CN115382571A - Preparation method of silicon-aluminum-phosphorus molecular sieve hydrogenation catalyst and application of catalyst in preparation of biofuel from kitchen waste oil - Google Patents
Preparation method of silicon-aluminum-phosphorus molecular sieve hydrogenation catalyst and application of catalyst in preparation of biofuel from kitchen waste oil Download PDFInfo
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- CN115382571A CN115382571A CN202211082709.1A CN202211082709A CN115382571A CN 115382571 A CN115382571 A CN 115382571A CN 202211082709 A CN202211082709 A CN 202211082709A CN 115382571 A CN115382571 A CN 115382571A
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 77
- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- -1 silicon-aluminum-phosphorus Chemical compound 0.000 title claims abstract description 47
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 35
- 239000002551 biofuel Substances 0.000 title claims abstract description 28
- 239000010806 kitchen waste Substances 0.000 title claims abstract description 24
- 239000003921 oil Substances 0.000 claims abstract description 71
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000011068 loading method Methods 0.000 claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 17
- 239000010703 silicon Substances 0.000 claims abstract description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002425 crystallisation Methods 0.000 claims abstract description 14
- 230000008025 crystallization Effects 0.000 claims abstract description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 14
- 239000011574 phosphorus Substances 0.000 claims abstract description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 37
- 238000001035 drying Methods 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 29
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 23
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 23
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 16
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 16
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 15
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 230000032683 aging Effects 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 4
- 239000005750 Copper hydroxide Substances 0.000 claims description 4
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 4
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 4
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 239000000347 magnesium hydroxide Substances 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 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 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- ZOAIGCHJWKDIPJ-UHFFFAOYSA-M caesium acetate Chemical compound [Cs+].CC([O-])=O ZOAIGCHJWKDIPJ-UHFFFAOYSA-M 0.000 claims description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- HEQUOWMMDQTGCX-UHFFFAOYSA-L dicesium;oxalate Chemical compound [Cs+].[Cs+].[O-]C(=O)C([O-])=O HEQUOWMMDQTGCX-UHFFFAOYSA-L 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 11
- 239000011148 porous material Substances 0.000 abstract description 6
- 239000006185 dispersion Substances 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 239000002028 Biomass Substances 0.000 abstract description 2
- 238000005342 ion exchange Methods 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract 2
- 239000002912 waste gas Substances 0.000 abstract 1
- 235000019198 oils Nutrition 0.000 description 58
- 239000000203 mixture Substances 0.000 description 48
- 238000006243 chemical reaction Methods 0.000 description 28
- 238000007789 sealing Methods 0.000 description 22
- 239000000047 product Substances 0.000 description 20
- 238000005406 washing Methods 0.000 description 14
- 238000001816 cooling Methods 0.000 description 13
- 239000004519 grease Substances 0.000 description 13
- 239000012265 solid product Substances 0.000 description 13
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 12
- 239000011363 dried mixture Substances 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 239000010457 zeolite Substances 0.000 description 8
- 229910021536 Zeolite Inorganic materials 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000005336 cracking Methods 0.000 description 6
- 238000006317 isomerization reaction Methods 0.000 description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 239000003350 kerosene Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000012075 bio-oil Substances 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 2
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 2
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical class [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- 241000208140 Acer Species 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 101150116295 CAT2 gene Proteins 0.000 description 1
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 1
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 101100342039 Halobacterium salinarum (strain ATCC 29341 / DSM 671 / R1) kdpQ gene Proteins 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 229910052678 stilbite Inorganic materials 0.000 description 1
- 239000005437 stratosphere Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
- C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a silicon-aluminum-phosphorus molecular sieve hydrogenation catalyst and application of the silicon-aluminum-phosphorus molecular sieve hydrogenation catalyst in preparation of biofuel from kitchen waste oil, wherein on the premise of not adding an organic template agent, water, a silicon source, an aluminum source, a phosphorus source, a Cs source and a Me source are mixed to prepare initial gel, then crystallization is carried out, the silicon-aluminum-phosphorus molecular sieve can be synthesized under the condition that the crystallization temperature is 150-200 ℃, and the bimetallic silicon-aluminum-phosphorus molecular sieve hydrogenation catalyst is obtained after loading active components. The preparation method of the catalyst disclosed by the invention is green and environment-friendly, the template agent is removed without high-temperature roasting, ion exchange is not needed, the generation of harmful waste gas is avoided, the catalyst for preparing the biofuel by biomass hydrogenation is obtained after the active components are loaded on the carrier, the metals in the catalyst pore channel and on the molecular sieve framework and the loaded metals have high-efficiency synergistic effect, and the dispersion degree of Ni is improved by introducing the second metal, so that the catalyst has more active sites.
Description
Technical Field
The invention belongs to the technical field of zeolite molecular sieve preparation, and particularly relates to a preparation method of a silicon-aluminum-phosphorus molecular sieve hydrogenation catalyst and application of the silicon-aluminum-phosphorus molecular sieve hydrogenation catalyst in preparation of biofuel from kitchen waste oil.
