CN87105326A - 烯烃齐聚方法 - Google Patents
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- 229930195733 hydrocarbon Natural products 0.000 claims description 6
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- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- -1 olefin hydrocarbon Chemical class 0.000 claims description 3
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- 238000011027 product recovery Methods 0.000 claims description 2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/14—Catalytic processes with inorganic acids; with salts or anhydrides of acids
- C07C2/20—Acids of halogen; Salts thereof ; Complexes thereof with organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
- C07C2521/04—Alumina
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/06—Halogens; Compounds thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/06—Halogens; Compounds thereof
- C07C2527/08—Halides
- C07C2527/12—Fluorides
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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Abstract
本发明为烯烃齐聚方法。为了避免环境污染及腐蚀问题,提出采用一种固体催化剂进行气相齐聚反应,该催化剂含有周期表第111、1V及或V主族元素的超酸性氟化物。该法可用于例如提高蒸汽裂解法的烯烃收率,或者用于由FCC废气制取发动机燃料组分。
Description
本发明涉及烯烃齐聚方法。
在许多聚合技术领域中都希望把聚合反应保持在齐聚阶段,並且避免高聚反应,从而获得特定的产品质量。因而这类齐聚反应对于制取特定产品通常是重要的反应,对其最终控制在方法技术上需予适当掌握。
在采用蒸汽裂解法制备烯烃过程中,单一烯烃收率可根据热力学或反应动力学进行预测。在不变的裂解深度下明显提高特定烯烃的收率显然只有通过产品回收才能实现。在含烃原料热裂解过程中,除乙烯和丙烯外,也产生不能回收的烯烃,如乙烯,因为它们在蒸汽裂解炉的裂解管内被迅速碳化。这就意味着烃类的损失。
开头所描述的这类反应也进一步应用在“流化催化裂化”(以下简称“FCC”)法废气处理上。FCC废气要采用耗时费工的方法通过烃基化或液相聚合才能转化成发动机燃料组分。将这种组分加入到无铅汽油中作为混合组分具有重要意义。众知,这种聚合就是作为齐聚来进行的。为此要将液化的FCC废气在分馏塔内加压脱除轻组分,並且要在一个反应室内用催化剂(主要为硫酸、磷酸或氢氟酸)使之发生转化。该反应产物还要在另一个分馏塔内分成聚合物或烷基化物作为塔底物,並且分为轻组分作为塔顶物。塔釜产物按沸点范围得到分馏,而废气返回流程。
迄今已知方法的缺点是,采用耗时费工方法所用的酸必须排除,並且明显引起局部环境污染及腐蚀问题。在采用溶解的催化剂(均相催化剂)时还必须将溶解的催化剂从产品中再次分离出来。
本发明所要完成的任务在于提供一种方法,该法与伴生组的种类无关,可完成所要达到的烯烃齐聚反应。
根据本发明该任务是这样完成的,即采用一种固体催化剂进行气相齐聚反应,该催化剂含有周期表第Ⅲ、Ⅳ及/或Ⅴ主族元素的超酸性含氟化物。
有利的是采用Al2O3载体和0.1至30重量%,最好为5至15重量%超酸性含氟化合物组成的催化剂。
作为超酸性含氟化合物可采用含有周期表第Ⅲ、Ⅳ及/或Ⅴ主族元素的各种酸。作为这类超强酸的代表性例子为HBF4,H2SiF6以及HPF6。使用这类超强酸的盐也能获得相同的良好的结果,例如使用NH4BF4或(NH4)2SiF6。在本发明范围内,除具体提到的酸外,也能成功地使用其它酸。
根据本发明齐聚反应所用的催化剂采用已知方式即能制得,即用超强酸或其盐的溶液浸渍载体,並随后锻烧而成,在该过程中超酸性组分与载体产生化学键合。
由于超强酸的载体固定化而使反应介质无腐蚀性,随着温和反应条件而来的益处是降低了设备投资。
这里所谓超强酸可理解为这样的酸,即把100%硫酸作为强酸,而超强酸PH值一般约为-0.5。
对周期表第Ⅲ、Ⅳ及/或Ⅴ主族元素的超酸性氟化物的选择至关重要,因为采用这类超酸性催化剂在烯烃齐聚反应中可在高选择性及温和反应条件下获得优异的收率。
本发明思想的进一步构成是,齐聚反应在压力为1和80巴,最好为5和50巴之间,温度为100和400℃,最好为100和300℃之间以及空速(“重量时空速度”,以下简称“WHSV”)为0.1和5克/克·小时之间进行。
根据本发明方法可完成预期的烯烃齐聚反应,特别是丁烯,并且对例如含烃原料热裂解法制得的烯烃具有突出的优点,在该过程中为了提高烯烃收率可回收部分产品用于裂解,並且还可通过FCC废气的齐聚反应用于制取发动机燃料组分。
研究蒸汽裂解法制取乙烯和丙烯表明,通过齐聚或聚合,特别是二聚、三聚及四聚,可将裂解过程中生成的烯烃转化为可回收的产品,而不需要送入蒸汽裂解装置。总之,通过丁烯的齐聚和回收可以提高烯烃收率,即是说,将乙烯和丙烯的收率提高约2重量%。
