CN105142776A - 用于多元醇氢解的催化剂 - Google Patents
用于多元醇氢解的催化剂 Download PDFInfo
- Publication number
- CN105142776A CN105142776A CN201480003841.6A CN201480003841A CN105142776A CN 105142776 A CN105142776 A CN 105142776A CN 201480003841 A CN201480003841 A CN 201480003841A CN 105142776 A CN105142776 A CN 105142776A
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- CN
- China
- Prior art keywords
- catalyst
- carrier
- zirconia
- bismuth
- antimony
- Prior art date
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- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 119
- 238000007327 hydrogenolysis reaction Methods 0.000 title claims abstract description 30
- 229920005862 polyol Polymers 0.000 title abstract 3
- 150000003077 polyols Chemical class 0.000 title abstract 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 128
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 79
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 41
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 35
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical group [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 33
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 32
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052802 copper Inorganic materials 0.000 claims abstract description 32
- 239000010949 copper Substances 0.000 claims abstract description 32
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052709 silver Inorganic materials 0.000 claims abstract description 17
- 239000004332 silver Substances 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 13
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 13
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 13
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 13
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 12
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 11
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 11
- 229910052718 tin Inorganic materials 0.000 claims abstract description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 10
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052737 gold Inorganic materials 0.000 claims abstract description 10