Background
The depletion of fossil energy and the stringent emission requirements of carbon dioxide have made traditional aviation fuels dual challenges in demand and emission standards. The carbon dioxide gas generated after the conventional aviation kerosene is combusted is directly discharged in a stratosphere, so that the harm of the greenhouse effect caused by the carbon dioxide gas is far higher than that of the carbon dioxide gas in other industries. In order to protect the living environment of human beings and reduce the emission of greenhouse gases, a new biological aviation kerosene needs to be developed, such as vegetable oil and animal oil and fat, including soybean oil, palm oil, castor oil, rapeseed oil, maple oil, lard, fish oil and the like, which are subjected to hydrodeoxygenation, cracking and isomerization to form biofuel,
the natural oil and fat can be used as biofuel through two-step processing. The natural oil contains a large amount of aldehyde, hydroxyl, phenol and other oxygen-containing functional groups, the oxygen content is too high, and the carbon chain also contains a large amount of unsaturated bonds, so that the stability of the biological oil is poor. The natural oil hydrodeoxygenation-hydrocracking/isomerization technical route can be divided into two steps, wherein in the first step, under the hydrogen atmosphere, the bio-oil is deoxidized to ensure that oxygen elements in oxygen-containing functional groups are converted into H 2 O、CO 2 Or CO, so as to improve the saturation of the bio-oil and obtain straight-chain alkane, and secondly, carrying out cracking isomerization treatment on the long-chain alkane to obtain short alkane with a branched chain, so as to reduce the viscosity of the bio-oil and improve the low-temperature fluidity, thereby achieving the oil product standard of the bio-aviation kerosene.
The biological oil hydrodeoxygenation catalyst consists of active metal and a molecular sieve carrier. A large amount of organic amine template is often needed in the synthesis process of the traditional molecular sieve. Although the use of the templating agent has led to the development of the synthesis and structure of the zeolite material, it has brought about a great problem in industrial production: firstly, the synthesis cost is increased; secondly, in order to obtain an open microporous pore channel, the organic template agent must be removed before the zeolite is used, and the common removal method is high-temperature roasting, so that the emission of greenhouse gases is increased, which is contrary to the national policy of energy conservation and emission reduction. On the other hand, a large amount of organic template agents are toxic and harmful, and the problem of environmental pollution is serious.
PCT/CN2019/106883 discloses a preparation method of a template-free synthesized porous structure silicon-aluminum-phosphorus carrier. The synthesis is carried out by adding organic amine template agent, permeating silicon source and alkali sourceAnd (3) obtaining the silicon-aluminum-phosphorus carrier with the porous structure by using a proper hydrothermal synthesis condition. And roasting the mixture to prepare the biofuel by hydrodeoxygenation and isomerization cracking of the vegetable oil. CN201711126785.7 discloses a hydrothermal synthesis method of Na-type sheet zeolite molecular sieve. The method takes a silicon source, an aluminum source, sodium hydroxide and zeolite seed crystals as raw materials, then directly adds natural stilbite seed crystals into initial gel, and hydrothermally synthesizes the Na-type sheet zeolite molecular sieve in a short crystallization time (3-4 days) and a low crystallization temperature (130-170 ℃). And subsequently, carrying out solid-liquid separation on the obtained hydrothermal crystallization product, washing and drying to obtain the Na-type sheet zeolite molecular sieve. The method can prepare the Na-type sheet zeolite with high crystallinity and uniform particle size under mild conditions, and has great application prospect in the fields of gas adsorption and separation, cation exchange and the like. CN202011480960.4 discloses a template-free SAPO-34 molecular sieve and a preparation method thereof. The method provides a method for preparing a template-free SAPO-34 molecular sieve by using a seed crystal method to assist hydrothermal synthesis, wherein the template-free SAPO-34 molecular sieve comprises the following components in parts by weight: si0 2 2-10 parts; al (aluminum) 2 0 3 15.5-25.5 parts: p 2 0 5 60-75.5 parts, and secondly, 1-6wt% of the total mass of the raw materials of the synthesized molecular sieve is required to be added as seed crystals in the synthesis process.
CN202110764889.0 discloses an SAPO-11 molecular sieve, a preparation method and an application thereof. According to the method, co is doped in the SAPO-11 molecular sieve, the Co doping can influence the coordination between silicon and aluminum in the molecular sieve, so that the property of B acid in the molecular sieve is changed, co replaces the original aluminum and enters an SAP0-11 framework to form an acid center, and the acid strength is enhanced; and Co doping can disperse silicon atoms in a crystal framework to generate new acid sites, and can increase the total acid site concentration, so that the catalytic activity of the molecular sieve catalyst is improved, and the yield of isomers is improved. CN202110504195.3 discloses a preparation method and application of an Au-Mg/SAPO-11 molecular sieve catalyst. The catalyst is prepared from SAPO-11 molecular sieve and composite nano metal Au-Mg. According to the method, a template agent is added into a silicon source, an aluminum source and a phosphorus source, and the SAPO-11 molecular sieve is obtained after high-temperature crystallization, separation and purification. Then loading Au salt and Mg salt, obtaining Au-Mg/SAPO-11 molecular sieve after sodium borohydride reduction, and applying in bisphenol F synthesis and alcohol oxidation reaction
CN104549381A discloses a synthetic method of an active silicon-phosphorus-aluminum material and application thereof. The material has pseudoboehmite crystalline phase, silicon source and phosphorus source are added into colloid formed by aluminum source and alkali liquor, the material is obtained after crystallization and roasting, and the anhydrous compound of the material comprises (0-0.2) Na in oxide weight ratio 2 O： (64-76)Al 2 O 3 ：(23-35)SiO 2 ：(1-7)P 5 O 2 . The material has a mesopore characteristic, and is used as an active component or an active matrix material for macromolecular cracking in a heavy oil catalytic cracking agent or an auxiliary agent.
