CN1069298C - 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
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- 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
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/06—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
- C07D307/08—Preparation of tetrahydrofuran
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- 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
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- B01J23/6567—Rhenium
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- 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
马来酸、马来酐或其它可氢化的前体被催化氢化成1,4-丁二醇和四氢呋喃。现已发现当氢化催化剂包括在炭载体上的钯、银和铼以及按下列步骤制备时可得到高产的1,4-丁二醇:(i)将炭载体用钯、银和铼源浸渍,其中所述的钯、银和铼是至少一种溶液,(ii)在每次浸渍步骤后,将浸渍过的炭载体干燥以除去溶剂,(iii)在还原条件下将浸渍后的炭载体在约120℃至约350℃的温度下加热。在所述催化剂中的钯是以平均粒径小于10nm的微晶形态存在的。
Description
本发明涉及将马来酸、马来酐或其它可氢化的前体氢化成为1,4-丁二醇和四氢呋喃的改进方法。该方法的特征在于使用了包括炭载体上的钯、银和铼的催化剂。该方法的特征还在于1,4-丁二醇的高产率以及副产物γ-丁内酯的生成达最低限度。
众所周知,四氢呋喃、γ-丁内酯和1,4-丁二醇是通过马来酐和相应的化合物的催化氢化得到的。四氢呋喃是天然和合成树脂的有用的溶剂并且是许多化学品和塑料制品生产中的一种有价值的中间体。γ-丁内酯是合成丁酸化合物、聚乙烯吡咯烷酮和蛋氨酸的一种中间体。γ-丁内酯是丙烯酸酯和苯乙烯聚合物的有用的溶剂,也是去涂料剂和织物助剂的有用成分。1,4-丁二醇常用作溶剂、湿润剂、增塑剂和药物的中间体、聚氨酯弹性体的交联剂、制备四氢呋喃中的前体,并被用于制备对苯二酸甲酯塑料。
在本发明中特别感兴趣的是用于将马来酐、马来酸和相应化合物氢化成四氢呋喃、γ-丁内酯和1,4-丁二酯的包含截于炭上的钯、银和铼的氢化催化剂。
英国专利1534232阐述了用由载于碳上的钯和铼组成的氢化催化剂将羧酸、内酯或酐氢化的方法。美国专利4550185和4609636阐述了在包含在炭载体上的钯和铼的催化剂的存在下,通过马来酸、马来酐或其它可氢化的前体的氢化来制备四氢呋喃和1,4-丁二醇的方法,其中钯和铼以微晶的形式存在,钯微晶的平均粒径为10至25nm、而铼微晶的平均粒径为小于2.5nm。这种催化剂的制备的特征在于在炭载体上将钯类物质沉积和还原后接着将铼类物质在这种钯浸渍过的炭载体上沉积和还原。
美国专利4985572阐述了用包含在炭载体上的铼、钯和银的催化剂将羧酸或其一种酸酐催化氢化成相应醇和/或羧酸的方式。这种催化剂制备的特征在于钯和银在炭载体上同时沉积后进行高温(600℃)热处理。然后将得到的铼沉积在钯/银浸渍过的炭载体上。然后将得到的催化剂还原。
一般来说,在马来酸、马来酐或其它可氢化的前体的氢化中,上面讨论的催化剂具有生成更多的四氢呋喃和γ-丁内酯而不是1,4-丁二醇的倾向。本发明的一个目的是提供一种方法和催化剂,它能最大程度地产生1,4-丁二醇和最小程度地产生γ-丁内酯。
马来酸、马来酐或其它可氢化的前体被催化氢化成1,4-丁二醇和四氢呋喃。现已发现当氢化催化剂包含在炭载体上的钯、银和铼并按下列步骤制备时可获得高产率的1,4-丁二醇:
(ⅰ)将炭载体用钯、银和铼源浸渍,其中所述的钯、银和铼源至少是一种溶液(即:一种或多种溶液),
(ⅱ)每次浸渍步骤后,将浸渍后的炭载体在约150℃下干燥以除去溶剂;
(ⅲ)在还原条件下将浸渍后的炭载体在大约100℃至350℃的温度下加热。
在这样制得的催化剂中,钯以微晶的形式存在,其平均粒径小于10nm。
将一种可氢化的前体催化氢化以提供高产率的1,4-丁二醇和较低产率的四氢呋喃以及形成最少程度的γ-丁内酯。
将至少一种可氢化的前体在催化剂的存在下与含氢气气体反应。
