CN1984859B - 用于氢化羰基化合物的催化剂和方法 - Google Patents
用于氢化羰基化合物的催化剂和方法 Download PDFInfo
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- CN1984859B CN1984859B CN2005800231749A CN200580023174A CN1984859B CN 1984859 B CN1984859 B CN 1984859B CN 2005800231749 A CN2005800231749 A CN 2005800231749A CN 200580023174 A CN200580023174 A CN 200580023174A CN 1984859 B CN1984859 B CN 1984859B
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- 238000000034 method Methods 0.000 title claims abstract description 47
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 24
- 239000003054 catalyst Substances 0.000 title description 22
- 150000001728 carbonyl compounds Chemical class 0.000 title description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000000463 material Substances 0.000 claims abstract description 46
- 239000010949 copper Substances 0.000 claims abstract description 38
- 229910052802 copper Inorganic materials 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 31
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000465 moulding Methods 0.000 claims abstract description 29
- 239000004568 cement Substances 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000010439 graphite Substances 0.000 claims abstract description 19
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 19
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 11
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 7
- 230000003647 oxidation Effects 0.000 claims description 43
- 238000007254 oxidation reaction Methods 0.000 claims description 43
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 13
- 229960004643 cupric oxide Drugs 0.000 claims description 12
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- 150000001875 compounds Chemical class 0.000 claims description 9
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- 229910052751 metal Inorganic materials 0.000 claims description 5
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- 230000008569 process Effects 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 8
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- 229910000431 copper oxide Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 26