在石脑油或柴油裂解过程中,一般的裂解条件产生约5-6重量%丁烯。根据本发明采用超酸性催化剂可将丁烯二聚、收率约为90%平均乙烯收率25%为这样制得的二聚物/三聚物汽油。这意味着乙烯总收率提高5×0.9×0.25=1.225重量%至6×0.9×0.25=1.35重量%,对丙烯来说当丙烯/乙烯比例为0.6时提高0.8重量%。
采用本发明催化剂除用于丁烯齐聚外,也可用于正烯烃异构为异烯烃。该异构化导致生成高抗震性多支化的产物。
根据适当的实例方式,在齐聚反应前先用已知方法从含丁烯的料流中萃取出丁二烯。
采用本发明方法,不需改变或改造裂解炉即可提高蒸汽裂解法制乙烯和丙烯的收率。
此外,C4-乙烯-二聚物或三聚物相互均可作为高辛烷值发动机燃料组分。
如前所述,借助本发明方法也能使含于FCC废气中的烯烃发生齐聚反应。采用该法能将FCC废气加工成高辛烷值混合组分。
C4-FCC废气绝大部分(约70%)由烯烃(10至15重量%为异丁烯、余者为1-丁烯、顺式及反式2-丁烯)及正、异丁烷所组成。
采用本发明方法可将丁烯齐聚,在该过程中将正丁烯同时异构为达到高辛烷值的异丁烯。
经过马达试验表明,MOZ(马达法辛烷值)达到85、ROZ(研究法辛烷值)达到100。这种齐聚物汽油与无铅标准汽油混合时,其混合辛烷值为MOZ达到89、ROZ达到108。
下面给出的两个实施例对本发明进一步说明。
实施例1:
将蒸汽裂解炉(原料为1号抽余油)生产的不含丁二烯的C4馏分在300℃及5巴压力下以WHSV为0.66克/克·小时通到150毫升超酸性催化剂上,该催化剂由例如Al2O3载体和10重量%HBF4组成。在催化剂作用下由于形成温和的反应条件而发生丁烯齐聚反应。将产品在冷阱中冷凝,並进行分析。
根据冷凝物及冷凝器废气分析表明,转化率达到90.5%(以丁烯计)。分别计算,齐聚产物由71.0重量%的二聚物和28.5重量%的三聚物所组成。此外,还可测出痕量的四聚物。
产物可回收用于热裂解,从而提高乙烯和丙烯收率。
实施例2:
将工业上FCC-C4馏分(16重量%1-丁烯,18重量%异丁烯、33重量%顺式/反式2-丁烯,33重量%异/正丁烷)在10巴、250℃及WHSV为0.66克/克·小时下进行转化反应。产物被卸压,在分离器内分成气体和液态产品。根据分析及气相和液相料流重量表明,转化率达到64重量%(以原料中所含烯烃计)。
90-200℃产品馏分(二聚物和三聚物)经马达试验表明,与无铅标准汽油的混合辛烷值为ROZ104,MOZ86,6。
Claims (7)
1、烯烃齐聚的方法,其特征是采用一种固体催化剂进行气相齐聚反应。该催化剂含有周期表第Ⅲ、Ⅳ及/或Ⅴ主族元素的超酸性氟化物。
2、根据权利要求1的方法,其特征是所用催化剂由AI2O3载体和0.1至30重量%,最好是5至15重量%超酸性氟化物所组成。
3、根据权利要求1或2的方法,其特征是所用超酸性氟化物为HBF4,NH4BF4,H2SiF5,(NH4)2SiF6或HPF6。
4、根据权利要求1至3中一项或几项的方法,其特征是齐聚反应在压力1和80巴,最好5和50巴之间,温度100和400℃,最好100至300℃之间,以及空速(WHSV)0.1至5克/克·小时之间进行。
5、根据权利要求1至4中一项或几项的方法,在含烃原料热裂解制取烯烃过程中,为了提高烯烃收率要将部分产品回收用于裂解,其特征是在裂解过程中产生的丁烯可采用含有超酸性氟化物的催化剂进行气相齐聚反应,並被回收用于裂解。
6、根据权利要求5的方法,其特征是在齐聚反应之前先萃取丁二烯。
7、根据权利要求1至4中一项或几项的方法,通过FCC废气齐聚反应制取发动机燃料组分,其特征是采用含有超酸性氟化物的催化剂进行气相齐聚反应。
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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DE03625571.8 | 1986-07-29 | ||
DE19863625572 DE3625572A1 (de) | 1986-07-29 | 1986-07-29 | Verfahren zur gewinnung von olefinen |
DEP3625572.6 | 1986-07-29 | ||
DE3625571A DE3625571A1 (de) | 1986-07-29 | 1986-07-29 | Verfahren zur gewinnung von kraftstoffkomponenten |
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CN87105326A true CN87105326A (zh) | 1988-04-06 |
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CN198787105326A Pending CN87105326A (zh) | 1986-07-29 | 1987-07-23 | 烯烃齐聚方法 |
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US (1) | US4837372A (zh) |
EP (1) | EP0254956A3 (zh) |
CN (1) | CN87105326A (zh) |
CA (1) | CA1286322C (zh) |
NO (1) | NO873160L (zh) |
Cited By (1)
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CN107001186A (zh) * | 2014-11-14 | 2017-08-01 | 巴斯夫欧洲公司 | 通过正丁烯脱氢制备1,3‑丁二烯且提供含有丁烷和2‑丁烯的料流的方法 |
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US5097087A (en) * | 1990-10-15 | 1992-03-17 | Texaco Chemical Company | Dimerization of long-chain olefins using a fluorocarbonsulfonic acid polymer on an inert support |
