CN105854872B - Catalyst and preparation method thereof for biological oil hydrodeoxygenation - Google Patents
Catalyst and preparation method thereof for biological oil hydrodeoxygenation Download PDFInfo
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- CN105854872B CN105854872B CN201610284189.0A CN201610284189A CN105854872B CN 105854872 B CN105854872 B CN 105854872B CN 201610284189 A CN201610284189 A CN 201610284189A CN 105854872 B CN105854872 B CN 105854872B
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- biological oil
- oxygen
- inorganic acid
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- 239000003054 catalyst Substances 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000002253 acid Substances 0.000 claims abstract description 38
- 125000004334 oxygen containing inorganic group Chemical group 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 22
- 230000008569 process Effects 0.000 claims abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 45
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 24
- 238000004073 vulcanization Methods 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 8
- 229910000765 intermetallic Inorganic materials 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 claims description 3
- 229940000488 arsenic acid Drugs 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- 238000012423 maintenance Methods 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 239000011572 manganese Substances 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- 229910052758 niobium Inorganic materials 0.000 claims 1
- 239000010955 niobium Substances 0.000 claims 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims 1
- 229910052702 rhenium Inorganic materials 0.000 claims 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims 1
- 229910052715 tantalum Inorganic materials 0.000 claims 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims 1
- 229910052713 technetium Inorganic materials 0.000 claims 1
- GKLVYJBZJHMRIY-UHFFFAOYSA-N technetium atom Chemical compound [Tc] GKLVYJBZJHMRIY-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 23
- 239000001257 hydrogen Substances 0.000 abstract description 22
- 238000001035 drying Methods 0.000 abstract description 17
- 238000006114 decarboxylation reaction Methods 0.000 abstract description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 12
- 238000006606 decarbonylation reaction Methods 0.000 abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 abstract description 7
- 150000007522 mineralic acids Chemical class 0.000 abstract description 6
- 239000011593 sulfur Substances 0.000 abstract description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 238000005984 hydrogenation reaction Methods 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 239000003921 oil Substances 0.000 description 24
- 235000019198 oils Nutrition 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 21
- 239000007864 aqueous solution Substances 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910019142 PO4 Inorganic materials 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 9
- 150000002431 hydrogen Chemical class 0.000 description 9
- 238000002347 injection Methods 0.000 description 9
- 239000007924 injection Substances 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 9
- 239000010452 phosphate Substances 0.000 description 9
- 241001465754 Metazoa Species 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 235000013311 vegetables Nutrition 0.000 description 8
- 239000003225 biodiesel Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 6
- 239000012075 bio-oil Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000006324 decarbonylation Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000002803 maceration Methods 0.000 description 6
- 229940093474 manganese carbonate Drugs 0.000 description 6
- 235000006748 manganese carbonate Nutrition 0.000 description 6
- 239000011656 manganese carbonate Substances 0.000 description 6
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 6
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000002283 diesel fuel Substances 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 241000219782 Sesbania Species 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 3
- -1 C12~C22Straight chain alkane Hydrocarbon Chemical class 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000004665 fatty acids Chemical group 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 235000016768 molybdenum Nutrition 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910000484 niobium oxide Inorganic materials 0.000 description 2
- 239000006259 organic additive Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000002560 therapeutic procedure Methods 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910003294 NiMo Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- XOCUXOWLYLLJLV-UHFFFAOYSA-N [O].[S] Chemical compound [O].[S] XOCUXOWLYLLJLV-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000012687 aluminium precursor Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 238000013441 quality evaluation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- IOWOAQVVLHHFTL-UHFFFAOYSA-N technetium(vii) oxide Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Tc+7].[Tc+7] IOWOAQVVLHHFTL-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical group [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
- B01J37/20—Sulfiding
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The catalyst and preparation method thereof that the present invention provides a kind of for biological oil hydrodeoxygenation.The preparation method comprises the following steps: taking the catalyst carrier for being impregnated with active component by roasting, so that it is adsorbed oxygen-containing inorganic acid, and handle through high temperature drying, carries out vulcanizing treatment later to get product；Wherein, the active component mainly by one of VB race metal or a variety of one of with VIIB race metal or a variety of forms.The present invention pre-processes catalyst using inorganic acid, increases the selectivity for adding hydrogen decarboxylation decarbonylation reaction, improves the sulfur fixation performance and thermal stability of catalyst.
Description
Technical field
The present invention relates to modifying oil product technical field, more particularly, to a kind of catalyst for biological oil hydrodeoxygenation and
Preparation method.
