CN1110468C - 苯部分氢化连续制备环己烯 - Google Patents
苯部分氢化连续制备环己烯 Download PDFInfo
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
- C07C5/11—Partial hydrogenation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
- C07C2523/46—Ruthenium, rhodium, osmium or iridium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
在高温、高压及水和钌催化剂存在的条件下使用连续法用氢将苯部分氢化制备环己烯，在该工艺中苯以气态导入，所得环己烯以气态出料，催化剂溶于或悬浮于液态水溶液中。
Description
本发明涉及连续制备环己烯的改进工艺，包括在水和钌催化剂存在下，于高温高压下用氢将苯部分氢化。
美国专利US4,678,861描述了在一悬浮液中将苯部分氢化制备环己烯的间歇法，该反应在一两相液体混合物中进行。该工艺的缺点在于从有机相中分离催化剂和可能的盐的排出。
欧洲专利EP-A-552,809描述了在一体系中，苯部分氢化生成环己烯，该体系由其中悬浮有催化剂的水相和含有待氢化烃的油相以及含有氢的气相组成。该工艺的缺点在于为了从水相中分出有机相，反应必须被间断。
欧洲专利EP-B-55,495记述了在气相中苯部分氢化至环己烯，得到的环己烯的最高产率仅8.4％。
本发明的目的在于提供连续制备环己烯的改进工艺，该工艺包括在水和钌催化剂的存在下，于高温高压下用氢将苯部分氢化，本工艺没有上述缺陷。
我们业已发现，通过在高温高压及水和钌催化剂存在的条件下将苯用氢部分氢化这一连续制备环己烯的工艺可达到上述目的，其中苯以气态导入，所得环己烯以气态出料，催化剂溶于或悬浮于液态水溶液中。
根据本发明的工艺，苯和氢可以一起或分别以气态导入，所得环己烯以气态出料。最好将苯与做为载体的惰性气体一起导入反应空间；该惰性气体，例如氮气氦气或氩气，优选通过苯饱和装置，苯以气态被吸收。通常20-250℃，优选50-170℃的惰性气流能进行有效负载，为此优选在此饱和装置上游加热惰性气体。饱和装置下游的压力最好选择与反应空间的总压一致。
当选用惰性气体做为苯的载气时，通常选用的苯浓度为0.1-99.9％(体积)，优选0.5-95％(体积)。
根据本发明的工艺，将与载气在或不在一起的气态苯加料于悬浮于或溶于液态水溶液相中的加氢催化剂。反应空间的苯分压通常选择为10KPa-1MPa，优选150KPa-0.5MPa。
时至今日的观察表明可以多种方法将气态苯导入反应空间，例如用或不用喷嘴，经一简单的导管导入液态水相或液体表面上部。
反应空间的氢气分压一般选择50KPa-5Ma，优选0.5MPa-4MPa。
反应最好在20-300℃，优选100-200℃下进行。
压力和温度最好互相协调以保持一个液态水相，导入的苯的量与有机物出料量相一致，该有机物基本由环己烯，环己烷和未转化的苯组成。在一个优选方案中，反应空间的压力用惰性气体，例如氮气，氩气或氦气，优选用氮气控制，反应空间的总压选择为0.1-20MPa，优选1-10MPa。
最好搅动该液态水相，优选搅拌；搅拌速率选择为300-1500转/分，优选750-1500转/分。
观察表明，所有已知的含钌均相或悬浮催化剂(载体催化剂或沉淀催化剂)均可用作本发明催化剂。这些催化剂记载在如美国专利4,678,861，EP-A 220,525，WO 93/16971，WO 93/16972和EP-A 554,765中；根据US 4,678,861实施例1制备的催化剂(氧化镧载体上的钌)，根据EP-A 220,525实施例1制备的催化剂(钌/锌沉淀催化剂)和根据DE-A 4,203,220实施例1制备的催化剂(钌/镍沉淀催化剂)尤为优选。
优先使用以所用苯量计的钌含量为0.01-100wt％的催化剂，优选0.1-80wt％。
本发明的反应在水的存在下完成。优选水与催化剂重量比为5∶1-1000∶1，50∶1-500∶1更为优选。
将水导入反应空间的速率通常以水以气态排出量为准，可用泵将水以液态形式导下，也可经例如饱和装置将水以气态导入。
苯和惰性气体(如果需要)的加入量最好使得催化剂总是完全存在于水溶液相。
根据催化剂体系的不同，反应可在碱性、中性或酸性范围内完成。
当反应在碱性介质中进行时，通常向水相中加入0.01-10mol/l，优选0.1-5mol/l的碱金属或碱土金属氢氧化物，氢氧化钠或氢氧化钾尤为优选。
当反应在酸性介质中进行时，通常向水相中加入过渡金属的酸式盐或有机或无机酸，加入量为0.001-10mol/l优选0.1-5mol/l。
水相中最好含有一种或几种可溶性的周期表2-8族的过渡金属阳离子、如铬、锰、铁、钴、铜或锌的阳离子，以及以其盐酸盐、硝酸盐、乙酸盐、磷酸盐或硫酸盐形式存在的铵。以水相计的金属盐量最好为0.01％wt-饱和浓度。
此外最好向反应混合物中加入至少一种选自氧化铝，氧化硅，二氧化锆，二氧化钛，二氧化铪，三氧化铬和氧化锌的金属氧化物，以使用的水量计的金属氧化物添加量优选0.001-1wt％。
主要含有环己烯、环己烷，未转化的苯和氢，并且可能含有惰性气体的气体混合物的出料通常用蒸馏方法完成，例如用冷凝法从混合物中分出有机相，然后用萃取蒸馏得到环己烯。
在一个优选方案中，反应中使用一个常规的搅拌釜。通过串联一系列搅拌釜可达到测流量管作用。观察结果表明也可采用如泡罩塔反应器的其它反应器。
用新的工艺制得的环己烯可适用于环己醇的制备，该环乙醇是制备纤维中间体的重要的起始原料。
本工艺的优点在于催化剂和存在盐不会被排出，盐的浓度可以保持恒定，环己烯选择性高于以往技术。
实施例
实施例1：
在一搅拌釜反应器中(650ml容积，Teflon全衬)，将5g钌/氧化镧催化剂(按美国专利4,678,861实施例1制备)与1g氯化锌和6.24g氢氧化钠用250ml蒸馏水层覆盖。关闭反应器后，将反应器的压力用氮升至5.0MPa。此后用氮气(300ml(S.T.P)/min，ml(S.T.P)＝以标准温度和压力(T＝273K，P＝101.325KPa)计的ml)将反应器冲洗4小时，同时剧烈搅拌(500rpm)，并加热至130℃。然后在剧烈搅拌下用氢/氮混合气(50ml(S.T.P)/min氢和300ml(S.T.P)/min氮进料)将催化剂活化12小时。然后将氮气通过一个充有苯的饱和器，在约65℃氮气流的负载有效。然后将载苯氮气流(260ml/min)与氢气流(90ml/min)合并并将其送入反应器。