- 239000010931 gold Substances 0.000 claims abstract description 10
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 10
- 239000011572 manganese Substances 0.000 claims abstract description 10
- 229910052716 thallium Inorganic materials 0.000 claims abstract description 10
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003426 co-catalyst Substances 0.000 claims description 86
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 47
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 34
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 34
- 239000000811 xylitol Substances 0.000 claims description 34
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- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 34
- 229960002675 xylitol Drugs 0.000 claims description 34
- 150000005846 sugar alcohols Polymers 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 28
- 235000011187 glycerol Nutrition 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 17
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 150000002815 nickel Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
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- 239000002585 base Substances 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 abstract 3
- 239000000243 solution Substances 0.000 description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 16
- 230000008569 process Effects 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 11
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 5
- 230000002045 lasting effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 238000001354 calcination Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 4
- 238000001802 infusion Methods 0.000 description 4
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- 229910052622 kaolinite Inorganic materials 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 3
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- QRKHFCODDWZNBA-UHFFFAOYSA-N [Cu].[Ni].[Bi] Chemical compound [Cu].[Ni].[Bi] QRKHFCODDWZNBA-UHFFFAOYSA-N 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
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- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910017770 Cu—Ag Inorganic materials 0.000 description 2
- 229910017932 Cu—Sb Inorganic materials 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- GUCDJRBEPRIEIM-UHFFFAOYSA-N antimony;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [Sb].OC(=O)CC(O)(C(O)=O)CC(O)=O GUCDJRBEPRIEIM-UHFFFAOYSA-N 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 235000013772 propylene glycol Nutrition 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910003322 NiCu Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- TUFZVLHKHTYNTN-UHFFFAOYSA-N antimony;nickel Chemical compound [Sb]#[Ni] TUFZVLHKHTYNTN-UHFFFAOYSA-N 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- LGRDPUAPARTXMG-UHFFFAOYSA-N bismuth nickel Chemical compound [Ni].[Bi] LGRDPUAPARTXMG-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical class CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
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- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
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- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000011846 petroleum-based material Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
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- 239000002356 single layer Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
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- 238000003756 stirring Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B01J23/835—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8435—Antimony
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
乙二醇和丙二醇可以通过多元醇的氢解来制造,所述氢解包括使多元醇与氢气在氢解催化剂的存在下反应的步骤。氢解包含镍、一种或更多种助催化剂以及一种或更多种载体。助催化剂选自铋、银、锡、锑、金、铅、铊、铈、镧和锰。载体选自氧化锆和碳。氧化锆载体包括氧化锆织构助催化剂,所述氧化锆织构助催化剂选自Cr、Mo、W、Nb、Ce、Ca、Mg、La、Pr、Nd、Al和P。如果载体包括碳,那么助催化剂选自铋和锑。在另一个实施方案中,如果载体包括碳,那么助催化剂选自铋和锑,并且催化剂包含铜。在另一个实施方案中,催化剂另外包含铜。
Description
背景
随着化学工业离开石油基的材料,由可再生的来源有效形成二醇是非常期望的反应途径。乙二醇是聚酯和聚对苯二甲酸乙二醇酯(PET)的前体,同时丙二醇在化学工业中被广泛使用。目前这些二醇由石油化工产品产生,然而它们也可以来源于可再生的生物质。
