CN102476980A - Application of tungsten-based catalyst in preparation of aromatic compound by catalytic hydrogenation of lignin - Google Patents
Application of tungsten-based catalyst in preparation of aromatic compound by catalytic hydrogenation of lignin Download PDFInfo
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- CN102476980A CN102476980A CN2010105878457A CN201010587845A CN102476980A CN 102476980 A CN102476980 A CN 102476980A CN 2010105878457 A CN2010105878457 A CN 2010105878457A CN 201010587845 A CN201010587845 A CN 201010587845A CN 102476980 A CN102476980 A CN 102476980A
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- China
- Prior art keywords
- tungsten
- catalyst
- loading
- xylogen
- lignin
- Prior art date
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Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 55
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000010937 tungsten Substances 0.000 title claims abstract description 43
- 229920005610 lignin Polymers 0.000 title claims abstract description 26
- 150000001491 aromatic compounds Chemical class 0.000 title abstract description 5
- 238000009903 catalytic hydrogenation reaction Methods 0.000 title abstract description 4
- 238000002360 preparation method Methods 0.000 title description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 26
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 10
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 9
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 9
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 9
- 239000002028 Biomass Substances 0.000 claims abstract description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 7
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 5
- 239000010941 cobalt Substances 0.000 claims abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000005336 cracking Methods 0.000 claims abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 239000010949 copper Substances 0.000 claims abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 3
- 150000003624 transition metals Chemical class 0.000 claims abstract description 3
- 229920001732 Lignosulfonate Polymers 0.000 claims abstract 2
- 238000011068 loading method Methods 0.000 claims description 38
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 16
- 238000005984 hydrogenation reaction Methods 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 13
- 238000003763 carbonization Methods 0.000 claims description 13
- 239000002808 molecular sieve Substances 0.000 claims description 12
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 9
- 229910002796 Si–Al Inorganic materials 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 239000004411 aluminium Substances 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000002023 wood Substances 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 239000004480 active ingredient Substances 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 5
- -1 peroxide tungstate Chemical class 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- 241000775848 Syringa oblata Species 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000004044 response Effects 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 238000004904 shortening Methods 0.000 claims description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 229910000906 Bronze Inorganic materials 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000010974 bronze Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 2
- 239000002798 polar solvent Substances 0.000 claims 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims 1
- 241000208140 Acer Species 0.000 claims 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims 1
- 235000017491 Bambusa tulda Nutrition 0.000 claims 1
- 235000018185 Betula X alpestris Nutrition 0.000 claims 1
- 235000018212 Betula X uliginosa Nutrition 0.000 claims 1
- 244000166124 Eucalyptus globulus Species 0.000 claims 1
- 240000000731 Fagus sylvatica Species 0.000 claims 1
- 235000010099 Fagus sylvatica Nutrition 0.000 claims 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims 1
- 244000082204 Phyllostachys viridis Species 0.000 claims 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims 1
- 241000351396 Picea asperata Species 0.000 claims 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims 1
- 241000018646 Pinus brutia Species 0.000 claims 1
- 235000011613 Pinus brutia Nutrition 0.000 claims 1
- 241000219000 Populus Species 0.000 claims 1
- 240000007313 Tilia cordata Species 0.000 claims 1
- 239000011425 bamboo Substances 0.000 claims 1
- 150000002191 fatty alcohols Chemical class 0.000 claims 1
- 235000019357 lignosulphonate Nutrition 0.000 claims 1
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 239000010902 straw Substances 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 11
- 238000004517 catalytic hydrocracking Methods 0.000 abstract description 4
- 150000002989 phenols Chemical class 0.000 abstract description 4
- 230000007062 hydrolysis Effects 0.000 abstract 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract 1
- 150000007522 mineralic acids Chemical class 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 14
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- 238000010792 warming Methods 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 229960003742 phenol Drugs 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 244000274847 Betula papyrifera Species 0.000 description 4
- 235000009113 Betula papyrifera Nutrition 0.000 description 4
- 235000009109 Betula pendula Nutrition 0.000 description 4
- 235000010928 Betula populifolia Nutrition 0.000 description 4
- 235000002992 Betula pubescens Nutrition 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 239000012018 catalyst precursor Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 150000003384 small molecules Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical class CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910020515 Co—W Inorganic materials 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 235000010980 cellulose Nutrition 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- PXIKRTCSSLJURC-UHFFFAOYSA-N Dihydroeugenol Chemical compound CCCC1=CC=C(O)C(OC)=C1 PXIKRTCSSLJURC-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the hydrocracking of lignin, in particular to a method for preparing aromatic compounds by catalyzing the hydrocracking of lignin by a tungsten-based catalyst; the catalyst used in the method takes non-zero-valent tungsten as a main active component, and takes one or more small amount of transition metals of zero-valent nickel, cobalt, ruthenium, iridium, palladium, platinum, iron, copper and the like as a second metal component. The method takes natural lignin, biomass hydrolysis residue, lignosulfonate, alkali lignin and the like as raw materials at the temperature of 120-450-oC, catalytic hydrogenation is carried out under the hydro-thermal condition that the hydrogen pressure is 1-20MPa, the high-selectivity cracking is carried out to obtain the phenolic compound of C6-C9, and the highest phenol yield can be 55.6%. Compared with the prior art, the method can use renewable natural biomass as the raw material, and the raw material is cheap and has wide sources; inorganic acid and alkali are not needed, so that the generation of a large amount of alkali liquor in the traditional lignin catalysis is avoided; the method also has the characteristics of low cost of the tungsten-based catalyst, green reaction process, atom economy and the like.