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 12
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 6
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- 238000007906 compression Methods 0.000 description 6
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- 239000012266 salt solution Substances 0.000 description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 description 6
- 235000017550 sodium carbonate Nutrition 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 5
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- YGHRJJRRZDOVPD-UHFFFAOYSA-N 3-methylbutanal Chemical compound CC(C)CC=O YGHRJJRRZDOVPD-UHFFFAOYSA-N 0.000 description 4
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000001879 copper Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002505 iron Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- OJVAMHKKJGICOG-UHFFFAOYSA-N 2,5-hexanedione Chemical compound CC(=O)CCC(C)=O OJVAMHKKJGICOG-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- FTZILAQGHINQQR-UHFFFAOYSA-N 2-Methylpentanal Chemical compound CCCC(C)C=O FTZILAQGHINQQR-UHFFFAOYSA-N 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
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- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
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- 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
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- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 159000000013 aluminium salts Chemical class 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 2
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 2
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- 125000004356 hydroxy functional group Chemical group O* 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
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- 239000007791 liquid phase Substances 0.000 description 2
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B41/00—Formation or introduction of functional groups containing oxygen
- C07B41/02—Formation or introduction of functional groups containing oxygen of hydroxy or O-metal groups
-
- 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
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- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- 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
- B01J23/72—Copper
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- 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
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- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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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)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明涉及一种用于氢化含有至少一个羰基的有机化合物的方法,包括使有机化合物在氢存在下与成形体接触。所述成形体可以通过下列方法制得:i)制备含有氧化铜、氧化铝和氧化铁的氧化材料,ii)往该氧化材料中加入粉状金属铜、铜片、粉状水泥、石墨或其混合物,和iii)将(ii)中获得的混合物成形,由此形成成形体。
Description
本发明涉及一种使用催化剂氢化具有至少一个羰基的有机化合物的方法,该催化剂包含氧化铜、氧化铝和氧化铁且通过加入氧化铁来形成,由此制得具有高选择性和同时具有高稳定性的催化剂。在此制备中可以另外加入铜粉、铜片或水泥。本发明同样涉及催化剂本身,并且更普遍地涉及镧氧化物在制备具有高选择性并同时具有高稳定性的催化剂中的应用。
羰基化合物如羧酸或羧酸酯的催化氢化在基础化学工业的生产线中占有重要地位。
在工业过程中,羰基化合物如羧酸酯的催化氢化几乎只在固定床反应器中进行。除了阮内型催化剂外,所使用的固定床催化剂尤其为负载催化剂,如铜、镍或贵金属催化剂。
例如,US 3,923,694描述了一种氧化铜/氧化锌/氧化铝型催化剂。这种催化剂的缺点是它在反应期间的机械稳定性不足并因此相对快地破碎。由于催化剂成形体的破碎,导致活性损失和跨反应器的压差的积累。因此必须过早地关闭装置。
DE 198 09 418.3描述了一种在催化剂存在下催化氢化羰基化合物的方法,所述催化剂包含主要含二氧化钛的载体和作为活性成分的铜或铜与至少一种选自锌、铝、铈、贵金属、VIII过渡族金属的金属的混合物,其中铜表面积不超过10m2/g。优选的载体材料是二氧化钛与氧化铝或氧化锆或者氧化铝与氧化锆的混合物。优选实施方式中,添加金属铜粉或铜片来成形所述催化剂材料。
DE-A 195 05 347非常概括地描述了一种制备高机械强度的催化剂片的方法,其中将金属粉末或金属合金粉末添加到待制片的材料中。所添加的金属粉末尤其是铝粉或铜粉或铜片。但是,在氧化铜/氧化锌/氧化铝催化剂的情形下添加铝粉时,所形成的成形体的侧向抗压强度比在没有添加铝粉的情形下所制得的成形体的侧向抗压强度差,并且当用作催化剂时该发明的成形体的转化活性比在没有添加铝粉的情形下所制得的催化剂的转化活性低。该文献同样公开了由NiO、ZrO2、MoO3和CuO组成的氢化催化剂,在制备过程中还将Cu粉混合到其中。但是,在该公开内容中并没作出关于选择性或活性的说明。
DE 256 515描述了一种从合成气制备醇的方法,该方法用通过与金属铜粉或铜片一起研磨并造粒获得的基于Cu/Al/Zn的催化剂。所述方法的主要目的是制备C1~C5醇的混合物,并且在其上三分之一层含有铜粉或铜片含量较高的催化剂而且下三分之一层含有铜粉或铜片含量较低的催化剂的反应器中进行该方法。
本发明的目的是克服现有技术的缺点并提供催化氢化羰基化合物的方法,和提供同时具有高机械稳定性和高氢化活性与选择性的催化剂。
我们已发现,该目的可通过同时沉淀铜化合物、铝化合物和铁化合物并随后干燥、煅烧、制片和通过添加金属铜粉、铜片、或水泥粉末或石墨或混合物,形成一种由于添加铁化合物而显示用作催化剂的成形体的高活性和选择性以及高稳定性的催化剂来实现。
因此,本发明涉及一种用于氢化具有至少一个羰基的有机化合物的方法,其包括使有机化合物在氢气存在下与成形体接触,其中所述成形体可以通过下列方法制得:
(i)获得含有氧化铜、氧化铝和氧化铁的氧化材料,
(ii)往该氧化材料中加入粉状金属铜、铜片、粉状水泥、石墨或其混合物,和
(iii)将(ii)中获得的混合物成形,由此形成成形体。