CN104815697A discloses a preparation method of a catalyst for biological aviation kerosene ultra-dispersion hydrodeoxygenation and hydroisomerization by using castor oil. The method comprises the steps of mixing and stirring deionized water, silica sol, phosphoric acid and pseudo-boehmite, and then adding di-n-propylamine and diisopropylamine as template agents to synthesize the carrier of the SAPO-11 with the multilevel pore channels. The method improves the dispersion degree of the active components through multiple times of dipping. In the invention, the use of the template agent in the process of synthesizing the silicon-aluminum-phosphorus molecular sieve is reduced mostly by a seed crystal induction method and an ion guide method.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a silicon-aluminum-phosphorus molecular sieve hydrogenation catalyst and application of the silicon-aluminum-phosphorus molecular sieve hydrogenation catalyst in preparation of biofuel from kitchen waste oil.
The technical scheme adopted by the invention is as follows: a preparation method of a silicon-aluminum-phosphorus molecular sieve hydrogenation catalyst comprises the steps of mixing water, a silicon source, an aluminum source, a phosphorus source, a Cs source and a Me source to prepare an initial gel, wherein the molar ratio of the oxides of the water, the silicon source, the aluminum source, the phosphorus source, the Cs source and the Me source is 50-100:0.2-1:1:0.5-1.0:0.1-2:0.1 to 2; and (3) crystallizing to prepare a silicon-aluminum-phosphorus molecular sieve, and loading active metal to obtain the bimetallic silicon-aluminum-phosphorus molecular sieve hydrogenation catalyst.
Preferably, me is one of Li, na, K, mg, ba, cu and Mn.
Preferably, the Me source is one of sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, barium hydroxide, copper hydroxide, and manganese hydroxide.
Preferably, the source of Cs is a combination of one or more of cesium hydroxide, cesium carbonate, cesium oxalate and cesium acetate.
Preferably, the silicon source is one or a combination of more of sodium silicate, silica sol, ethyl orthosilicate and white carbon black;
the aluminum source is one or the combination of more of sodium metaaluminate, aluminum hydroxide and pseudo-boehmite;
the phosphorus source is phosphoric acid.
Preferably, the crystallization temperature is 150-200 ℃.
Preferably, the active component is Ni-xCs, the mass of the active component accounts for 10-30% of the total mass of the catalyst, and x is the mass percentage of the simple substance Cs to the simple substance Ni, wherein x ranges from 5 to 20.
Preferably, soluble salt of the active component is dissolved into deionized water with the mass of the carrier being one time of the water absorption rate, a silicon-aluminum-phosphorus molecular sieve is added, the mixture is placed still, aged, dried and roasted, and hydrogen is reduced to prepare the hydrogenation catalyst of the bimetallic silicon-aluminum-phosphorus molecular sieve.
The preparation method of the silicon-aluminum-phosphorus molecular sieve hydrogenation catalyst is used for preparing the bimetallic silicon-aluminum-phosphorus molecular sieve hydrogenation catalyst.
The application of a bimetallic silicon-aluminum-phosphorus molecular sieve hydrogenation catalyst in the preparation of biofuel;
preferably, the method is applied to the preparation of biofuel from kitchen waste oil.
Preferably, the kitchen waste oil is pretreated firstly, and the method specifically comprises the following steps:
weighing phosphoric acid or citric acid solution 0.5-1% of the kitchen waste oil by mass, adding the solution into the oil, stirring and reacting at the temperature of 80-85 ℃, adding distilled water 5-8% of the kitchen waste oil by mass, stirring and reacting at the temperature of 70-75 ℃, standing at constant temperature, centrifuging, and collecting an oil layer;
adding distilled water 8-15% of the oil layer, stirring at 70-75 deg.C, centrifuging, and collecting oil layer;
adding acid clay 8-10% of the mass of the secondary collected oil layer, heating to 100-110 ℃, stirring, centrifuging, and collecting the treated kitchen waste oil.
The invention has the advantages and positive effects that: the molecular sieve synthesized by the preparation method is green and environment-friendly, does not need high-temperature roasting to remove a template agent and ion exchange, and can be used in the fields of biomass hydrogenation preparation of biofuel and the like after loading active components; the constructed NiCs/CsMeAPO-11 molecular sieve has high-efficiency synergistic effect of Cs metal and Me metal in pore channels and on a molecular sieve framework and load metal, has proper acid strength and acid content, and has wide prospect in the aspect of catalyzing the hydroisomerization cracking of biological oil to prepare biological aviation kerosene.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of the products prepared in inventive example 1 and comparative examples 2-3;
FIG. 2 is a scanning electron micrograph of a product prepared in example 1 of the present invention.
Detailed Description
Embodiments of the present invention will be described below with reference to the accompanying drawings.
The invention discloses a preparation method of a silicon-aluminum-phosphorus molecular sieve hydrogenation catalyst, which is characterized in that a silicon-aluminum-phosphorus molecular sieve is synthesized in a focusing mode without a template, a silicon source, an aluminum source, a phosphorus source, cesium salt and Me salt are used as raw materials, and the preparation method is different from the traditional hydrothermal synthesis and is used for synthesizing a double-metal silicon-aluminum-phosphorus molecular sieve under the microwave condition. When in preparation, water, a silicon source, an aluminum source, a phosphorus source, a Cs source and a Me source are mixed to prepare initial gel, wherein the molar ratio of the water, the silicon source, the aluminum source, the phosphorus source, the Cs source and the Me source is 50-100:0.2-1:1:0.5-1.0:0.1-2:0.1-2; then carrying out crystallization reaction for 1-6h at the temperature of 150-200 ℃ by microwave to obtain a silicon-aluminum-phosphorus molecular sieve, and loading active metal to obtain the hydrogenation catalyst of the bimetallic silicon-aluminum-phosphorus molecular sieve.