Description
Technical field
The present invention relates to the preparation of aromatics, the hydrocracking of specifically a kind of loading type carbonization tungsten catalyst catalysis xylogen resource prepares the method for single phenols aromatics.
Background technology
The high speed development of world economy has benefited from fossil energy, like the widespread use of oil, Sweet natural gas, coal.Along with can not constantly consuming by the round-robin fossil resource, it is increasingly serious that energy dilemma and environmental problem have become.Develop renewable new forms of energy and replace the inexorable trend that fossil resource becomes social development.
Biomass resource is present in nature in a large number, is the abundantest on the earth, the most cheap and meets the renewable resources of Sustainable development requirement.In biomass, the content of xylogen is only second to Mierocrystalline cellulose, is the abundantest natural aromatic compound resource of occurring in nature, and all regenerate with 50,000,000,000 tons speed every year.Pulp and paper industry will be isolated about 1.4 hundred million tons of Mierocrystalline celluloses every year from plant, obtain the xylogen sub product about 5,000 ten thousand tons simultaneously.But up to now; The trans-utilization of xylogen still lacks effective way; Surpass 95% xylogen and enter rivers with " black liquor " form or burn, not only wasted biomass resource, and severe contamination environment; Consequent waste water accounts for 30% of national amount of industrial wastewater, is first object of China's trade effluent control.
Aromatics has very important use in chemical industry; For example phenol and terephthalic acid and verivate thereof are not only widely used bulk chemical, also are simultaneously the important source material of producing resin, rubber, medicine intermediate and other fine chemicals.See that from structure xylogen is to be the three-dimensional netted polymkeric substance of main structure body with the aromatic ring, mainly comprises three kinds of structural units: guaiacyl, Syringa oblata Lindl. base, para hydroxybenzene based structures.Link to each other through ehter bond or carbon-carbon bond between the structural unit.Through the design appropriate catalyst; Selectivity is to the xylogen hydrogenating reduction; Cut off the link between the structural unit, can realize preparing the aromatic series phenolic cpd, thereby be applied to every field as the substitute of fossil resource by the xylogen resource; Alleviate the awkward situation of world energy sources crisis to a certain extent, also avoided the discharging of discarded " black liquor " simultaneously.
But,, there is greatly difficulty in its catalytic pyrolysis because of xylogen complicated structure and obstinate physicochemical property.USP (US 4,900,873) uses biphenyl or naphthalene to prepare aromatics as the solvent pyrolysis lignin at 300-400 ℃, but productive rate less than 20%.USP (US5,807,952) prepares phenolic cpd 400-600 ℃ of highly basic catalysis xylogen pyrolysis under air atmosphere such as following KOH, and the phenol maximum output can reach 60%, but severe reaction conditions, and produce a large amount of waste lyes.World patent (WO99/10450) 260-310 ℃ in nitrogen atmosphere with base catalysis xylogen hydrogenation preparing gasoline component, but the complete hydrogenation of phenyl ring needs more hydrogen sources, and alkaline catalysts produces a large amount of waste liquids, contaminate environment.Canadian Patent adopts metallic sulfide be catalyzer in 250-450 ℃ with 15-45MPa under the catalysis lignin degradation obtain phenolic cpd, the highest 40% phenol productive rate that obtains.It is the bimetallic catalyst catalysis xylogen hydrogenation of main active component that Chinese patent (CN 101768052A) has been described with zeroth order Ni, and the raw material peak rate of conversion reaches 53%.See from the finding of document; The xylogen hydrogenation catalyst of report is many at present is main with precious metals such as Pd, Pt; It is to be raw material with the xylogen that any report is not arranged as yet, and, highly selective catalyzed degradation efficient under non-alkaline condition through cheap non-zero valence tungsten-based catalyst produced aromatics.
