CN101528649A - 制备亚烷基二醇的方法 - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 38
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
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Classifications
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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
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/12—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
- C07D317/38—Ethylene carbonate
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
一种用于制备亚烷基二醇的方法，所述方法包括在催化剂存在下使对应的碳酸亚烷基酯与水反应，其中所述催化剂包含固定在固体载体上的碳酸氢根作为活性相，所述固体载体具有一个或多个正电性位点。
Description
技术领域
本发明涉及通过使对应的碳酸亚烷基酯催化水解而制备亚烷基二醇的方法。
背景技术
亚烷基二醇、特别是单亚烷基二醇具有确定的商业利益。例如，单亚烷基二醇用于防冻组合物中、用作溶剂和用作生产例如用于纤维或瓶子的聚对苯二酸亚烷基酯的基本材料。
已知通过环氧烷烃的液相水解生产亚烷基二醇。通常通过加入大量过量的水例如每摩尔环氧烷烃20-25摩尔的水进行水解。该反应被认为是亲核取代反应，其中水作为亲核试剂，由此打开了环氧烷烃的环。因为主要形成的单亚烷基二醇也作为亲核试剂，所以通常形成单亚烷基二醇、二亚烷基二醇和更高亚烷基二醇的混合物。为增大对单亚烷基二醇的选择性，需要抑制主产物和环氧烷烃之间的副反应，该副反应与环氧烷烃的水解产生竞争。
抑制副反应的一种有效方法是增大反应混合物中存在的水的相对量。虽然该方法增大了对生产单亚烷基二醇的选择性，但是它产生了在回收产物中必须去除大量水的问题。
已经付出了大量的努力寻找在增大反应选择性同时无需使用大量过量的水的替代方法。在催化体系中可以使用少量过量的水使环氧烷烃水解成亚烷基二醇。因此，这些努力通常集中于选择活性更高的水解催化剂，和文献中已经公开了多种催化剂。
此外，现有技术中已经描述了用于从环氧烷烃生产亚烷基二醇的方法，包括两步法。这些方法包括在催化剂存在下使环氧烷烃与二氧化碳反应，之后使所得碳酸亚烷基酯热水解或催化水解。这类两步法的实例包括JP-A-57106631、JP-A-59013741和US-B-6080897中描述的那些。
US-A-4283580中描述了适用于使碳酸亚烷基酯水解的催化剂，其中涉及使用金属或化合物形式的钼或钨作为催化剂，通过取代或未取代碳酸亚乙基酯与水反应生产取代或未取代乙二醇。
虽然在碳酸亚烷基酯水解方面已经取得了进展，但是仍然需要允许容易地纯化所需产物的催化剂体系。
发明内容
申请人目前已经出人意料地发现通过固定在固体载体上的碳酸氢根可以有效催化碳酸亚烷基酯水解(即碳酸亚烷基酯与水催化转化)成对应的亚烷基二醇。因此本发明提供一种用于制备亚烷基二醇的方法，所述方法包括在催化剂存在下使对应的碳酸亚烷基酯与水反应，其中所述催化剂包含固定在固体载体上的碳酸氢根作为活性相，所述固体载体具有一个或多个正电性位点。
该非均相体系允许容易地使所需产物与催化组合物分离。可以无需在为纯化亚烷基二醇通常所需的高温下在所述催化剂组合物存在下蒸馏产物而实现该分离。另一个优点是在相同反应器体积下，催化剂的浓度高得多。含有碳酸氢根作为活性相的优点是可能从催化剂滤出的仅有产物是二氧化碳和水，而它们是反应的副产物或反应物。因此，没有外来分子构成产物物流的一部分。
在本发明方法中用作起始物料的碳酸亚烷基酯具有它的常规定义，即分子中含有碳酸根基团的化合物。
特别适合的是通式(I)的具有五元碳酸亚烷基酯环(1，3-二氧杂环戊-2-酮)的碳酸亚烷基酯，