认为氧化铁的含义为Fe(III)氧化物。
优选实施方式中,本发明的成形体用作均匀组成的催化剂、浸渍催化剂、涂覆催化剂和沉淀催化剂。
本发明方法中使用的催化剂特征在于铜活性组份、铝组份和铁组份优选地用碳酸钠溶液来同时或相继地沉淀,接着进行干燥、煅烧、制片和再次煅烧。
下列沉淀方法是特别适合的:
A)铜盐溶液、铝盐溶液和铁盐溶液,或者含有铜盐、铝盐和铁盐的溶液平行地或相继地用碳酸钠溶液沉淀。沉淀的材料随后干燥,并且如果合适的话煅烧。
B)将铜盐溶液和铁盐溶液或者含有铜盐和至少一种铁盐的溶液沉淀在预制的氧化铝载体上。特别优选的实施方式中,其呈水悬浮液中的粉末形态。但是,载体材料也可以呈球体、挤出物、碎料或丸剂形式。
B1)在实施方式(I)中,沉淀铜盐溶液和铁盐溶液或者含有铜盐和铁盐的溶液,优选用碳酸钠溶液沉淀。使用载体材料氧化铝的水悬浮液作为初始进料。
由A)或B)产生的沉淀以常规方法来过滤,并且优选地洗涤至不含碱,例如如DE 198 09 418.3中所描述的那样。
来自A)的最终产物和来自B)的那些都在50~150℃、优选在120℃下干燥,并随后如果合适,优选地在通常为200~600℃、尤其是在300~500℃下煅烧2小时。
作为用于A)和/或B)的原材料,原则上公知使用可溶于用于施用于该载体上的溶剂的所有Cu(I)和/或Cu(II)盐,例如硝酸盐、碳酸盐、醋酸盐、草酸盐或铵络合物,类似的铝盐和铁盐。对于方法A)和B)来说,特别优选使用硝酸铜。
本发明方法中,优选地将上述干燥的和可能煅烧的粉末加工为片剂、圆环、环状片、挤出物、蜂巢或类似的成形体。可用于此目的的方法是现有技术中的所有公知的适宜方法。
氧化材料的组成通常使得氧化铜的比例范围为40~90重量%、氧化铁的比例范围为0~50重量%和氧化铝的比例范围最高为50重量%,每种情形中均基于上述氧化组份的总重,煅烧之后三种氧化物一起构成氧化材料的至少80重量%,并且在上述意义中不包含水泥作为氧化材料的一部分。
优选实施方式中,本发明因此提供了一种如上所述的方法,其中该氧化材料包括:
(a)比例范围为50≤x≤80重量%、优选55≤x≤75重量%的氧化铜,
(b)比例范围为15≤y≤35重量%、优选20≤y≤30重量%的氧化铝,
(c)比例范围为1≤z≤30重量%、优选2≤z≤25重量%的氧化铁,
每种情形中均基于煅烧之后的氧化材料总重,其中80≤x+y+z≤100、尤其是95≤x+y+z≤100。
本发明方法和本发明催化剂的特征在于以下事实,在沉淀中添加铁导致用作催化剂的成形体的高稳定性。
通常,粉状铜、铜片或粉状水泥或石墨或其混合物加入到氧化材料中的用量范围为1~40重量%、优选为2~20重量%且特别优选为3~10重量%,每种情形中均基于氧化材料的总重。
作为水泥,优选使用高铝水泥。高铝水泥特别优选基本上由氧化铝和氧化钙组成,并且特别地其包含约75~85重量%的氧化铝和约15~25重量%的氧化钙。也可以使用基于氧化镁/氧化铝、氧化钙/二氧化硅和氧化钙/氧化铝/氧化铁的水泥。
特别地,氧化材料可以另外包含比例基于氧化材料总重不超过10重量%、优选不超过5重量%的选自元素Re、Fe、Ru、Co、Rh、Ir、Ni、Pd和Pt的至少一种额外的组份。
在本发明方法的另一优选实施方式中,在成形为成形体之前除了铜粉、铜片或粉状水泥或它们的混合物之外,还将石墨添加到氧化材料中。石墨添加量优选地使得成形为成形体可以更容易地进行。优选实施方式中,石墨添加量基于氧化材料总重为0.5~5重量%。在这一点上,是否在铜粉、铜片或粉状水泥或它们的混合物之前或之后或同时将石墨加入氧化材料中并不重要。
因此,本发明也提供了如上所述的方法,其中将石墨以基于氧化材料总重为0.5~5重量%的用量添加到氧化材料中或添加到(ii)获得的混合物中。
优选实施方式中,本发明因此也提供了一种成形体,该成形体包含氧化材料,该氧化材料包含
(a)比例范围为50≤x≤80重量%、优选55≤x≤75重量%的氧化铜,
(b)比例范围为15≤y≤35重量%、优选20≤y≤30重量%的氧化铝,
(c)比例范围为1≤z≤30重量%、优选2≤z≤25重量%的氧化铁,
每种情形中均基于煅烧之后的氧化材料总重,其中80≤x+y+z≤100、尤其是95≤x+y+z≤100;
金属铜粉、铜片或水泥粉末或其混合物,比例范围基于氧化材料总重为1~40重量%;
石墨,比例范围基于氧化材料总重为0.5~5重量%;
其中,氧化材料、金属铜粉、铜片或水泥粉末或其混合物与石墨的比例之和构成该成形体的至少95重量%。
在将铜粉、铜片或水泥粉末或其混合物和如果期望的话石墨添加到氧化材料中之后,如果期望的话将成形后获得的成形体煅烧至少一次,时间一般为0.5~10小时,优选0.5~2小时。该煅烧步骤的温度通常为200~600℃、优选为250~500℃且特别优选为270~400℃。
在用水泥粉成形的情形下,可以有益的是,在煅烧之前用水使获得的成形体变得潮湿,并随后将其干燥。