Wherein, the Me source is one of Li, na, K, mg, ba, cu and Mn; the Me source is one of sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, barium hydroxide, copper hydroxide and manganese hydroxide; the cesium source is one or a combination of cesium hydroxide, cesium carbonate, cesium oxalate and cesium acetate; the silicon source is one or a combination of more of sodium silicate, silica sol, ethyl orthosilicate and white carbon black; the aluminum source is one or the combination of more of sodium metaaluminate, aluminum hydroxide and pseudo-boehmite; the phosphorus source is phosphoric acid; each component in the molecular sieve forms a framework structure of the molecular sieve, and the loaded active component is attached to the framework structure and plays a role in activating hydrogen bonds; wherein the active component is Ni-xCs, the mass of the active component accounts for 10-30% of the total mass of the catalyst, x is the mass percent of the simple substance Cs to the simple substance Ni, and the range of x is 5-20.
The preparation method comprises the following steps:
the method comprises the following steps: mixing water, a silicon source, an aluminum source, a phosphorus source, a Cs source and a Me source according to the mole ratio of oxides of 50-100:0.2-1:1:0.5-1.0:0.1-2: mixing 0.1-2 times, and stirring for 3-5h to obtain initial gel;
step two: transferring the initial gel into a glass tube of a microwave synthesizer, sealing, and performing crystallization reaction at 150-200 ℃ for 1-24h, preferably 1-6h; after the reaction is finished, standing and cooling, centrifugally washing and drying the solid product to obtain a silicon-aluminum-phosphorus molecular sieve; the solid-liquid separation mode can adopt suction filtration or centrifugation, drying can be carried out at the temperature of 75-100 ℃, and the drying time can be set according to the drying temperature and can be generally 6-12h;
step three: according to the proportion that the mass of the active simple substance component accounts for 10-30% of the total mass of the catalyst, soluble salt of the required active component is dissolved into deionized water with the mass of one time of the water absorption of the molecular sieve carrier, the mixture is added into the washed silicon-aluminum-phosphorus molecular sieve after being fully stirred for 2h, the mixture is dried after being kept stand and aged for 12h, the mixture is roasted for 3h in the air atmosphere at 500 ℃, and then hydrogen is reduced for 2h at 400 ℃ to obtain the bimetallic silicon-aluminum-phosphorus carrier hydrogenation catalyst; wherein the active component is Ni-xCs, the mass of the active component accounts for 10-30% of the total mass of the catalyst, wherein x is the mass percentage of the simple substance Cs relative to the simple substance Ni, and the range of x is 5-20. In certain embodiments of the invention, the soluble salt of the active component is nickel nitrate, cesium hydroxide.
Compared with the traditional synthesis of an AlPO-11 molecular sieve and an SAPO-11 molecular sieve, after hetero atoms are introduced into the AlPO-n molecular sieve, the number of B acid sites and the number of L acid sites of the molecular sieve are greatly increased, and the acid strength of the molecular sieve carrier is effectively improved. While the supported Ni provides hydrogenation/dehydrogenation activity, making the isomerization process occurring at the acid sites the rate limiting step of the reaction. The introduction of the second metal Cs improves the dispersion degree of Ni, thereby improving the activity of hydrogenation and dehydrogenation. Secondly, the presence of Cs further improves the reducibility of some NiO and also prevents Ni from sintering during the reaction. The Cs metal and the Me metal in the pore channel and on the molecular sieve framework of the constructed NiCs/CsMeAPO-11 molecular sieve have high-efficiency synergistic action with the load metal, have proper acid strength and acid content, and are suitable for preparing biofuel.
In some embodiments of the invention, a microwave synthesizer can be used for microwave crystallization, so that the crystallization time is short, and the method is suitable for synthesizing a small-dose sample; in other embodiments of the present invention, a hydrothermal synthesis kettle may be used for crystallization, the crystallization time is long, generally may exceed 24 hours, such as 24-48 hours, a large amount of samples can be synthesized, and the present invention is suitable for industrial production.
In certain embodiments of the invention, the prepared bimetallic silicon-aluminum-phosphorus supported hydrogenation catalyst can be used for preparing biofuel from grease.
The specific hydrodeoxygenation steps are as follows: the weighed catalyst is filled in a constant temperature interval of a reactor, and a ceramic ring is filled at the upper end of a reaction tube, so that the raw material with lower temperature is preheated. Before the reaction, the catalyst is added in H 2 Pretreating at a certain temperature (generally 400 ℃) for 2 hours in an atmosphere (160 mL/min) to reduce the supported oxide to a zero valence state, and then setting the temperature, pressure and hydrogen flow rate required by the reaction for evaluation (under the hydrogen pressure of 3-10WPa, the hydrogen-oil ratio is 800-2000, and the reaction temperature is 300-400 ℃). The batch was taken up every hour and the product was analyzed by gas chromatography.
In some embodiments of the invention, the grease is kitchen waste oil, and the oil is pretreated before being introduced into the reactor, and the pretreatment can be carried out according to one or more of the following treatment methods:
pretreatment of kitchen waste oil:
1. weighing phosphoric acid or citric acid solution with the mass of 0.7% of that of the kitchen waste oil, adding the phosphoric acid or citric acid solution into the oil, stirring and reacting at 85 ℃ for 30min, then adding distilled water with the mass of 6% of that of the kitchen waste oil, stirring and reacting at 75 ℃ for 30min, standing at constant temperature for 2h, centrifuging, and collecting an oil layer; the first step uses a three-neck flask, an oil bath pan, and a three-neck flask plus a condensing device.
2. Adding distilled water with the mass of 10% of that of the oil layer, stirring vigorously at 70 ℃ and over 600 rpm for 15min, centrifugally collecting the oil layer, and removing water from the oil layer at 105 ℃;
3. adding acid clay 10% of the oil layer, heating to 110 deg.C, stirring at 500 rpm for 1 hr, centrifuging, and collecting oil.