其中R1-R4独立地表示氢原子或具有1-6个碳原子的任选取代烷基。由R1、R2、R3和/或R4表示的任意烷基优选具有1-3个碳原子。作为取代基，可以存在非活性部分例如羟基。优选地，R1、R2和R3表示氢原子和R4表示未取代C1-C3烷基，和更优选地R1、R2、R3和R4都表示氢原子。
因此，适合的碳酸亚烷基酯的实例包括碳酸亚乙基酯、碳酸亚丙基酯、碳酸1，2-亚丁基酯和碳酸2，3-亚丁基酯。在本发明中，最优选的通式(I)的碳酸亚烷基酯是碳酸亚乙基酯，其中R1、R2、R3和R4都表示氢原子。
本领域技术人员已公知碳酸亚烷基酯的制备。它们可通过包括在催化剂存在下使对应的环氧烷烃与二氧化碳接触的方法制得。
特别适合的是具有通式(II)的环氧烷烃，
其中R1-R4对应于对应的碳酸亚烷基酯的R1-R4。因此适合的环氧烷烃包括环氧乙烷、环氧丙烷、1，2-环氧丁烷和2，3-环氧丁烷。在本发明中，最优选的通式(I I)的环氧烷烃是环氧乙烷，其中R1、R2、R3和R4都表示氢原子。
本领域技术人员已公知环氧烷烃的制备。当是环氧乙烷的情况下，它可以通过公知的乙烯直接氧化(即通过空气或氧氧化)制备，其中使用银基催化剂和通常也存在有机减速剂例如有机卤化物(参见例如Kirk Othme r′s Encyclopedia of Chemical Technology，第4版，Vol.9，第923-940页)。
本发明的催化剂包含固定在固体载体上的碳酸氢根作为活性相，所述固体载体具有一个或多个正电性位点。对于催化剂的活性，无需由作为活性相的碳酸氢根开始。也可以由固定在固体载体上的羟基基团或碳酸根基团开始。这些基团被认为是作为该反应的活性相的碳酸氢根的前体。在催化反应的初始阶段期间，由于当碳酸亚烷基酯被转化时形成的大量CO2和水或醇的存在，羟基基团或碳酸根基团被转化成碳酸氢根活性相。
适合地，用于本发明方法的碳酸氢根的量是0.0001-0.5mol/mol碳酸亚烷基酯。优选地，碳酸氢根的存在量是0.001-0.1mol/mol碳酸亚烷基酯。
固体载体是具有一个或多个正电性位点的载体。适合的具有一个或多个正电性位点的固体载体包括无机天然物质例如碳、二氧化硅、二氧化硅-氧化铝、沸石、玻璃和粘土如水滑石的那些。这些固体载体可以含有通过吸附、反应或接枝而键接的阳离子。另外，根据本发明也将固定的复合大环例如冠醚认为是具有一个或多个正电性位点的固体载体，这是因为这些材料能够键接阳离子。优选地，固体载体含有季铵、季磷鎓、季砷鎓、季锑鎓或叔硫鎓阳离子或复合大环。更优选地，所述阳离子是季铵或季磷鎓离子。
有利地，本发明中使用包括强碱性离子交换树脂的固体载体，其中所述阳离子连接到聚合物主链上。聚合物主链可包括高分子量聚合物和共聚物，包括聚亚烷基、聚酯、聚碳酸酯、聚氨酯、甲醛树脂等。适合的市售离子交换树脂包括含聚丙烯酸酯或苯乙烯-二乙烯基苯共聚物作为聚合物主链的那些。也可使用具有二氧化硅基聚合物主链的树脂例如聚硅氧烷以及在其聚合物主链中并入了乙烯基吡啶单体的树脂。本发明方法中适用的市售离子交换树脂包括但不限于：Lewatit500KR(Lewatit 是商标)，Amberlite IRA-900，AmberliteIRA-458(Amberlite是商标)，Amberjet 4200，Amberjet4400(Amberjet是商标)，DOWEX1×16(DOWEX是商标)，ReillexHPQ(Reillex是商标)，Marathon-A，Marathon-MSA(Marathon是商标)和DELOXAN AMP(DELOXAN是商标)。其它适合的离子交换树脂包括根据由Nishikubo等人在J.Polym.Sci.，Part A：Polym.Chem.，(1993)31，939-947中描述的方法制备的那些。这些树脂具有所谓的间隔基团，包括连接聚合物主链与阳离子的化学结构。适合地，间隔基团含有任选被一个或多个氧原子间断的亚烷基。
可通过本领域技术人员已知的任意技术将碳酸氢根或者它的前体羟基或碳酸根中的一种固定在固体载体上。这些技术包括孔体积浸渍、浸渍、沉淀和离子交换。优选地，经过离子交换将碳酸氢根或它的前体之一固定在固体载体上。离子交换包括使固体载体与溶液接触。在优选的固定碳酸氢根的情况下，所述溶液可以包含过量的碳酸氢钠或者它可以是用CO2饱和的水。当使用CO2饱和水溶液时，重复交换反应直至流出物的pH与CO2饱和溶液的pH相近。该步骤之后可以是水洗步骤。优选地，在0-100℃的温度下、更优选在20-90℃的温度下进行离子交换。优选地，在大气压下进行离子交换。