Summary of the invention
The object of the present invention is to provide a kind of method of tungsten-based catalyst catalysis xylogen raw material degraded system aromatics; It can be implemented under the reaction conditions of hydro-thermal hydrogenation, and the high yield of catalysis xylogen, highly selective are converted into single phenols aromatics.
For realizing above-mentioned purpose, the technical scheme that the present invention takes is:
The xylogen hydrocracking catalyst that is used for according to the invention is the non-zero valence tungsten-based catalyst, is described below:
Said tungsten-based catalyst can be loading type carbonization tungsten catalyst, is made up of active ingredient wolfram varbide and carrier.Carrier is one or more in gac, aluminum oxide, silicon oxide, titanium oxide, zirconium white, titanium oxide, Si-Al molecular sieve, the phosphate aluminium molecular sieve; The loading of tungsten in carrier is 5-80wt%, and preferred loading is 10-50wt%, and more preferably loading is 15-40wt%;
Said loading type carbonization tungsten catalyst also can be made up of main active component, carrier and second metal component, three parts.Said main active component is a wolfram varbide, and the loading of tungsten in carrier is 5-80wt%, and preferred loading is 10-50wt%, and more preferably loading is 15-40wt%; Said carrier is one or more in gac, aluminum oxide, silicon oxide, titanium oxide, zirconium white, titanium oxide, Si-Al molecular sieve, the phosphate aluminium molecular sieve; In the nickel that said second metal component is a metallic state, iridium, platinum, ruthenium, rhodium, palladium, iron, cobalt, copper, aluminium, tin, molybdenum, chromium, the strontium one or more, one or more in preferred nickel, iridium, ruthenium, palladium, the platinum; The loading of second metal component in carrier is 0.05-30wt%, and preferred loading is 0.1-15wt%, and more preferably loading is 0.2-5wt%.
Said tungsten-based catalyst can be composite catalyst; Comprise catalyst A and catalyst B; The activeconstituents of catalyst A is one or more in the transition metal iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, platinum of the 8th, 9,10 families, and the activeconstituents of catalyst B is one or more in the oxyhydroxide, tungsten bronze(s), wolframic acid, tungstate, metatungstic acid, metatungstate, para-tungstic acid, para-tungstate, peroxide wolframic acid, peroxide tungstate, heteropoly tungstic acid of muriate, the tungsten of sulfide, the tungsten of oxide compound, the tungsten of tungsten; The metal active composition of catalyst A and the activeconstituents of catalyst B (in tungsten weight) weight ratio are between 0.02-3000 times of scope.
Said catalyst A can be loaded catalyst, and carrier is gac, aluminum oxide, silicon oxide, silit, zirconium white, zinc oxide, titanium oxide is a kind of or the complex carrier more than two kinds; The content of activity component metal on catalyzer is 0.05-50wt%, preferably at 1-30wt%.
Said catalyst A also can be unsupported, with the skeleton metal catalyst of active ingredient as catalyst backbone.
Said loaded catalyst adopts the load method preparation, and the active ingredient salts solution is supported on the carrier, obtains catalyst precursor.After 100-160 ℃ of drying, carry out the temperature programmed reduction(TPR) reaction at hydrogen or methane/hydrogen (methane content is 10-100%v/v).
The reduction temperature of said loading type carbonization tungsten catalyst is between 600-900 ℃, and preferred reduction temperature is 700-800 ℃, and reducing atmosphere is hydrogen or methane/hydrogen (methane content is 20%v/v), and carbonization time is no less than 0.5 hour.