Background technique
With increasingly sharpening for crude oil heaviness and environmental pollution, liquefied coal coil, Fischer-Tropsch synthesis oil and bio oil are (various dynamic
Vegetable oil) as ideal fungible energy source by the concern of researcher, especially bio oil, because it is with pollutant emission
Less, the short feature of cycle period and become research focus.Compared with crude oil, the content of oxygenatedchemicals is higher in bio oil,
Main oxygenatedchemicals type includes phenols, furans, esters and ketone etc..It is raw due to the presence of a large amount of oxygenatedchemicals
The oxygen content of object oil product is sometime up to 50 weight % or more, so that bio oil be caused to have, combustion heat value is low, chemical property is unstable
It is straight as vehicle fuel seriously to hinder it compared with the unfavorable feature such as strong, big to the corrosivity of equipment for fixed, heating easily polymerization, acidity
Connect use, it is therefore desirable to which upgrading is carried out to bio oil by hydrogenation deoxidation.
The main component of vegetable and animals oils is triglyceride, and fatty acid chain length is generally C14~C22, wherein C16With
C18Account for about the 90% of all fatty acids.The diesel component that vegetable and animals oils hydrogenation deoxidation is prepared is mainly by C12~C22Straight chain alkane
Hydrocarbon composition, Cetane number can reconcile in any proportion up to 90~100 with petroleum diesel, and no sulphur, no aromatic hydrocarbons is not oxygen-containing,
NOx emission is few, environmental-friendly, and storage stability is good, can be used as the use of high cetane number diesel oil addO-on therapy.Therefore, it moves and plants
Object oil hydrogenation deoxidation prepares biodiesel technology, acts on the blueness of the novel renewable automobile-used supplement of one kind and alternative fuel by people
It looks at.
Vegetable and animals oils contain a variety of chemical reactions during adding hydrogen to prepare diesel component, mainly there is insatiable hunger in vegetable and animals oils
With fatty acid plus hydrogen saturation, hydrogenation deoxidation plus hydrogen decarboxylation, plus hydrogen de-carbonyl reaction, other also hydroisomerization reaction
Deng.Currently, the reaction of vegetable and animals oils hydrogenation deoxidation mainly uses sulphided state CoMo/Al2O3Or NiMo/Al2O3Catalyst, it is this kind of to urge
Agent hydrodesulfurization with higher and hydrogenation deoxidation activity, while hydrogenation deoxidation initial activity also with higher, but the disadvantage is that
Poor catalyst stability, it is easy to inactivate.
For example, CN101831315A discloses a kind of catalyst of the use based on nickel and molybdenum with restricted decarboxylation conversion ratio
It will be derived from the method for the raw material hydrogenation deoxidation of renewable source.The invention finds the activity mutually using the one kind for being selected from VIII group
Or various metals can especially with suitable Ni/Mo atomic ratio with the atomic ratio of one or more metals selected from group vib
To control and enhance the selectivity of hydrogenation deoxidation reaction, to limit decarboxylation/decarbonylation reaction, and therefore limit by oxycarbide
Form caused disadvantage.But catalyst the disadvantages of that there are stability is poor, easy in inactivation.
CN102427880A discloses a kind of catalyst comprising metal phosphide, is used to prepare biodiesel, also public affairs
Opened it is a kind of using the catalyst to vegetable oil carry out hydrotreating, thus the method for preparing biodiesel.The catalyst
Advantage is: when using the biodiesel comprising metal phosphide, the preparation of the biodiesel of hydrotreating
It is active high, in this embodiment it is not even necessary to vulcanizing agent without interruption, and hydrotreating carries out simultaneously with isomerization reaction, and thus, it is possible to obtain
The low high-quality hydrotreating biodiesel of pour point.Equally, the catalyst there is also hydrothermal stabilities poor, catalyst activity phase
The disadvantages of easily aggregation inactivates.
Therefore, need to develop a kind of hydrogenation deoxidation catalyst for being used to prepare biodiesel of high stability at present.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of catalyst for biological oil hydrodeoxygenation, the systems
Preparation Method pre-processes catalyst using inorganic acid, and selects suitable active component, increases plus hydrogen decarboxylation decarbonylation is anti-
The selectivity answered improves the sulfur fixation performance and thermal stability of catalyst.
Another object of the present invention is to provide a kind of catalyst for biological oil hydrodeoxygenation, the catalyst tool
Have and adds the features such as hydrogen decarboxylation decarbonylation selectivity is high, sulfur fixation performance and thermal stability are high.
A kind of preparation method of the catalyst for biological oil hydrodeoxygenation, comprising the following steps:
The catalyst carrier for being impregnated with active component by roasting is taken, so that it is adsorbed oxygen-containing inorganic acid, carries out sulphur later
Change processing to get product；
Wherein, the active component is mainly by one of VB race metal or a variety of one of with VIIB race metal or more
Kind composition.