反应器中反应6小时后取出第一份样品(实验1a)，此后根据表1改变苯和氢气的分压(实验1b和1c)，每种情况反应时间均为3小时。经过10天未发现催化剂失活。
气态反应混合物的组成用气相色谱分析。
结果汇总于表1
表1
| 实施例1 | 反应时间[h](总) | P(H2)[kpa] | P(苯)[kpa] | 转化率[％] | 选择性[％] | 产率[％] |
| abc | 6912 | 152312021189 | 624437 | 14.529.240.5 | 80.468.757.5 | 11.620.123.3 |
将美国专利4,678,861的实施例42-44用做对比例。实施例1中给出的是不同的选择性。将这些值与美国专利4,678,861中相应的值比较，使用如下公式计算实施例1的积分选择性： 式中Sint是积分选择性，Sdiff是不同的选择性，Uend是反应结束时的转化率。
图1给出了实验结果。
○代表美国专利4,678,861的实施例42-44的结果，
□代表实验1a-1c的结果，
…代表对□算得的积分选择性。
实施例2
除进行下述改变外均按相同的条件重复实施例1：10.0g催化剂，2.0g氯化锌和6.32g氢氧化钠。
结果汇总于表2。
表2
实施例3(串联搅拌釜)
| 实施例2 | 反应时间[h](总) | P(H2)[kpa] | P(苯)[kpa] | 转化率[％] | 选择性[％] | 产率[％] |
| abcde | 1218243036 | 764757743732786 | 8677575135 | 14.933.340.541.144.3 | 81.967.060.861.359.1 | 12.222.324.625.226.2 |
为模拟串联搅拌釜，将下述催化剂体系装在实施例1的搅拌釜反应器中。
5.0g钌/氧化镧催化剂(同实施例1)，1.2gZnCl2，6.34gNaOH和250ml蒸馏水。依据前述各实施例进行催化剂的活化。此后使在105℃载有苯的氮气流(350ml(S.T.P)/min)与氢(75ml(S.T.P.)/min)一起进入反应器。用气相色谱分析产物中的烃组分。具有来自第一次反应的产物气流组成的烃混合物再次进入反应器以模拟第二串联反应器。按此方式进行其余三个反应，从而得以模拟由五个搅拌釜组成的串联搅拌釜。
每次反应的时间为6个小时。
结果汇总于表3并图示于附图1(Δ)。
表3
| 反应器编号 | P(H2)[PKa] | P(C6H6)[kpa] | P(C6H10)[kpa] | P(C6H12)[％] | 转化率[％] | 选择性[％] | 产率[％] |
| 12345 | 786785785785786 | 158147135124112 | 9.016.624.430.535.8 | 1.33.05.68.612.7 | 6.111.818.224.030.1 | 87.484.781.378.073.8 | 5.310.014.818.722.1 |
Claims (5)
1.一种连续制备环己烯的工艺，该工艺包括在温度为20-300℃、总压为0.1-20MPa、水及钌催化剂存在的条件下用氢将苯部分氢化，其中苯以气态导入，所得环己烯以气态出料，催化剂溶于或悬浮于液态水溶液中。
2.根据权利要求1的工艺，其中的反应在氢分压50kPa-5MPa条件下进行。
3.根据权利要求1或2的工艺，其中反应在苯分压10kPa-1MPa条件下进行。
4.根据权利要求1或2的工艺，其中反应在水与催化剂重量比为5∶1-1000∶1的条件下进行。
5.根据权利要求3的工艺，其中反应在水与催化剂重量比为5∶1-1000∶1的条件下进行。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4423725.1 | 1994-07-08 | ||
| DE4423725A DE4423725A1 (de) | 1994-07-08 | 1994-07-08 | Verfahren zur kontinuierlichen Herstellung von Cyclohexen durch partielle Hydrierung von Benzol |
| US08/498,845 US6344593B1 (en) | 1994-07-08 | 1995-07-06 | Continuous preparation of cyclohexene by partial hydrogenation of benzene |
Publications (2)
| Publication Number | Publication Date |
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| CN1128746A CN1128746A (zh) | 1996-08-14 |
| CN1110468C true CN1110468C (zh) | 2003-06-04 |
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| Country | Link |
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| US (1) | US6344593B1 (zh) |
| EP (1) | EP0691320B1 (zh) |
| JP (1) | JP3579507B2 (zh) |
| CN (1) | CN1110468C (zh) |
| CA (1) | CA2153456C (zh) |
| DE (2) | DE4423725A1 (zh) |
| ES (1) | ES2098160T3 (zh) |
