phosphoric acid.
7. The method according to claim 5 or 6, wherein, in the step (4-1), the impregnation is an equal-volume impregnation or an over-volume impregnation;
preferably, the impregnation method comprises: soaking for 5-20min under ultrasonic condition, and soaking for 20-30h under air isolation condition;
preferably, the noble metal is Pd and/or Pt;
preferably, the noble metal is Pd and Pt;
more preferably, the respective contents of Pd and Pt in the solution of the precursor containing noble metal are such that Pd and Pt are supported on the mesoporous niobium zirconium phosphate in a molar ratio of 2-8: 1;
preferably, the solution of the precursor containing the noble metal and the mesoporous niobium zirconium phosphate are each used in an amount such that the noble metal is supported in an amount of 0.1 to 5% by weight, based on the total dry weight of the resulting catalyst, in terms of the noble metal element.
8. The method according to claim 5 or 6, wherein in step (4-2), the method of second contacting comprises:
(i) adding carboxylate into a polyol solution containing a precursor of a noble metal, and forming a black sol;
(ii) adding the mesoporous niobium zirconium phosphate into the black sol for second contact;
preferably, in the step (i), the total concentration of the noble metal in the polyol solution of the precursor containing the noble metal is 0.01-0.05 mol/L;
preferably, the polyol is a C2-C4 polyol;
preferably, the ratio of the amount of carboxylic acid salt to the amount of noble metal is greater than 5 on a molar basis;
preferably, the noble metal is Pd and/or Pt;
preferably, the noble metal is Pd and Pt;
more preferably, the respective contents of Pd and Pt in the solution of the precursor containing noble metal are such that Pd and Pt are supported on the mesoporous niobium zirconium phosphate in a molar ratio of 2-8: 1;
preferably, the solution of the precursor containing the noble metal and the mesoporous niobium zirconium phosphate are respectively used in an amount such that the noble metal is supported in an amount of 0.1 to 5 wt% in terms of noble metal element based on the total dry weight of the obtained catalyst;
preferably, in step (ii), the conditions of the second contacting include: the contact time is 5-20min under the ultrasonic condition, and then the contact time is 2-3h under the air isolation condition.
9. The method as claimed in claim 8, wherein, in the step (4-2), the noble metals are Pd and Pt, and before adding the carboxylate to the polyol solution containing the precursor of the noble metal, an alkali substance is added for treatment so that Pd and Pt form a bimetallic complex.
10. A hydroisomerization bifunctional catalyst prepared by the process of any of claims 5-9.
11. Use of a hydroisomerisation bifunctional catalyst according to any one of claims 1-4 and 10 for the hydroisomerisation of olefins.
12. A preparation method of exo-tetrahydrodicyclopentadiene is characterized by comprising the following steps: contacting dicyclopentadiene with a hydroisomerization bifunctional catalyst as defined in any of claims 1-4 and 10 under dicyclopentadiene hydroisomerization conditions to obtain exo-tetrahydrodicyclopentadiene.
13. The process of claim 12, wherein the conditions for the hydroisomerization of dicyclopentadiene comprise: the feeding temperature is 40-100 ℃, the hydrogen partial pressure is 2-6MPa, and the volume space velocity is 0.5-4h-1The volume ratio of hydrogen to oil is 400-600: 1;
preferably, the dicyclopentadiene is dissolved in exo-tetrahydrodicyclopentadiene, and after the dissolution, the concentration of the dicyclopentadiene is 20 to 40 vol%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010753303.6A CN114054056B (en) | 2020-07-30 | 2020-07-30 | Hydroisomerization bifunctional catalyst, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010753303.6A CN114054056B (en) | 2020-07-30 | 2020-07-30 | Hydroisomerization bifunctional catalyst, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114054056A true CN114054056A (en) | 2022-02-18 |
| CN114054056B CN114054056B (en) | 2023-12-22 |
Family
ID=80227183
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010753303.6A Active CN114054056B (en) | 2020-07-30 | 2020-07-30 | Hydroisomerization bifunctional catalyst, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114054056B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117339636A (en) * | 2023-09-27 | 2024-01-05 | 黑龙江大学 | Method for preparing hierarchical porous zeolite supported bimetallic alloy bifunctional catalyst by adopting room-temperature electron reduction method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06316539A (en) * | 1991-03-11 | 1994-11-15 | Jgc Corp | Production of alkylaromatic hydrocarbon |
| CN106699499A (en) * | 2016-12-27 | 2017-05-24 | 中央军委后勤保障部油料研究所 | Method for improving isomeric selectivity of endo-tetrahydrodicyclotadiene |