Usually, the main reason for vegetable and animals oils hydrogenation deoxidation catalyst inactivates has carbon deposit, the exchange of oxygen sulphur and carrier
Carrier specific surface area caused by being hydrated reduces and activity mutually aggregation etc..Therefore inhibit carrier be hydrated caused by specific surface area reduce with
And the aggregation of active phase, play a significant role for the raising of hydrogenation deoxidation catalyst stability.However the prior art is usually not
It can take into account and inhibit carrier hydration and high two effects of reaction selectivity.By taking existing alumina support as an example, hydrogenation deoxidation catalysis
Aluminium oxide used by agent is spinel-like type structure, and a large amount of cations in surface and anion vacancy play alumina hydration
Key effect, therefore widespread practice is all auxiliary agent atom to be added and occupies alumina carrier surface vacancy by support modification,
To inhibit carrier to be hydrated；However, the shortcomings that way, is to reduce interaction force between active metal and carrier, thus one
Determine the active facies type for influencing vulcanization rear catalyst in degree, and reduces the selectivity of hydrogenation deoxidation and decarboxylation in turn.
And preparation method of the invention by vulcanization before to oxidized catalyst carry out oxygen-containing inorganic acid pretreatment and with
VB race and VIIB race are three measures of active component, not only inhibit the aquation of carrier, play increase acidity of catalyst and
Active phase dispersion, and increase decarboxylation decarbonylation reaction in turn to the selectivity of dehydration, and also improve consolidating for catalyst
Sulphur performance not easily runs off the sulphur in catalyst during the reaction, even if not adding vulcanizing agent, sulphidity is still higher than routine
The catalyst of method preparation.
Catalyst of the present invention be mainly used for vegetable and animals oils hydrogenation deoxidation modification, naturally it is also possible to for gasoline,
Other modifying oil products such as petroleum, coal tar, even more technical fields.
The above-mentioned preparation method of the present invention can also be further improved, such as:
Oxygen-containing inorganic acid of the present invention refers to any oxygen containing inorganic acid, the preferably oxygen-containing inorganic acid of VA race, preferably
For one of phosphoric acid, arsenic acid, metaantimmonic acid etc. or a variety of, preferably phosphoric acid.The stability of these inorganic acids is high, can be improved catalysis
The thermal stability of agent.
About the dosage of oxygen-containing inorganic acid, for example, on the basis of the catalyst carrier, VA race oxygen-containing inorganic acid
Dosage can be 0.1-10wt%, preferably 0.2-5wt%, more preferably 0.2-3wt%.VA race oxygen-containing inorganic acid can be with
It uses, can also be used in the form of its aqueous solution, preferably the latter in pure form.In addition, when the VA race is oxygen-containing inorganic
Acid is in the form of its aqueous solution in use, in VA race oxygen-containing inorganic acid aqueous solution, the weight of VA race oxygen-containing inorganic acid and water
Measuring ratio can be 1:1-80, preferably 1:2-10.At this point, the organic additive relative to hydrogenation catalyst above-mentioned dosage not
Dosage including water.
The present invention is not particularly limited the mode for contacting the hydrogenation catalyst with VA race oxygen-containing inorganic acid, example
Such as, hydrogenation catalyst can be mixed with VA race oxygen-containing inorganic acid, the aqueous solution containing organic additive can also be constantly sprayed
On hydrogenation catalyst.Preferably, the method for the absorption inorganic acid are as follows: (more preferably at 200 DEG C or less by the solution of inorganic acid
120 DEG C) under contacted with the oxidized catalyst, and after the absorption and before the vulcanizing treatment further include
It is dry under 200-250 DEG C (more preferable 230 DEG C).It is adsorbed under the above heating modified conducive to the front of catalyst.
Preferably, the mode hydrogenation catalyst contacted with VA race oxygen-containing inorganic acid are as follows: by the oxygen-containing nothing of VA race
Machine aqueous acid is continuously injected into the fixed bed reactors for being filled with the hydrogenation catalyst, is enabled to so pretreated
Hydrogenation catalyst directly applies in animal oil hydrogenation deoxidation reactor, simplifies technique.Further: urging the oxidation state
Agent and the inorganic acid react in fixed bed reactors, and keeping the temperature in reactor is 200 DEG C or less (more preferable
120 DEG C), partial pressure is 1-8MPa (more preferable 3MPa), and gas flow is 50-70L/h (more preferable 60L/h).Process above
Under the conditions of, preprocessing process will not have a negative impact to the mechanical strength of catalyst.(in the present invention, pressure refers both to gauge pressure)
Catalyst carrier of the present invention can use the available type of any conventional, such as alumina support or oxygen
Change the mixture of at least one of aluminium and silica, titanium oxide and zirconium oxide；Wherein, the aluminium oxide for example can be γ-oxygen
Change at least one of aluminium, η-aluminium oxide, θ-aluminium oxide, δ-aluminium oxide and χ-aluminium oxide.In addition, the carrier can be three leaves
Careless shape, butterfly, cylinder, hollow cylindrical, quatrefoil, five shapes such as leaf, spherical.Above-mentioned carrier can be obtained by commercially available