The following describes the scheme of the present invention with reference to the accompanying drawings, wherein experimental methods without specific description of operation steps are all performed according to corresponding commercial specifications, and instruments, reagents and consumables used in the examples can be purchased from commercial companies without specific description. The following examples are intended to enable one of ordinary skill in the art to more fully understand the present invention or make certain insubstantial improvements and modifications within the scope of the present invention, but are not intended to be limiting as to the scope of the claims, which are included but not to be construed as being exhaustive of the invention.
Example 1
(1) The preparation method of the bimetallic silicon-aluminum-phosphorus carrier by the template-free method comprises the following steps: 13g of deionized water, 2.3g of phosphoric acid, 1.42g of pseudoboehmite, 0.80g of silica sol and 0.96g of cesium hydroxide and 0.22g of sodium hydroxide were mixed and stirred at 20 ℃ for 1 hour. And then transferring the mixture into a microwave synthesizer, sealing, crystallizing at 190 ℃ for 2h, standing after the reaction is finished, cooling, centrifuging, washing and drying the solid product to obtain an initial product A.
(2) Loading of active components: dissolving 10.79g of nickel nitrate and 0.71g of cesium hydroxide in 8g of deionized water, fully stirring for 2h, adding the mixture into 8g of carrier A, standing and aging for 24h, drying the mixture, and roasting the dried mixture in an air atmosphere at 400 ℃ for 3h to obtain the catalyst for preparing the biofuel oil by grease hydrodeoxygenation, which is recorded as cat1.
The X-ray powder diffraction pattern and the scanning electron microscope photograph of cat1 catalyst are shown in fig. 1 and fig. 2, respectively. The XRD result shows that the synthesized molecular sieve has a good crystal structure, and Na and Cs enter a molecular sieve framework; the scanning electron microscope photo shows the particle size and morphology of the molecular sieve, the molecular sieve is in a quadrangular shape, and the particle size is 5-8 microns.
Example 2
(1) The preparation method of the bimetallic silicon-aluminum-phosphorus carrier by the template-free method comprises the following steps: 13g of deionized water, 2.3g of phosphoric acid, 1.42g of pseudoboehmite, 0.80g of silica sol, 0.96g of cesium hydroxide and 0.31g of potassium hydroxide were mixed and stirred at 20 ℃ for 1 hour. And then transferring the mixture into a microwave synthesizer, sealing, crystallizing at 190 ℃ for 2h, standing after the reaction is finished, cooling, centrifuging, washing and drying the solid product to obtain an initial product. And then transferring the mixture into a microwave synthesizer, sealing, crystallizing at 190 ℃ for 2h, standing after the reaction is finished, cooling, centrifuging, washing and drying the solid product to obtain an initial product A.
(2) Loading of active components: dissolving 10.79g of nickel nitrate and 0.71g of cesium hydroxide in 8g of deionized water, fully stirring for 2h, adding the mixture into 8g of carrier A, standing and aging for 24h, drying the mixture, and roasting the dried mixture in an air atmosphere at 400 ℃ for 3h to obtain the catalyst for preparing the biofuel oil by grease hydrodeoxygenation, which is recorded as cat2.
Example 3
(1) The preparation method of the bimetallic silicon-aluminum-phosphorus carrier by the template-free method comprises the following steps: 13g of deionized water, 2.3g of phosphoric acid, 1.42g of pseudoboehmite, 0.80g of silica sol, 0.96g of cesium hydroxide and 0.13g of lithium hydroxide were mixed and stirred at 20 ℃ for 1 hour. And then transferring the mixture into a microwave synthesizer, sealing, crystallizing at 190 ℃ for 2h, transferring the mixture into the microwave synthesizer, sealing, crystallizing at 190 ℃ for 2h, standing after the reaction is finished, cooling, and centrifuging, washing and drying the solid product to obtain an initial product A.
(2) Loading of active components: dissolving 10.79g of nickel nitrate and 0.71g of cesium hydroxide in 8g of deionized water, fully stirring for 2h, adding the mixture into 8g of carrier A, standing and aging for 24h, drying the mixture, and roasting the dried mixture in an air atmosphere at 400 ℃ for 3h to obtain the catalyst for preparing the biofuel oil by grease hydrodeoxygenation, which is recorded as cat3.
Example 4
(1) The preparation method of the bimetallic silicon-aluminum-phosphorus carrier by the template-free method comprises the following steps: 13g of deionized water, 2.3g of phosphoric acid, 1.42g of pseudoboehmite, 0.80g of silica sol, 0.96g of cesium hydroxide and 0.32g of magnesium hydroxide were mixed and stirred at 20 ℃ for 1 hour. And then transferring the mixture into a microwave synthesizer, sealing, crystallizing at 190 ℃ for 2h, transferring the mixture into the microwave synthesizer, sealing, crystallizing at 190 ℃ for 2h, standing after the reaction is finished, cooling, and centrifuging, washing and drying the solid product to obtain an initial product A.
(2) Loading of active components: dissolving 10.79g of nickel nitrate and 0.71g of cesium hydroxide in 8g of deionized water, fully stirring for 2h, adding the mixture into 8g of carrier A, standing and aging for 24h, drying the mixture, and roasting the dried mixture in an air atmosphere at 400 ℃ for 3h to obtain the catalyst for preparing the biofuel oil by grease hydrodeoxygenation, which is recorded as cat4.
