CN1110472C - 将马来酸氢化成1,4－丁二醇的改进方法 - Google Patents
将马来酸氢化成1,4－丁二醇的改进方法 Download PDFInfo
- Publication number
- CN1110472C CN1110472C CN98125255A CN98125255A CN1110472C CN 1110472 C CN1110472 C CN 1110472C CN 98125255 A CN98125255 A CN 98125255A CN 98125255 A CN98125255 A CN 98125255A CN 1110472 C CN1110472 C CN 1110472C
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- Prior art keywords
- iron
- acid
- hydrogenatable precursor
- palladium
- catalyzer
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 title claims abstract description 29
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title claims description 25
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 18
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 title abstract description 15
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 title abstract description 4
- 239000011976 maleic acid Substances 0.000 title abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000002243 precursor Substances 0.000 claims abstract description 32
- 229910052742 iron Inorganic materials 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 42
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 28
- 229910052763 palladium Inorganic materials 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 16
- 229910052702 rhenium Inorganic materials 0.000 claims description 15
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 14
- 229910052709 silver Inorganic materials 0.000 claims description 14
- 239000004332 silver Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 10
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 5
- 239000010970 precious metal Substances 0.000 claims description 5
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- 239000001530 fumaric acid Substances 0.000 claims description 4
- 229910052697 platinum Inorganic materials 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
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 claims description 3
- PMVSDNDAUGGCCE-TYYBGVCCSA-L Ferrous fumarate Chemical compound [Fe+2].[O-]C(=O)\C=C\C([O-])=O PMVSDNDAUGGCCE-TYYBGVCCSA-L 0.000 claims description 2
- CHYQSXLXQCXPAA-UHFFFAOYSA-H butanedioate;iron(3+) Chemical compound [Fe+3].[Fe+3].[O-]C(=O)CCC([O-])=O.[O-]C(=O)CCC([O-])=O.[O-]C(=O)CCC([O-])=O CHYQSXLXQCXPAA-UHFFFAOYSA-H 0.000 claims description 2
- OBGMEWPQYAPZTF-UHFFFAOYSA-N butanoic acid;iron Chemical compound [Fe].CCCC(O)=O OBGMEWPQYAPZTF-UHFFFAOYSA-N 0.000 claims description 2