这里所用的“可氢化的前体”是指任何氢化后可生成1,4-丁二醇的羧酸或其酸酐、羧酸酯、内酯或其混合物。代表性的可氢化的前体包括马来酸、马来酐、富马酸、琥珀酐、琥珀酸、琥珀酸二甲酯、γ-丁内酯或其混合物。优选的可氢化的前体是马来酸、马来酐、琥珀酸、琥珀酐或其混合物。
最优选的可氢化前体是马来酸、它一般制备的途径是通过在催化剂的存在下将正丁烷或苯在含氧气体中反应而在气相中将正丁烷或苯氧化成马来酐然后通过水骤冷收集水溶液形式的马来酐。正丁烷或苯的氧化温度一般在300至600℃,压力约0.5至20大气压(50至2000KPa)。
一般来说,含氢气(H2)气体是无任何稀释气体的工业纯的氢气。然而,除氢气(H2)外这种含氢气体也会含有氮气(N2)、气态烃(如甲烷)以及碳氧化物(如一氧化碳、二氧化碳)。
在本发明中使用的催化剂包含载于炭上的钯、银和铼。用于本发明的炭的BET表面积至少为200m2/g,最好在500-1500m2/g的范围内。所述催化剂组合物包含约0.1至约20重量百分比的钯,最好是约2至约8重量百分比的钯;约0.1至约20重量百分比的银,最好是约1至约8重量百分比的银;和约0.1至约20重量百分比的铼,最好是约1至约10重量百分比的铼。钯与银的比率是10比1到1比10之间。这种催化剂组合物还可通过混入一种或多种选自ⅠA或ⅡA族的金属而进一步改性。
本发明的催化剂可用一种溶液或多种至少含一种钯、银或铼化合物的溶液,以一个或多个浸渍步骤、通过炭载体的浸渍来按常规制备。这里所述的炭载体的浸渍是指炭载体被填满、浸透、渗透、饱和或包覆。浸渍溶液可选择地包含络合剂以助于溶解一种或多种金属化合物。这种催化剂在每次浸渍步骤后均被干燥以除去载体溶剂。干燥温度在约80℃至约150℃之间。
钯化合物、银化合物和铼化合物的各种溶液可以通过将载体材料在溶液中浸润或悬浮或通过将溶液喷雾到载体上而被施加到所述炭上。含钯化合物的溶液一般是一种水溶液,含有可产生具所需量钯的催化剂产物量的钯化合物。这种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。含银化合物的溶液一般是一种水溶液,含有能产生具所需量银的催化剂产物量的银化合物。这种钯和银化合物应是可热分解和可还原成金属的化合物。含铼化合物的溶液一般是水溶液,含有能产生具所需量铼的催化剂产物量的铼化合物。这种铼化合物一般是高铼酸、高铼酸铵或一种高铼酸碱金属盐。
用钯、银和铼浸渍并干燥后,通过将浸渍后的炭载体在还原条件下在120-350℃、最好是150-300℃的温度下加热而将催化剂活化。用氢气或氢气和氮气的混合物与催化剂接触的方法可方便地用于催化剂的还原。浸渍过的炭载体的还原只是在炭载体已用钯、银和铼浸渍后进行。在具有多次浸渍步骤和多次干燥的情况下,催化剂的还原在最后一次干燥后进行。
在本发明的催化剂中的钯是以微晶的形态存在的,微晶的平均粒径小于100_(10nm)。更具体地说,当所用的在炭载体上新还原的钯/银/铼样品通过X-射线衍射(XRD)和扫描透射式电子显微镜(STEM)分析时,催化剂中的含钯粒子(即钯粒子或钯或银的粒子)是细分散的,其微晶非常小,粒径小于约50_(5nm)。铼的分散程度非常之细,通过XRD或STEM测不到铼的粒子。用STEM分析,计算出平均的含钯粒状微晶粒径小于34_(3.4nm)。本文所用的“粒径分布”和“平均粒径”可见J.R.Anderson著,Academic Press出版的“Strnc-ture of Metal Catalysts”一书358-359页的定义,该书在此中被一并收到参考文献中。
最后,本文所述的催化剂的制备正象美国专利4985572中所述的那样,没有使用大量必须在干燥步骤中除去的过量水,也没有使用高温(即约600℃)处理步骤。
进行所述处理的方法包括在氧化催化剂的存在下将可氢化前体和含氢气气体反应和通过蒸馏回收和纯化反应产物。
本发明的液相氢化反应可在搅拌釜反应器或在固定床反器上采用常规装置和技术来进行。可使用单级或多级反应器。催化剂的需要量差异很大,它取决于诸如反应器尺寸和设计、接触时间等诸多因素。
含氢气气体是连续供应的,一般氢气的化学计量量是大大超过其它反应剂的。未反应的氢气可作为循环气流返回到反应器中。前体溶液如马来酸溶液被连接供应,溶液的浓度范围从稀溶液到接近最大溶解度水平,一般为约30%(重量)至约50%(重量)。
最好氢化步骤在约50℃至350℃的温度、氢气压力约20-400大气压、氢气和可氢化前体比率(H2/P)为5比1到1000比1之间、接触时间0.1分钟至20小时的情况下进行。
反应产物1,4-丁二醇、四氢呋喃、γ-丁内酯或其混合物可通过分馏而得到有效的分离。少量形成的副产物或未反应的原料诸如象琥珀酐或琥珀酸被可选地返回到氢化阶段。γ-丁内酯也可再循环到氢化反应器中。
使用本发明的方法,更具体地说使用本文所述的氢化催化剂的方法将马来酸在简单反应中实际上定量地转换。所获的1,4-丁二醇和四氢呋喃的产率约为80%(摩尔)或更高,一般约90%(摩尔)或更高,产物的大部分是1,4-丁二醇。反应副产物可能包括正丁醇、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,无用的副产物很少生成。