Example 5
(1) The preparation method of the bimetallic silicon-aluminum-phosphorus carrier by the template-free method comprises the following steps: 13g of deionized water, 2.3g of phosphoric acid, 1.42g of pseudoboehmite, 0.80g of silica sol, 0.96g of cesium hydroxide and 1.74g of barium hydroxide were mixed and stirred at 20 ℃ for 1 hour. And then transferring the mixture into a microwave synthesizer, sealing, crystallizing at 190 ℃ for 2h, transferring the mixture into the microwave synthesizer, sealing, crystallizing at 190 ℃ for 2h, standing after the reaction is finished, cooling, and centrifuging, washing and drying the solid product to obtain an initial product A.
(2) Loading of active components: dissolving 10.79g of nickel nitrate and 0.71g of cesium hydroxide in 8g of deionized water, fully stirring for 2h, adding the mixture into 8g of carrier A, standing and aging for 24h, drying the mixture, and roasting the dried mixture in an air atmosphere at 400 ℃ for 3h to obtain the catalyst for preparing the biofuel oil by grease hydrodeoxygenation, which is recorded as cat5.
Example 6
(1) The preparation method of the bimetallic silicon-aluminum-phosphorus carrier by the template-free method comprises the following steps: 13g of deionized water, 2.3g of phosphoric acid, 1.42g of pseudoboehmite, 0.80g of silica sol and 0.96g of cesium hydroxide and 0.538g of copper hydroxide were mixed and stirred at 20 ℃ for 1 hour. And then transferring the mixture into a microwave synthesizer, sealing, crystallizing at 190 ℃ for 2h, transferring the mixture into the microwave synthesizer, sealing, crystallizing at 190 ℃ for 2h, standing after the reaction is finished, cooling, and centrifuging, washing and drying the solid product to obtain an initial product A.
(2) Loading of active components: dissolving 10.79g of nickel nitrate and 0.71g of cesium hydroxide in 8g of deionized water, fully stirring for 2h, adding the mixture into 8g of carrier A, standing and aging for 24h, drying the mixture, and roasting the dried mixture in an air atmosphere at 400 ℃ for 3h to obtain the catalyst for preparing the biofuel oil by grease hydrodeoxygenation, which is recorded as cat6.
Example 7
(1) The preparation method of the bimetallic silicon-aluminum-phosphorus carrier by the template-free method comprises the following steps: 13g of deionized water, 2.3g of phosphoric acid, 1.42g of pseudoboehmite, 0.80g of silica sol and 0.96g of cesium hydroxide and 0.491g of manganese hydroxide were mixed and stirred at 20 ℃ for 1 hour. And then transferring the mixture into a microwave synthesizer, sealing, crystallizing at 190 ℃ for 2h, transferring the mixture into the microwave synthesizer, sealing, crystallizing at 190 ℃ for 2h, standing after the reaction is finished, cooling, and centrifuging, washing and drying the solid product to obtain an initial product A.
(2) Loading of active components: dissolving 10.79g of nickel nitrate and 0.71g of cesium hydroxide in 8g of deionized water, fully stirring for 2h, adding the mixture into 8g of carrier A, standing and aging for 24h, drying the mixture, and roasting the dried mixture in an air atmosphere at 400 ℃ for 3h to obtain the catalyst for preparing the biofuel oil by grease hydrodeoxygenation, which is recorded as cat7.
Comparative example 1
(1) The preparation method of the bimetallic silicon-aluminum-phosphorus carrier by the template-free method comprises the following steps: 13g of deionized water, 2.3g of phosphoric acid, 1.42g of pseudoboehmite and 0.80g of silica sol were mixed and stirred at 20 ℃ for 1 hour. And then transferring the mixture into a microwave synthesizer, sealing, crystallizing at 190 ℃ for 2h, transferring the mixture into the microwave synthesizer, sealing, crystallizing at 190 ℃ for 2h, standing after the reaction is finished, cooling, and centrifuging, washing and drying the solid product to obtain an initial product A.
(2) Loading of active components: dissolving 10.79g of nickel nitrate and 0.71g of cesium hydroxide in 8g of deionized water, fully stirring for 2h, adding the mixture into 8g of carrier A, standing and aging for 24h, drying the mixture, and roasting the dried mixture in an air atmosphere at 400 ℃ for 3h to obtain the catalyst for preparing the biofuel oil by grease hydrodeoxygenation, which is recorded as cat8.
Comparative example 2
(1) The preparation method of the bimetallic silicon-aluminum-phosphorus carrier by the template-free method comprises the following steps: 13g of deionized water, 2.3g of phosphoric acid, 1.42g of pseudoboehmite, 0.80g of silica sol and 0.96g of cesium hydroxide were mixed and stirred at 20 ℃ for 1 hour. And then transferring the mixture into a microwave synthesizer, sealing, crystallizing for 2 hours at 190 ℃, transferring the mixture into the microwave synthesizer, sealing, crystallizing for 2 hours at 190 ℃, standing, cooling after the reaction is finished, and centrifuging, washing and drying the solid product to obtain an initial product A.
(2) Loading of active components: dissolving 10.79g of nickel nitrate and 0.71g of cesium hydroxide in 8g of deionized water, fully stirring for 2h, adding the mixture into 8g of carrier A, standing and aging for 24h, drying the mixture, and roasting the dried mixture in an air atmosphere at 400 ℃ for 3h to obtain a catalyst for preparing the biofuel oil by grease hydrodeoxygenation, which is recorded as cat9
Comparative example 3
(1) The preparation method of the bimetallic silicon-aluminum-phosphorus carrier by the template-free method comprises the following steps: 13g of deionized water, 2.3g of phosphoric acid, 1.42g of pseudoboehmite, 0.80g of silica sol and 0.44g of sodium hydroxide were mixed and stirred at 20 ℃ for 1 hour. And then transferring the mixture into a microwave synthesizer, sealing, crystallizing at 190 ℃ for 2h, transferring the mixture into the microwave synthesizer, sealing, crystallizing at 190 ℃ for 2h, standing after the reaction is finished, cooling, and centrifuging, washing and drying the solid product to obtain an initial product A.