当成形体用作氧化态的催化剂时,在与氢化溶液接触之前,用还原气体例如氢气、优选氢气/惰性气体混合物、尤其是氢气/氮气混合物,在100~500℃、优选150~350℃和尤其是180~200℃下预还原所述成形体。在这方面优选使用氢含量范围为1~100体积%、特别优选范围为1~50体积%的混合物。
优选实施方式中,在用作催化剂之前以本身公知的方法通过用还原介质处理来活化本发明的成形体。活化作用预先在还原炉中发生或者在安装在反应器中之后发生。如果催化剂已预先在还原炉中活化,则将它安装在反应器中并立即在氢气压力下直接供应氢化溶液。
通过本发明的方法制备的成形体的优选应用领域为具有羰基的有机化合物在固定床中的氢化。但是,其它实施方式也是可能的,例如使用向上和向下旋涡运动的催化剂材料的流化床反应。氢化可在气相中或在液相中进行。氢化优选在液相中进行,例如以向下流动模式或向上流动模式。
当以向下流动模式进行氢化时,使含待氢化的羰基化合物的液体原材料滴流在氢压力下的反应器中的催化剂床上,在催化剂上形成薄液体膜。另一方面,当以向上流动模式进行氢化时,将氢气通入到液体反应混合物流过的反应器中,并且氢气作为上升的气泡通过催化剂床。
一种实施方式中,将待氢化的溶液单程泵送穿过催化剂床。在本发明方法的另一实施方式中,在通过反应器后将一部分产物作为产物流连续地取出,并且如果期望的话使其通过如上所定义的第二反应器。将另外部分产物连同新鲜的含有碳基化合物的原材料一起再次送到反应器中。在下文中该操作模式称为循环法。
如果选择向下流动模式作为本发明方法的实施方式,那么优选循环模式。进一步优选以采用主反应器和后反应器的循环模式来进行氢化。
本发明的方法适用于将羰基化合物如醛和酮、羧酸、羧酸酯或羧酸酐氢化成相应的醇,优选为脂肪族和脂环族、饱和和不饱和的羰基化合物。羰基化合物可以带有其它官能团如羟基或氨基。不饱和的羰基化合物通常被氢化为相应的饱和醇。本发明中所用术语“羰基化合物”包括所有具有C=O基的化合物,包括羧酸及其衍生物。当然,也可氢化两种或多种羰基化合物的混合物。另外,每种待氢化的单个羰基化合物也可以含有一个以上的羰基。
本发明的方法优选用于氢化脂族醛、羟基醛、酮、酸、酯、酐、内酯和糖。
优选的脂肪醛为支化的和非支化的,饱和和/或不饱和的脂肪族C2-C30醛,例如通过羰基合成从具有内双键或末端双键的直链或支化烯烃可获得的那些。也可氢化含有30个以上羰基的低聚化合物。
脂族醛的实例为:
甲醛、丙醛、正丁醛、异丁醛、戊醛、2-甲基丁醛、3-甲基丁醛(异戊醛)、2,2-二甲基丙醛(新戊醛)、己醛、2-甲基戊醛、3-甲基戊醛、4-甲基戊醛、2-乙基丁醛、2,2-二甲基丁醛、3,3-二甲基丁醛、辛醛、癸醛、戊二醛。
除了所述的短链醛之外,长链脂族醛也是特别适合的,例如通过羰基合成从直链α-烯烃获得的那些。
特别优选烯醛化产物,如2-乙基己烯醛、2-甲基戊烯醛、2,4-二乙基辛烯醛或2,4-二甲基庚烯醛。
优选的羟基醛为C3-C12羟基醛,例如可通过脂肪族和脂环族醛和酮与它们自身或甲醛的醇醛缩合反应获得的那些。实例为3-羟基丙醛、二羟甲基乙醛、三羟甲基乙醛(季戊四醛)、3-羟基丁醛(丁间醇醛)、3-羟基-2-乙基己醛(2-乙基-1,3-己二醇)、3-羟基-2-甲基戊醛(戊间醇醛)、2-羟甲基丙醛、2,2-二羟甲基丙醛、3-羟基-2-甲基丁醛、3-羟基戊醛、2-羟甲基丁醛、2,2-二羟甲基丁醛、羟基新戊醛。特别优选羟基新戊醛(HPA)和二羟甲基丁醛(DMB)。
优选的酮为丙酮、丁酮、2-戊酮、3-戊酮、2-己酮、3-己酮、环己酮、异佛尔酮、甲基异丁基酮、异亚丙基丙酮、苯乙酮、苯基丙基甲酮、二苯甲酮、亚苄基丙酮、二亚苄基丙酮、亚苄基苯乙酮、2,3-丁二酮、2,4-戊二酮、2,5-己二酮和甲基乙烯基酮。
另外,可以反应羧酸及其衍生物,优选具有1~20个碳原子的那些。特别地,可以列举下列化合物:
羧酸,如甲基、乙酸、丙酸、丁酸、异丁酸、正戊酸、三甲基乙酸(新戊酸)、己酸、庚酸、辛酸、癸酸、月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、丙烯酸、甲基丙烯酸、油酸、反油酸、亚油酸、亚麻酸、环己烷羧酸、苯甲酸、苯乙酸、邻甲基苯甲酸、间甲基苯甲酸、对甲基苯甲酸、邻氯苯甲酸、对氯苯甲酸、邻硝基苯甲酸、对硝基苯甲酸、水杨酸、对羟基苯甲酸、邻氨基苯甲酸、对氨基苯甲酸、草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、马来酸、富马酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸;
羧酸酯,如上述羧酸的C1-C10烷基酯,特别是甲酸甲酯,乙酸乙酯,丁酸丁酯,邻苯二甲酸、间苯二甲酸、对苯二甲酸、己二酸、马来酸的二烷基酯,例如这些酸的二甲酯,(甲基)丙烯酸甲酯,丁内酯,己内酯和聚羧酸酯,例如聚丙烯酸和聚甲基丙烯酸酯和它们的共聚物和聚酯,例如聚甲基丙烯酸甲酯,对苯二甲酸酯和其它工程塑料,在这种情形中尤其进行的反应为氢解,即将酯转化为相应的酸和醇的反应;
脂肪;
羧酸酐,如上述羧酸的酐,特别是乙酸酐、丙酸酐、苯甲酸酐和马来酸酐;