It arrives, it can also be according to well known to a person skilled in the art various methods to be prepared.For example, alumina support can be by by oxygen
Change the roasting of aluminium precursor, is converted into it in gama-alumina, η-aluminium oxide, θ-aluminium oxide, δ-aluminium oxide and χ-aluminium oxide extremely
Few one kind.Optionally, before firing and/or later, first aluminium oxide precursor can be formed, to prepare suitable practical operation
Required shape (such as spherical shape, sheet, bar shaped).The molding can be carried out according to the method for this field routine, such as spin
Method, pressed disc method and extrusion method etc..In forming process, such as during extruded moulding, in order to guarantee it is molding go on smoothly,
Water, extrusion aid and/or peptizing agent can be added into the aluminium oxide precursor, and be optionally added expanding agent, be then extruded into
Type is dried later and roasts.The extrusion aid, the type of peptizing agent and expanding agent and dosage can be using conventional places
Reason, for example, common extrusion aid can in sesbania powder, methylcellulose, starch, polyvinyl alcohol and polyethanol at least one
Kind, the peptizing agent can be Organic Alcohol and/or organic acid, the expanding agent can for starch, synthetic cellulose, polymeric alcohol and
At least one of surfactant.Wherein, the synthetic cellulose is preferably hydroxymethyl cellulose, methylcellulose, ethyl
At least one of cellulose and hydroxyl fiber fat alcohol polyethylene ether.The polymeric alcohol be preferably polyethylene glycol, poly- propyl alcohol and
At least one of polyvinyl alcohol.The surfactant be preferably fat alcohol polyethylene ether, fatty alkanol amide and its derivative,
Molecular weight is at least one of propylene alcohol copolymer and maleic acid copolymer of 200-10000.The dry item of item will be squeezed out
Part generally includes: drying temperature can be 40-350 DEG C, preferably 100-200 DEG C；Drying time can be 1-24 hours, preferably
It is 2-12 hours.The condition of extrusion item roasting after drying is generally included: maturing temperature can be 350-1000 DEG C, preferably
600-950℃；Calcining time can be 1-10 hours, preferably 2-6 hours.The aluminium oxide precursor can be selected from three hydrations
At least one of aluminium oxide, monohydrate alumina, amorphous hydroted alumina etc..
VB race and VIIB race of the present invention metal component is usually added in the form of the oxide, it is of course possible to use it
Its feasible chemical form, such as nitrate, carbonate, sulfate, meta-acid salt, ammonium salt etc..Wherein, VB race metal component
Example include but is not limited to: vanadium oxide (V2O5), niobium oxide (Nb2O5) and tantalum oxide (Ta2O5).VIIB race metal component
Example include but is not limited to: manganese oxide, technetium oxide, rheium oxide etc..
In the hydrogenation catalyst, preferably, VB race metal component is V2O5, VIIB race metal component
For MnO.
The temperature of the roasting is preferably 400-600 DEG C, and more preferably 420-500 DEG C；The time of the roasting is preferably
2-8h, more preferably 3-6h.Catalyst plus hydrogen decarboxylation decarbonylation selectivity can be improved by the above preferred roasting condition,
And thermal stability, extend the cycle of operation of oil product processing unit (plant).
About the dosage of active component, on the basis of the catalyst carrier, the content of VB race metallic compound is 0.01-
11.5wt%, preferably 1-10wt%；The content of VIIB race metallic compound is 0.01-10wt%, preferably 1-8wt%.
In catalyst carrier there are many kinds of the methods of impregnating metal active component, such as infusion process, spraying.Preferably,
By carrier impregnation in the maceration extract of the compound of metallic components, then it is dried.Wherein, the solvent in maceration extract can be with
For the various inertia liquids that can dissolve VB race metallic compound and VIIB race metallic compound, for example, can be with
Selected from least one of water, alcohol, ether, aldehyde and ketone.
In addition, can finally be vulcanized using dry pre-sulfiding or wet process to the vulcanizing treatment of catalyst.Specifically, for dry method
For vulcanization, the curing medium used can be H2And H2The mixture of S, and H in the curing medium2The volumetric concentration of S can be with
For 0.1-5v%, preferably 1-2v%.For wet process vulcanization, generallys use and face hydrogen vulcanization, the curing medium of use can
Think the mixture of diesel oil and disulphide and/or mercaptan, and the volumetric concentration of sulphur-containing substance can be in the curing medium
0.1-10v%, preferably 0.1-3.5v%, more preferably 0.4-2v%.Wherein, the disulphide can be CS2、CH3-S-
S-CH3And CH3-S-S-C2H5At least one of.The mercaptan can be C4H9SH、C2H5SH and CH3At least one of SH.
Preferred dry pre-sulfiding method are as follows: risen to the temperature of vulcanizing system from 20-40 DEG C with the rate of 25-35 DEG C/h
160-180 DEG C, and start into H2S；The temperature of vulcanizing system is risen to 220-240 DEG C with the rate of 10-20 DEG C/h again, and at this
At a temperature of maintain vulcanizing system in gas phase H2S concentration is constant and constant temperature vulcanizes 2-6h；Body will be vulcanized with the rate of 5-15 DEG C/h again
The temperature of system rises to 270-290 DEG C and constant temperature vulcanization 2-6h；Then again with the rate of 5-15 DEG C/h by the temperature liter of vulcanizing system
To 300-370 DEG C, and gas phase H in vulcanizing system is maintained at such a temperature2S concentration is constant and constant temperature vulcanizes 2-6h.