为说明本发明的情况,提供下列实施例。实施例1-催化剂制备-3.5wt%(重量百分数)Pd/3.5wt%Ag/5.3wt%Re/C催化剂
制备在活化的炭载体(ACL10,由法国的CECA S.A.生产,在美国由Atochem.North America Inc.销售)上具有大致3.5wt%Pd、3.5wt%Ag和5.3wt%Re的催化剂。获得的这种载体是挤压成1.5mm形式的,其被磨细并过筛并取其30至70目的筛分。通过将这种炭载体用一种包含钯、银和铼的溶液浸渍来制备所述催化剂。
具体的Pd/Ag/Re溶液如下制备:将109.8g硝酸钯溶液(7.26%Pb)、14.6g硝酸银和27g高铼溶液(52%Re)置于250c.c.溶量瓶中,加入乙腈至刻度。该溶液的重量是273.96g。
将198g 30/70筛目ACL40用253.7g Pd/Ag/Re溶液浸渍并解置4小时。然后将催化剂在120℃于烘箱中干燥过夜。
用STEM分析,这种催化剂(象在实施例2所述的那样还原后)的含钯粒子微晶粒径为3.4nm。比较例A-3.6wt%Pd/5.5wt%Re/C催化剂
在类似于实施例1的方式制备在30/70筛目ACL40上具有约3.6wt%Pd和5.5wt%Re的催化剂。
具体地说,Pd/Re溶液是如下制备的:将11.86g硝酸钯溶液(7.26%Pd)和2.7g高铼酸溶液(52%Re)置于25c.c.容量瓶中,加乙腈至刻度。该溶液重量是26.63g。
将19.8g 30/70筛目ACL40用24.7g Pd/Re溶液浸渍并静置4小时。然后将这种催化剂于120℃在烘箱中干燥过夜。
这种催化剂(象在实施例2中所述的那样还原后)的XRD分析表明没有衍射峰,这表明不存在大量大于5nm的含钯粒子。
实施例2-催化剂测定
将38c.c.实施例1中制备的Pd/Ag/Re催化剂置于外径为0.5英寸的Hastelloy C27b反应器中。然后在常压下将0.5SLM的H2流过催化剂而将其还原,这种还原按下列时间/温度程序进行:用11小时将温度从室温升至280℃,然后保持在280℃5小时。
在1300psig(psig=磅/平方英寸(表压))和180℃(平均设定温度)下用含35.5wt%马来酸/64.5wp%H2O的原料进行催化剂测定。经过约30小时后,将H2GHSV和MAC LHSV分别逐渐从2097h-1和0.38h-1提高到3021h-1和0.55h-1。
表1总结了在生产中47小时后获得的该方法的参数和产物选择性。
为进行比较,将38c.c.象比较例A那样制备的催化剂Pd/Rc/C如上所述的那样测定。其结果总结在表1中。
表1说明本发明的Pd/Ag/Re/C催化剂比本领域所熟知的不含银催化剂活性更高。具体地说,Pd/Ag/Re/C催化剂比Pd/Re/C催化剂可制出更多的1.4-丁二醇和更少的γ-丁内酯或其它反应产物。实施例3-3.3wt%Pd/3.2wt%Ag/6.6wt%Re/C催化剂的制备
在ACL40炭载体上具有约3.3wt%Pd、3.2wt%Ag和6.6wt%Re的催化剂按下列途径制备:将130.25g硝酸钯溶液(7.7%Pd)、16.5g硝酸银和41.5g高铼酸(52.6%Re)置于250c.c.容量瓶中。加入乙腈并摇动以溶解固体。加乙腈至刻度。该溶液的重量是296.2g。
表1:马来酸的氢化
生产
时间 压力 温度 GHSV LHSV %丁 %四氢 选择性催化剂 (h) (Dsie)〖马来酸〗(℃) (h-1)(h-1) H2/马来酸 二醇 呋喃 %γ- %丁醇 %其它
丁内酯3.5%Pd/ 47 1300 35.5 180 3625 0.66 64 53.8 36.2 4.1 4.5 1.43.5%Ag/5.3%Re/C3.6%Pd/ 47 1300 35.5 180 3625 0.66 64 43.9 32.2 20.2 2.4 1.35.5%Re/C#平均设定温度
将276.5g 1.5mm ACL40压出物用286.4g Pd/Ag/Re溶液浸渍。将该混合物放置5.75小时后在约120℃的烘箱中干燥过液。
该催化剂(象实施例4中所述的那样还原后)的XRD分析表明除那些证实为银金属的峰外没有可观察到的衍射峰,这表明所存在的含钯微晶平均小于5nm。比较实施例B-先有技术Pd/Ag/Re/C催化剂的制备
制备在美国专利4985572中所述类型的Pd/Ag/Re/C催化剂。在炭载体上这种催化剂含有约3.3wt%Pd、3.2wt%Ag、6.6wt%Re。制备按照在美国专利4985572中所述的步骤(其特征在于钯和银在炭载体上同时沉积,接着进行高温(600℃)热处理)进行,并用高铼酸铵代替七氧化铼。
将24.35g硝酸钯溶液(7.7%Pd)和2.9g硝酸银溶于100c.c.蒸馏水中。将50g 1.5mmACL40压出物加到该溶液中,用旋转蒸发器在约70℃将水除去。然后将这种Pd/Ag/ACL40在烘箱中于120℃干燥过液。
