CN1201407A - 1,3－丙二醇的制备方法 - Google Patents

1,3－丙二醇的制备方法 Download PDF

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CN1201407A
CN1201407A CN96198050A CN96198050A CN1201407A CN 1201407 A CN1201407 A CN 1201407A CN 96198050 A CN96198050 A CN 96198050A CN 96198050 A CN96198050 A CN 96198050A CN 1201407 A CN1201407 A CN 1201407A
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cobalt
water
carbonyl
hydrogenation
hydroformylation
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CN1090059C (zh
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K·T·拉姆
J·B·泊威尔
P·R·威德
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

制备1,3－丙二醇的方法,该方法包括如下步骤:(a)将选自氢氧化钴、氧化钴(Ⅱ、Ⅲ)和碳酸钴的至少一种钴盐与合成气在基本上与水不相混溶的液体介质中、在能够有效生成含有至少一种活性羰基钴加氢甲酰化催化剂的羰基钴反应产物混合物的条件下反应;(b)将环氧乙烷与合成气在基本上与水不相混溶的液体介质中、在催化量的羰基钴反应产物混合物和有效量的助催化剂的存在下、在能够有效生成含有低于15%(重量)3－羟基丙醛的中间体产物混合物的反应条件下接触;(c)向所述中间体产物混合物中加入含水液体并将大部分3－羟基丙醛萃取到所述含水液体中,从而得到含有3－羟基丙醛的浓度大于中间体产物混合物中3－羟基丙醛浓度的水相,以及含有大部分羰基钴的有机相;(d)将水相与有机相分离;(e)将至少大部分有机相再次用于步骤(b)的方法中;(f)将含有3－羟基丙醛的水相与氢气在氢化催化剂存在下于氢化条件下接触,生成含有1,3－丙二醇的氢化产物混合物;然后(g)从氢化产物混合物中回收1,3－丙二醇。

Description

1，3-丙二醇的制备方法
本发明涉及1，3-丙二醇的制备方法。一方面，本发明涉及钴催化生产1，3-丙二醇的方法。具体地讲，本发明涉及在钴催化生产1，3-丙二醇的方法中可循环使用的钴催化剂的制备方法。
1，3-丙二醇(PDO)是生产纤维和胶片所用聚酯的中间体。已知可用两步法制备PDO，所述方法包括(1)环氧乙烷经钴催化加氢甲酰化反应(与合成气即H2/CO反应)生成中间体3-羟基丙醛(HPA)，和(2)将HPA氢化生成PDO。已开发了一种改进合成方法，该方法能够在相对低的温度和压力下选择性地进行加氢甲酰化步骤。为了使该方法产生经济效益，需要将基本上所有的钴加氢甲酰化催化剂以简便方式回收并再循环到加氢甲酰化反应器中。
用于加氢甲酰化步骤的活性钴催化剂是羰基钴化合物。为了产生经济效益，羰基钴催化剂通常是从钴(II)盐如辛酸钴或乙酸钴制备的。一般通过将钴的羧酸盐在升高的温度和压力下还原而将这些盐转变成羰基钴化合物。然而，在所需羰基钴化合物产生的同时，还生成了游离的有机酸。本发明人发现，在改进的PDO制备方法中对环氧乙烷进行加氢甲酰化时，这些羧酸能够改变催化剂的性质并使钴的回收和再循环过程复杂化。因此，人们希望能够在PDO制备方法中产生羰基钴的同时不发生会干扰催化剂回收和再循环的副反应。