It is of the present invention to be typically referred in routine techniques " by the catalyst carrier for being impregnated with active component of roasting "
Not through the catalyst of over cure, which is used directly for the hydrogenation deoxidation of bio oil, but institute of the present invention is not achieved
The technical effect reached.In conjunction with the present invention, the temperature of the roasting is preferably 400-600 DEG C, and more preferably 420-500 DEG C；Institute
The time for stating roasting is preferably 2-8h, more preferably 3-6h.Adding for catalyst can be improved by the above preferred roasting condition
The selectivity and thermal stability of hydrogen decarboxylation decarbonylation extend the cycle of operation of oil product processing unit (plant).
The catalyst as made from above technical scheme shows plus hydrogen decarboxylation decarbonylation more higher than existing catalyst
The features such as selectivity and higher sulfur fixation performance and thermal stability.
Compared with prior art, invention achieves following technical effects:
(1) using VB race metal and VIIB race metal as active component, in conjunction with the pretreatment of oxygen-containing inorganic acid, catalysis is improved
The sulfur fixation performance of agent, thermal stability, and add the selectivity of hydrogen decarboxylation decarbonylation reaction；
(2) it can be used for vegetable and animals oils and prepare diesel oil；
(3) specific area of catalyst of the present invention and sulphidity are more stable.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with specific embodiment, but ability
Field technique personnel will be understood that following described embodiments are some of the embodiments of the present invention, instead of all the embodiments,
It is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.The person that is not specified actual conditions in embodiment, carries out according to conventional conditions or manufacturer's recommended conditions.Agents useful for same or instrument
Production firm person is not specified, is the conventional products that can be obtained by commercially available purchase.
Air speed of the present invention refers both to " volume space velocity ".
Embodiment 1
(1) oxidized catalyst is prepared:
It weighs 1000 grams of dry glue powders and 30 grams of sesbania powders and is uniformly mixed, the water-soluble of 900 milliliters of nitric acid containing 28g is added later
Liquid is extruded into the cylindrical wet bar of outer diameter φ 1.4mm on plunger type bar extruder.Then cylindrical wet bar is small in 120 DEG C of dryings 4
When, it is roasted 3 hours then at 600 DEG C, obtains carrier Z, Kong Rongwei 0.62mL/g, specific surface area 280m2/g。
Will 50g ammonium metavanadate, 50g manganese carbonate and 1000g citric acid be added 400mL aqueous solution in, heat and stir to
After being completely dissolved, maceration extract 500mL is obtained.The above-mentioned carrier Z of 400g is taken, above-mentioned maceration extract is all uniformly sprayed on carrier Z,
Then half obtained dry catalyst is put into baking oven and is dried 4 hours in 120 DEG C, then in 400 DEG C in ventable tube furnace
Constant temperature calcining 3 hours, obtain oxidized catalyst C1.
(2) pretreatment before vulcanization:
VA race oxygen-containing inorganic acid selects phosphoric acid, total injection rate 100g.Specifically, 200g phosphoric acid is mixed into system with 300g water
At the phosphate aqueous solution of 40 weight % of phosphoric acid.In a nitrogen atmosphere, phosphate aqueous solution is above-mentioned with the rate injection of 100g/h
In hydrogenation deoxidation reactor, maintaining reaction bed temperature during this period is 120 DEG C, nitrogen partial pressure 3.0MPa, nitrogen flow
For 60L/h.
After phosphate aqueous solution all injection, reaction bed temperature is risen to 230 DEG C, in a nitrogen atmosphere to catalyst
High temperature drying processing is carried out, controlling reactor inlet temperature during this period is 230 DEG C, and reactor outlet temperature is 230 DEG C, nitrogen
Partial pressure is 2.0MPa, and nitrogen flow 60L/h, drying time is 6 hours.Reaction bed temperature is down to after drying
145 DEG C, then introduce hydrogen.
(3) vulcanize:
The temperature of vulcanizing system is risen to 180 DEG C from 30 DEG C with the rate of 30 DEG C/h, and is started into H2S；Again with 10 DEG C/h
Rate the temperature of vulcanizing system is risen to 240 DEG C, and at such a temperature maintain vulcanizing system in gas phase H2S concentration is constant and permanent
Temperature vulcanization 4h；The temperature of vulcanizing system is risen to 290 DEG C with the rate of 15 DEG C/h again and constant temperature vulcanizes 6h；Then again with 15 DEG C/h
Rate the temperature of vulcanizing system is risen to 320 DEG C, and at such a temperature maintain vulcanizing system in gas phase H2S concentration is constant and permanent
Temperature vulcanization 5h.