通过下列程序,在氮气流中加热这种Pd/Ag/ACL40完成高温热处理步骤:
用8小时从室温升到600℃。
保持600℃ 8小时。
冷却到室温。
将5.5g高铼酸铵溶解在100c.c.蒸馏水中。然后将Pd/Ag/ACL40加到该溶液中。用旋转蒸发器在70℃将水除去。在烘相中于120℃将制得的Pd/Ag/Re/ACL40进一步干燥过液。
实施例4-催化剂测定
将如在实施例3和比较例B(40c.c.)中那样制备的Pd/Ag/Re/ACL40催化剂分别装入外径0.5英寸的Hastcloy C274反应器中,在常压下流过0.5SLM的氢气进行还原,并使用下列温度阶梯:用11小时从室温升到280℃;然后维持280℃5小时;冷却至室温。
用含35.5wt%马来酸/64.5wt%水的原料在2500psig的压力下进行催化剂测定。在下表面2中所列的数据是在生产中于160℃、H2GHSV=2760h-1、LHSV=0.55h-1和H2/马来酸=65在约109小时时获得的。产品选择性是按C4摩尔数为基础计算的。
表2:在2500psig下马来酸的氢化
选择性
四氢 γ-催化剂 %丁二醇 %呋喃 %丁内酯 %丁醇 %丙醇 %其它实施例3 73.6 16.9 1.2 7.0 0.5 0.9比较实施例B 57.0 17.4 20.8 3.0 0.3 1.5上述数据说明实施例3所制备的催化剂比按美国专利4985572所制备的比较实施例B的催化剂能选择性地制备出更多的1,4-丁二醇和少得多的γ-丁内酯。此外,实施例3催化剂对1,4-丁二醇和四氢呋喃的总选择性(90.5%)大大地超过比较例B催化剂的总选择性(74.4%)。
实施例4和比较例C和D
象实施例1所述的那样制备3.6wt%Pd/3.6wt%Ag/3.6wt%Re/C催化剂(实施例4)。将这种催化剂和按照美国专利4550185的实施例1制备的两种3wt%Pd/3wt%Re/C催化剂(比较例C和D)相比。(美国专利4550185没有说明煅烧介质。比较例C在空气中煅烧而比较例D在氮气中煅烧)。每种催化剂均按实施例2中所述的步骤测定,操作参数的任何修改或变更均在表3中列出。比较的结果也列于表3中。
表3:马来酸的氢化
实施例 | 催化剂 | TOS(h) | 压力(psig) | 马来酸 | 温度(℃) | LHSV(h-1) | H2/马来酸 | 丁%二醇 | 四氢%呋喃 | 选择性%γ-丁 | %丁醇 |
4 | 3.6%Pd/3.6%Ag/3.6%Re/C | 46.70 | 1300 | 23 | 178 | 0.60 | 64 | 50.76 | 39.40 | 内酯4.34 | 4.25 |
51.00 | 1300 | 23 | 180 | 0.60 | 64 | 41.41 | 51.54 | 1.13 | 4.60 | ||
C | 3%Pd/3%Re/C | 31.70 | 1300 | 23 | 175 | 0.65 | 64 | 15.33 | 76.10 | 1.51 | 6.07 |
49.90 | 1300 | 23 | 175 | 0.65 | 64 | 29.08 | 60.21 | 5.49 | 4.22 | ||
69.30 | 1300 | 23 | 175 | 0.65 | 64 | 28.97 | 57.89 | 6.65 | 4.55 | ||
89.00 | 1300 | 23 | 175 | 0.65 | 64 | 24.18 | 60.75 | 8.39 | 4.57 | ||
D | 3%Pd/3%Re/C | 34.66 | 1300 | 23 | 175 | 0.65 | 64 | 8.34 | 71.33 | 12.27 | 5.89 |
58.66 | 1300 | 23 | 175 | 0.42 | 64 | 7.75 | 80.70 | 0.13 | 9.70 | ||
81.16 | 1300 | 23 | 170 | 0.65 | 64 | 13.44 | 45.04 | 36.51 | 3.70 | ||
104.40 | 1300 | 23 | 170 | 0.65 | 64 | 13.44 | 46.47 | 35.89 | 3.22 |
表3的数据表明按本发明方法制备的催化剂与不含银且按不同方法制备并对四氢呋喃的产出具有高选择性的先有技术的催化剂相比,对1,4-丁二醇的产出具有更高的选择性并可使γ-丁内酯的产出达到最小。
可以理解本发明并不受所述的实施例的限制。这些实施例只用来演示可操作性以及催化剂、金属源、炭载体、浓度、接触时间、固体填充剂、原料、反应条件、和产物的选择,即使有限制的话,可从提供的总体的说明书公开来判定,在没有背离公开和所述的本发明的精神下,本发明的范围包括在所附权利要求要求书范围内的各种修改和变更。
Claims (11)