(2) Loading of active components: dissolving 10.79g of nickel nitrate and 0.71g of cesium hydroxide in 8g of deionized water, fully stirring for 2h, adding the mixture into 8g of carrier A, standing and aging for 24h, drying the mixture, and roasting the dried mixture in an air atmosphere at 400 ℃ for 3h to obtain a catalyst for preparing bio-fuel oil by grease hydrodeoxygenation, which is recorded as cat10
Comparative example 4
(1) The preparation method of the bimetallic silicon-aluminum-phosphorus carrier by the template-free method comprises the following steps: 13g of deionized water, 2.3g of phosphoric acid, 1.42g of pseudoboehmite, 0.80g of silica sol, 0.96g of cesium hydroxide and 0.22g of sodium hydroxide were mixed and stirred at 20 ℃ for 1 hour. And then transferring the mixture into a microwave synthesizer, sealing, crystallizing at 190 ℃ for 2h, transferring the mixture into the microwave synthesizer, sealing, crystallizing at 190 ℃ for 2h, standing after the reaction is finished, cooling, and centrifuging, washing and drying the solid product to obtain an initial product A.
(2) Loading of active components: dissolving 10.79g of nickel nitrate into 8g of deionized water, fully stirring for 2h, adding the mixture into 8g of carrier A, standing and aging for 24h, drying the mixture, and roasting the dried mixture for 3h in an air atmosphere at 400 ℃ to obtain a catalyst for preparing the biofuel oil by grease hydrodeoxygenation, which is recorded as cat11
Example 8: catalyst evaluation
1. Kitchen waste oil pretreatment
Weighing phosphoric acid or citric acid solution with the mass of 0.7% of that of the kitchen waste oil, adding the phosphoric acid or citric acid solution into the oil, stirring and reacting at 85 ℃ for 30min, then adding distilled water with the mass of 6% of that of the kitchen waste oil, stirring and reacting at 75 ℃ for 30min, standing at constant temperature for 2h, centrifuging, and collecting an oil layer; this step uses a three-neck flask, an oil bath, a three-neck flask plus a condensing unit. Then adding distilled water with the mass of 10% of that of the oil layer, violently stirring for 15min at 70 ℃ and over 600 revolutions, centrifugally collecting the oil layer, and removing water from the oil layer at 105 ℃; adding acid clay 10% of the oil layer, heating to 110 deg.C, stirring at 500 rpm for 1 hr, centrifuging, and collecting oil.
2. Catalyst evaluation
The weighed catalyst is filled in a constant temperature interval of a reactor, and a ceramic ring is filled at the upper end of a reaction tube, so that the raw material with lower temperature is preheated. Before the reaction, the catalyst is added in H 2 Pretreating at a certain temperature (generally 400 ℃) for 2 hours in an atmosphere (160 mL/min) to reduce the supported oxide to a zero valence state, and then setting the temperature, pressure and hydrogen flow rate required by the reaction for evaluation (under the hydrogen pressure of 3-10WPa, the hydrogen-oil ratio is 800-2000, and the reaction temperature is 300-400 ℃). The pretreated kitchen waste oil is treated by 0.1-The feed was continuously fed into the fixed bed reactor at a rate of 1.0mL/min, and then the feed was taken up every hour and the product was analyzed by gas chromatography. Table 1 is a table for evaluating the performance of the products prepared in examples 1 to 7 of the present invention and comparative examples 1 to 4, and the performance of the catalytic kitchen waste oil hydrodeoxygenation in each example and comparative example can be determined from table 1.
TABLE 1
The evaluation results are shown in table 1. Under the same conditions of temperature and space velocity, the product of the catalyst loaded with the bimetal obtains better alkane yield which can reach 60-80 percent. The yield of the single metal or the alkane without metal load is about 30 to 40 percent. Probably because the constructed bimetallic molecular sieve, the metal in the pore canal and on the molecular sieve framework and the loaded metal have high-efficiency synergistic action, and the reaction is favorably carried out in the hydrodeoxygenation direction. Secondly, under the same reaction conditions, the bimetallic-loaded catalyst obtains higher selectivity of C9-C16 components, probably because the introduction of a second metal improves the dispersion degree of Ni, and the catalyst has more active sites and is beneficial to the reaction isomerization and cracking.
The embodiments of the present invention have been described in detail, but the description is only for the preferred embodiments of the present invention and should not be construed as limiting the scope of the present invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.
Claims (10)
1. The preparation method of the silicon-aluminum-phosphorus molecular sieve hydrogenation catalyst is characterized by comprising the following steps: mixing water, a silicon source, an aluminum source, a phosphorus source, a Cs source and a Me source to prepare initial gel, wherein the molar ratio of the water, the silicon source, the aluminum source, the phosphorus source, the Cs source and the Me source is 50-100:0.2-1:1:0.5-1.0:0.1-2:0.1 to 2; and (3) crystallizing to prepare a silicon-aluminum-phosphorus molecular sieve, and loading active metal to obtain the bimetallic silicon-aluminum-phosphorus molecular sieve hydrogenation catalyst.
2. The preparation method of the silicoaluminophosphate molecular sieve hydrogenation catalyst according to claim 1, characterized in that: me is one of Li, na, K, mg, ba, cu and Mn;
preferably, the Me source is one of sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, barium hydroxide, copper hydroxide, and manganese hydroxide.
