CN1102930C - 环氧丙烷的制备方法 - Google Patents
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Abstract
环氧丙烷的一种制备方法，在含钛固体催化剂存在下，用固定床流动反应器，氢过氧化物与丙烯反应，其中所述的催化剂用包含对反应惰性的、在400K导热系数为约10Wm-1K-1或更大的固体无机化合物的稀释剂稀释。
Description
本发明涉及环氧丙烷的制备方法。更具体地说，本发明涉及在含钛固体催化剂存在下，氢过氧化物与丙烯用固定床流动反应器制备环氧丙烷的方法，以改善预期生成的环氧丙烷的选择性，并抑制氢过氧化物的分解。
环氧丙烷是一种有用的工业化学制品，例如用作生产聚氨酯的原料，等等。
人们知道，烯烃化合物与有机氢过氧化物在含钛固体催化剂存在下反应，将烯烃化合物转化成环氧乙烷化合物。所用的含钛固体催化剂通常用将钛承载在二氧化硅等载体上的方法制备(参见例如日本专利申请公告号(JP-B)56-35941，54-40525，54-40526和50-30049，日本专利申请公开号(JP-A)平8-269031等)。然而，当使用这些方法制得的催化剂，用固定床流动反应器进行丙烯环氧化反应时，产生的问题是形成不可取的副产物，并且环氧丙烷的选择性不够，同时由于反应放热加速过氧化氢的分解反应。
在这些情况下，本发明人已深入细致地研究出不存在上述问题的一种制备环氧丙烷的方法，结果发现，使用用包含固体无机化合物的稀释剂稀释的含钛固体催化剂，用固定床流动反应器将氢过氧化物与丙烯反应制备环氧丙烷时，副产物的形成能被抑制，预期的环氧丙烷的选择性提高，并且过氧化氢的分解被抑制，从而完成了本发明。
即，本发明涉及在含钛固体催化剂存在下，用固定床流动反应器，将氢过氧化物与丙烯反应制备环氧丙烷的方法，其中所述的催化剂用包含固体无机化合物的稀释剂稀释，这种无机化合物对反应惰性并且在400K导热系数为约10Wm-1K-1或更大。
本发明使用的催化剂是含钛(下文写作“Ti”)固体催化剂。作为含Ti固体催化剂，例如，有把钛化合物承载在各种载体上制得的化合物，用共沉淀法或溶胶凝胶法与其它氧化物络合得到的化合物，以及含钛的基于沸石的氧化物。优先使用与固体二氧化硅和/或无机硅酸盐化学键合的含钛的所谓钛-二氧化硅催化剂。这种催化剂可用JP-B 56-35941，54-40525，54-40526，50-30049等日本专利所述的方法制备。
使用含Ti固体催化剂，用固定床流动反应器，氢过氧化物与烯烃进行环氧化反应。
氢过氧化物的例子包括有机氢过氧化物。
有机氢过氧化物是用通式R-O-O-H表示的化合物(式中R是一价烃基)，它与烯烃化合物反应形成环氧乙烷和用通式R-OH表示的化合物。R基最好具有3-20个碳原子，特别优选的是3-10个碳原子的烃基，尤其是仲或叔烷基或芳烷基。其中，叔烷基和仲或叔芳烷基是特别优选的，具体例子包括叔丁基，叔戊基，环戊基，1-苯基乙基-1基和2-苯基丙基-2基，而且还可以举出从1，2，3，4-四氢化萘分子的脂族侧链上除去一个氢原子而生成的各种1，2，3，4-四氢化萘基。
当使用氢过氧化乙苯时，所得羟基化合物是1-苯基乙醇，它可通过脱水反应转化成苯乙烯。当使用氢过氧化异丙基苯时，得到的羟基化合物是2-苯基-2-丙醇，它可通过脱水反应转变成α-甲基苯乙烯。苯乙烯和α-甲基苯乙烯两者都是工业上有用的物质。
用氢过氧化叔戊基得到的叔戊醇的脱水反应生成的叔戊烯是作为异丙烯的前体的一种有用物质。叔戊醇也是作为辛烷助促进剂的甲基叔戊醚前体的有用物质。使用氢过氧化叔丁基得到的叔丁醇是作为辛烷助促进剂甲基叔丁基醚的前体的一种有用物质。
作为除了有机氢过氧化物之外的过氧化氢，能举出的是过氧化氢。
过氧化氢是用化学式HOOH表示的化合物，通常以水溶液形式获得。它与烯烃化合物反应形成环氧乙烷化合物和水。
作为原料使用的过氧化氢可以是稀的或浓的提纯的或未提纯的物质。
环氧化反应可通过使用溶剂在液相中进行。此溶剂最好是在反应温度和压力下呈液态的物质，并且对反应物和产物基本上是惰性的。该溶剂可以是在氢过氧化物溶液中存在的物质，例如，当氢过氧化乙苯(EBHP)是由EBHP和乙苯(是它的一种原料)组成的混合物时，乙苯被用作溶剂的替代物而无需另外加入溶剂。
作为本发明的工业实施方案，适合采用经济和操作性能具佳的用固定床流动反应器的连续方法。
在固定床流动反应中，由固体颗粒组成的催化剂保持在反应管中，方便地使氢过氧化物原料液和丙烯通过该管。反应温度优选约0℃-200℃，特别优选从约30℃-150℃。当温度较低时，有时反应速度变慢，而当温度较高时，反应选择性有时会降低。反应压力最好为约1atm到约100atm，更优选从约10atm到约70atm。当压力较低时，丙烯可蒸发，反之，当压力较高时，设备费用太高。