1.制备四氢呋喃和1,4-丁二醇的方法,包括将可氢化前体与含氢气气体和含在炭载体上的钯、银和铼的氢化催化剂接触进行催化氢化制备出大部分为1,4-丁二醇的产品,其中所述方法的温度在50-350℃之间,所述含氢气气体的压力在20-400大气压之间,所述氢气与可氢化前体的比例为5∶1至1000∶1并且其中所述氢化催化剂按下列步骤制备:
(ⅰ)在一个或多个包括将炭载体与钯、银和铼源接触的浸渍步骤中将炭载体用钯、银和铼源浸渍,所述钯、银和铼处于至少一种溶液中;
(ⅱ)每次浸渍步骤后,将浸渍后的炭载体在80-150℃的温度下干燥以除去溶剂;和
(ⅲ)在还原条件下将浸渍后的炭载体在100℃至350℃的温度下加热。
2.权利要求1的方法,其中可氢化的前体选自马来酸、马来酐、富马酸、琥珀酐、琥珀酸、琥珀酸二甲酯、γ-丁内酯和它们的混合物。
3.权利要求2的方法,其中所述的可氢化前体是马来酸、马来酐、琥珀酸、琥珀酐或其混合物。
4.权利要求1的方法,其中所述的钯源是硝酸钯。
5.权利要求2的方法,其中所述的银源是硝酸银。
6.权利要求2的方法,其中所述的铼源是高铼酸。
7.权利要求1的方法,其中所述的钯、银和铼源被组合成单一溶液,在单个浸渍步骤中钯、银和铼被沉积在炭载体上。
8.权利要求1的方法,其中所述氢化催化剂包括0.1-20%(重量)的钯、0.1-20%(重量)的银和0.1-20%(重量)的铼。
9.权利要求8的方法,其中所述氢化催化剂包括2-8%(重量)的钯、1-8%(重量)的银和1-10%(重量)的铼。
10.权利要求1的方法,其中所述的钯是以平均粒径小于10nm的含钯微晶的形态存在的。
11.权利要求10的方法,其中所述的钯是以平均粒径小于5nm的含钯微晶的形态存在的。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/373,666 US5473086A (en) | 1995-01-17 | 1995-01-17 | Process for the hydrogenation of maleic acid to 1,4-butanediol |
US373,666 | 1995-01-17 |
Publications (2)
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CN1129206A CN1129206A (zh) | 1996-08-21 |
CN1069298C true CN1069298C (zh) | 2001-08-08 |
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CN95115198A Expired - Fee Related CN1069298C (zh) | 1995-01-17 | 1995-10-06 | 将马来酸氢化成1,4-丁二醇的改进方法 |
Country Status (10)
Country | Link |
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US (1) | US5473086A (zh) |
EP (1) | EP0722923B1 (zh) |
JP (2) | JP3830565B2 (zh) |
KR (1) | KR100264544B1 (zh) |
CN (1) | CN1069298C (zh) |
AT (1) | ATE178878T1 (zh) |
DE (1) | DE69509060T2 (zh) |
ES (1) | ES2130538T3 (zh) |
MX (1) | MX9504147A (zh) |
TW (1) | TW307749B (zh) |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
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US5698749A (en) * | 1995-09-06 | 1997-12-16 | The Standard Oil Company | Catalysts for the hydrogenation of aqueous maleic acid to 1,4-butanediol |
US5639242A (en) * | 1995-10-23 | 1997-06-17 | Wilson; Laura Lee | Children's educational daily responsibilities learning system in game format |
SG74602A1 (en) * | 1996-12-20 | 2000-08-22 | Standard Oil Co | Improved catalysts for the hydrogenation of maleic acid to 1,4-butanediol |