- 229960000225 ferrous fumarate Drugs 0.000 claims description 2
- 235000002332 ferrous fumarate Nutrition 0.000 claims description 2
- 239000011773 ferrous fumarate Substances 0.000 claims description 2
- HEAFJVLUNSWSQJ-UHFFFAOYSA-N iron;propanoic acid Chemical compound [Fe].CCC(O)=O HEAFJVLUNSWSQJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 40
- 239000000243 solution Substances 0.000 description 21
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 20
- 239000002994 raw material Substances 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000007598 dipping method Methods 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- -1 butyric acid compound Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- 150000002941 palladium compounds Chemical class 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
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- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 239000007864 aqueous solution Substances 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- QSHYGLAZPRJAEZ-UHFFFAOYSA-N 4-(chloromethyl)-2-(2-methylphenyl)-1,3-thiazole Chemical compound CC1=CC=CC=C1C1=NC(CCl)=CS1 QSHYGLAZPRJAEZ-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000013461 design Methods 0.000 description 3
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
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- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 3
- 229940100890 silver compound Drugs 0.000 description 3
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- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
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- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- WECIKJKLCDCIMY-UHFFFAOYSA-N 2-chloro-n-(2-cyanoethyl)acetamide Chemical compound ClCC(=O)NCCC#N WECIKJKLCDCIMY-UHFFFAOYSA-N 0.000 description 1
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- 229910052775 Thulium Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
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- 239000003153 chemical reaction reagent Substances 0.000 description 1
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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
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/177—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with simultaneous reduction of a carboxy group
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Abstract