本发明方法的特征在于使用固体无机化合物，作为催化剂的稀释剂填充在固定床流动反应器中该化合物对反应呈惰性，并且在400K的导热系数为约10Wm-1K-1或更大，优选约20Wm-1K-1或更大。固体无机化合物的导热系数通常用静态热流法测定(例如，将热源置于圆柱形样品的一端，测定静态条件下距离热源不同距离的两点的温度)。该测量方法的细节在教科书“4th edition Shin Jikken KagakuKoza”(由MARUZEN Co.出版)中第4卷第419页已被说明，各种固体无机化合物的热传导系数的值在教科书“Kagaku Binran”(编辑Nippon KagakuKai，MARUZEN Co.出版)等中已被说明。通过用稀释剂稀释催化剂，作为稀释剂使用的无机化合物在400K的导热系数约为10Wm-1K-1或者更大，如上述的方法测得，并进行反应，可以抑制副产物的形成，且预期的环氧丙烷(下文写作“PO”)的选择性提高。而且，氢过氧化物的分解被抑制(其原因是假设由于环氧化作用产生的热而引起的催化剂床温度的局部和急剧的升高，通过使用稀释剂来抑制)。
固体无机化合物的例子包括金属氧化物，金属碳化物，金属氮化物，以及其它的各种固体陶瓷。最好是固体无机化合物有小的表面积，因为所需的稀释剂应对反应惰性。因此，稀释剂的表面积最好是约100m2/g或者更小，优选为约10m2/g或者更小，更优选为1m2/g或者更小。这类稀释剂的实例包括氧化铝，氧化镁，碳化硅等，使用低表面积的α-氧化铝是特别优选的。
作为用这些稀释剂稀释催化剂的方法，可举出的有：稀释剂与形成的催化剂一起填充在反应器中的方法，催化剂和稀释剂形成的混合物填充在反应器中的方法等等，但不限于这些稀释法。
稀释剂与催化剂的加入比例(稀释比)无特别限制，最好为从约10％重量到约90％重量，更优选从约30％重量到约70％重量。当稀释比太低时，改进PO选择性的效果有时变差，稀释比太高，有时反应容器体积增大，产率下降，并且经济效益下降。
由此得到的环氧化反应溶液中未反应的丙烯，通过蒸馏分离后可循环至环氧化反应工艺中使用。从除去绝大部分未反应丙烯的反应液中分离环氧丙烷，可使用诸如蒸馏、洗涤等常规操作容易进行。
根据本发明，在含钛固体催化剂存在下，用固定床流动反应器，氢过氧化物与丙烯反应制备环氧丙烷时，副产物的形成被抑制，预期的环氧丙烷的选择性提高，并且氢过氧化物的分解被抑制。
实施例
参考例1
将市售硅胶(10-40目，表面积300m2，平均孔径10nm，50g)，四异丙基钛酸酯(2.2g)，乙酰丙酮(1.64g)和异丙醇(200ml)混合，于室温下搅拌30分钟，然后，过滤该混合物。将固体部分浸在异丙醇(50ml)中，搅拌，洗涤，然后过滤分离此溶液，该操作重复三次。固体部分在氮气流下于500℃干燥2小时，在空气流下于600℃进一步熔烧4小时。将该物质(10g)，六甲基二硅氮烷(4g)和甲苯(50g)混合，并于压力下200℃加热搅拌1小时。用过滤从混合物中分离出液体部分，用甲苯(50g)洗涤，并减压干燥(120℃，10mmHg，3小时)，得到催化剂。
(EBHP溶液的碱洗)
EBHP溶液(15％重量，3000g)和氢氧化钠(0.5g重量，1000g)于60℃混合搅拌15分钟，再在此温度下保持15分钟，然后分离该溶液。分出的油层用1000g水在60℃洗涤15分钟。所得油层在60℃，50mmHg下浓缩，得到35％重量EBHP溶液。
实施例1
按参考例1的制备方法合成的催化剂(Ti含量0.7％重量)用α-氧化铝(在400K的导热系数为26Wm-1K-1)稀释，体积比为1∶1，并将该混合物填充在反应器中，使用参考例1的洗涤方法得到的EBHP溶液(EBHP35％重量，EB58％重量)和丙烯在固定床流动反应装置中进行环氧化反应。用内径10mm的不锈钢管作为反应管，热电偶扦入管中，测定内温。反应在丙烯/EBHP摩尔比为12，LHSV＝6h-1(根据EBHP溶液和丙烯的总流量对不含稀释剂的催化剂体积计算)和反应压力为40kg/cm2的条件下进行。结果示于表1。
比较例1
用实施例1相同的方法进行反应，只是催化剂用二氧化硅(在400K的导热系数为1Wm-1K-1)稀释，体积比为1∶1。结果列于表1。
比较例2
用实施例1相同的方法进行反应，只是催化剂不稀释。结果列于表1。
实施例1满足本发明的条件，反应温度降低，催化床的升温小，并且预期环丙烷产物的选择性提高，氢过氧化乙苯的分解产物乙酰苯的形成减少。另一方面，比较例1用在400K导热系数低的稀释剂和比较例2不用稀释剂，副产物乙酰苯的形成增加，预期环氧丙烷的选择性低。
表1
| 实施例1 | 比较例1 | 比较例2 | |
| 反应温度℃催化床入口温度催化床最高温度ΔT反应结果EBHP转化率PO选择性ACP选择性 | 57.259.72.586.997.51.1 | 70.378.58.290.091.32.0 | 72.679.46.890.593.92.2 |
ΔT：催化床升高的温度(℃)
ACP：乙酰苯(EBHP的分解产物)
Claims (3)