DE19750532A1 (de) * | 1997-11-14 | 1999-05-20 | Basf Ag | Verfahren zur Herstellung von 1,6-Hexandiol und 6-Hydroxycapronsäure bzw. deren Estern |
US6486367B1 (en) | 1997-12-01 | 2002-11-26 | The Standard Oil Company | Process for the hydrogenation of maleic acid to 1,4-butanediol |
BE1011870A6 (fr) * | 1998-04-09 | 2000-02-01 | Pantochim Sa | Procede de production de butanediol. |
EP1077080B1 (en) * | 1999-08-18 | 2006-11-22 | Ineos Usa Llc | Improved catalysts for the hydrogenation of maleic acid to 1,4-butanediol |
SG84543A1 (en) * | 1999-09-08 | 2001-11-20 | Standard Oil Co | Improved catalysts for the hydrogenation of maleic acid to 1,4-butanediol |
JP2001246254A (ja) * | 1999-12-28 | 2001-09-11 | Tonen Chem Corp | ジカルボン酸類の水素化触媒 |
DE10009817A1 (de) * | 2000-03-01 | 2001-09-06 | 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 |
US7019155B2 (en) * | 2001-11-13 | 2006-03-28 | Invista North America S.A.R.L. | Hydrogenation of tetrahydroxybutane to tetrahydrofuran |
GB0325526D0 (en) | 2003-10-31 | 2003-12-03 | Davy Process Techn Ltd | Process |
US7935834B2 (en) * | 2004-07-01 | 2011-05-03 | Isp Investments Inc. | Catalysts for maleic acid hydrogenation to 1,4-butanediol |
WO2011104719A1 (en) * | 2010-02-23 | 2011-09-01 | Dow Global Technologies Llc | Process for making polyol ethers |
EP3664932A1 (en) * | 2017-08-10 | 2020-06-17 | Shell Internationale Research Maatschappij B.V. | Method for preparing a catalyst and method for producing 1,4-butanediol and/or tetrahydrofuran from furan |
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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 |
US4985572A (en) * | 1987-03-31 | 1991-01-15 | The British Petroleum Company, P.L.C. | Catalyzed hydrogenation of carboxylic acids and their anhydrides to alcohols and/or esters |
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US3948805A (en) * | 1973-08-03 | 1976-04-06 | Deutsche Texaco Aktiengesellschaft | Catalysts for converting maleic anhydride to alpha-butyrolactone |
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 |