羧酰胺,如甲酰胺、乙酰胺、丙酰胺、硬脂酰胺、对苯二甲酰胺。
也可以反应羟基羧酸,例如乳酸、苹果酸、酒石酸或柠檬酸;或氨基酸,例如甘氨酸、丙氨酸、脯氨酸和精氨酸;和肽。
特别优选氢化的有机化合物为饱和或不饱和的羧酸、羧酸酯、羧酸酐或内酯或它们中的两种或多种的混合物。
因此,本发明也提供了如上所述的方法,其中有机化合物为羧酸、羧酸酯、羧酸酐或内酯。
这些化合物的实例尤其为马来酸、马来酸酐、琥珀酸、琥珀酸酐、己二酸、6-羟基己酸、2-环十二烷基丙酸、上述酸的酯,例如甲酯、乙酯、丙酯或丁酯。其它实例为γ-丁内酯和己内酯。
在非常特别优选的实施方式中,本发明提供了如上所述的方法,其中有机化合物为己二酸或己二酸酯。
可将待氢化的羰基化合物单独地或者作为与氢化反应产物的混合物送到氢化反应器中,并且可以以未稀释的形式或者在使用额外溶剂的情况下进行。适宜的额外溶剂特别为水,醇如甲醇、乙醇和在反应条件下产生的醇。优选的溶剂为水、THF和NMP;特别优选水。
各自均优选以循环模式进行的向上流动模式和向下流动模式的氢化,通常在50~350℃、优选为70~300℃、特别优选为100~270℃的温度下,和压力范围为3~350巴、优选为5~330巴、特别优选为10~300巴下进行。
在非常特别优选的实施方式中,本发明的催化剂用于制备己二醇和/或己内酯的方法,如DE 196 07 954、DE 196 07 955、DE 196 47 348和DE 19647 349中所述。
在使用本发明催化剂的本发明方法中获得了高转化率和选择性。同时,本发明的催化剂显示出高的化学和机械稳定性。
因此,本发明非常普遍地提供了粉状金属铜或粉状水泥或其混合物作为添加剂在制备催化剂中用于同时增加催化剂的机械稳定性和活性与选择性的用途。
优选实施方式中,本发明提供了如上所述的用途,其中该催化剂包含作为活性组份的铜。
固态催化剂且特别是本发明催化剂的机械稳定性是由在各种状态(氧化、还原、还原并悬浮在水中)的侧向抗压强度参数来描述的。
出于本专利申请的目的,侧向抗压强度是用由Zwick(Ulm)提供的“Z2.5/T 919”型仪器测定的。在还原的催化剂和使用过的催化剂这两种情况下都在氮气气氛下进行测定,由此避免催化剂的再氧化。
实施例
实施例1:催化剂1的制备
催化剂的制备
将12.41kg浓度为19.34%的硝酸铜溶液、14.78kg浓度为8.12%的硝酸铝溶液和1.06kg浓度为37.58%的硝酸铁×9H2O溶液的混合物溶解于1.5L水中(溶液1)。溶液2包含60kg浓度为20%的无水Na2CO3。通过分开的管线将溶液1和溶液2引入装配有搅拌器并含有10L加热到80℃的水的沉淀容器中。通过适当调节溶液1和溶液2的进料速率,使得pH达到6.2。
在保持pH恒定在6.2和温度在80℃的同时,整个溶液1与碳酸钠发生反应。然后将这样形成的悬浮液再搅拌1小时,其中通过偶尔添加稀硝酸或碳酸钠溶液2使pH升至7.2。过滤该悬浮液并用蒸馏水洗涤至洗涤液的硝酸盐含量小于10ppm。
滤饼在120℃下干燥16小时,并随后在300℃下煅烧2小时。将这样获得的催化剂粉末与1重量%的石墨预压制。将获得的坯块与5重量%的Unicoat铜片混合,并随后与2重量%的石墨混合并压成直径3mm和高度3mm的片剂。最后将片剂在350℃下煅烧2小时。
这样制得的催化剂具有的化学组成为:57%CuO/28.5%Al2O3/9.5%Fe2O3/5%Cu。
氧化态的侧向抗压强度为117N,还原态下为50N,如表1中所示。
实施例2:己二酸二甲酯在催化剂1上的氢化
在充填了200ml催化剂1的立管式反应器中,在200巴的压力和190℃的反应温度下,以0.3kg/(L*h)的WHSV在具有循环(进料/循环=10/1)的向下流动模式中连续地氢化己二酸二甲酯。该实验持续共7天。GC分析发现190℃下的反应产物中酯转化率为99.9%,己二醇选择性为97.5%。从反应器中除去之后,发现催化剂仍然十分完整且具有高机械稳定性。实验结果汇总于表1中。
实施例3:在不使用铁的情况下制备对比催化剂
对比催化剂的制备与催化剂2类似,但是没有添加硝酸铁溶液:以类似于催化剂1的方式,用碳酸钠溶液沉淀14.5kg浓度为19.34%的硝酸铜溶液和14.5kg浓度为8.12%的硝酸铝溶液(溶液1)。
这样制得的催化剂具有的化学组成为:66.5%CuO/28.5%Al2O3/5%Cu。氧化态和还原态下的侧向抗压强度示于表1中。
实施例4:己二酸二甲酯在对比催化剂上的氢化
在充填了200ml催化剂2的立管式反应器中,在200巴的压力和190℃的反应温度下,以0.3kg/(L*h)的WHSV在具有循环(进料/循环=10/1)的向下流动模式中连续地氢化己二酸二甲酯。该实验持续共7天。GC分析发现220℃和240℃下的反应产物中,酯转化率在每种情形下均为80.2%,己二醇含量为86.6%。从反应器中除去之后,发现催化剂仍然十分完整且具有高机械稳定性。实验结果汇总于表1中。
下面表1中的数据表明,本发明的催化剂相对于对比催化剂在190℃下具有明显较高的氢化活性,即较高的己二酸二甲酯转化率;并且也获得了对所期望产物的较高选择性,即反应器排出物中目标产物己二醇的含量更高。