1.环氧丙烷的制备方法，所述方法是在含钛固体催化剂的存在下，使氢过氧化物与丙烯通过固定床流动反应进行反应，其中，所述催化剂用一种含固体无机化合物的稀释剂稀释，所述稀释剂是对所述反应呈惰性的、选自氧化铝，氧化镁和碳化硅的至少一种化合物。
2.根据权利要求1的方法，其中，所述氢过氧化物是有机氢过氧化物。
3.根据权利要求2的方法，其中，所述有机氢过氧化物是氢过氧化乙苯。
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| US6369245B1 (en) * | 1999-08-13 | 2002-04-09 | Colorado State University Research Foundation | Epoxidation of olefins |
| US6686483B2 (en) | 1996-10-08 | 2004-02-03 | Colorado State University Research Foundation | Catalytic asymmetric epoxidation |
| EP1071676A4 (en) | 1998-04-16 | 2004-09-29 | Univ Colorado State Res Found | KINETIC RESOLUTION OF OLEFINS |
| IT1313572B1 (it) * | 1999-07-27 | 2002-09-09 | Enichem Spa | Procedimento per la preparazione di epossidi. |
| JP4325045B2 (ja) * | 1999-11-09 | 2009-09-02 | 住友化学株式会社 | チタン含有珪素酸化物触媒の製造方法、該触媒及び該触媒を用いたオキシラン化合物の製造方法 |
| JP3920020B2 (ja) * | 1999-12-24 | 2007-05-30 | 株式会社日本触媒 | 含酸素有機化合物製造用触媒および含酸素有機化合物の製造方法 |
| JP2001270879A (ja) * | 2000-03-24 | 2001-10-02 | Sumitomo Chem Co Ltd | オキシラン化合物の製造方法 |
| US6337412B1 (en) | 2000-04-25 | 2002-01-08 | Chemical Research & Licensing Company | Three stage propylene oxide process |
| US6455712B1 (en) * | 2000-12-13 | 2002-09-24 | Shell Oil Company | Preparation of oxirane compounds |
| DE10137543A1 (de) * | 2001-08-01 | 2003-02-13 | Basf Ag | Verfahren zur Herstellung von Propylenoxid |
| US7193093B2 (en) | 2003-06-30 | 2007-03-20 | Shell Oil Company | Process for producing alkylene oxide |
| EP1666443B1 (en) * | 2003-09-25 | 2011-04-20 | Sumitomo Chemical Company, Limited | Process for producing cumene and process for propylene oxide production including the production process |
| JP4385700B2 (ja) * | 2003-09-26 | 2009-12-16 | 住友化学株式会社 | プロピレンオキサイドの製造方法 |
| CN101817804B (zh) * | 2010-03-16 | 2011-10-05 | 华东理工大学 | 压力振荡丙烯环氧化制备环氧丙烷的方法 |
| CN108912071B (zh) * | 2018-07-24 | 2022-04-19 | 河北美邦工程科技股份有限公司 | 一种环氧丙烷的制备方法 |
| CN109999728A (zh) * | 2019-04-08 | 2019-07-12 | 江苏扬农化工集团有限公司 | 一种降低hppo工艺催化剂床层温升的方法 |
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| NL1010372C2 (nl) | 1999-07-13 |
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| ES2147713A1 (es) | 2000-09-16 |
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