The reduction temperature of said loaded catalyst A is between 250-800 ℃, and preferred reduction temperature is 300-500 ℃, and reducing atmosphere is hydrogen or methane/hydrogen (methane content is 20%v/v), and carbonization time is no less than 0.5 hour.
The reaction process that realizes xylogen shortening cracking system phenolic cpd is following: said xylogen raw material hydrogenation DeR is carried out in airtight autoclave, and the mass ratio of reaction raw materials and solvent is 1: 500-1: 1, preferred 1: 100-1: 5; Catalyst levels is getting final product of catalytic amount, is fast reaction speed, and the mass ratio of xylogen and catalyzer is generally 1: 2-100: 1, and preferred proportion is 2: 1-20: 1; The original pressure of filling hydrogen under the room temperature in the reaction kettle is 1-20MPa, preferred 3-10MPa; Temperature of reaction is 120-450 ℃, preferred 150-300 ℃; Reaction times is 10min-24h.
Compared with prior art, the present invention has following advantage:
1. raw material wood element of the present invention is the abundantest natural reproducible aromatic compound resource of occurring in nature, and wide material sources are with low cost.Prepare aromatic compound with existing petroleum base industry synthetic route and compare, the present invention does not consume fossil resource, has the advantage of regenerated raw materials, meets the requirement of Sustainable development.
2. the present invention has reduced the pollution because of industrial lignin discharges and burning is caused for the utilization of industrial lignin provides new way.
3. catalyzer is main active component with non-zero valence tungsten, and is with low cost, and active high, single phenolic cpd productive rate is up to 55.6%.
4. the reaction system environmental friendliness is pollution-free when being solvent with water; Do not use mineral acid, alkali in the reaction process, avoided common problem of environmental pollution in the lignin degradation technology.
Further specify through specific embodiment below.
Embodiment
Embodiment 1
Activated carbon supported nickel-tungsten carbide catalyzer (Ni-W
2C/AC) preparation: is that 15: 1 ratio is processed mixing solutions with metatungstic acid ammonia and nickelous nitrate according to tungsten/nickel weight ratio, and wherein, the mass concentration of metatungstic acid ammonia is 0.4g/ml.Then, with the method for incipient impregnation with mixing solutions Immesion active carbon carrier (AC).Behind 120 ℃ of oven drying 12h; Place H2 atmosphere to carry out temperature programming carbon thermal response catalyst precursor; Concrete reaction process is: the 1.0g precursor is warming up to 400 ℃ by room temperature 1h in crystal reaction tube; Then be warming up to 700 ℃ and keep 1h to carry out carbonization with 1 ℃/min, hydrogen flow rate is 60ml/min.Obtaining the tungsten loading is that 30wt%, nickel loading are the Ni-W of 2wt%
2The C/AC catalyzer is expressed as Ni-W
2C/AC (2wt%Ni-30wt%W
2C).
Other condition is constant, only changes the concentration of metatungstic acid ammonia and nickelous nitrate in the steeping fluid, perhaps through dipping repeatedly, can obtain active ingredient loading different catalyst; It is formed as follows: the Ni loading is 2wt%, and the tungsten loading is respectively 5wt%, 10wt%, 15wt%, 60wt%, the Ni-W of 80wt%
2The C/AC catalyzer, and the tungsten loading is 30wt%, the nickel loading is respectively 0.05wt%, 0.2wt%, 5wt%, 10wt%, the Ni-W of 30wt%
2The C/AC catalyzer.
Embodiment 2
The Ni-WxC/AC Preparation of catalysts: the preparation process is similar to embodiment 1, and difference is that carbonization temperature is 850 ℃, and obtaining the tungsten loading is that 30wt%, nickel loading are the Ni-WxC/AC catalyzer of 2wt%, and wherein, WxC is W
2The crystalline phase of mixing of C and WC, 1＜x＜2.Be expressed as Ni-WxC/AC (2wt%Ni-30wt%WxC).
Embodiment 3
The WxC/AC Preparation of catalysts: the preparation process is similar to embodiment 1, and difference is only to have used metatungstic acid ammonia in the precursor and does not add nickelous nitrate, and carbonization temperature is 800 ℃, obtains W thus
2The C/AC catalyzer; Or, obtain the WxC/AC catalyzer 850 ℃ of following carbonizations, be W
2The crystalline phase of mixing of C and WC, 1＜x＜2.