表1
催化剂 | 反应温度[℃] | 己二酸二甲酯转化率% | 己二醇选择性[%] | 氧化态/还原态下的侧向抗压强度(N) |
催化剂1 | 190 | 99.9 | 97.5 | 117/50 |
催化剂2 | 190 | 80.2 | 86.6 | 77/45 |
Claims (14)
1.一种氢化含有至少一个羰基的有机化合物的方法,包括使有机化合物在氢气存在下与成形体接触,其中所述成形体可以通过下列方法制得:
(i)获得含有氧化铜、氧化铝和氧化铁的氧化材料,
(ii)往该氧化材料中加入粉状金属铜、铜片、粉状水泥、石墨或其混合物,和
(iii)将(ii)中获得的混合物成形,由此形成成形体,其中该氧化材料包含:
(a)比例范围为50≤x≤80重量%的氧化铜,
(b)比例范围为15≤y≤35重量%的氧化铝,
(c)比例范围为1≤z≤30重量%的氧化铁,
每种情形中均基于煅烧之后的氧化材料总重,其中80≤x+y+z≤100,且在上述意义中不包含水泥作为氧化材料的一部分。
2.权利要求1的方法,其中粉状金属铜、铜片、粉状水泥或石墨或其混合物的添加量基于氧化材料总重为1~40重量%。
3.权利要求1或2的方法,其中向氧化材料或(ii)中获得的混合物中加入用量基于氧化材料总重为0.5~5重量%的石墨。
4.权利要求1或2的方法,其中有机化合物为羧酸、羧酸酯、羧酸酐或内酯。
5.权利要求4的方法,其中有机化合物为己二酸或己二酸的酯。
6.权利要求1或2的方法,其中氧化铜的比例范围是55≤x≤75重量%。
7.权利要求1或2的方法,其中氧化铝的比例范围是20≤y≤30重量%。
8.权利要求1或2的方法,其中氧化铁的比例范围是2≤z≤25重量%。
9.权利要求1或2的方法,其中95≤x+y+z≤100。
10.一种成形体,其包含
氧化材料,该氧化材料包含
(a)比例范围为50≤x≤80重量%的氧化铜,
(b)比例范围为15≤y≤35重量%的氧化铝,
(c)比例范围为1≤z≤30重量%的氧化铁,
每种情形中均基于煅烧之后的氧化材料总重,其中80≤x+y+z≤100;
金属铜粉、铜片或水泥粉末或其混合物,比例范围基于氧化材料总重为1~40重量%;
石墨,比例范围基于氧化材料总重为0.5~5重量%;
其中,氧化材料、金属铜粉、铜片或水泥粉末或其混合物与石墨的比例之和构成该成形体的至少95重量%。
11.权利要求10的成形体,其中氧化铜的比例范围是55≤x≤75重量%。
12.权利要求10或11的成形体,其中氧化铝的比例范围是20≤y≤30重量%。
13.权利要求10或11的成形体,其中氧化铁的比例范围是2≤z≤25重量%。
14.权利要求10或11的成形体,其中95≤x+y+z≤100。
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AU2008286950B2 (en) * | 2007-08-10 | 2013-11-07 | Res Usa, Llc | Precipitated iron catalyst for hydrogenation of carbon monoxide |
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US20110313187A1 (en) | 2009-02-09 | 2011-12-22 | Christof Wilhelm Wigbers | Method for improving the catalytic activity of monolithic catalysts |
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US20110313188A1 (en) | 2009-02-09 | 2011-12-22 | Basf Se | Method for improving the catalytic activity of monolithic catalysts |
TWI490034B (zh) | 2009-11-17 | 2015-07-01 | Basf Se | 製備具有增強氫化活性之經承載氫化觸媒之方法 |
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CN105622345B (zh) * | 2014-11-04 | 2018-07-20 | 中国石油化工股份有限公司 | 一种制备β-二醇的方法 |
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US3923694A (en) * | 1969-03-04 | 1975-12-02 | Ici Ltd | Methanol synthesis catalyst |
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