因此，本发明的目的是提供PDO的制备方法，该方法可以制得可再循环的羰基钴加氢甲酰化催化剂而不形成干扰催化剂回收和/或再循环的副产物。
本发明提供制备1，3-丙二醇的方法，其中包括如下步骤：
(a)将选自氢氧化钴、氧化钴(II、III)和碳酸钴的至少一种钴盐与合成气在基本与水不相混溶的液体介质中、在能够有效生成含有至少一种活性羰基钴加氢甲酰化催化剂的羰基钴反应产物混合物的条件下反应；
(b)将环氧乙烷与一氧化碳和氢气在基本与水不相混溶的溶剂中、在催化量的羰基钴反应产物混合物和有效量助催化剂存在下、在能够有效生成含有低于15％(重量)3-羟基丙醛的中间体产物混合物的反应条件下接触；
(c)向所述中间体产物混合物中加入含水液体并将大部分3-羟基丙醛萃取到所述含水液体中，从而得到其中3-羟基丙醛的浓度大于中间体产物混合物中3-羟基丙醛浓度的水相，以及其中大部分为至少一种羰基钴的有机相；
(d)将水相与有机相分离；
(e)将至少大部分有机相再次用于步骤(b)的方法中；
(f)将含有3-羟基丙醛的含水相与氢气在氢化催化剂存在下于氢化条件下接触，生成含有1，3-丙二醇的氢化产物混合物；然后
(g)从氢化产物混合物中回收1，3-丙二醇。
本发明能够通过下述方法制备PDO，在该方法中，在生成用于加氢甲酰化步骤的活性羰基钴化合物的同时并不形成干扰催化剂有效回收和/或再循环的副产物。
图1是本发明1，3-丙二醇制备方法的一个实施方案的流程简图。
可以参照图1方便地对本发明的1，3-丙二醇制备方法进行描述。将单独的或混合的一氧化碳和氢气流1和选自氢氧化钴、氧化钴和碳酸钴的羰基钴前体2加入混合容器3内，并于还原条件下在液体介质中接触。为了使整个方法最大限度地发挥经济效益，制备羰基钴时所选用的介质优选与加氢甲酰化步骤所选的介质(参见以下详细描述)相同。通常优选的介质是甲基叔丁基醚。前体钴盐可以是氢氧化钴、氧化钴或碳酸钴。其中，优选氢氧化钴，因为其反应速率快并且副产物是水。
制备催化剂的步骤在升高的温度和压力下进行，适宜温度是约60-约160℃，优选约80-120℃；适宜的压力是约400-约2500磅/平方英寸，优选约1000-约1600磅/平方英寸。合成气中H2∶CO的比例在约1∶2至约8∶1的范围内，优选约1∶1至约5∶1。在这些条件下，向所需羰基钴化合物的转变非常迅速，通常停留时间大约仅需不到60分钟。
优选在少量种子化合物存在下引发制备催化剂的步骤。适宜的种子化合物包括贵金属如铂和钯的化合物以及胺如壬基吡啶。优选的种子化合物是八羰基合钴。种子羰基钴的含量应足以促进Co+2向Co0的转变并有助于钴前体在液体介质中的溶解，以钴的总摩尔数计，其含量通常为至少约0.4％(摩尔)。种子化合物仅在反应引发时使用，该反应一旦被引发后便“自我接种”。可以在向反应器通入合成气之前，通过向反应浆液中在室温下加入催化剂前体和种子化合物来引发催化剂的制备。反应引发后，便可在催化剂制备条件下将催化剂前体优选地以浓溶液的形式直接注射到反应混合物中。催化剂制备步骤的产物中含有八羰基合二钴和氢化羰基合钴中的至少一种，通常是这些羰基钴化合物的混合物。
为了提高反应速率，催化剂制备反应混合物中还可视具体情况而定但同时又是优选地含有少量的水。可通过向液体介质中加入足量的水使其中水的含量以液体介质重量为基准计达到约0.5-约3％来达到最佳含水量。应避免过量的水，以防止在反应进行中形成分离的水相。