| CN107469844A (en) * | 2016-06-08 | 2017-12-15 | 中国石油化工股份有限公司 | A kind of deoxidation method of hydrotreating of catalyst with deoxidation hydrogenating function and preparation method thereof and carbonyls |
| CN110092708A (en) * | 2019-05-17 | 2019-08-06 | 中国科学院广州能源研究所 | A kind of method that lignocellulosic catalytic hydrogenation prepares ethyl alcohol |
| CN110302815A (en) * | 2019-06-20 | 2019-10-08 | 广西科技大学鹿山学院 | A kind of Ag@SiO2The synthetic method of loaded mesoporous phosphate niobium catalyst and its preparing the application in 5 hydroxymethyl furfural |
-
2020
- 2020-07-30 CN CN202010753303.6A patent/CN114054056B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06316539A (en) * | 1991-03-11 | 1994-11-15 | Jgc Corp | Production of alkylaromatic hydrocarbon |
| CN107469844A (en) * | 2016-06-08 | 2017-12-15 | 中国石油化工股份有限公司 | A kind of deoxidation method of hydrotreating of catalyst with deoxidation hydrogenating function and preparation method thereof and carbonyls |
| CN106699499A (en) * | 2016-12-27 | 2017-05-24 | 中央军委后勤保障部油料研究所 | Method for improving isomeric selectivity of endo-tetrahydrodicyclotadiene |
| CN110092708A (en) * | 2019-05-17 | 2019-08-06 | 中国科学院广州能源研究所 | A kind of method that lignocellulosic catalytic hydrogenation prepares ethyl alcohol |
| CN110302815A (en) * | 2019-06-20 | 2019-10-08 | 广西科技大学鹿山学院 | A kind of Ag@SiO2The synthetic method of loaded mesoporous phosphate niobium catalyst and its preparing the application in 5 hydroxymethyl furfural |
Non-Patent Citations (1)
| Title |
|---|
| 方祝青等: "挂式四氢双环戊二烯合成工艺研究进展", 精细化工, vol. 37, no. 1, pages 11 - 19 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117339636A (en) * | 2023-09-27 | 2024-01-05 | 黑龙江大学 | Method for preparing hierarchical porous zeolite supported bimetallic alloy bifunctional catalyst by adopting room-temperature electron reduction method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114054056B (en) | 2023-12-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104232140A (en) | Method for synthesizing high-density aviation fuel by using cyclopentanone as raw material | |
| US3859370A (en) | Massive nickel catalysts and use in hydrogenation processes | |
| WO2016114659A1 (en) | Process for preparing ethylene glycol from a carbohydrate source | |
| CN109534939B (en) | Method for directly preparing alpha-olefin in high selectivity at one step by catalyzing synthesis gas with Co-based catalyst | |
| CN102688768A (en) | Cobalt-based catalyst for synthesizing ethanol, preparation method and application thereof | |
| WO2022247717A1 (en) | Method for synthesizing higher alcohol by means of catalytic conversion of ethanol | |
| CN109894147B (en) | Supported cobalt-based catalyst and preparation method and use method thereof | |
| WO2018170932A1 (en) | Catalyst for preparing 1,5-pentanediol via hydrogenolysis of tetrahydrofurfuryl alcohol, method and application thereof | |
| CN108623436B (en) | Method for converting cellulose into bioethanol by one-pot method | |
| CN103127945B (en) | Method for preparing catalyst used for preparing acetaldehyde through direct dehydrogenation of ethanol and application of catalyst | |
| CN104072335B (en) | A kind of cellulose catalytic converts dihydroxylic alcohols processed, hexahydroxylic alcohols and the method for gamma-valerolactone | |
| CN113289632A (en) | Catalyst for preparing ethanol by dimethyl oxalate hydrogenation and preparation method and application thereof | |
| AU2018446561A1 (en) | Catalyst for synthesizing oxalate by co coupling reaction, preparation and uses | |
| CN114054056B (en) | Hydroisomerization bifunctional catalyst, and preparation method and application thereof | |
| CN111229247B (en) | Catalyst for preparing ethanol by oxalate hydrogenation and preparation method and application thereof | |
| CN106268828B (en) | Copper-based ester through hydrogenation carbon monoxide-olefin polymeric and its preparation method and application | |
| CN110551893B (en) | Diluent and its preparing process | |
| CN109748777B (en) | Method for preparing 1, 6-hexanediol by catalytic hydrogenolysis of 1,2, 6-hexanetriol | |
| CN109704918B (en) | Method for continuously catalytically preparing 2, 6-di-tert-butyl-4-methylcyclohexanol | |
| CN107970929A (en) | A kind of alkynes and alkadienes liquid phase selective hydrogenation catalyst, preparation method and application | |
| CN103130625A (en) | Method for preparing acetaldehyde and co-producing acetal by using ethanol | |
| KR101468377B1 (en) | Ordered mesoporous carbon based catalysts for the production of oxygenated carbon compound and production method of oxygenated carbon compound using thereof | |
| CN100413828C (en) | Method for producing ethene and hexene through dismutation of butylene | |
| CN106215943B (en) | Ester through hydrogenation catalyst and its preparation method and application | |
| CN110327923B (en) | Biomass sugar alcohol hydrogenolysis catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |