CN1109009C - 脂族醇的制备方法 - Google Patents
脂族醇的制备方法 Download PDFInfo
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- CN1109009C CN1109009C CN98805932A CN98805932A CN1109009C CN 1109009 C CN1109009 C CN 1109009C CN 98805932 A CN98805932 A CN 98805932A CN 98805932 A CN98805932 A CN 98805932A CN 1109009 C CN1109009 C CN 1109009C
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- -1 aliphatic alcohols Chemical class 0.000 title abstract description 5
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- 150000002148 esters Chemical class 0.000 claims abstract description 10
- 150000002596 lactones Chemical class 0.000 claims abstract description 9
- 230000000737 periodic effect Effects 0.000 claims abstract description 7
- 238000005984 hydrogenation reaction Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 150000008065 acid anhydrides Chemical class 0.000 claims description 8
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 8
- 229910052697 platinum Inorganic materials 0.000 abstract description 8
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 abstract description 7
- 229910052747 lanthanoid Inorganic materials 0.000 abstract description 2
- 150000002602 lanthanoids Chemical class 0.000 abstract description 2
- 150000008064 anhydrides Chemical class 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- QGLBZNZGBLRJGS-UHFFFAOYSA-N Dihydro-3-methyl-2(3H)-furanone Chemical compound CC1CCOC1=O QGLBZNZGBLRJGS-UHFFFAOYSA-N 0.000 description 7
- 229910052763 palladium Inorganic materials 0.000 description 7
- MWCBGWLCXSUTHK-UHFFFAOYSA-N 2-methylbutane-1,4-diol Chemical compound OCC(C)CCO MWCBGWLCXSUTHK-UHFFFAOYSA-N 0.000 description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- IWTBVKIGCDZRPL-LURJTMIESA-N 3-Methylbutanol Natural products CC[C@H](C)CCO IWTBVKIGCDZRPL-LURJTMIESA-N 0.000 description 5
- LJPCNSSTRWGCMZ-UHFFFAOYSA-N 3-methyloxolane Chemical compound CC1CCOC1 LJPCNSSTRWGCMZ-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 150000002191 fatty alcohols Chemical class 0.000 description 5
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 5
- 229940071536 silver acetate Drugs 0.000 description 5
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 4
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 4
- 229910003446 platinum oxide Inorganic materials 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- SVMCDCBHSKARBQ-UHFFFAOYSA-N acetic acid;cobalt Chemical compound [Co].CC(O)=O SVMCDCBHSKARBQ-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229940051250 hexylene glycol Drugs 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- GUWZGMWHDAJAOC-UHFFFAOYSA-N oxoplatinum;hydrate Chemical compound O.[Pt]=O GUWZGMWHDAJAOC-UHFFFAOYSA-N 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N pentadecanoic acid Chemical compound CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- NYHNVHGFPZAZGA-UHFFFAOYSA-N 2-hydroxyhexanoic acid Chemical compound CCCCC(O)C(O)=O NYHNVHGFPZAZGA-UHFFFAOYSA-N 0.000 description 1
- IWHLYPDWHHPVAA-UHFFFAOYSA-N 6-hydroxyhexanoic acid Chemical compound OCCCCCC(O)=O IWHLYPDWHHPVAA-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- PGZSVAXKRVWAHV-UHFFFAOYSA-N [Re].[Os] Chemical compound [Re].[Os] PGZSVAXKRVWAHV-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- XBTDOLHWUMORHO-UHFFFAOYSA-N nitric acid;triphenylphosphane Chemical compound O[N+]([O-])=O.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 XBTDOLHWUMORHO-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- JXJTWJYTKGINRZ-UHFFFAOYSA-J silicon(4+);tetraacetate Chemical compound [Si+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O JXJTWJYTKGINRZ-UHFFFAOYSA-J 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6567—Rhenium
-
- 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
- B01J23/70—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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
在一种制备脂族醇的方法中,它是在一种含有Pt和Re的催化剂存在下,每种元素是以金属或氧化物形式存在的,通过氢化脂族羧酸或酸酐或其酯或内酯而实现的,其中所述的催化剂还含有至少另外一种元素选自元素周期表的第5-12族和第14族和镧系元素,是以金属或氧化物形式存在的。
Description
本发明涉及一种脂族醇的制备方法,它是在一种催化剂存在下、通过氢化脂族羧酸或酸酐或其酯或内酯而实现的。
采用不同的方法氢化脂族羧酸以制备脂族醇是公知的技术。
在一种含有负载在炭载体上的Re2O7和OsO4的催化剂存在下、氢化己酸和癸酸以制备相应的醇的方法,公开在K.Yoshino等人的“在铼-锇双金属催化剂存在下的羧酸氢化反应”,JAOCS,卷67第1期,1990,1月,21-24页。
DE-A-2715667描述了一种制备1,4-丁二醇的方法,是采用负载在一种特定的乙酸硅上的Pd和Re作为催化剂,以氢化马来酸酐、马来酸或富马酸而实现的。反应温度为205-230℃。
EP-B-0417867描述了用于羧酸及其酸酐的氢化制备酸或酯的催化剂。所采用的催化剂包括,例如,负载在炭上的Pd、Pd/Re、Ag/Pd、Ag/Pd/Re。对乙酸形成乙醇的转化率和马来酸酐形成γ-丁内酯的转化率作了描述。反应是在194-251℃下进行的。
US 4214106描述了一种由羟基乙酸制备乙二醇的方法。反应是在145-241℃下,在Pd/Re、Pd/Ag、Ru/Rh、Pd/Au、Re/Ag、Pt/Rh或Pd/Re/Ag催化剂表面上进行的。
已知的催化剂在某些应用中其活性和选择性都不够高。
而且,使用羧酸、特别是其水溶液形式,会使与羧酸接触的设备例如反应器的物质结构蒙受腐蚀的危险。由于这个原因,设备需要采用非常厚的钢材或贵重且费用高的材料。因而,需要有一种能显著降低腐蚀问题的方法。
本发明的一个目的是提供一种制备脂族醇的方法,是在一种含有Pt和Re各是以金属或氧化物形式存在-的催化剂存在下,通过氢化脂族羧酸或其酸酐或酯或内酯而制备,这种方法不会存在现有技术方法中的缺点。
我们发现,这个目的通过采用一种下述催化剂而实现,该催化剂含有各以其金属或氧化物形式存在的Pt和Re和至少另外一种选自元素周期表第5-12族和第14族和镧系中的元素,该元素是以金属或氧化物形式存在。
本发明还提供了这样一类催化剂和它在氢化脂族羧酸或其酸酐和其酯或内酯中的用途。
本发明人发现,采用本发明的催化剂,上述提及的反应可在低的温度下进行,优选是在至多200℃下进行,它可明显地降低设备中的腐蚀问题。
按本发明的或按本发明使用的催化剂包括或者,特别地,是由Pt、Re和至少另外一种选自元素周期表的第5-12族和第14族和镧系元素(第IV主族、第I、第II、第V、第VI、第VII、第VIII副族)中的元素组成,每种元素是以其金属或氧化物形式存在,任选地是负载在载体上的。
本发明还提供一种催化剂,它可通过还原Pt、Re和至少另外一种选自元素周期表第5-12族和第14族和镧系元素中的元素的氧化物、氧化物水合物、碳酸盐、硝酸盐、羧酸盐、螯合物、硫酸盐、磷酸盐和/或卤化物的含水悬浮物和/或溶液而得到。
所述的至少另外一种元素优选选自元素周期表的第6、10和11族。它是以金属或氧化物的形式使用的。特别优选的元素为Sn、V、Cr、Mo、W、Mn、Fe、Ru、Os、Co、Ni、Pd、Cu、Ag、Au、Zn、La和Ce。尤其优选的是以金属或氧化物形式的Mo、Ag、Au和/或Pd。在本发明的一个实施例中,催化剂仅含有一种以金属或氧化物形式存在的所说另外的元素。
这种催化剂可用作非负载型催化剂或负载型催化剂。当用作负载型催化剂时,所有适合的载体物质都可采用,例如活性炭、SiO2、Al2O3、TiO2、ZrO2、粘土如蒙脱土、沸石或其混合物。催化剂可以不同的方法进行制备。例如,催化剂可通过还原Pt、Re和至少另外一种选自元素周期表的第5-12族和第14族和镧系元素中的一种氧化物、氧化物水合物、碳酸盐、硝酸盐、羧酸盐、螯合物、特别是与1,3-二酮类化合物的螯合物、硫酸盐、磷酸盐和/或卤化物的含水悬浮物和/或溶液而可得到。这种催化剂可通过起始就加入全部的组分,然后还原起始物料,优选是用氢还原而制成。尽管如此,还原也可相继地进行。在这种情况下,催化剂或催化剂前体的活化或还原优选是在200-500℃下进行的,特别优选是在210-400℃下进行的,更优选是在220-300℃下进行。在经过还原之后,催化剂常常不再以金属间(intermetallische)化合物形式存在,或仅有很少量这样的化合物存在。
例如,将PtO2、一种Re化合物如Re2O7和至少一种第三种组分的另外化合物引入到水中,并用氢还原。以这种方法所得到的催化剂,可直接用于氢化反应。负载型催化剂可以这样的方法制备,例如,使氧化铂或氧化铂的水合物负载在载体上,它可通过氧化铂前体或氧化铂水合物前体和载体物质的浸渍或共沉淀和随后的焙烧而制得Pt/载体混合物。Re化合物和另外的组分也可通过浸渍或沉淀的方法加入。例如,在氧化铂或氧化铂水合物在载体上的还原之前进行浸渍或沉淀是可能的。
Pt与Re的重量比或Pt与至少一种另外元素的重量比优选为100-0.01,特别优选为50-0.05,更优选为10-0.1。在还原或活化之前,Pt优选是采用氧化物或氧化物水合物的形式。Pt组分优选是以PtO2的形式存在。可以采用的Re源为通常的Re化合物;优选采用的为Re2O7。
催化剂可制成粉末状或成型颗粒如挤出物、片状、小球,或作为固定床。
原则上,所有的脂族羧酸或其酸酐或酯或内酯,都可在本发明的方法中进行加氢,制得脂族醇。
所述的脂族羧酸优选含有至少3个碳原子,特别优选地含有至少4个碳原子。碳原子数目指的是单个的酸并包括羧基。羧酸的衍生物相应地具有更多的碳原子。
在一个实施例中,羧酸不合有任何OH基团与羧基相邻,或者根本不含有任何羟基。
羧酸中的羧基数目不是重要的。单羧酸、二羧酸、三羧酸或四羧酸通常都可采用,单羧酸或二羧酸是特别优选的。
羧酸中的碳原子数目也不是重要的。羧酸优选含有3-30个碳原子,特别优选为4-20个碳原子,尤其优选是4-10个碳原子。脂族部分可以是线性的或支链的。在其骨架中可含有一个或多个双键和/或三键。
通常的酸酐或酯可替代游离的羧酸,用在本发明的方法之中。
适合的羧酸实例为单羧酸,如丙酸、丁酸、正戊酸、己酸、十五烷酸、十六烷酸、十七烷酸和十八烷酸。单羧酸可以是不饱和的。适合的二羧酸的实例为琥珀酸、富马酸、马来酸和己二酸。
内酯的实例为丁内酯、甲基丁内酯或己内酯。
如果骨架中有双键或三键存在,它们在氢化作用中会同时发生氢化,形成饱和的化合物。如果有羰基存在,则它们也会发生氢化。
所得到的醇具有很多用途,例如可用作溶剂、中间体或聚合物中的醇组分。
二羧酸可以未稀释的形式或以溶液或悬浮液的形式用于氢化反应。适合的溶剂包括所有在反应条件下呈惰性的物质,如水、二氧杂环乙烷、四氢呋喃、乙二醇醚类、烃类如己烷或醇类如甲醇、乙醇或反应产物本身。例如,在丁酸的氢化反应中,是采用丁醇。氢化反应可以连续地进行,也可分批地进行。如果反应是分批进行的,则催化剂可以采用如粉末形式的。如果反应是连续进行的,则催化剂可以安排成一个固定床,而且这种方法可使产物进行循环。
氢化温度优选至多为200℃。氢化温度优选为30-200℃,特别优选为100-185℃,更优选为120-170℃。反应压力通常是可用氢气调节的,优选为1-350巴。气相反应压力优选为1-80巴,液相反应压力优选为20-330巴,特别优选为100-300巴。
氢化反应可在水存在的条件下进行。
在本发明催化剂存在下的脂族二羧酸或其酸酐或酯的氢化反应中,除了脂族二醇外,还可能通过闭环形成内酯。二醇或内酯的选择性可通过适当选用催化剂中的至少一种另外元素而得到控制。例如,如果采用乙酸钴作为所述另外元素的来源,则在衣康酸的还原中主要形成的为甲基丁内酯。如果采用乙酸钯作为所述另外元素的来源,则主要形成的为2-甲基丁二醇。
下述的实施例将对本发明作详细的说明。
实施例
实施例1
将0.1g的PtO2、0.2g的Re2O7、0.1g的乙酸银和9g水投入到金属高压反应釜中。注入氢气的压力为60巴,在搅拌下加热混合物至270℃。经一小时后,冷却混合物至室温,使反应釜卸压,并加入1g的己二酸。注入氢气的压力为100巴,在搅拌下加热混合物至150℃。二小时后,再一次地进行冷却和卸压操作。采用气相色谱对反应流出物进行分析。发现有81.3%的1,6-己二醇,己二酸全部发生转化。剩余物含有正己醇、6-羟基己酸和己二醇与羟基己酸的酯。
实施例2
采用实施例1的方法,对衣康酸进行加氢。在反应的流出物中发现有45.2%的2-甲基丁二醇和47.9%的甲基丁内酯,转化率为100%。剩余物中主要含有3-甲基四氢呋喃、2-甲基丁醇和3-甲基丁醇。
实施例3
采用乙酸钴替代实施例2中乙酸银,制得催化剂。随后的氢化反应同实施例2,在反应流出物中有17.1%的2-甲基丁二醇和75.6%的甲基丁内酯。剩余物中主要含有3-甲基四氢呋喃、2-甲基丁醇和3-甲基丁醇。
实施例4
采用硝酸三苯基膦合金盐替代实施例2中的乙酸银,制得催化剂。随后的氢化反应同实施例1,在反应流出物中有62.5%的2-甲基丁二醇和24.4%的甲基丁内酯。剩余物中主要含有3-甲基四氢呋喃、2-甲基丁醇和3-甲基丁醇。
实施例5
采用乙酸钯替代实施例2中的乙酸银,制得催化剂。随后的氢化反应同实施例2,在反应流出物中有76.7%的2-甲基丁二醇和1.8%的甲基丁内酯。剩余物中主要含有3-甲基四氢呋喃、2-甲基丁醇和3-甲基丁醇。
实施例6
用三氧化钼替代实施例2中的乙酸银,制得催化剂。随后的氢化反应同实施例2,在反应流出物中有73.3%的2-甲基丁二醇和8.8%的甲基丁内酯。剩余物中主要含有3-甲基四氢呋喃、2-甲基丁醇和3-甲基丁醇。
实施例7
采用实施例1的方法,在140℃下对马来酸进行加氢。在反应的流出物中发现有70%的1,4-丁二醇,转化率为100%。剩余物中主要含有四氢呋喃、γ-丁内酯、4-羟基丁醛和丁醇。
Claims (6)
1.一种制备脂族二醇或内酯的方法,它是在一种含有各以金属或氧化物形式存在的Pt和Re的催化剂存在下,通过氢化含至少3个碳原子的脂族二元羧酸或其酸酐或酯而实现的,其特征在于,所述的催化剂还含有至少另外一种选自元素周期表的第6和11族、Co和Ni的一种元素,该元素是以金属或氧化物形式存在的。
2.权利要求1所述的方法,其特征在于,所述的催化剂含有以金属或氧化物形式存在的Mo、Ag和/或Au。
3.权利要求1所述的方法,其特征在于,氢化反应温度至多为200℃。
4.权利要求1所述的方法,其特征在于,氢化反应是在水存在下进行的。
5.权利要求1所述的方法,其特征在于,Pt组分在用氢还原之前是以PtO2的形式存在的。
6.权利要求1所述的方法,其中二元羧酸选自琥珀酸、富马酸、马来酸、衣康酸和己二酸。
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US5254518A (en) * | 1992-07-22 | 1993-10-19 | Exxon Research & Engineering Company | Group IVB oxide addition to noble metal on rare earth modified silica alumina as hydrocarbon conversion catalyst |
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1997
- 1997-05-16 DE DE19720657A patent/DE19720657A1/de not_active Withdrawn
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1998
- 1998-05-12 DE DE59806195T patent/DE59806195D1/de not_active Expired - Lifetime
- 1998-05-12 CN CN98805932A patent/CN1109009C/zh not_active Expired - Fee Related
- 1998-05-12 US US09/423,876 patent/US6204417B1/en not_active Expired - Lifetime
- 1998-05-12 ES ES98925581T patent/ES2187029T3/es not_active Expired - Lifetime
- 1998-05-12 EP EP98925581A patent/EP0983219B1/de not_active Expired - Lifetime
- 1998-05-12 WO PCT/EP1998/002777 patent/WO1998052891A1/de active IP Right Grant
- 1998-05-12 JP JP54989498A patent/JP4138025B2/ja not_active Expired - Fee Related
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US4214106A (en) * | 1977-04-07 | 1980-07-22 | Hoechst Aktiengesellschaft | Process for the preparation of ethylene glycol |
US5149680A (en) * | 1987-03-31 | 1992-09-22 | The British Petroleum Company P.L.C. | Platinum group metal alloy catalysts for hydrogenation of carboxylic acids and their anhydrides to alcohols and/or esters |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN100450984C (zh) * | 2004-04-02 | 2009-01-14 | 花王株式会社 | 脂肪醇的制造方法 |
Also Published As
Publication number | Publication date |
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EP0983219B1 (de) | 2002-11-06 |
US6204417B1 (en) | 2001-03-20 |
ES2187029T3 (es) | 2003-05-16 |
DE59806195D1 (de) | 2002-12-12 |
WO1998052891A1 (de) | 1998-11-26 |
JP2001526670A (ja) | 2001-12-18 |
DE19720657A1 (de) | 1998-11-19 |
CN1259112A (zh) | 2000-07-05 |
EP0983219A2 (de) | 2000-03-08 |
JP4138025B2 (ja) | 2008-08-20 |
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