Embodiment 4-9
Co-W
2C/AC, Fe-W
2C/AC, Pt-W
2C/AC, Ru-W
2C/AC, Ir-W
2C/AC, Pd-W
2The C/AC Preparation of catalysts: the preparation process is similar to embodiment 1; Difference is to have used Xiao Suangu, iron nitrate, Platinic chloride, ruthenium chloride, chloro-iridic acid and Palladous chloride in the precursor respectively but not nickelous nitrate; The W loading is 30wt% in the catalyzer; Co, Fe, Pt, Ru, Ir, Pd loading are respectively 2wt%, 2wt%, 1wt%, 1wt%, 1wt% and 1wt%, obtain Co-W thus
2C/A, Fe-W
2C/AC, Pt-W
2C/AC, Ru-W
2C/AC, Ir-W
2C/AC and Pd-W
2The C/AC catalyzer.
Embodiment 10-15
Ni-WC supports preparation loading type Ni-WC catalyzer on aluminum oxide, silicon oxide, titanium oxide, zirconium white, titanium oxide, Si-Al molecular sieve respectively: the preparation process is similar to embodiment 1; Difference is that carrier uses respectively is aluminum oxide, silicon oxide, titanium oxide, zirconium white, titanium oxide, Si-Al molecular sieve and charcoal non activated; Simultaneously, carbonization gas is changed to CH by hydrogen
4/ H
2(volume ratio 1: 4); The W loading is 30wt% in the catalyzer; The Ni loading is 2wt%, and the wolfram varbide crystalline phase is WC, obtains Ni-WC thus and supports on aluminum oxide, silicon oxide, titanium oxide, zirconium white, titanium oxide, Si-Al molecular sieve, phosphate aluminium molecular sieve totally seven kinds of catalyzer.
Embodiment 16
The preparation of loaded catalyst Pt/AC: the 0.279g Platinic chloride is dissolved in the 4ml water, and incipient impregnation behind 120 ℃ of dry 12h, obtains catalyst precursor on the 2g absorbent charcoal carrier.Catalyst precursor carries out the temperature programmed reduction(TPR) reaction in nitrogen atmosphere.Concrete reaction process is: precursor is warming up to 350 ℃ by room temperature 1h in crystal reaction tube, and keeps 2h, hydrogen flow rate is 120ml/min, obtains the Pt/AC catalyzer of 5wt%.
The preparation process of said other loaded catalyst A is similar.Xiao Suangu, nickelous nitrate, ruthenium chloride, chloro-iridic acid and Palladous chloride with different mass is carried on the porous support respectively, in nitrogen atmosphere, makes Co/AC, Ni/AC, Ru/AC, Ir/AC, Pd/AC in 450 ℃ of temperature programmed reduction(TPR)s.
Embodiment 17
Different tungsten carbide catalyst catalysis natural lignins hydrogenation reaction in the aqueous solution: the 1.0g white birch wood powder that will contain natural lignin; 0.4g catalyzer and 100ml water join in the 300ml reaction kettle; After feeding three gases of hydrogen exchange; Fill hydrogen to 6MPa, stir, be warming up to 235 ℃ of reaction 4h with the speed of 1000 commentaries on classics/min.Reaction is reduced to room temperature after finishing, the centrifugal back of supernatant liquid sampling analysis.The catalyzer that uses corresponds in table 1 successively: (1) 30wt%W
2C/AC, (2) 30wt%WxC/AC (1＜x＜2), (3) Ni-W
2C/AC (4wt%Ni-30wt%W
2C), (4) Ni-WxC/AC (4wt%Ni-30wt%WxC, 1＜x＜2), (5) Pt-W
2C/AC (1wt%Pt-30wt%W
2C), (6) Ru-W
2C/AC (1wt%Ru-30wt%W
2C), (7) Ir-W
2C/AC (1wt%Ir-30wt%W
2C), (8) Pd-W
2C/AC (1wt%Pd-30wt%W
2C), (9) Ni-W
2C/Al
2O
3, (10) Ni-W
2C/SiO
2, (11) Pd-W
2C/Al
2O
3, (12) 0.05wt%Ni-80wt%W
2C/AC, (13) 20wt%Ni-5wt%W
2C/AC.The product qualitative analysis is through GC-MS coupling technique and standard specimen contrast, and quantitative analysis realizes through the gc marker method.The result sees table 1.Product also comprises the phenolic cpd of C6-C9 such as phenol, 2-methylphenol, 4-ethylphenol except guaiacyl propane, Syringa oblata Lindl. base propane, guaiacyl propyl alcohol and the Syringa oblata Lindl. base propyl alcohol, in table, classifies as other phenol.