本发明方法可以在适于水解过程的任意反应系统中进行。
用于本发明方法的碳酸亚烷基酯可包括纯化的碳酸亚烷基酯或任意其它适合的碳酸亚烷基酯。碳酸亚烷基酯也可以是来自碳酸亚烷基酯生产装置的粗产物，其中在催化剂存在下使对应的环氧烷烃与二氧化碳接触。催化剂可能仍然存在于该粗产物中。
优选地，供应至反应器的水的总量为至少0.5mol/mol碳酸亚烷基酯的量，优选至少为1mol/mol碳酸亚烷基酯。优选供应至反应器的水的总量为至多20mol/mol碳酸亚烷基酯的量，更优选为至多5mol/mol碳酸亚烷基酯的量，甚至更优选为至多2mol/mol碳酸亚烷基酯。
本发明方法可以以间歇操作方式进行。然而，特别是对于大规模实施方案，优选连续操作所述方法。
可以在上流式或下流式操作的固定床反应器中进行该连续过程。其它反应器选择包括鼓泡塔反应器和流化床反应器。
本发明的反应器可以维持在等温、绝热或混合条件下。等温反应器通常是壳式和管式反应器，主要是多管类型，其中所述管含有催化剂，和冷却剂在所述管的外部通过。绝热反应器不进行冷却，而可以在单独的换热器中冷却离开它们的产物物流。
对于本发明方法而言，将反应器出料的一部分循环至相同反应器的至少一个入口可能是有利的，因为这样最小化了反应器顶部和底部之间可能产生的任意温差。因此，与常规反应器相比，需要更少的外部温度控制以维持反应温度。在等温条件是优选的情况下，这是特别有利的。在反应器出料已经离开反应器之后，可以便利地使待循环的反应器出料部分与不循环的部分分离；或作为替代，可以经与从中移除不循环的反应器出料部分的反应器出口不同的反应器出口，便利地从反应器中移除待循环的反应器出料部分。可以改变待循环的反应器出料混合物的量，以根据所使用的其它反应参数获得最佳性能。
在使用含上述的季基或叔基基团的催化剂的一些过程中偶尔可能发生的问题是产物物流中存在少量的杂质。例如，当将强碱性阴离子交换树脂(其中的碱性基团含有季铵或磷鎓基团)用作催化基团的固体载体时，已经发现在操作期间，少量的胺或磷化氢倾向于从树脂滤出至产物物流中。产物物流中的其它杂质可以包括源自缓蚀剂的胺，所述缓蚀剂可能被加入过程中使用的水中。虽然到达最终产物的这些污染物的量通常非常小，但是它们可能影响最终产物的质量，所以可能需要将这些量降至尽可能低从而不影响产物的质量。例如，到达最终产物的三甲基胺(TMA)和/或二甲基胺(DMA)的量可能是至多10ppm，但当含量低至1ppb时就可以检测出TMA的鱼腥味。
去除这些污染物的一种有效方法是使用含酸性物种、特别是强酸性离子交换树脂的后反应器床层，所述强酸性离子交换树脂有效捕获这些污染物。强酸性离子交换树脂可以是磺酸类型的。市售的实例是以商标AMBERLYST 15、AMBERJET 1500H、AMBERJET 1200H、DOWEX MSC-1、DOWEX 50W、DIANON SK1B、LEWATIT VP OC 1812、LEWATIT S 100MB和LEWATIT S 100G1已知的那些。这些强酸性离子交换树脂可以以H+型或盐型例如Na+型获得。当在后反应器保护床层中仅使用H+型强酸性树脂时，通过它之后的产物物流可能变成酸性。使用H+型和盐型强酸性离子交换树脂的混合物的优点是产物物流的pH保持接近中性。
这样的后反应器床层可以位于其中进行本发明反应过程的水解反应床层之后。在其中已经使碳酸亚烷基酯水解形成对应的亚烷基二醇的反应器床层之后放置强酸性后反应器床层的一个附加优点是使产物亚烷基二醇的产物物流中可能仍然存在的任何剩余的碳酸亚烷基酯水解成亚烷基二醇。
为了在操作期间允许排出和置换或再生强酸性离子交换树脂，有利的是在两个或更多个单独的容器中操作后反应器床层以允许在两个容器之间切换过程从而维持连续操作。
可通过用酸例如HCl和H2SO4处理使废的强酸性离子交换树脂再生。已证明0.1-2N的热硫酸是有效的。
为与操作期间仍然可能发生的催化剂的任何膨胀相适应，反应器体积可以有利地大于由其中的催化剂所占据的体积，优选大出10-70vol％。