Embodiment 2
(1) oxidized catalyst is prepared:
It weighs 1000 grams of dry glue powders and 30 grams of sesbania powders and is uniformly mixed, the water-soluble of 900 milliliters of nitric acid containing 28g is added later
Liquid is extruded into the cylindrical wet bar of outer diameter φ 1.4mm on plunger type bar extruder.Then cylindrical wet bar is small in 120 DEG C of dryings 4
When, it is roasted 3 hours then at 600 DEG C, obtains carrier Z, Kong Rongwei 0.62mL/g, specific surface area 280m2/g。
28g ammonium metavanadate, 18g manganese carbonate are added in 350mL aqueous citric acid solution, heat and stir to ammonium metavanadate and
After citric acid is completely dissolved, maceration extract 500mL is obtained.It is obtained using method impregnated carrier Z in the same manner as in Example 1 plus hydrogen is de-
VPO catalysts C2.
(2) pretreatment before vulcanization
VA race oxygen-containing inorganic acid selects phosphoric acid, total injection rate 100g.Specifically, 100g phosphoric acid is mixed into system with 900g water
At the phosphate aqueous solution of 10 weight %.In a nitrogen atmosphere, hydrogen is added to take off so that the rate injection of 100g/h is above-mentioned phosphate aqueous solution
In oxygen reactor, maintaining reaction bed temperature during this period is 120 DEG C, nitrogen partial pressure 3.0MPa, nitrogen flow 60L/
h。
After phosphate aqueous solution all injection, reaction bed temperature is risen to 230 DEG C, in a nitrogen atmosphere to catalyst
High temperature drying processing is carried out, controlling reactor inlet temperature during this period is 230 DEG C, and reactor outlet temperature is 230 DEG C, nitrogen
Partial pressure is 2.0MPa, and nitrogen flow 60L/h, drying time is 6 hours.Reaction bed temperature is down to after drying
150 DEG C, then introduce hydrogen.
(3) vulcanize:
It is same as Example 1.
Embodiment 3
(1) oxidized catalyst is prepared:
It weighs 1000 grams of dry glue powders and 30 grams of sesbania powders and is uniformly mixed, the water-soluble of 900 milliliters of nitric acid containing 28g is added later
Liquid is extruded into the cylindrical wet bar of outer diameter φ 1.4mm on plunger type bar extruder.Then cylindrical wet bar is small in 120 DEG C of dryings 4
When, it is roasted 3 hours then at 600 DEG C, obtains carrier Z, Kong Rongwei 0.62mL/g, specific surface area 280m2/g。
60g ammonium metavanadate, 70g manganese carbonate are added in 350mL aqueous solution, heats and stirs to ammonium metavanadate and citric acid
After being completely dissolved, maceration extract 500mL is obtained.Hydrogenation deoxidation catalysis is obtained using method impregnated carrier Z in the same manner as in Example 1
Agent C3.
(2) pretreatment before vulcanization
VA race oxygen-containing inorganic acid selects phosphoric acid, total injection rate 100g.Specifically, 100g phosphoric acid is mixed into system with 900g water
At the phosphate aqueous solution of 10 weight %.In a nitrogen atmosphere, hydrogen is added to take off so that the rate injection of 100g/h is above-mentioned phosphate aqueous solution
In oxygen reactor, maintaining reaction bed temperature during this period is 120 DEG C, nitrogen partial pressure 3.0MPa, nitrogen flow 60L/
h。
After phosphate aqueous solution all injection, reaction bed temperature is risen to 230 DEG C, in a nitrogen atmosphere to catalyst
High temperature drying processing is carried out, controlling reactor inlet temperature during this period is 230 DEG C, and reactor outlet temperature is 230 DEG C, nitrogen
Partial pressure is 2.0MPa, and nitrogen flow 60L/h, drying time is 6 hours.Reaction bed temperature is down to after drying
150 DEG C, then introduce hydrogen.
(3) vulcanize:
It is same as Example 1.
Embodiment 4-5
Embodiment 4-5 is only that metal active constituent is different from the difference of embodiment 1, mole of VB race metallic element
Number, the molal quantity of VIIB race metallic element are identical as embodiment, and the compound of active component is respectively as follows:
Nb2O5/ MnO, ammonium metavanadate+Nb2O5(the two is mixed with equimolar)/MnO.
Embodiment 6-8
Embodiment 6-8 is only that the active component dosage of dipping is different from the difference of embodiment 1, and dosage is respectively as follows: 0.1g
Ammonium metavanadate/100g manganese carbonate, 115g ammonium metavanadate/100g manganese carbonate, 100g ammonium metavanadate/80g manganese carbonate.
Embodiment 9-10
The difference of embodiment 9-10 and embodiment 1 is only that oxygen-containing inorganic acid type used in the preceding pretreatment of vulcanization not
Together, but dosage is identical (weight percent), and oxygen-containing inorganic acid is respectively as follows: arsenic acid, metaantimmonic acid.