在贵金属催化剂存在下将马来酸和/或其它可氢化前体氢化为1，4-丁二醇。通在可氢化前体的原料中加入铁来提高1，4-丁二醇的产量和收率。
Description
本发明涉及一种将马来酸，马来酐或其它可氢化的前体氢化成1，4-丁二醇和四氢呋喃的改进方法。改进包括向马来酸，马来酐或其它可氢化的前体原料中加入铁。在原料中加入铁能改善催化剂的性能，使得反应产物中1，4-丁二醇的收率较高，副产物形成较少。
人们已经熟知，通过催化氢化马来酐和相关的化合物获得四氢呋喃，γ-丁内酯及1，4-丁二醇。四氢呋喃是可用于天然及合成的树脂中的有用溶剂，也是用于制备许多化工原料及塑料的有价值的中间体。γ-丁内酯是用于合成丁酸化合物，聚乙烯吡咯烷酮及甲硫氨酸的中间体。γ-丁内酯是用于丙烯酸及苯乙烯聚合物中有用的溶剂，也是脱漆剂及纺织助剂中有用的成分。1，4-丁二醇(即1，4-butylene glycol)可用作溶剂，湿润剂，增塑剂及药物的中间体，用于聚氨基甲酸乙酯高弹体的交联剂，制备四氢呋喃的前体，也可用于制备对苯二甲酸酯塑料。
现已公开许多用于将马来酸，马来酐或其它可氢化前体氢化成四氢呋喃，γ-丁内酯及1，4-丁二醇的催化剂和方法。本发明的特征是用载有贵金属的催化剂进行催化的方法。本领域已知这样的催化剂也可以包括铁。
例如，U.S.4,985,572公开了一种将羧酸或其酐催化氢化成相应的醇和/或羧酸酯的方法，其中使用的催化剂包括在碳载体上的铼，钯和至少一种可与钯合金化的其它金属。可与钯形成合金的金属优选为银，但金，铜，镍，铑，锡，钴，铝，锰，镓，铁，铬和铂也是已知的。制备这种催化剂的特征在于，将钯和银同时沉积在碳载体上再经高温(600℃)热处理。然后将铼沉积在渗透了钯/合金化金属的碳载体上。再还原得到的催化剂。
另外，WO92/02298公开了一种氢化催化剂，其中在载体上含有钯，铼及一种或一种以上选自下面组中的金属：铑，钴，铂，钌，铁，铥，铈，钇，钕，铝，镨，钬，铪，锰，钒，铬，金，铽，镥，镍，钪和铌。
通常，在马来酸，马来酐或其它可氢化前体的氢化过程中，上述催化剂有生成多于1，4-丁二醇的四氢呋喃和γ-丁内酯的倾向。本发明的目的在于提供一种使1，4-丁二醇产量最高而使γ-丁内酯产量最低的方法。
本发明提供一种制备1，4-丁二醇的方法，其中包括将含有可氢化前体的原料和铁与含氢气体接触进行催化氢化。
在贵金属催化剂存在下将马来酸或其它可氢化的前体氢化成1，4-丁二醇。通过向原料中加入铁或含铁化合物，可以提高1，4-丁二醇的产量和收率。反应物
在本发明的方法中，至少一种可氢化的前体在催化剂存在下与含氢气体进行反应。这里使用的“可氢化的前体”指用于当氢化制备1，4-丁二醇时任意的羧酸或其酐，羧酸酯，内酯或其混合物。具有代表性的可氢化前体包括马来酸，马来酐，富马酸，琥珀酐，琥珀酸，琥珀酸酯如C1-C8琥珀酸二烷基酯(如琥珀酸二甲酯)，马来酸酯如C1-C8马来酸二烷基酯(如马来酸二甲酯)，γ-丁内酯或其混合物。优选的可氢化前体为马来酸，马来酐，琥珀酸，琥珀酐，富马酸，C4酸酯，γ-丁内酯或其混合物。
最优选的可氢化前体为马来酸，它通常是这样制得的，即通过将正丁烷或苯在催化剂存在下与含氧气体进行反应，使正丁烷或苯在汽相中被氧化成马来酐，然后通过水冷却收集马来酐并在水溶液中制备出马来酸。正丁烷或苯的氧化通常在约300℃-600℃及0.5-20个大气压(50-2000KPa)下进行。
通常，含氢(H2)气体为商业纯的氢气，不含稀释气体。然而，含氢气体除了含氢气(H2)外也可以含有氮气(N2)，任意的气态烃(如甲烷)，以及气态的碳氧化物(如一氧化碳，二氧化碳)。
催化剂
用于本发明的催化剂包括选自元素周期表中VIII族的贵金属，其中至少含有钯，钌，铑，锇，铱和铂中的一种。这些包括：(i)UK No.01551741中描述的也至少含有一种铼，锰或碲的催化剂，(ii)U.S.4,096,156中描述的也至少含有一种银和金的催化剂，(iii)U.S.5,149,680描述的催化剂，其中也至少含有一种能与VIII族贵金属形成合金的金属，以及含有至少一种铼，钨或钼。其它合适的催化剂的例子包括UK No.01543232及U.S.4,659,686中描述的在碳载体上含有钯和铼。这些催化剂的组成也可以通过掺合选自IA，IIA或VIII族的一种或一种以上金属进一步改性。
本发明中使用的优选催化剂包括钯，银和铼载在碳上的催化剂。本发明使用的碳具有至少200m2/g的BET表面积，优选范围为500-1500m2/g。U.S.5,149,680中描述了这种型号的催化剂。
优选的催化剂组成包括约0.1-20％(重量)钯，优选约2-8％(重量)钯；约0.1-20％(重量)银，优选约1-8％(重量)银；约0.1-20％(重量)铼，优选约1-10％(重量)铼。钯和银的比例为10-1至1-10。正如前面提到的，这种催化剂的组成也可以通过掺合选自IA或IIA族的一种或一种以上金属进一步改性。
用于本发明优选的催化剂，可以通过用含有至少一种钯，银或铼化合物的溶液，经一步或多步浸渍碳载体而方便的制得。这里使用的碳载体的浸渍指的是填充，浸透，渗透，饱和或涂渍碳载体。浸渍溶液可以任意包含配位剂，以帮助加溶一种或一种以上的金属化合物。每步浸渍后，烘干催化剂以除去任何载体溶剂。干燥温度在约80℃-150℃范围内。
在制备优选催化剂时，可以使用钯化合物，银化合物和铼化合物的溶液处理碳，通过将载体材料浸渍或悬浮在溶液中，或者在碳上喷射溶液。含钯化合物的溶液通常是含有一定量钯化合物的水溶液，以制得含有所需量的钯的催化剂产物。钯化合物可以是硝酸钯或一种钯化合物如氯化物，碳酸盐，羧酸盐，乙酸盐，乙酰丙酮化物或胺盐。含银化合物的溶液通常是含有一定量银化合物的水溶液，以制得含有所需量的银的催化剂产物。钯和银化合物必须可以热分解和还原成金属。含铼化合物的溶液通常是含有一定量铼化合物的水溶液，以制得含有所需量的铼的催化剂产物。铼化合物通常是高铼酸，高铼酸铵或高铼酸的碱金属盐。