根据本发明，用于使碳酸亚烷基酯催化水解的适合的反应温度通常是20-200℃，优选60-130℃的温度。
通常选定反应压力为100-5000kPa，优选200-3000kPa，最优选200-1500kPa。
下面的实施例将描述本发明。
催化剂制备
在装水的玻璃管中将150ml氯根型的季铵类湿离子交换树脂(Amberjet 4200，获自Rohm & Haas，交换容量1.3meq/ml)调成浆液。通过用碳酸氢钠溶液(2500g水中10倍摩尔过量)处理交换氯根阴离子约5小时(液时空速为41/1.h)。接下来，用1200ml水洗涤交换后的树脂约2小时(液时空速为41/1.h)。在所得的催化剂中，来自Amberjet 4200的氯根阴离子已经基本完全被所需的碳酸氢根阴离子交换，最终的氯根含量小于100ppm。
实验1
在120m l玻璃高压釜中进行这些实验。反应器填充有35g碳酸亚乙基酯和21.5g水。加入足够量的水解催化剂以提供4.1mmol的催化剂。用CO2吹扫反应器，并用4.5bar(450kPa)的CO2气氛对反应器加压。将反应器内容物加热至110℃，同时维持压力在4.5bar下。以规则的30分钟的时间间隔提取试样，和通过气液色谱法(GLC)进行分析。结果示于表I中。
表I
| 催化剂 | 量(g) | 量(mmol) | EC转化率(％；150分钟时) | MEG选择性(％；100％转化率下) |
| - | - | - | 13.1 | - |
| K2CO3 | 0.283 | 2.1 | 95.5 | 99.7 |
| KHCO3 | 0.411 | 4.1 | 95.5 | 99.8 |
| Amberjet4200/HCO3 | 2.75ml | 4.1 | 54 | 99.6 |
实验2
在固定床活塞流反应器中，在连续流动条件下测试制备的Amberjet 4200/碳酸氢根催化剂(IER容量为1.3meq/ml)大于2000小时。在两个不同的实验中，以0.51和0.751/1.h两个液体时空速度(LHSV)测试催化剂的性能。
通过将20ml催化剂放置于65cm长0.5英寸宽并配有使用热油系统的加热护套的Hoke管中测试催化剂性能。用HPLC泵将含17.5wt％EC的碳酸亚乙基酯(EC)/水混合物泵送向下流过温度为约90℃和压力为1000kPa的催化剂床层至少2000小时。通过热油系统的温度控制反应温度。在催化剂床层中心放置带有热电偶的热电偶套管，以测量床层温度。在产物容器中冷却和收集反应器流出物，从中提取试样用于GLC分析。表II中概述了结果。
表II
| 实验2a | 实验2b | |
| LHSV(1/1/h) | 0.51 | 0.75 |
| 温度(℃) | 89.7 | 88.2 |
| 选择性(mol％) | ＞99.9 | ＞99.9 |
| 运行时间(小时) | 转化率(％) | 转化率(％) |
| 93.5 | 90.2 | 65.9 |
| 164.5 | 88.3 | 68.5 |
| 244.5 | 86.0 | 67.1 |
| 838.5 | 91.6 | 72.1 |
| 910.0 | 92.0 | 73.4 |
| 1005.0 | 92.4 | 72.6 |
| 1078.5 | 92.6 | 75.0 |
| 1174.5 | 89.3 | 68.9 |
| 1246.0 | 89.4 | 68.8 |
| 1342.0 | 89.5 | 68.8 |
| 1419.5 | 90.3 | 70.4 |
| 1510.0 | 90.7 | 71.6 |
| 1580.5 | 91.2 | 71.1 |
| 1702.5 | 92.1 | 70.5 |
| 1780.0 | 93.3 | 72.1 |
| 1870.5 | 91.4 | 73.8 |
| 2015.0 | 91.1 | 72.3 |
| 2111.0 | 92.2 | 73.9 |
| 2207.0 | 92.1 | 73.3 |
| 2277.0 | 92.1 | 74.8 |
表II中示出的结果清楚地证明了在经过延长的时间段后，催化剂仍然具有活性。
Claims (8)
1.一种用于制备亚烷基二醇的方法，所述方法包括在催化剂存在下使对应的碳酸亚烷基酯与水反应，其中所述催化剂包含固定在固体载体上的碳酸氢根作为活性相，所述固体载体具有一个或多个正电性位点。