Embodiment 11-15
The dosage of phosphoric acid used in pretreatment is different before embodiment 11-15 is only that vulcanization from the difference of embodiment 1, with
On the basis of the quality of Z, dosage is respectively as follows: 0.1%, 0.2%, 3%, 5%, 10%.
Embodiment 16-18
Embodiment 16-18 is only that step (1) maturing temperature is different from the difference of embodiment 1, is respectively as follows: 420 DEG C, 500
℃、600℃。
Embodiment 19-21
Embodiment 19-21 is only that step (1) calcining time is different from the difference of embodiment 1, is respectively as follows: 2h, 6h, 8h.
Embodiment 22-23
Pretreated reaction temperature is different before embodiment 22-23 is only that vulcanization from the difference of embodiment 1, is respectively as follows: 100
℃、140℃。
Embodiment 24-25
Pretreated drying temperature is different before embodiment 24-25 is only that vulcanization from the difference of embodiment 1, is respectively as follows: 200
℃、250℃。
Embodiment 26-27
Embodiment 26-27 is only that gaseous environment when vulcanizing preceding pretreatment reaction is different from the difference of embodiment 1, respectively
Are as follows: 1MPa+50L/h, 8MPa+70L/h.
Comparative example 1
(1) the carrier Z for taking 400g embodiment 1 to prepare contains 90 grams per liter MoO with 500 milliliters3With seven molybdenums of 32 grams per liter NiO
Sour ammonium and nickel nitrate mixed solution filter after impregnating 1 hour, then dry 4 hours in 120 DEG C, roast 2 hours then at 400 DEG C,
Reference oxidized catalyst DC1 is obtained, is directly vulcanized, vulcanization process is the same as embodiment 1.
Comparative example 2
(1) DC1 for taking comparative example 1 carries out vulcanization pre-treatment using method same as Example 1, after cure, vulcanization
Method is the same as embodiment 1.
Comparative example 3
Catalyst C1 prepared by Example 1 is packed into hydrogenation deoxidation reactor, saves pretreatment stage before vulcanization, directly
It into sulfurating stage and reacts, vulcanization process is the same as embodiment 1.
The quality evaluation of catalyst:
Firstly, by embodiment 1 to 27, comparative example 1 to 3 reaction pressure be 5.0MPa, 355 DEG C of temperature, liquid hourly space velocity (LHSV) 2h-1, under the conditions of hydrogen to oil volume ratio is 700, hydrogenation deoxidation modification is carried out to palm oil, evaluates each catalyst performance, as a result such as 2 He of table
Shown in 3.The results show that all embodiments show following characteristics: the catalyst of all embodiments of the invention is being run
After 100h, adds hydrogen decarboxylation and add hydrogen decarbonylation selectivity between 25-35%, V sulphidity is 70% or more on unloading rear catalyst
(unloading rear catalyst is characterized with x-ray photoelectron spectroscopy technology, is impregnated with V, and on catalyst+2 ,+3 and+4
Valence vanadium atom accounts for the ratio of total V atom to represent V sulphidity；It is impregnated with molybdenum, it is former to account for total Mo with+4 valence molybdenum atoms on catalyst
The ratio of son represents Mo sulphidity), unload the specific surface area of rear catalyst in 270m2/ g or more, and the diesel oil obtained evaporates
Dividing can reconcile in any proportion with petroleum diesel, and no sulphur, no aromatic hydrocarbons, not oxygen-containing, NOx emission is few, environmental-friendly, stable storing
Property it is good, can be used as high cetane number diesel oil addO-on therapy use.
Secondly, in reaction pressure being 5.0MPa, 355 DEG C of temperature, liquid hourly space velocity (LHSV) 2h by embodiment 1 and comparative example 1-1, hydrogen oil
Under the conditions of volume ratio is 700, hydrogenation deoxidation modification is carried out to gutter oil (property is as shown in table 1), evaluates each catalyst performance, is tied
Fruit is as shown in table 4.
The concrete outcome of section Example is listed below, as shown in table 2 to 4, table 2 be run 24 hours after as a result,
Table 3 and table 4 are the result run after 100h.
Table 1
| Project | Gutter oil |
| Density (20 DEG C)/(g/cm3) | 0.9214 |
| Viscosity (40 DEG C)/(mm2/s) | 47.64 |
| Total acid number/(mgKOH/g) | 3.38 |
| Condensation point/DEG C | 28 |
| Sulfur content/(μ g/g) | 24 |
| Nitrogen content/(μ g/g) | 78 |
| Oxygen content/% | 12.14 |
| D-2887 boiling range/DEG C | |
| IBP/10% | 529/575 |
| 30%/50% | 590/594 |
| 70%/90% | 601/618 |
| 95%/FBP | --/676 |
Table 2
Table 3
Table 4
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (18)
1. a kind of preparation method of the catalyst for biological oil hydrodeoxygenation, which comprises the following steps:
The catalyst carrier for being impregnated with active component by roasting is taken, oxidized catalyst is named as, urges the oxidation state
Agent adsorbs oxygen-containing inorganic acid, carries out vulcanizing treatment later to get product；
Wherein, the active component is mainly by one of VB race metal or one of a variety of and VIIB race metal or a variety of groups
At；
The method of the absorption oxygen-containing inorganic acid are as follows: be catalyzed the solution of oxygen-containing inorganic acid with the oxidation state at 200 DEG C or less
Agent contact, and further include dry at 200-250 DEG C after the absorption and before the vulcanizing treatment.