浸渍溶液可任意地包含金属配位剂，以帮助加溶一种或一种以上的金属化合物。在浸渍溶液中加入乙腈，使得钯，银和铼可以一步加入。也可以在浸渍溶液中加入硝酸。
用钯，银和铼进行浸渍和干燥后，通过在120-350℃，优选150-300℃的还原条件下，加热浸渍了的碳载体来活化优选的催化剂。将氢气或氢气和氮气的混合物与催化剂接触的方法可以方便的用于催化还原。还原浸渍了的碳载体仅在用钯，银和铼浸渍完碳载体之后进行。在多步浸渍和干燥的情况下，在最后干燥步骤之后再还原催化剂。
方法
实施本反应的方法包括在铁和氢化催化剂的存在下，将可氢化的前体与含氢气体反应，通过蒸馏回收和纯化反应产物。
在本发明中，向可氢化前体中加入铁是在向氢化反应器中加入可氢化前体之前或就地。通常铁是作为铁盐形式加入。加入到液体的可氢化前体原料中的优选的铁的浓度范围为1-10,000ppm(重量比重量基准)。优选原料中铁的浓度为约20-160ppm之间。可以使用广范围的铁盐，包括乙酸铁，丙酸铁，丁酸铁，马来酸铁，琥珀酸铁和富马酸铁。优选的盐的阴离子应该不干扰氢化反应，或使氢化催化剂中毒。
本发明的液相氢化反应能够通过在搅拌釜反应器或固定床反应器中使用常用的装置和技术实施。也可以使用单级或多级反应器。所需催化剂的量变化范围较广，并取决于许多因素如反应器尺寸和设计，接触时间等。
通常将含氢气体，以氢气显著的化学过量连续地加入到其它反应剂中。未反应的氢气作为循环气流返回至反应器中。连续加入前体溶液，如马来酸(或其它可氢化前体)溶液，其浓度范围从稀溶液到接近最大溶解度。前体溶液可含有约10-60％(重量)马来酸(或其它可氢化的前体)，浓度越高越经济越优选，因为只有少量的水需循环或处理。优选前体溶液含有约20-50％(重量)马来酸(或其它可氢化的前体)。
优选进行氢化反应步骤的温度约50℃-350℃，氢气压力约20-400大气压，其中氢气和可氢化前体的比例(H2/P)为5-1至1000-1，接触时间为0.1分钟-20小时。
通过分馏较好地分离出反应产物，1，4-丁二醇，四氢呋喃，γ-丁内酯或其混合物。形成的少量的副产物或未反应的原料，如琥珀酐或琥珀酸，可以任意地返回至氢化步骤中。也可以将γ-丁内酯循环至氢化反应器中。
使用本发明的方法，更确切地说是使用这里描述的氢化催化剂，马来酸基本上可以在简单的反应中定量转化。得到的1，4-丁二醇和四氢呋喃的收率约80％(摩尔)以上，通常约90％(摩尔)或更高，其中产率的大部分为1，4-丁二醇。反应副产物包括正丁醇，正丁酸，正丙醇，丙酸，甲烷，丙烷，正丁烷，一氧化碳和二氧化碳。然而不可利用的副产物的形成是少量的。
具体实施例
为了描述本发明提供下述实施例。实施例1：制备含有钯+银+铼载于碳上的催化剂
将132.4g硝酸钯溶液(8.5wt％Pd)，17.3g硝酸银，28g浓硝酸(70wt％)和乙腈(约40cc)放入250cc的烧瓶中。摇晃混合物以溶解硝酸银，然后缓慢加入45g高铼酸(53.3wt％Re)。然后再在烧瓶中加入乙腈使溶液正好250cc。
用上述的溶液逐渐浸渍280.5g1.5mm(直径)CECA ACL40的碳挤出物。混合物静置4小时，然后在烘箱中120-130℃下干燥20.25小时。
为了测试，用剃刀片将催化剂挤出物切割，使得挤出物的最大长度为约1.5mm。实施例2：氢化含水的马来酸及催化剂的测试
在串联的两台哈斯特洛伊耐蚀镍基(Hasteloy)C276反应器中，使用加热的哈斯特洛伊耐蚀镍基(Hasteloy)C276管测试实施例1的催化剂。反应器的内径为0.516”，每台装有1/8”轴向Hasteloy C276温度计插孔。
装入反应器前，将催化剂与50/70目石英片(每克催化剂0.625克石英)混合。在第一反应器中装入20cc(12.15g)催化剂，第二反应器中40cc(24.3g)。测试前大气压下在流动的氢气(400sccm)中，通过将催化剂逐渐加热至230℃约13-18小时以上还原催化剂，然后使催化剂在230℃下保持约5小时。
在2500-4000psig的压力下，广泛测试催化剂几千小时以上。反应器在氢气回流下操作。放空一小部分的氢气以防止不可凝气体的聚集。用于加铁研究的含水的马来酸原料中含有少量其它列于表1的有机酸。将铁以乙酸铁(II)的形式加入至马来酸中，制得40ppm(w/w)含铁的溶液。铁很容易溶于溶液中。在4450-4550小时及下述反应条件的气流中评价在马来酸原料中加入铁的效果：
压力：4000psig
H2/(MAC+FAC)原料比：92
H2补充循环比：0.083
第一反应器：
平均设定温度：130℃
第二反应器：
平均设定温度：162℃表2列出了在马来酸原料中加入铁和不加入铁的效果。按摩尔C4基准测定产物选择性。在马来酸原料中加入铁的BDO收率明显较高。
表1-马来酸原料的组成 组分
wt％马来酸 33.4富马酸 0.41丙烯酸 0.21乙酸 0.72苹果酸 0.40
表2-催化剂性能(选择性)数据
％BDO
％THF
％GBL
％BuOH
％PrOH
％SAC加铁 69.2 19.75 5.38 2.86 0.63 2.04未加铁 61.7 28.02 4.63 3.11 0.63 1.74其中：BDO＝1，4-丁二醇 THF＝四氢呋喃 GBL＝γ-丁内酯BuOH＝丁醇 PrOH＝丙醇 SAC＝琥珀酸
可以理解为本发明并不局限于这里提到的实施例。提供这些仅仅是表明适用性，催化剂，金属原料，碳载体，浓度，接触时间，固体填充物，原料，反应条件及产品的选择，由说明书的全部公开内容决定，但不超出这里公开和描述的发明构思，本发明的范围包括落在权利要求范围内的修饰和改变。
Claims (12)