将含有活性羰基钴催化剂的催化剂反应混合物通过4加入到加氢甲酰化容器5内。尽管图1所说明的实施方案中，是在单独的反应容器中制备羰基钴，然后将制得的产物加入加氢甲酰化容器中的，但也可以在加氢甲酰化容器中制备活性羰基钴化合物，优选将前体钴盐直接加入加氢甲酰化容器中并就地制备羰基钴。
在加氢甲酰化容器5中，将活性催化剂与环氧乙烷6和合成气7在与水不相混溶的液体介质中混合。加氢甲酰化容器是分批或连续操作的适宜的压力反应容器，如泡罩塔和/或搅拌槽。通常以约1∶2至约8∶1，优选约1.5∶1至约5∶1的摩尔比将氢气和一氧化碳通入反应容器。加氢甲酰化反应混合物中钴的含量依据其它反应条件而改变，但通常在约0.01-约1％(重量)的范围内，优选约0.05-约0.3％(重量)，以反应混合物的重量为基准计。
完成反应的条件应能够有效生成含有大部分3-羟基丙醛(HPA)和少部分乙醛的加氢甲酰化反应产物混合物，并且保持反应混合物中3-羟基丙醛的含量低于15％(重量)，优选在约5至约10％(重量)的范围内。(为了保证溶剂具有不同的密度，反应混合物中HPA的所需浓度用摩尔浓度表示时应低于1.5M，优选在约0.5-约1M的范围内)。
通常，加氢甲酰化反应在低于100℃的升高的温度下进行，优选约60-约90℃，最优选约75-85℃，反应压力在约500-约5000磅/平方英寸的范围内，优选(为了使该方法产生经济效益)约1000-约3500磅/平方英寸，为了能有较高的选择性，优选上述范围内较高的压力。可以通过调节反应条件，例如环氧乙烷的浓度、催化剂的浓度、反应温度以及停留时间来控制中间体产物混合物中3-羟基丙醛的浓度。通常，优选相对低的反应温度(低于约90℃)和相对短的停留时间(约20分钟至约1小时)。在本发明方法的实践中，HPA的收率可以超过80％(以环氧乙烷的转化率为基准计)，以超过30h-1的速率形成高于7％(重量)的HPA。(催化速率在本文中指术语“周转频率”或TOF，用每小时每摩尔钴的摩尔数或h-1的单位来表示)。
加氢甲酰化反应在对反应试剂呈惰性的液体溶剂中进行。“惰性”是指该溶剂在反应过程中不被消耗。通常，该方法的理想溶剂能够溶解一氧化碳，基本上与水不相混溶并且具有低至中等的极性，从而可以使3-羟基丙醛中间产物在加氢甲酰化条件下可以溶解到至少约5％(重量)的所需浓度，并且在用水萃取后仍有相当数量溶剂以分离的相保留下来。“基本上与水不相混溶”是指25℃时，该溶剂在水中的溶解度低于25％(重量)，从而在用水从加氢甲酰化反应混合物中萃取HPA后可以形成分离的、富含烃的相。优选该溶解度低于约10％，最优选低于约5％(重量)。用奥斯特瓦尔德系数表示，一氧化碳在选定溶剂中的溶解性通常大于0.15v/v(1atm，25℃)，优选大于0.25v/v。
优选的溶剂类型是醇和醚，可将其用如下结构式表示，
R2-O-R1其中R1是氢或C1-20直链、支链、环状或芳香烃基，或单或聚氧化烯；R2是C1-20直链、支链、环状或芳香烃基、烷氧基或或单或聚氧化烯。最优选的加氢甲酰化溶剂可用如下结构式表示：其中R1是氢或C1-8烃基，R3、R4和R5彼此独立地选自C1-8烃基、烷氧基和氧化烯。所述醚包括，例如甲基叔丁基醚、乙基叔丁基醚、二乙醚、苯基异丁基醚、乙氧基乙基醚、二苯醚和二异丙基醚。也可以使用溶剂的混合物如四氢呋喃/甲苯、四氢呋喃/庚烷以及叔丁醇/己烷来达到所需的溶剂性质。通常优选的溶剂是甲基叔丁基醚，因为可以在温和的反应条件下得到高产率的HPA。
优选在加氢甲酰化反应混合物中含有助催化剂以加快反应速率。适宜的助催化剂包括可以提供一价或多价弱碱金属阳离子的物质，如碱金属、碱土金属和稀土金属的羧酸盐。其它适宜并优选的是亲脂性助催化剂例如亲脂性鏻盐和胺，它们可以加快加氢甲酰化反应速率而不会使活性催化剂具有亲水性(水溶性)。本文使用的“亲脂性”是指用水萃取HPA后，助催化剂倾向于保留在有机相中。助催化剂的含量通常为约0.01-约0.6摩尔/摩尔钴。适宜的金属盐包括钠、钾和铯的乙酸盐、丙酸盐和辛酸盐；碳酸钙和乙酸镧。通常优选的加氢甲酰化反应助催化剂是四丁基乙酸鏻。
通常优选调节加氢甲酰化反应混合物中水的浓度，因为过量的水会使(HPA+PDO)的选择性降低到可接受的水平以下，并且会导致形成第二个液相。在低浓度下，水有助于促进所需的羰基钴催化剂的形成。可接受的水含量取决于所用的溶剂，更具极性的溶剂通常更易于接受更高的水浓度。例如，据信在用甲基叔丁基醚溶剂进行的加氢甲酰化反应中，最佳水含量为约1-2.5％(重量)。
加氢甲酰化反应后，将含有3-羟基丙醛、反应溶剂、1，3-丙二醇、钴催化剂和少量反应副产物的加氢甲酰化反应产物混合物8冷却并转移到萃取容器9中，通过10向其中加入含水液体以萃取并浓缩HPA以用于随后的氢化步骤，所述含水液体通常是水和视具体情况而存在的混溶性溶剂。可通过任何适宜装置例如混合澄清槽、填料或塔板萃取塔、或转盘式抽提器完成液体萃取过程。如需要，萃取可分多级进行。也可以视具体情况而定将含水加氢甲酰化反应产物混合物转移到澄清槽(未示出)内以使混合物分成水相和有机相。加入到加氢甲酰化反应产物混合物中的水量通常应能够提供约1∶1至约1∶20、优选约1∶5至约1∶15范围内的水：混合物比。在该反应阶段加入水的另一优点是可以抑制不利的重尾馏份的形成。用相对少量的水进行萃取可以得到超过20％(重量)HPA、优选超过35％(重量)HPA的水相，从而可以经济地将HPA氢化成PDO并回收PDO产物。优选在约25℃至约55℃的温度下进行水萃取，应避免使温度进一步升高以便最大限度地减少缩合产物(重尾馏份)的形成和最大限度地抑制催化剂歧化反应以免形成无活性的、水溶性钴化合物。为了最大限度的回收催化剂，优选在50-200磅/平方英寸一氧化碳和25-55℃进行水萃取。
可通过11将含有反应溶剂和大部分钴催化剂的有机相从萃取容器再循环到加氢甲酰化反应中。可视具体情况而定将含水萃取液12通过一个或多个酸性离子交换树脂床13以除去所含的任何钴催化剂，然后将脱钴的含水产物混合物14加入到氢化容器15中，并在氢化催化剂的存在下与氢气16反应，生成含有1，3-丙二醇的氢化产物混合物17。氢化步骤还可以使一些重尾馏份复原成PDO。可通过在塔18中蒸馏来回收溶剂和萃取剂水19，在通过进一步蒸馏(未示出)分离并除去轻馏份后将其重新用于水萃取步骤。可将含有PDO的物流产物20通入到蒸馏塔21中，以便从重尾馏份23中回收PDO22。
将HPA转变成PDO的氢化反应可以在含水溶液中、在升高的温度及至少约100磅/平方英寸、通常在约200至约2000磅/平方英寸的氢气压力下进行，所述温度在氢化步骤的至少部分时间内为约40℃，一般在约50至约175℃的范围内。反应在氢化催化剂的存在下进行，所述催化剂是例如任何基于VIII族金属，包括镍、钴、钌、铂和钯，以及铜、锌和铬以及它们的混合物和合金的催化剂。包括本体(bulk)、承载的和固定床形式在内的镍催化剂，可以在中等价格的基础上提供可接受的活性和选择性。在微酸性的反应条件下可以得到最高的产率。
工业化生产需要有效地回收钴催化剂，即基本上将全部钴在加氢甲酰化反应中再循环。催化剂回收过程优选包括两个步骤，从上述加氢甲酰化反应产物混合物中水萃取HPA过程开始。一部分钴催化剂保留在有机相中，其余的钴催化剂进入水相。可将有机相再循环到加氢甲酰化反应器中，视具体情况而定除去重尾馏份。视具体情况而定，可通过任何适宜的方法进一步对水层中的催化剂进行脱钴处理，例如将钴完全或部分氧化并随后析出沉淀并过滤、蒸馏、沉积在固体载体上，或用适宜的萃取剂萃取，优选在通过离子交换(13)最终除去钴之前进行上述过程。
本发明的方法可以在中等温度和压力下选择性并经济地合成PDO，同时将羰基钴加氢甲酰化催化剂基本上全部再循环。
实施例1用氢氧化钴在无水MTBE中制备羰基钴
向装有内部红外光学镜片的30ml不锈钢高压釜内加入404mg(4.3毫摩尔)氢氧化钴和17ml无水MTBE。将反应器密封，用氮气排空并置于1200磅/平方英寸的2∶1合成气(H2∶CO)下。将密封的反应器在数分钟内加热到140℃并使内部压力升至1470磅/平方英寸。在320分钟内未观察到氢氧化钴的转化。在2100至1960cm-1之间的红外光谱中未观察到羰基钴的形成。未观察到合成气的消耗。在140℃搅拌320分钟后，将反应混合物冷却并排出混合物。无色澄清的上清液和亮粉色的悬浮固体表明，在既不含水也不含种子化合物的条件下不发生预形成作用。实施例2用氢氧化钴在含水MTBE中制备羰基钴
该实施例说明水对于本发明催化剂分离过程的促进作用。向装有内部红外光学镜片的30ml不锈钢高压釜内加入210mg(2.16毫摩尔)氢氧化钴和35mg(0.102毫摩尔)八羰基合二钴种子。向其中加入17ml含1％水的MTBE。将反应器密封，用氮气排空并置于980磅/平方英寸的1∶1合成气(H2∶CO)下。将密封的反应器在数分钟内加热到120℃并使内部压力上升。通过红外光谱的改变定量监测氢氧化钴的转化进程。通过在3630cm-1的O-H拉伸频率示踪氢氧化钴的浓度，通过在2100至1960cm-1的区域内羰基金属键的增长来监测羰基钴的形成。红外光谱分析表明了氢氧化钴的溶解以及随后氢氧化钴向羰基钴的迅速转化。在羰基钴形成的同时，合成气迅速消耗。在达到120℃后35分钟内观察到完全转化(＞98％，通过羰基金属区域内的吸收强度来测定)。在羰基金属区域内观察到的曲线表明，该溶液是Co4(CO)12、Co2(CO)8和HCo(CO)4、以及少量[Co(CO)4]-的平衡混合物。当将反应混合物冷却并排出液体后，得到特征为均匀深咖啡棕色溶液的羰基钴混合物。未观察到任何类型的沉淀。实施例3使用乙酸钴的比较预形成实验
在1加仑的搅拌反应器中，将含有15.8g四水合乙酸钴、3.72g壬基吡啶助催化剂和18.75g甲苯标记物的1837g甲基叔丁基醚溶液在120℃及1400磅/平方英寸的2∶1 H2/CO下加热以制备羰基钴催化剂。根据从反应器取出的样品中不含固体这一事实作为判断标准，证实预形成在2.5小时内完成。
将反应器冷却至80℃并注入115g环氧乙烷。40分钟后，观察到4.8％(重量)所需的3-羟基丙醛(HPA)中间体。将反应器冷却至25℃并加入175g去离子水以萃取产物。分离得到214.6g含有24％(重量)HPA和1892ppm钴的含水层。剩余的1900.6g有机溶剂含有2250ppm钴。因此，有91％的钴催化剂保留在有机溶剂层中并可在反应中再循环使用。
除去水后，通过将反应混合物重新加热至80℃、加入110-125g环氧乙烷、反应约1小时、冷却并用175g去离子水萃取，将反应/萃取顺序重复两次。在进行第二次和第三次时，含水层分别含有1463和893ppm的钴，相当于用上层溶剂层再循环了88％和93％剩余的钴。
重新加入原料重复整个实验，用25.3g去离子水进行萃取。与以上最初反应中观察到的1892ppm相比，含水产物中含有3300ppmw的钴。用有机溶剂层仅再循环了80％的钴。实施例4用八羰基合二钴进行钴预形成
将实施例3的预形成实验重复两次，向反应混合物中加入25g去离子水(以模拟循环条件)并用10.875g八羰基合二钴代替乙酸钴。在两次实验中，含水产物中分别仅含有610和328ppm的钴，表明有机层再循环了96和98％的钴。因此，当不含从乙酸钴预形成催化剂过程产生的乙酸副产物时，钴在有机溶剂中的循环得到了改善。实施例5用2-乙基己酸钴(辛酸钴)进行钴预形成
向300ml搅拌反应器中加入0.87g八羰基合二钴、0.30g壬基吡啶、1.5g甲苯标记物、2.0g去离子水、143g甲基叔丁基醚和4.5g 2-乙基己酸进行加氢甲酰化反应。后一用量被计算为在使用2-乙基己酸钴作为补充钴损失的盐、并用水萃取以回收3-HPA产物的过程中聚集的预期的有机酸稳态浓度。对有机溶液和含水溶液之间的平衡分配分别进行了研究以便进行该项评估。
在1400磅/平方英寸的2∶1 H2/CO下加入13g环氧乙烷并且进行加氢甲酰化70分钟。冷却至室温后，将反应混合物用34g去离子水萃取，得到38g含有2004ppm钴的含水层和116.8g含621ppm钴的上层有机层。水萃取后，仅有49％的钴保留在有机层内。
该试验表明，在代表所计算的稳态操作的辛酸浓度下，如果用“辛酸钴”(2-乙基己酸钴)前体向系统中补充钴，则在水提取后将会损失显著量的钴。实施例6用氢氧化钴进行钴预形成
加入0.40g氢氧化钴但不加酸重复实施例5。(相对于从水萃取步骤中再循环的甲基叔丁基醚溶剂中所含的2％(重量)的水而言，在预形成后氢氧化钴仅释放出少量的水副产物)。氢氧化钴溶液的预形成过程不需要助催化剂，但需用0.10g八羰基合二钴引发。在140℃及1400磅/平方英寸的2∶1H2/CO下进行预形成操作8小时后得到的红外光谱表明，氢氧化钴已完全预形成为羰基钴。
将温度降至80℃，加入0.52g四正丁基乙酸鏻以促进加氢甲酰化反应，产生的乙酸浓度数量级低于实施例3。在室温下加入33.3g水进行萃取。分离得到35.8g含有185ppm钴的含水产物。溶剂萃取后从上层溶剂层中再循环得到97％的钴催化剂。实施例7用氧化钴进行钴预形成
该实验说明在水和催化剂种子存在下从氧化钴预形成钴催化剂。
向装有内部红外光学镜片的30ml不锈钢高压釜内加入332mg(1.38毫摩尔)粉末状氧化钴(II，III)和75mg(0.219毫摩尔)八羰基合二钴。向其中加入17ml含1％(重量)水的MTBE。将反应器密封，用氮气排空并置于1125磅/平方英寸的1∶1合成气(H2∶CO)下。将密封的反应器在数分钟内加热到120℃并使内部压力上升。通过红外光谱的改变和合成气的消耗定量监测反应的进展。通过在2100至1960cm-1的区域内出现羰基金属带的生长来监测羰基钴的形成。在羰基钴形成的同时，合成气迅速消耗。在达到120℃后70分钟内观察到氧化钴完全转化成羰基钴。当将反应混合物冷却并排出液体后，得到特征为均匀深咖啡棕色溶液的羰基钴混合物。未观察到任何类型的沉淀。实施例8用氧化钴进行钴预形成
该实验说明在水和催化剂种子存在下从碳酸钴预形成钴催化剂。
向装有内部红外光学镜片的30ml不锈钢高压釜内加入660mg(4.25毫摩尔)碳酸钴和75mg(0.219毫摩尔)八羰基合二钴。向其中加入17ml含1％(重量)水的MTBE。将反应器密封，用氮气排空并置于1050磅/平方英寸的1∶1合成气(H2∶CO)下。将密封的反应器在数分钟内加热到120℃并使内部压力上升。通过红外光谱的改变和合成气的消耗定量监测反应的进展。通过在2100至1960cm-1的区域内出现羰基金属带的生长来监测羰基钴的形成。在羰基钴形成的同时，合成气迅速消耗。在达到120℃后50分钟内观察到碳酸钴完全转化成羰基钴。当将反应混合物冷却并排出液体后，得到特征为均匀深咖啡棕色溶液的羰基钴混合物。未观察到任何类型的沉淀。实施例9水对预形成过程产生的影响
向装有内部红外光学镜片的50ml不锈钢高压釜内加入450mg(4.84毫摩尔)氢氧化钴。向其中加入25ml无水MTBE。将反应器密封，用氮气排空并置于1000磅/平方英寸的1∶1合成气(H2∶CO)下。将密封的反应器在数分钟内加热到120℃并使内部压力上升，使温度保持稳定。用更高的合成气压力将40mg八羰基合二钴(0.117毫摩尔)的2ml无水MTBE溶液注射到氢氧化钴浆液中。通过红外光谱的改变和合成气的消耗定量监测氢氧化钴的转化情况。在加入羰基钴种子后约250分钟内观察到完全转化(＞98％，通过羰基金属区域内的吸收强度来测定)。当将反应混合物冷却并排出液体后，得到特征为均匀深咖啡棕色溶液的羰基钴混合物。未观察到任何类型的沉淀。
用水饱和MTBE代替无水MTBE重复该反应。在加入羰基钴种子后约30分钟内观察到氢氧化钴完全转化为羧基钴。在冷却的反应混合物中未观察到任何类型的沉淀。

Claims (9)

1.制备1，3-丙二醇的方法，该方法包括如下步骤：
(a)将选自氢氧化钴、氧化钴(II、III)和碳酸钴的至少一种钴盐与合成气在基本上与水不相混溶的液体介质中、在能够有效生成含有至少一种活性羰基钴加氢甲酰化催化剂的羰基钴反应产物混合物的条件下反应；
(b)将环氧乙烷与合成气在基本上与水不相混溶的液体介质中、在催化量的羰基钴反应产物混合物和有效量的助催化剂存在下、在能够有效生成含有低于15％(重量)3-羟基丙醛的中间体产物混合物的反应条件下接触；
(c)向所述中间体产物混合物中加入含水液体并将大部分3-羟基丙醛萃取到所述含水液体中，从而得到含有3-羟基丙醛的浓度大于中间体产物混合物中3-羟基丙醛浓度的水相，以及含有大部分羰基钴的有机相；
(d)将水相与有机相分离；
(e)将大部分有机相再次用于步骤(b)的方法中；
(f)将含有3-羟基丙醛的水相与氢气在氢化催化剂存在下于氢化条件下接触，生成含有1，3-丙二醇的氢化产物混合物；然后
(g)从氢化产物混合物中回收1，3-丙二醇。
2.权利要求1的方法，其中步骤(a)和(b)中的液体介质是醚。
3.权利要求1的方法，其中步骤(a)和(b)中的液体介质是甲基叔丁基醚。
4.权利要求1的方法，其中步骤(a)在约60-约140℃的温度和约400-约2500磅/平方英寸的压力下进行。
5.权利要求1的方法，其中步骤(a)在以液体介质重量为基准计约0.5-约2.0％(重量)水存在下进行。
6.权利要求1的方法，其中步骤(a)中的钴盐是氢氧化钴。
7.权利要求1的方法，其中步骤(a)是在少量加入的羰基钴存在下引发的。
8.权利要求1的方法，其中步骤(a)在催化剂制备容器中进行，步骤(b)在另外一个加氢甲酰化容器中进行。
9.权利要求1的方法，其中步骤(b)在加氢甲酰化容器中进行，步骤(a)在加氢甲酰化容器中就地进行。
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