2.权利要求1的方法，其中所述固体载体是强碱性离子交换树脂，其中阳离子连接到聚合物主链上。
3.权利要求1或2的方法，其中所述固体载体含有季铵、季磷鎓、季砷鎓、季锑鎓或叔硫鎓阳离子。
4.权利要求3的方法，其中所述固体载体含有季铵或季磷鎓阳离子。
5.权利要求1-4任一项的方法，其中所述催化剂初始含有固定在固体载体上的碳酸根基团、碳酸氢根基团或羟基基团。
6.权利要求1-5任一项的方法，其中所述方法在40-200℃的温度和100-5000kPa的压力下进行。
7.权利要求1-6任一项的方法，其中所述碳酸亚烷基酯是碳酸亚乙基酯。
8.一种用于制备亚烷基二醇的方法，所述方法包括以下步骤：
-通过在催化剂存在下使对应的环氧烷烃与二氧化碳接触制备碳酸亚烷基酯
-随后通过权利要求1-7任一项的方法使碳酸亚烷基酯与水和/或醇反应。
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| US20070203352A1 (en) | 2005-12-22 | 2007-08-30 | Bolk Jeroen W | Method Of Installing An Epoxidation Catalyst In A Reactor, A Method Of Preparing An Epoxidation Catalyst, An Epoxidation Catalyst, A Process For The Preparation Of An Olefin Oxide Or A Chemical Derivable From An Olefin Oxide, And A Reactor Suitable For Such A Process |
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| US20080154051A1 (en) | 2006-12-20 | 2008-06-26 | Jeroen Willem Bolk | Method of installing an epoxidation catalyst in a reactor, a method of preparing an epoxidation catalyst, an epoxidation catalyst, a process for the preparation of an olefin oxide or a chemical derivable from an olefin oxide, and a reactor suitable for such a process |
| US20080154052A1 (en) | 2006-12-20 | 2008-06-26 | Jeroen Willem Bolk | Method of installing an epoxidation catalyst in a reactor, a method of preparing an epoxidation catalyst, an epoxidation catalyst, a process for the preparation of an olefin oxide or a chemical derivable from an olefin oxide, and a reactor suitable for such a process |
-
2007
- 2007-09-05 US US11/850,544 patent/US7462748B2/en not_active Expired - Fee Related
- 2007-09-07 EP EP07820058A patent/EP2069274A1/en not_active Withdrawn
- 2007-09-07 CA CA002662824A patent/CA2662824A1/en not_active Abandoned
- 2007-09-07 CN CN200780039278.8A patent/CN101528649B/zh not_active Expired - Fee Related