DE2605107C3 (de) * | 1976-02-10 | 1983-12-29 | Chemische Werke Hüls AG, 4370 Marl | Verfahren zur Herstellung von Diolen durch katalytische Hydrierung der entsprechenden Dicarbonsäuren |
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 |
-
1995
- 1995-01-17 US US08/373,666 patent/US5473086A/en not_active Expired - Lifetime
- 1995-09-13 AT AT95306409T patent/ATE178878T1/de active
- 1995-09-13 ES ES95306409T patent/ES2130538T3/es not_active Expired - Lifetime
- 1995-09-13 DE DE69509060T patent/DE69509060T2/de not_active Expired - Lifetime
- 1995-09-13 EP EP95306409A patent/EP0722923B1/en not_active Expired - Lifetime
- 1995-09-29 MX MX9504147A patent/MX9504147A/es unknown
- 1995-09-29 KR KR1019950033156A patent/KR100264544B1/ko not_active IP Right Cessation
- 1995-10-03 JP JP25632095A patent/JP3830565B2/ja not_active Expired - Lifetime
- 1995-10-06 CN CN95115198A patent/CN1069298C/zh not_active Expired - Fee Related
- 1995-10-27 TW TW084111382A patent/TW307749B/zh not_active IP Right Cessation
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2006
- 2006-04-28 JP JP2006126890A patent/JP2006219495A/ja not_active Withdrawn
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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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 |
US4985572A (en) * | 1987-03-31 | 1991-01-15 | The British Petroleum Company, P.L.C. | Catalyzed hydrogenation of carboxylic acids and their anhydrides to alcohols and/or esters |
Also Published As
Publication number | Publication date |
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EP0722923A2 (en) | 1996-07-24 |
JPH08193040A (ja) | 1996-07-30 |
US5473086A (en) | 1995-12-05 |
ATE178878T1 (de) | 1999-04-15 |
DE69509060D1 (de) | 1999-05-20 |
EP0722923A3 (zh) | 1996-08-28 |
EP0722923B1 (en) | 1999-04-14 |
JP3830565B2 (ja) | 2006-10-04 |
CN1129206A (zh) | 1996-08-21 |
DE69509060T2 (de) | 1999-08-05 |
MX9504147A (es) | 1997-01-31 |
JP2006219495A (ja) | 2006-08-24 |
TW307749B (zh) | 1997-06-11 |
ES2130538T3 (es) | 1999-07-01 |
KR100264544B1 (ko) | 2000-09-01 |
KR960029301A (ko) | 1996-08-17 |
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