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| CN101628862B (zh) * | 2009-08-11 | 2012-02-29 | 河北石焦化工有限公司 | 一种以焦化苯为原料生产环己酮的方法 |
| CN103288576B (zh) * | 2012-02-29 | 2015-12-16 | 北京安耐吉能源工程技术有限公司 | 一种制备环己烯的方法 |
| CN104525192B (zh) * | 2014-12-22 | 2017-01-18 | 浙江大学 | 一种苯选择加氢制环己烯催化剂的制备方法 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0055495A1 (en) * | 1980-12-31 | 1982-07-07 | Stamicarbon B.V. | Process for the preparation of a cycloalkene through partial hydrogenation of the corresponding aromatic hydrocarbon |
| CN1080274A (zh) * | 1992-02-26 | 1994-01-05 | 催化剂股份有限公司 | 将芳烃部分氢化制备环烯烃的方法和催化剂 |
| CN1080273A (zh) * | 1992-02-26 | 1994-01-05 | 催化剂股份有限公司 | 部分氢化芳烃生产环烯烃的改进方法及经洗涤的催化剂 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1267914A (en) | 1985-10-03 | 1990-04-17 | Hajime Nagahara | Process for producing cycloolefins |
| US4678861A (en) | 1985-10-23 | 1987-07-07 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for producing a cycloolefin |
| TW218865B (zh) | 1992-01-24 | 1994-01-11 | Asahi Carbon Kabushiki Kaisha | |
| DE4203220A1 (de) | 1992-02-05 | 1993-08-12 | Basf Ag | Verfahren zur herstellung von cyclohexen durch partielle hydrierung von benzol |
-
1994
- 1994-07-08 DE DE4423725A patent/DE4423725A1/de not_active Withdrawn
-
1995
- 1995-06-27 JP JP16118495A patent/JP3579507B2/ja not_active Expired - Fee Related
- 1995-06-29 EP EP95110139A patent/EP0691320B1/de not_active Expired - Lifetime
- 1995-06-29 DE DE59500126T patent/DE59500126D1/de not_active Expired - Fee Related
- 1995-06-29 ES ES95110139T patent/ES2098160T3/es not_active Expired - Lifetime
- 1995-07-06 US US08/498,845 patent/US6344593B1/en not_active Expired - Fee Related
- 1995-07-07 CN CN95109156A patent/CN1110468C/zh not_active Expired - Fee Related
- 1995-07-07 CA CA002153456A patent/CA2153456C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0055495A1 (en) * | 1980-12-31 | 1982-07-07 | Stamicarbon B.V. | Process for the preparation of a cycloalkene through partial hydrogenation of the corresponding aromatic hydrocarbon |
| CN1080274A (zh) * | 1992-02-26 | 1994-01-05 | 催化剂股份有限公司 | 将芳烃部分氢化制备环烯烃的方法和催化剂 |
| CN1080273A (zh) * | 1992-02-26 | 1994-01-05 | 催化剂股份有限公司 | 部分氢化芳烃生产环烯烃的改进方法及经洗涤的催化剂 |
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| Publication number | Publication date |
|---|---|
| DE4423725A1 (de) | 1996-01-11 |
| JP3579507B2 (ja) | 2004-10-20 |
| JPH0853376A (ja) | 1996-02-27 |
| DE59500126D1 (de) | 1997-04-10 |
| ES2098160T3 (es) | 1997-04-16 |
| US6344593B1 (en) | 2002-02-05 |
| CN1128746A (zh) | 1996-08-14 |
| CA2153456A1 (en) | 1996-01-09 |
| CA2153456C (en) | 2006-07-04 |
| EP0691320A1 (de) | 1996-01-10 |
| EP0691320B1 (de) | 1997-03-05 |
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