- 2007-09-07 AR ARP070103962A patent/AR062705A1/es not_active Application Discontinuation
- 2007-09-07 TW TW096133629A patent/TWI405748B/zh not_active IP Right Cessation
- 2007-09-07 JP JP2009527146A patent/JP2010502677A/ja not_active Withdrawn
- 2007-09-07 WO PCT/EP2007/059385 patent/WO2008028953A1/en active Application Filing
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012063A (zh) * | 2011-09-28 | 2013-04-03 | 中国石油化工股份有限公司 | 一种制备丙二醇的方法 |
| CN103012063B (zh) * | 2011-09-28 | 2014-12-03 | 中国石油化工股份有限公司 | 一种制备丙二醇的方法 |
| CN105085187A (zh) * | 2014-05-14 | 2015-11-25 | 中国石油化工股份有限公司 | 碳酸乙烯酯水解制备乙二醇的方法 |
| CN105085187B (zh) * | 2014-05-14 | 2017-08-11 | 中国石油化工股份有限公司 | 碳酸乙烯酯水解制备乙二醇的方法 |
| CN105272822A (zh) * | 2014-07-03 | 2016-01-27 | 中国石油化工股份有限公司 | 用于碳酸乙烯酯水解制备乙二醇的方法 |
| CN105272823A (zh) * | 2014-07-03 | 2016-01-27 | 中国石油化工股份有限公司 | 制备c2-10链烷二醇的方法 |
| CN105272823B (zh) * | 2014-07-03 | 2017-04-19 | 中国石油化工股份有限公司 | 制备c2‑10链烷二醇的方法 |
| CN105272822B (zh) * | 2014-07-03 | 2017-04-19 | 中国石油化工股份有限公司 | 用于碳酸乙烯酯水解制备乙二醇的方法 |
| CN105268485A (zh) * | 2014-07-24 | 2016-01-27 | 中国石油化工股份有限公司 | 生产c2-10链烷二醇的方法 |
| CN105268485B (zh) * | 2014-07-24 | 2018-01-09 | 中国石油化工股份有限公司 | 生产c2‑10链烷二醇的方法 |
| CN105503529A (zh) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | 用于碳酸乙烯酯水解制备乙二醇的方法 |
| CN105503529B (zh) * | 2014-09-25 | 2017-10-27 | 中国石油化工股份有限公司 | 用于碳酸乙烯酯水解制备乙二醇的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2662824A1 (en) | 2008-03-13 |
| TW200827328A (en) | 2008-07-01 |
| CN101528649B (zh) | 2013-05-29 |
| US20080064881A1 (en) | 2008-03-13 |
| EP2069274A1 (en) | 2009-06-17 |
| US7462748B2 (en) | 2008-12-09 |
| TWI405748B (zh) | 2013-08-21 |
| JP2010502677A (ja) | 2010-01-28 |
| WO2008028953A1 (en) | 2008-03-13 |
| AR062705A1 (es) | 2008-11-26 |
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