已知将糖醇转化为多元醇(主要是乙二醇(EG)、丙二醇(PG)和甘油(GLY))的概念已经有七十多年。关于这个主题已经出版了许多研究论文和专利。除了这三种主要的产物之外,次要产物包括伯醇比如乙醇和丙醇、丁二醇类,甚至微量二醇(adols)和酸。根据反应条件,气体产物将包括CO2、CO和甲烷。这些过程中的共同特征是作为溶剂的水的存在。
过程的商业化的主要障碍包括对商品的低选择性和由于提高的操作压力及温度(通常大于100巴和200℃)的高生产成本,以及产物分离中的困难。并且发现,较高的pH对于增加反应速率和产物选择性是必要的。这另外使得非均相催化剂的适当的操作变得更糟,并且能够导致载体的分解,以及活泼金属的浸出和烧结。这些条件对于通常可得的材料用于负载型非均相催化剂提出了重大挑战。
以前的工作已经确定了负载型的基于Ru-、Rh-、Ir-、Ni-、Re-和Pd-的材料作为催化剂用于由诸如山梨醇和木糖醇的木质纤维素多元醇产生二醇。例如,2001年9月18日授权的、Chopade等人的美国专利第6,291,725号公开了氧化铝、氧化锆和碳载体上的Ru;2007年12月6日提交的、Hoffer等人的PCT公布第WO2008/071616号公开了包含选自碳、氧化钛和碳酸钙的载体上的铱用于由多元醇产生EG、PG的催化剂。然而,还没有具有足够选择性的经济上可行的催化剂以产生二醇以被广泛地在化学工业中实施的报道。
2010年3月3日的、Lui等人的美国专利公布第2011/0301021号中描述了制备多元酸稳定化的氧化锆载体的方法,该氧化锆载体在水相氢化和氢解反应中是水热稳定的。2010年3月3日提交的、Lui等人的美国专利公布第2011/0319672号中描述了用于通过使用多元酸稳定化的氧化锆将糖、糖醇或甘油转化为短链二醇、EG和PG的过程。族(VIII)和族11及其组合的活泼金属被描述为用于该过程的助催化的氧化锆载体的催化剂,特别是Ni、Cu和锡助催化的Ni。美国专利公布第2011/0301021号和第2011/0319672号通过引用以其整体并入本文。
期望在多元醇的氢解期间增加EG和PG的选择性。
简要概述
催化剂包含镍、一种或更多种助催化剂以及一种或更多种载体。助催化剂选自铋、银、锡、锑、金、铅、铊、铈、镧和锰。载体选自氧化锆和碳。氧化锆载体包括氧化锆织构助催化剂,所述氧化锆织构助催化剂选自Cr、Mo、W、Nb、Ce、Ca、Mg、La、Pr、Nd、Al和P。如果载体包括碳,那么助催化剂选自铋和锑。在另一个实施方案中,如果载体包括碳,那么助催化剂选自铋和锑,并且催化剂包含铜。在另一个实施方案中,催化剂另外包含铜。
用于通过多元醇的氢解来制备乙二醇和丙二醇的方法包括使多元醇与氢气在催化剂的存在下反应的步骤。催化剂包含镍、一种或更多种助催化剂以及一种或更多种载体。助催化剂选自铋、银、锡、锑、金、铅、铊、铈、镧和锰。载体选自氧化锆和碳。氧化锆载体包括氧化锆织构助催化剂,所述氧化锆织构助催化剂选自Cr、Mo、W、Nb、Ce、Ca、Mg、La、Pr、Nd、Al和P。如果载体包括碳,那么助催化剂选自铋和锑。在另一个实施方案中,如果载体包括碳,那么助催化剂选自铋和锑,并且催化剂包含铜。在另一个实施方案中,催化剂另外包含铜。
用于制造氢解催化剂的方法包括以下步骤:提供镍盐和一种或更多种助催化剂盐的溶液;提供一种或更多种载体;使该溶液与该载体合并以形成催化剂前体;干燥并煅烧该催化剂前体。然后,催化剂前体通过将其在比如氢气的还原性气氛的存在下加热而被活化。助催化剂选自铋、银、锡、锑、金、铅、铊、铈、镧和锰。载体选自氧化锆和碳。氧化锆载体包括氧化锆织构助催化剂,所述氧化锆织构助催化剂选自Cr、Mo、W、Nb、Ce、Ca、Mg、La、Pr、Nd、Al和P。如果载体包括碳,那么助催化剂选自铋和锑。在另一个实施方案中,如果载体包括碳,那么助催化剂选自铋和锑,并且催化剂包含铜。在另一个实施方案中,催化剂另外包含铜。
这些和其他的目标和优势将从附图和其描述中变得明显。
详述
通过使用氢解催化剂,多元醇(比如木糖醇、山梨醇、甘油及其混合物)可以被转化为乙二醇、丙二醇或两者。在水介质中和催化剂的存在下用氢气处理多元醇。催化剂包含载体上的助催化的镍催化剂。在一个实施方案中,催化剂包含铜。催化剂能够有效地产生乙二醇、丙二醇或两者,伴随很少副产物。
在一个实施方案中,催化剂包含镍、一种或更多种助催化剂以及一种或更多种载体。助催化剂选自铋、银、锡、锑、金、铅、铊、铈、镧和锰。载体选自氧化锆和碳。氧化锆载体包括氧化锆织构助催化剂,所述氧化锆织构助催化剂选自Cr、Mo、W、Nb、Ce、Ca、Mg、La、Pr、Nd、Al和P。如果载体包括碳,那么助催化剂选自铋和锑。在另一个实施方案中,如果载体包括碳,那么助催化剂选自铋和锑,并且催化剂包含铜。在另一个实施方案中,催化剂另外包含铜。
在一个实施方案中,催化剂包含镍、一种或更多种助催化剂以及一种或更多种载体。助催化剂选自铋和锑。载体选自氧化锆和碳。在一个实施方案中,催化剂另外包含铜。
在一个实施方案中,催化剂包含镍、一种或更多种助催化剂以及一种或更多种载体。助催化剂选自铋、银、锡、锑、金、铅、铊、铈、镧和锰。载体包括氧化锆和氧化锆织构助催化剂。氧化锆织构助催化剂选自Cr、Mo、W、Nb、Ce、Ca、Mg、La、Pr、Nd、Al和P。在一个实施方案中,催化剂另外包含铜。
在一个实施方案中,催化剂包含镍、一种或更多种助催化剂以及一种或更多种载体。助催化剂选自铋和锑。载体包括氧化锆和氧化锆织构助催化剂。氧化锆织构助催化剂选自Cr、Mo、W、Nb、Ce、Ca、Mg、La、Pr、Nd、Al和P。在一个实施方案中,催化剂另外包含铜。
助催化剂通常增加催化剂活性和对二醇的选择性,同时抑制副反应,比如甲烷形成。在一个实施方案中,助催化剂选自铋、银、锡、锑、金、铅、铊、铈、镧和锰。在一个实施方案中,助催化剂选自铋、锑和银。在另一个实施方案中,助催化剂选自铋和锑。载体选自氧化锆和碳。在一个实施方案中,催化剂包含总催化剂重量的从约0.01%至约3%的一种或更多种助催化剂,比如从约0.5%至约2.5%,或1.5%至约2%。在一个实施方案中,助催化剂包含总催化剂重量的从约0.1%至约3wt%的银,比如约0.5%至约2.5wt%,或1.5%至约2wt%。在一个实施方案中,助催化剂包含总催化剂重量的在约0.01%至约2wt%之间的Bi,比如从约0.05%至约1wt%,或约0.1%至约0.5wt%。在一个实施方案中,助催化剂包含总催化剂重量的在约0.01%至约1.5wt%之间的Sb,比如约0.02%至约1wt%,或约0.03%至约0.07wt%。在一个实施方案中,当载体包括碳时,助催化剂选自铋和锑。
在一个实施方案中,助催化剂另外包含铜金属。在另一个实施方案中,助催化剂选自铋、锑和银。在另一个实施方案中,助催化剂包含铜金属和选自铋、锑和银的金属。催化剂可以包含按重量计多至约10%的铜,比如约0.1%至约10wt%、约0.2%至约6wt%,或约0.3%至约3wt%。在一个实施方案中,在催化剂中铜的量小于镍的量。在催化剂中按重量计铜的量可以少于镍的一半的量。
载体为镍和助催化剂提供了结构支撑。其还可以影响催化剂的反应性和选择性。在一个实施方案中,载体是氧化锆,其在室温下通常是单斜晶相。氧化锆载体包括织构助催化剂。织构助催化剂稳定氧化锆的正方晶相,且抑制该相向单斜晶相的转化。织构助催化剂可以改善抗压强度和载体的水热稳定性,并且稳定载体的表面积和孔体积。氧化锆织构助催化剂可以选自Cr、Mo、W、Nb、Ce、Ca、Mg、La、Pr、Nd、Al和P。在另一个实施方案中,氧化锆织构助催化剂选自Cr、Mo、W、Nb、Ce和La。在一个实施方案中,氧化锆织构助催化剂的量小于总催化剂重量的10%。在一个实施方案中,氧化锆与织构助催化剂的比率为约2:1至约20:1;比如从约4:1至约18:1;或从约8:1至约16:1。氧化锆载体可以根据美国专利公布第2011/0301021号中的方法制备,具有至少80-85%的稳定化的正方晶相。氧化锆载体可以作为粉末、小球或挤出物使用。
氧化锆载体通过将氧化锆载体前体与织构助催化剂合并来制备。锆和织构助催化剂被沉淀、干燥、成形,然后被煅烧。在煅烧之前将织构载体添加至锆。挤压的或其他形状的载体可以在范围从约300℃至1000℃的温度下煅烧持续大约2至12小时,比如从约400℃至700℃持续大约3至5小时。在一个实施方案中,挤压的锆载体在约600℃下煅烧持续大约三小时。可选地,挤压的锆载体可以在1度每分钟(缩写为“deg/m”或“℃/m”或“°/min”)的升温速率(ramp)下煅烧至600℃且停留持续大约3小时。在另一个实施方案中,挤压的锆载体在约300℃至约1000℃下、或在约400℃至约700℃下、或约500℃至约600℃下煅烧持续大约2至12小时。通过将已经含有织构载体的煅烧的载体与Ni和助催化剂混合来制备催化剂,随后可再次煅烧所述催化剂。
在一个实施方案中,如通过使用在J.Am.Chem.Soc.(1938)60第309-919页(其以其整体并入本文)中描述的BET方法的氮气吸附所测量的,氧化锆载体的表面积为约30至约150m2/g。在一个实施方案中,氧化锆载体的孔体积(PV)为约0.15mL/g至约0.4mL/g。在一个实施方案中,根据氧化锆载体的用途,氧化锆载体的抗压强度为至少1lb/mm、至少2lb/mm、或至少5lb/mm。催化剂或催化载体的抗压强度可以使用ASTMD6175-03(2008),用于挤压催化剂和催化剂载体颗粒的径向抗压强度的标准试验方法(StandardTestMethodforRadialCrushStrengthofExtrudedCatalystandCatalystCarrierParticles)来测量。
在一个实施方案中,载体是碳。碳载体的实例包括但不限于活性炭和碳纳米管。在一个实施方案中,如通过氮气吸附所测量的,碳载体的表面积为约200至约400m2/g。大的表面积促进载体表面上极佳的金属分散。在一个实施方案中,存在二项孔隙分布(binomialporedistribution),并且最常见的孔隙直径在约和约在一个实施方案中,小孔隙的直径在从约至约的范围中,比如从约至约或约至约在一个实施方案中,大孔隙的直径在约至的范围中,比如从约至约或从约至约
在一个实施方案中,催化剂包含总催化剂重量的从约1%至约40%的镍,比如从约2%至约20%、从约2%至约14%、或约2.5%至约5%。具有低负载的Ni的催化剂提供出众的金属分散和较高的产物收率。在一个实施方案中,相对于总催化剂重量,按重量计,催化剂包含约3wt%至约20wt%的镍和约0.01wt%至约3wt%的助催化剂。在另一个实施方案中,相对于总催化剂重量,按重量计,催化剂包含约3wt%至约20wt%的镍、多至约5wt%的铜、以及约0.01wt%至约3wt%的附加助催化剂。在催化剂中镍的质量大于助催化剂的总质量。在催化剂中镍的质量还大于铜的质量。在一个实施方案中,镍的质量大于助催化剂和铜的总质量。
在一个实施方案中,通过将作为浓缩的溶解的镍盐溶液的镍添加至载体来制备催化剂。镍盐溶液可以是硝酸镍溶液。助催化剂同样作为溶解的盐与镍同时地引入,或顺序地引入。在一个实施方案中,助催化剂盐包括助催化剂的硝酸盐。在另一个实施方案中,盐包括助催化剂的柠檬酸盐,比如柠檬酸锑。助催化剂盐溶液可以包含多于一种的助催化剂。
在示例性过程中,通过使用浸渍法来制备催化剂。在金属硝酸盐溶液中金属的量超过载体的承载能力(大于单层表面覆盖度)。在金属硝酸盐溶液中轻轻地搅拌载体,持续约30-60分钟。在一个实施方案中,对于CrZr载体上的镍-铋或镍-铜-铋催化剂,在金属硝酸盐溶液中镍与铋的重量比率为约5.0至约0.3。铜可以任选地以稍微大于铋的量添加(按重量计镍比铜为约5.0至约0.5)。
在另一个示例性过程中,通过初湿含浸法(incipientwetnessmethod)来制备催化剂。将期望的量的金属前体溶解以形成溶液,将该溶液滴加到催化剂载体上直至催化剂载体完全变湿。换言之,添加的前体溶液的体积等于催化剂载体的孔体积。可以重复该过程,以便得到期望的金属负载。
镍和助催化剂被添加至载体之后,将产生的湿材料在烘箱中在约100至约120℃下干燥持续2至12h,并在约400至约600℃下煅烧持续2至6h。煅烧过程是任选的,尤其对于碳载体,其应仅在惰性气氛下煅烧。可以通过在还原性气氛中加热来活化催化剂前体。还原性气氛可以是氢气或气体的混合物,比如合成气体(H2和N2)。加热温度可以是从约400℃至约550℃。在活化的催化剂中,镍和助催化剂元素可以完全或部分被还原。在一个实施方案中,可以在氢解反应期间活化催化剂前体。
多元醇是具有多个醇官能团的碳链。多元醇可以是直链或支链的。多元醇可以是单一多元醇或多元醇的混合物。在一个实施方案中,多元醇是糖醇,比如C5或C6糖醇,比如木糖醇、山梨醇、甘油及其混合物。
用于将多元醇转化为乙二醇、丙二醇或两者的过程可以在间歇式反应器或固定床反应器中进行。在一个实施方案中,在间歇式反应器中,催化剂、碱和脱气的多元醇进料溶液在室温下被混合。反应器在搅拌下用氢气加压,并且加热至反应温度。在一个实施方案中,反应温度为约150℃至约350℃,比如约200℃至约250℃、约190℃至约250℃、或约190℃至约220℃。在一个实施方案中,氢气压力为约50至约200巴,比如约60至约150巴、约65至约120、或约70至约120巴。较高的氢气压力导致较高的EG和PG选择性以及在气相中来源于蒸汽重整反应的较少的CO2。
用于间歇式反应器或固定床反应器的进料由在水中的诸如木糖醇的多元醇(多至50wt%)以及诸如NaOH的碱组成。多元醇与碱的摩尔比率在约3:1至约50:1之间,比如约5:1至约25:1,或约5:1至约15:1。碱充当辅催化剂以增加二醇的收率。碱可以是醇盐、氢氧化物、或者钙或钠或钾的氧化物。在一个实施方案中,反应时间为约4小时或更少。如果反应进行持续太长,对期望产物的选择性可能下降。在一个实施方案中,反应在约210℃下发生,具有由约25wt%的木糖醇以及在10和12之间的摩尔比率的木糖醇:NaOH组成的进料。
在一个实施方案中,在固定床反应器中,在反应之前,催化剂或催化剂前体在氢气流动中原位装载及活化。随后将催化剂床加压至反应压力,且随后加热至反应温度。在一个实施方案中,反应温度为约180℃至约350℃,比如约200℃至约250℃、约190℃至约250℃、或约190℃至约240℃。在一个实施方案中,氢气压力为约50至约230巴,比如约60至约200巴、约65至约150、或约70至约150巴。
在床的入口处将两种液流引入并预混合:一种是含有诸如木糖醇的多元醇的含水进料(多至约50wt%),而另一种是诸如氢氧化钠的含水碱溶液。将合并的流在从约0.2至4.0h-1的液时空速下(LHSV)进料至反应器中。在一个实施方案中,反应在从约190℃至约240℃且从约80至约120巴的H2下,在约0.5和约3.0h-1之间的LHSV下发生,具有由约15wt%至约25wt%的木糖醇组成的预混合进料以及在反应条件下从约11.5至约12.0的起始pH。
以碳为基础计算二醇选择性,使得对于所有产物的总选择性合计100%。例如:
对于木糖醇氢解来说,如果木糖醇在C2和C3之间是选择性地裂解,那么对于EG的理论上最大的碳选择性是40%,且对于PG的最大的碳选择性是60%。在一个实施方案中,木糖醇的氢解产生22%或更高的乙二醇(EG)选择性。在一个实施方案中,木糖醇的氢解产生45%或更大的丙乙醇选择性。
虽然本公开内容通过描述已阐明若干实施方案,并且虽然说明性的实施方案已被相当详细地描述,但是本申请人不意图将所附权利要求的范围约束或以任何方式限制于这样的细节。另外的优势和修改对本领域技术人员可以是容易想到的。
实施例
实施例1:通过浸渍法的Cr-助催化的氧化锆载体上的镍-铜-铋催化剂
将CrZr-氧化物挤出物(0.8mm直径,1g)浸入3mL的含有75mg/mL镍(来自硝酸镍)、7.5mg/mL铜(来自硝酸铜)以及4.5mg/mL铋(来自硝酸铋)的2MHNO3溶液中。将溶液轻轻地搅拌,且在60℃下保持1小时的时间段,在这之后,将剩下的溶液轻轻倒出。随后将催化剂在120℃下干燥持续2小时,且在450℃下在空气中煅烧持续2小时。在引入木糖醇进料溶液之前,将催化剂在300sccm的合成气体(5%H2/余量N2)中加热至450℃,且在此温度下还原持续8小时。
实施例2:通过初湿含浸法的Cr-助催化的氧化锆载体上的镍-铜-铋催化剂
制备含有150mg/mL镍(来自硝酸镍)、30mg/mL铜(来自硝酸铜)以及6mg/mL铋(来自硝酸铋)的混合金属硝酸盐溶液(0.35mL)。将该混合金属硝酸盐溶液逐滴地添加至1g的0.8mm直径的CrZr-氧化物挤出物,且将变湿的挤出物剧烈地涡旋持续1分钟。随后将催化剂在120℃下干燥持续2小时,且在450℃下在空气中煅烧持续2小时。在引入木糖醇进料溶液之前,将催化剂在300sccm的合成气体(5%H2/余量N2)中加热至450℃,且在此温度下还原持续8小时。
实施例3:通过浸渍法的Cr-助催化的氧化锆载体上的镍-锑催化剂
将CrZr-氧化物挤出物(0.8mm直径,1g)浸入3mL的含有75mg/mL镍(来自硝酸镍)和0.75mg/mL锑(来自柠檬酸锑)的水溶液中。将溶液轻轻地搅拌,且在60℃下保持1小时的时间段,在这之后,将剩下的溶液轻轻倒出。随后将催化剂在120℃下干燥持续2小时,且在450℃下在空气中煅烧持续2小时。在引入木糖醇进料溶液之前,将催化剂在300sccm的合成气体(5%H2/余量N2)中加热至450℃,且在此温度下还原持续8小时。
实施例4:通过浸渍法的Cr-助催化的氧化锆载体上的镍-铜-银催化剂
将CrZr-氧化物挤出物(0.8mm直径,1g)浸入3mL的含有75mg/mL镍(来自硝酸镍)、7.5mg/mL铜(来自硝酸铜)以及15mg/mL银(来自硝酸银)的2MHNO3溶液中。将溶液轻轻地搅拌,且在60℃下保持1小时的时间段,在这之后,将剩下的溶液轻轻倒出。随后将催化剂在120℃下干燥持续2小时,且在450℃下在空气中煅烧持续2小时。在引入木糖醇进料溶液之前,将催化剂在300sccm的合成气体(5%H2/余量N2)中加热至450℃,且在此温度下还原持续8小时。
实施例5:通过初湿含浸法的碳纳米管(CNT)载体上的镍-铜-银催化剂
制备含有150mg/mL镍(来自硝酸镍)、30mg/mL铜(来自硝酸铜)以及45mg/mL银(来自硝酸银)的混合金属硝酸盐溶液。将该混合金属硝酸盐溶液(0.3mL)逐滴地添加至0.3g的1.6mm直径的CNT挤出物(Hyperion),且将变湿的挤出物剧烈地涡旋持续1分钟。然后将催化剂在120℃下干燥持续2小时。在引入木糖醇进料溶液之前,将催化剂在300sccm的合成气体(5%H2/余量N2)中加热至450℃,且在此温度下还原持续8小时。
实施例6
为了固定床测试的目的,将上文提及的实施例按比例增大以制备50g的每种催化剂。在反应之前,在具有1000h-1的气时空速(GHSV)的氢气流中,采用5℃/min的加热斜率,在450℃下将催化剂原位活化持续4h。
实施例7:通过Ni-Cu-Bi/CrZr催化剂在间歇式微反应器中氢解木糖醇
将还原的Ni-Cu-Bi/CrZr催化剂(0.2g)与含有25wt%的木糖醇和12:1的摩尔比率的木糖醇:NaOH的1.8mL的脱气的含水进料溶液在间歇式反应器中合并。反应器用H2加压至1015psi(~70巴),且加热至210℃同时在800rpm下涡旋。反应继续持续4小时,在这之后,将反应器减压并冷却,并且分析产物。
这些实施例对于期望的EG和PG产物显示了比对照实施例高的选择性。此外,一些实施例具有比对照实施例高的木糖醇转化率。第二个益处是,这些实施例对于GLY具有相同或较低的选择性,GLY是较不期望的产物。
表1:在间歇式微反应器中的木糖醇氢解
EG=乙二醇;PG=1,2丙二醇;GLY=甘油;CNT=碳纳米管;*对照
实施例8:通过Ni-Cu-Sb/CrZr催化剂在固定床反应器中氢解木糖醇
使用的不锈钢(SS)球将催化剂(15mL)以1比1的体积比率稀释,且装载到固定床反应器中(FBR)。将稀释的催化剂床夹在用于支撑以及用于气/液进料分布的两个SS球层之间。催化剂在测试之前原位活化。测试在80至120巴的氢气压力之间、在210℃至230℃下、采用从0.8h-1至3h-1变化的液时空速(LHSV)而进行。液体进料含有具有10:1的木糖醇:NaOH摩尔比率的25wt%的木糖醇。贯穿整个测试,氢气/木糖醇的摩尔比率维持在10。在测试期间每8至10h对液体产物取样,且通过用WatersIC-PAKTM离子排斥柱的HPLC分析。测试经历具有总数340操作小时(hour-on-stream,HOS)的4个测试阶段,没有观察到任何钝化。表2中总结了固定床反应器测试结果。
这些实施例对于期望的EG和PG产物显示了比对照实施例高的选择性。此外,一些实施例具有比对照实施例高的木糖醇转化率。第二个益处是,这些实施例对于GLY具有相同或较低的选择性,GLY是较不期望的产物。
表2:固定床反应器中的木糖醇氢解
EG=乙二醇;PG=1,2-丙二醇;GLY=甘油;GLY=甘油;*对照
实施例9:Ni-Cu-Sb/CrZr和Ni-Sb/CrZr上的固定床反应器中的甘油氢解
研究了ZrCr上的Sb助催化的NiCu和Ni催化剂用于甘油氢解。测试通过将进料从木糖醇转换为甘油,在木糖醇氢解的340HOS评价之后进行。测试在220℃下、在120巴氢气压力下、采用2h-1的LHSV、10的甘油/NaOH摩尔比率、10的氢气/甘油摩尔比率进行。进料甘油浓度为32wt%。表3中总结了结果。
表3:固定床反应器中的甘油氢解
实施例10
这个实施例证实了实施例1的按比例增大的催化剂的耐久性。在实施例8列出的条件下、在固定床反应器中测试Ni-Cu-Bi/ZrCr催化剂,且与相似条件下测试的参照的Ni/Al催化剂(NiSAT208)比较。表4和表5列出了液体产物中的金属含量(从催化剂浸出)。发现铝在测试期间浸出,而Ni-Cu-Bi/CrZr催化剂上没有金属浸出。且耗费的Ni-Cu-Bi/CrZr催化剂维持了机械和化学完整性。
表4:来自NiSAT208上的木糖醇氢解的液体产物中的金属含量
表5:来自NiCuBi/CrZr上的木糖醇氢解的液体产物中的金属含量
Claims (15)
1.一种催化剂,其包含镍、一种或更多种助催化剂以及一种或更多种载体;
其中所述助催化剂选自铋、银、锡、锑、金、铅、铊、铈、镧和锰;
其中所述载体选自氧化锆和碳;
其中所述氧化锆载体包括氧化锆织构助催化剂;其中所述氧化锆织构助催化剂选自Cr、Mo、W、Nb、Ce、Ca、Mg、La、Pr、Nd、Al和P;
其中如果所述载体是碳,那么所述助催化剂选自铋和锑。
2.如权利要求1所述的催化剂,其中所述催化剂另外包含铜。
3.如权利要求1所述的催化剂,其中所述助催化剂选自铋、锑和银。
4.如权利要求1所述的催化剂,其中所述氧化锆织构助催化剂选自Cr、Mo、W、Nb、Ce和La。
5.如权利要求1所述的催化剂,其中所述催化剂包含按重量计约1%至约40%的镍,以及约0.01%至约3%的助催化剂。
6.如权利要求2所述的催化剂,其中所述催化剂包含按重量计约1%至约40%的镍、按重量计多至约10%的铜,以及约0.01%至约3%的助催化剂。
7.一种用于多元醇的氢解的方法,所述方法包括在催化剂的存在下使多元醇与氢气反应的步骤;
其中所述催化剂包含镍、一种或更多种助催化剂以及一种或更多种载体;
其中所述助催化剂选自铋、银、锡、锑、金、铅、铊、铈、镧和锰;
其中所述载体选自氧化锆和碳;
其中所述氧化锆载体包括氧化锆织构助催化剂;其中所述氧化锆织构助催化剂选自Cr、Mo、W、Nb、Ce、Ca、Mg、La、Pr、Nd、Al和P;
其中如果所述载体是碳,那么所述助催化剂选自铋和锑。
8.如权利要求7所述的方法,其中所述多元醇包括糖醇,所述糖醇选自木糖醇、山梨醇、甘油及其混合物。
9.如权利要求7所述的方法,其中所述氢解在碱的存在下进行。
10.如权利要求9所述的方法,其中所述多元醇与碱的摩尔比率为约5:1至约50:1。
11.如权利要求7所述的方法,其中所述氢解在约180℃至约350℃的温度下进行。
12.如权利要求7所述的方法,其中所述氢解在约50至约150巴的压力下进行。
13.如权利要求7所述的方法,其中木糖醇的氢解产生22%或更高的乙二醇选择性。
14.一种用于制造氢解催化剂的方法,所述方法包括:
提供镍盐和一种或更多种助催化剂盐的溶液;
提供一种或更多种载体;
使所述溶液与所述载体合并以形成催化剂前体;
干燥所述催化剂前体;
在还原性气氛的存在下加热所述催化剂前体;
其中所述助催化剂选自铋、银、锡、锑、金、铅、铊、铈、镧和锰;
其中所述载体选自氧化锆和碳;
其中所述氧化锆载体包括氧化锆织构助催化剂;其中所述氧化锆织构助催化剂选自Cr、Mo、W、Nb、Ce、Ca、Mg、La、Pr、Nd、Al和P;
其中如果所述载体是碳,那么所述助催化剂选自铋和锑。
15.如权利要求14所述的方法,其中所述催化剂另外包含铜。
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