The different tungsten carbide catalysts of table 1 are attend natural lignin's Catalytic Hydrogenation Properties relatively
From table, can find out that the promoted tungsten carbide catalyst of different metal can both obtain fragrant phenolic compound by catalysis xylogen hydrogenation, different carrier loaded tungsten carbide catalysts all have excellent catalytic activity.
Embodiment 18
Different composite type catalyst A-B (A and B mass ratio are 1: 3) catalysis natural lignin hydrogenation reaction in the aqueous solution: the 1.0g white birch wood powder that will contain natural lignin; 0.4g catalyzer and 100ml water join in the 300ml reaction kettle; After feeding three gases of hydrogen exchange; Fill hydrogen to 6MPa, stir, be warming up to 235 ℃ of reaction 4h with the speed of 1000 commentaries on classics/min.Reaction is reduced to room temperature after finishing, the centrifugal back of supernatant liquid sampling analysis.Product analysis method is with embodiment 17.The result sees table 2.
Table 2 composite catalyst A-B catalysis natural lignin hydrogenation performance relatively
Embodiment 19
Natural lignin is catalytic conversion reaction in small molecules solution: will contain the 1.0g white birch wood powder of natural lignin, 0.4g Ni-W
2C/AC (4wt%Ni-30wt%W
2C) catalyzer and 100ml small molecules solvent join in the 300ml reaction kettle, feed three gases of hydrogen exchange after, fill hydrogen to 6MPa, stir with the speed of 1000 commentariess on classics/min, be warming up to 235 ℃ simultaneously and react 4h.Reaction is reduced to room temperature after finishing, the centrifugal back of supernatant liquid sampling analysis.Product analysis method is with embodiment 17.The result sees table 3.
From table, can find out that in forming the small molecules solvent of hydrogen bond, the hydrogenation reaction of xylogen is carried out more easily, when wherein being solvent with terepthaloyl moietie, Ni-W
2Fragrant phenol yield is up to 50.6% on the C/AC catalyzer.Its reason is that through the hydrogen bond action between xylogen and small molecules solvent the lignin dissolution degree increases, thereby has increased the surface in contact of xylogen and catalyzer, makes catalyzed reaction more be prone to carry out.
Ni-W in table 3 different solvents
2The hydrogenation result of C/AC catalysis natural lignin
Embodiment 20
Different xylogen catalytic material hydrogenation reactions: with the xylogen raw material (40 order particle) of 1.0g different sources, 0.4g Ni-W
2C/AC (4wt%Ni-30wt%W
2C) catalyzer and 100ml water join in the 300ml reaction kettle, feed three gases of hydrogen exchange after, fill hydrogen to 6MPa, stir with the speed of 1000 commentariess on classics/min, be warming up to 235 ℃ simultaneously and react 4h.Reaction is reduced to room temperature after finishing, the centrifugal back of supernatant liquid sampling analysis.Product analysis method is with embodiment 17.The result sees table 4.
Table 4Ni-W
2The different xylogen raw material of C/AC catalysis hydrogenation result
Embodiment 21
The catalytic hydrogenation reaction of natural lignin under the differential responses condition: with the white birch wood powder (40 order) and the catalyzer (4wt%Ni-30wt%W of different mass
2C/AC) mix with 100ml water, join in the 300ml reaction kettle, feed three gases of hydrogen exchange after, fill hydrogen to formulating pressure, stir with the speed of 1000 commentariess on classics/min, be warming up to formulation thermotonus certain hour simultaneously.Other process is with embodiment 17.The result sees table 5.
The shortening cracking result of table 5 natural lignin under the differential responses condition
Claims (13)
1. the application of tungsten-based catalyst in xylogen shortening system aromatics; It is characterized in that: tungsten-based catalyst with have under the polar solvent effect that forms the hydrogen bond ability, xylogen highly effective hydrogenation cracking in airtight autoclave prepares phenylol, Syringa oblata Lindl. base and pockwood phenolic group aromatics.
2. according to the described application of claim 1, it is characterized in that: said xylogen is one or more in biomass, biomass by hydrolyzation residue and the industrial lignin that contains xylogen.