1.一种制备1，4-丁二醇的方法，包括将可氢化前体与含氢气体及含有至少一种选自元素周期表VIII族贵金属的氢化催化剂接触进行催化氢化，其中在可氢化前体中加入铁。
2.根据权利要求1的方法，其中可氢化前体选自：马来酸，马来酐，富马酸，琥珀酸，琥珀酐，C1-C8琥珀酸二烷基酯，C1-C8马来酸二烷基酯，γ-丁内酯及其混合物。
3.根据权利要求2的方法，其中可氢化前体至少一种选自：马来酸，琥珀酸或γ-丁内酯。
4.根据权利要求1的方法，其中VIII族的贵金属选自：钯，铂，铑和钌。
5.根据权利要求1的方法，其中氢化催化剂包括钯和铼。
6.根据权利要求1的方法，其中氢化催化剂包括钯，铼和银附在碳载体上。
7.根据权利要求1的方法，其中铁为选自乙酸铁，丙酸铁，丁酸铁，马来酸铁，琥珀酸铁，富马酸铁及其混合物的铁盐。
8.根据权利要求1的方法，其中加入到可氢化前体中铁的浓度范围为1-10,000ppm(重量比重量基准)。
9.根据权利要求1的方法，其中加入到液相可氢化前体中铁的浓度范围为20-160ppm(重量比重量基准)。
10.根据权利要求1的方法，其中氢气和可氢化前体的比例为约5-1至约1000-1。
11.根据权利要求1的方法，其中含氢气体的压力为约20-400大气压。
12.根据权利要求1的方法，其中接触时间为约0.1分钟至约20小时。
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| EP1077080B1 (en) * | 1999-08-18 | 2006-11-22 | Ineos Usa Llc | Improved catalysts for the hydrogenation of maleic acid to 1,4-butanediol |
| DE10014646A1 (de) * | 2000-03-24 | 2001-09-27 | Basf Ag | Verfahren zur Herstellung von Alkoholen an rheniumhaltigen Aktivkohle-Trägerkatalysatoren |
| KR100863174B1 (ko) * | 2000-08-29 | 2008-10-13 | 이네오스 유에스에이 엘엘씨 | 말레산의 1,4-부탄디올로의 수소화를 위한 2단계 방법 |
| US7935834B2 (en) * | 2004-07-01 | 2011-05-03 | Isp Investments Inc. | Catalysts for maleic acid hydrogenation to 1,4-butanediol |
| JP5510844B2 (ja) * | 2009-11-10 | 2014-06-04 | 独立行政法人産業技術総合研究所 | フルフラールからの１００％植物由来化成品の製造方法とその化成品 |
| KR102086324B1 (ko) | 2012-06-05 | 2020-03-09 | 미쯔비시 케미컬 주식회사 | 폴리부틸렌테레프탈레이트의 제조 방법 |
| US9108895B2 (en) | 2012-10-26 | 2015-08-18 | Eastman Chemical Company | Promoted ruthenium catalyst for the improved hydrogenation of carboxylic acids to the corresponding alcohols |
| CN104892363A (zh) * | 2015-06-15 | 2015-09-09 | 江苏常州酞青新材料科技有限公司 | 一种制作丁二醇的生产方法 |
| WO2020008617A1 (ja) * | 2018-07-06 | 2020-01-09 | Ｔｏｙｏ Ｔｉｒｅ株式会社 | 水素化用触媒及びジオールの製造方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3344721A (en) | 1965-08-13 | 1967-10-03 | Chevron Res | Pneumatic compaction of asphalt compositions |
| DE2519817A1 (de) * | 1975-05-03 | 1976-11-11 | Hoechst Ag | Verfahren zur herstellung von butandiol-(1.4) |
| DE2553761A1 (de) | 1975-11-29 | 1977-06-02 | Hoechst Ag | Verfahren zur katalytischen herstellung von gamma-butyrolacton |
| US4659686A (en) | 1983-12-22 | 1987-04-21 | E. I. Du Pont De Nemours And Company | Method for treating carbon supports for hydrogenation catalysts |
| US4609636A (en) | 1983-12-22 | 1986-09-02 | E. I. Du Pont De Nemours And Company | Pd/Re hydrogenation catalyst for making tetrahydrofuran and 1,4-butanediol |
| US4550185A (en) | 1983-12-22 | 1985-10-29 | E. I. Du Pont De Nemours And Company | Process for making tetrahydrofuran and 1,4-butanediol using Pd/Re hydrogenation catalyst |
| GB8509530D0 (en) | 1985-04-13 | 1985-05-15 | Bp Chem Int Ltd | Hydrogenation of carboxylic acids |
| 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 |
| GB8707595D0 (en) | 1987-03-31 | 1987-05-07 | British Petroleum Co Plc | Chemical process |
| US4827001A (en) * | 1987-11-02 | 1989-05-02 | The Standard Oil Company | Preparation of γ-butyrolactone and 1,4-butanediol by catalytic hydrogenation of maleic acid |
| US4973713A (en) | 1989-11-28 | 1990-11-27 | E. I. Du Pont De Nemours And Company | Catalytic hydrogenation of carboxylic anhydrides to esters or lactones |
| JPH06501875A (ja) | 1990-07-27 | 1994-03-03 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | 水素化触媒およびテトラヒドロフランの製造方法 |
| US5473086A (en) | 1995-01-17 | 1995-12-05 | The Standard Oil Co. | Process for the hydrogenation of maleic acid to 1,4-butanediol |
-
1997
- 1997-12-01 US US08/980,542 patent/US6486367B1/en not_active Expired - Lifetime
-
1998
- 1998-11-09 AU AU91414/98A patent/AU756102B2/en not_active Ceased
- 1998-11-11 SG SG1998004651A patent/SG74671A1/en unknown
- 1998-11-26 DE DE69803822T patent/DE69803822T2/de not_active Expired - Lifetime
- 1998-11-26 ES ES98309711T patent/ES2172865T3/es not_active Expired - Lifetime
- 1998-11-26 EP EP19980309711 patent/EP0919530B1/en not_active Expired - Lifetime
- 1998-11-30 MY MYPI98005419A patent/MY127864A/en unknown
- 1998-11-30 CN CN98125255A patent/CN1110472C/zh not_active Expired - Fee Related
- 1998-11-30 KR KR1019980051894A patent/KR100676117B1/ko not_active IP Right Cessation
- 1998-12-01 JP JP34222898A patent/JP4354556B2/ja not_active Expired - Fee Related
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1999
- 1999-02-24 TW TW87119806A patent/TW401317B/zh not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| KR19990062647A (ko) | 1999-07-26 |
| DE69803822D1 (de) | 2002-03-21 |
| ES2172865T3 (es) | 2002-10-01 |
| JPH11240846A (ja) | 1999-09-07 |
| MY127864A (en) | 2006-12-29 |
| AU9141498A (en) | 1999-06-17 |
| US6486367B1 (en) | 2002-11-26 |
| CN1229072A (zh) | 1999-09-22 |
| TW401317B (en) | 2000-08-11 |
| JP4354556B2 (ja) | 2009-10-28 |
| KR100676117B1 (ko) | 2007-06-04 |
| EP0919530A1 (en) | 1999-06-02 |
| DE69803822T2 (de) | 2002-06-27 |
| AU756102B2 (en) | 2003-01-02 |
| EP0919530B1 (en) | 2002-02-13 |
| SG74671A1 (en) | 2000-08-22 |
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