3. The preparation method of the silicoaluminophosphate molecular sieve hydrogenation catalyst according to claim 1, characterized in that: the Cs source is one or more of cesium hydroxide, cesium carbonate, cesium oxalate and cesium acetate.
4. The preparation method of the silicoaluminophosphate molecular sieve hydrogenation catalyst according to claim 1, characterized in that: the silicon source is one or a combination of more of sodium silicate, silica sol, ethyl orthosilicate and white carbon black;
the aluminum source is one or the combination of more of sodium metaaluminate, aluminum hydroxide and pseudo-boehmite;
the phosphorus source is phosphoric acid.
5. The process of any of claims 1 to 4, wherein the hydrogenation catalyst comprises: the crystallization temperature is 150-200 ℃.
6. The preparation method of the silicoaluminophosphate molecular sieve hydrogenation catalyst according to claim 5, characterized in that: the active component is Ni-xCs, the mass of the active component accounts for 10-30% of the total mass of the catalyst, and x is the mass percentage of the simple substance Cs to the simple substance Ni, wherein the range of x is 5-20.
7. The preparation method of the silicoaluminophosphate molecular sieve hydrogenation catalyst according to claim 6, characterized in that: dissolving soluble salt of the active component into deionized water with the mass of one time of the water absorption rate of the carrier, adding the silicon-aluminum-phosphorus molecular sieve, standing, aging, drying, roasting, and reducing hydrogen to obtain the bimetallic silicon-aluminum-phosphorus molecular sieve hydrogenation catalyst.
8. The catalyst for hydrogenation of silicoaluminophosphate molecular sieve prepared by the method of any one of claims 1 to 7.
9. Use of the bimetallic silicoaluminophosphate molecular sieve hydrogenation catalyst of claim 8 in the preparation of biofuels; preferably, the method is applied to the preparation of biofuel from kitchen waste oil.
10. The use of the bimetallic silicoaluminophosphate molecular sieve hydrogenation catalyst of claim 9 in the preparation of biofuels, characterized in that: the method comprises the following steps of firstly pretreating the kitchen waste oil:
weighing phosphoric acid or citric acid solution 0.5-1% of the kitchen waste oil by mass, adding the phosphoric acid or citric acid solution into the oil, stirring and reacting at 80-85 ℃, adding distilled water 5-8% of the kitchen waste oil by mass, stirring and reacting at 70-75 ℃, standing at constant temperature, centrifuging, and collecting an oil layer;
adding distilled water with the mass of 8-15% of the oil layer, violently stirring at 70-75 ℃, centrifuging for the second time, and collecting the oil layer;
adding acid clay 8-10% of the mass of the secondary collected oil layer, heating to 100-110 ℃, stirring, centrifuging, and collecting the treated kitchen waste oil.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL6604373A (en) * | 1965-04-01 | 1966-10-03 | ||
| CN105126898A (en) * | 2015-08-11 | 2015-12-09 | 华东师范大学 | Preparation of hydrodeoxygenation isomerization catalyst and application thereof in preparation of diesel oil from illegal cooking oil |
| CN107088436A (en) * | 2017-04-10 | 2017-08-25 | 南开大学 | Selective hydrogenation of acetylene prepares the catalyst and preparation method and application of ethene |
| CN109868149A (en) * | 2019-03-13 | 2019-06-11 | 重庆大学 | A method of green diesel is prepared using kitchen abandoned oil zero hydrogen consumption one still process |
| CN110354874A (en) * | 2019-08-13 | 2019-10-22 | 南开大学 | The preparation method of the sial phosphorus carrier hydrogenation catalyst of porous structure and preparing the application in bio-fuel |
| CN111389456A (en) * | 2020-04-10 | 2020-07-10 | 浙江糖能科技有限公司 | Supported bifunctional catalyst, preparation method and application thereof |
| CN112403511A (en) * | 2020-11-26 | 2021-02-26 | 中国科学院上海高等研究院 | Preparation method of limited-domain bifunctional catalyst |
-
2022
- 2022-09-06 CN CN202211082709.1A patent/CN115382571B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL6604373A (en) * | 1965-04-01 | 1966-10-03 | ||
| CN105126898A (en) * | 2015-08-11 | 2015-12-09 | 华东师范大学 | Preparation of hydrodeoxygenation isomerization catalyst and application thereof in preparation of diesel oil from illegal cooking oil |
| CN107088436A (en) * | 2017-04-10 | 2017-08-25 | 南开大学 | Selective hydrogenation of acetylene prepares the catalyst and preparation method and application of ethene |
| CN109868149A (en) * | 2019-03-13 | 2019-06-11 | 重庆大学 | A method of green diesel is prepared using kitchen abandoned oil zero hydrogen consumption one still process |
| CN110354874A (en) * | 2019-08-13 | 2019-10-22 | 南开大学 | The preparation method of the sial phosphorus carrier hydrogenation catalyst of porous structure and preparing the application in bio-fuel |
| CN111389456A (en) * | 2020-04-10 | 2020-07-10 | 浙江糖能科技有限公司 | Supported bifunctional catalyst, preparation method and application thereof |
| CN112403511A (en) * | 2020-11-26 | 2021-02-26 | 中国科学院上海高等研究院 | Preparation method of limited-domain bifunctional catalyst |
Non-Patent Citations (1)
| Title |
|---|
| JIN HAO ET AL.: "Influence of Cs Substitution on the Structural Properties and Catalytic Performance of Ni-H3PW12O40/SiO2 Catalysts", 《ACTA PHYS. -CHIM. SIN.》, vol. 30, no. 3, pages 527 - 534 * |
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