3. according to the described application of claim 2, it is characterized in that: the said biomass that contain xylogen are one or more in birch, poplar, toothed oak wood, linden, beech, maple, dragon spruce, pine, Eucalyptus, bamboo, the agricultural crop straw, but are not limited to this; Said industrial lignin is one or more in sulfonated lignin, alkali lignin or the dealkalize xylogen.
4. according to the described application of claim 1; It is characterized in that: said have a polar solvent that forms the hydrogen bond ability, can be water, dioxane, THF, phenol and short chain saturated fatty alcohol like one or more in methyl alcohol, ethanol, terepthaloyl moietie, butanols, the butyleneglycol.
5. according to the described application of claim 1; It is characterized in that: said tungsten-based catalyst is a loading type carbonization tungsten catalyst, and carrier is one or more in gac, aluminum oxide, silicon oxide, titanium oxide, zirconium white, titanium oxide, Si-Al molecular sieve, the phosphate aluminium molecular sieve.
6. according to the described application of claim 5, it is characterized in that: the loading of tungsten in carrier is 5-80 wt%, and preferred loading is 10-50 wt%, and more preferably loading is 15-40 wt%.
7. according to the described application of claim 1, it is characterized in that: tungsten-based catalyst is a loading type carbonization tungsten catalyst, is made up of main active component, carrier and second metal component, three parts;
Said main active component is a wolfram varbide; Said carrier is one or more in gac, aluminum oxide, silicon oxide, titanium oxide, zirconium white, titanium oxide, Si-Al molecular sieve, the phosphate aluminium molecular sieve; In the nickel that said second metal component is a metallic state, iridium, platinum, ruthenium, rhodium, palladium, iron, cobalt, copper, aluminium, tin, molybdenum, chromium, the strontium one or more.
8. according to the described application of claim 7, it is characterized in that:
The loading of tungsten in carrier is 5-80 wt%, and preferred loading is 10-50 wt%, and more preferably loading is 15-40 wt%;
In the preferred nickel of said second metal component, iridium, ruthenium, palladium, the platinum one or more;
The loading of second metal component in carrier is 0.05-30 wt%, and preferred loading is 0.1-15 wt%, and more preferably loading is 0.2-5 wt%.
9. according to the described application of claim 1; It is characterized in that: said tungsten-based catalyst is a composite catalyst; Comprise catalyst A and catalyst B; The activeconstituents of catalyst A is one or more in the transition metal iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, platinum of the 8th, 9,10 families, and the activeconstituents of catalyst B is one or more in the oxyhydroxide, tungsten bronze(s), wolframic acid, tungstate, metatungstic acid, metatungstate, para-tungstic acid, para-tungstate, peroxide wolframic acid, peroxide tungstate, heteropoly tungstic acid of muriate, the tungsten of sulfide, the tungsten of oxide compound, the tungsten of tungsten;
The metal active composition of catalyst A and the activeconstituents of catalyst B (in tungsten weight) weight ratio are between 0.02-3000 times of scope.
10. according to the described application of claim 9, it is characterized in that: said catalyst A is a loaded catalyst, and said carrier is gac, aluminum oxide, silicon oxide, silit, zirconium white, zinc oxide, titanium oxide is a kind of or the complex carrier more than two kinds; The content of activity component metal on catalyzer is 0.05-50 wt%, preferably at 1-30 wt%.
11., it is characterized in that according to the described application of claim 9: said catalyst A also can be unsupported, with the skeleton metal catalyst of active ingredient as catalyst backbone.
12. according to the described application of claim 1, it is characterized in that: the mass ratio of said xylogen raw material and solvent is 1:500-1:1; Catalyst levels is getting final product of catalytic amount; The original pressure of filling hydrogen under the room temperature in the reaction kettle is 1-20 MPa; Temperature of reaction is 120-450
oC; Reaction times is 10 min –, 24 h.
13. according to the described application of claim 12, it is characterized in that: the mass ratio of said xylogen raw material and solvent is 1:100-1:5; For adding fast response, the mass ratio of xylogen and catalyzer is generally 1:2-100:1, and preferred proportion is 2:1-20:1; The original pressure of filling hydrogen under the room temperature in the reaction kettle is 3-10 MPa; Temperature of reaction is 150-300
oC.
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