2. the preparation method of the catalyst according to claim 1 for biological oil hydrodeoxygenation, which is characterized in that described
Oxygen-containing inorganic acid is the oxygen-containing inorganic acid of VA race.
3. the preparation method of the catalyst according to claim 2 for biological oil hydrodeoxygenation, which is characterized in that described
Oxygen-containing inorganic acid is one of phosphoric acid, arsenic acid, metaantimmonic acid or a variety of.
4. the preparation method of the catalyst according to claim 3 for biological oil hydrodeoxygenation, which is characterized in that described
Oxygen-containing inorganic acid is phosphoric acid.
5. the preparation method of the catalyst according to claim 1 for biological oil hydrodeoxygenation, which is characterized in that described
Catalyst carrier is alumina support；VB race metal is at least one of vanadium, niobium and tantalum, and VIIB race metal is
At least one of manganese, technetium and rhenium.
6. the preparation method of the catalyst according to claim 5 for biological oil hydrodeoxygenation, which is characterized in that described
Active component is vanadium and manganese.
7. the preparation method of the catalyst according to claim 1-6 for biological oil hydrodeoxygenation, the suction
The method of attached oxygen-containing inorganic acid are as follows: react the oxidized catalyst and the oxygen-containing inorganic acid in fixed bed reactors,
And keeping the temperature in reactor is 120-200 DEG C, partial pressure 1-8MPa, gas flow 50-70L/h.
8. the preparation method of the catalyst according to claim 1-6 for biological oil hydrodeoxygenation, feature
It is, when carrying out the absorption, on the basis of the catalyst carrier, the dosage of the oxygen-containing inorganic acid are as follows: 0.1-10wt%.
9. the preparation method of the catalyst according to claim 8 for biological oil hydrodeoxygenation, which is characterized in that carry out
When the absorption, on the basis of the catalyst carrier, the dosage of the oxygen-containing inorganic acid is 0.2-5wt%.
10. the preparation method of the catalyst according to claim 9 for biological oil hydrodeoxygenation, which is characterized in that into
When the row absorption, on the basis of the catalyst carrier, the dosage of the oxygen-containing inorganic acid is 0.2-3wt%.
11. the preparation method of the catalyst according to claim 1 for biological oil hydrodeoxygenation, which is characterized in that institute
The temperature for stating roasting is 400-600 DEG C.
12. the preparation method of the catalyst according to claim 11 for biological oil hydrodeoxygenation, which is characterized in that institute
The temperature for stating roasting is 420-500 DEG C.
13. the preparation method of the catalyst according to claim 12 for biological oil hydrodeoxygenation, which is characterized in that institute
The time for stating roasting is 2-8h.
14. the preparation method of the catalyst according to claim 13 for biological oil hydrodeoxygenation, which is characterized in that institute
The time for stating roasting is 3-6h.
15. the preparation method of the catalyst according to claim 1 for biological oil hydrodeoxygenation, which is characterized in that institute
Stating vulcanizing treatment is that dry pre-sulfiding or wet process vulcanizes；
The dry pre-sulfiding method are as follows: the temperature of vulcanizing system is risen to from 20-40 DEG C by 160- with the rate of 25-35 DEG C/h
180 DEG C, and start into H2S；The temperature of vulcanizing system is risen to 220-240 DEG C with the rate of 10-20 DEG C/h again, and in the temperature
Gas phase H in lower maintenance vulcanizing system2S concentration is constant and constant temperature vulcanizes 2-6h；Again with the rate of 5-15 DEG C/h by vulcanizing system
Temperature rises to 270-290 DEG C and constant temperature vulcanization 2-6h；Then the temperature of vulcanizing system is risen to the rate of 5-15 DEG C/h again
300-370 DEG C, and gas phase H in vulcanizing system is maintained at such a temperature2S concentration is constant and constant temperature vulcanizes 2-6h.
16. the preparation method of the catalyst according to claim 1 for biological oil hydrodeoxygenation, which is characterized in that with
On the basis of the catalyst carrier, the content of VB race metallic compound is 0.01-11.5wt%；VIIB race metallic compound contains
Amount is 0.01-10wt%.
17. the preparation method of the catalyst according to claim 16 for biological oil hydrodeoxygenation, which is characterized in that with
On the basis of the catalyst carrier, the content of VB race metallic compound is 1-10wt%；The content of VIIB race metallic compound is
1-8wt%.
18. being used for the catalyst of biological oil hydrodeoxygenation, which is characterized in that by the described in any item preparation sides claim 1-17
Method is made.
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