US5276239A (en) * | 1992-07-27 | 1994-01-04 | Texaco Chemical Company | Dimerization of long-chain olefins using a silica gel alkylsulfonic acid |
US20060047176A1 (en) * | 2004-08-25 | 2006-03-02 | Gartside Robert J | Butane removal in C4 upgrading processes |
US8471084B2 (en) | 2010-03-31 | 2013-06-25 | Uop Llc | Process for increasing weight of olefins |
US8128879B2 (en) | 2010-03-31 | 2012-03-06 | Uop Llc | Apparatus for increasing weight of olefins |
US9522373B2 (en) | 2012-11-12 | 2016-12-20 | Uop Llc | Apparatus for oligomerizing light olefins |
WO2014074833A1 (en) | 2012-11-12 | 2014-05-15 | Uop Llc | Process for making gasoline by oligomerization |
US9441173B2 (en) | 2012-11-12 | 2016-09-13 | Uop Llc | Process for making diesel by oligomerization |
US9914673B2 (en) | 2012-11-12 | 2018-03-13 | Uop Llc | Process for oligomerizing light olefins |
US9834492B2 (en) | 2012-11-12 | 2017-12-05 | Uop Llc | Process for fluid catalytic cracking oligomerate |
US9522375B2 (en) | 2012-11-12 | 2016-12-20 | Uop Llc | Apparatus for fluid catalytic cracking oligomerate |
US10508064B2 (en) | 2012-11-12 | 2019-12-17 | Uop Llc | Process for oligomerizing gasoline without further upgrading |
US9663415B2 (en) | 2012-11-12 | 2017-05-30 | Uop Llc | Process for making diesel by oligomerization of gasoline |
US9434891B2 (en) | 2012-11-12 | 2016-09-06 | Uop Llc | Apparatus for recovering oligomerate |
US9567267B2 (en) | 2012-11-12 | 2017-02-14 | Uop Llc | Process for oligomerizing light olefins including pentenes |
US9644159B2 (en) | 2012-11-12 | 2017-05-09 | Uop Llc | Composition of oligomerate |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2734047A (en) * | 1956-02-07 | Olefin polymerization with sbss catalyst | ||
US3678120A (en) * | 1970-01-29 | 1972-07-18 | Universal Oil Prod Co | Hydrocarbon conversion catalyst and process |
US3925194A (en) * | 1973-11-21 | 1975-12-09 | Mobil Oil Corp | Hydrocarbon conversion with catalyst of sbf' 5 'on silica |
US3925251A (en) * | 1973-11-21 | 1975-12-09 | Mobil Oil Corp | Antimony pentafluoride hydrocarbon conversion catalyst |
IT1136674B (it) * | 1981-06-18 | 1986-09-03 | Anic Spa | Sistemi catalitici cationici eterogeneizzati adatti alla oligomerizzazione di olefine lineari interne e procedimento per la preparazione di detti oligomeri impiegante gli stessi |
US4465893A (en) * | 1982-08-25 | 1984-08-14 | Olah George A | Oxidative condensation of natural gas or methane into gasoline range hydrocarbons |
GB8432042D0 (en) * | 1984-12-19 | 1985-01-30 | Shell Int Research | Preparation of dimerization products |
-
1987
- 1987-07-15 EP EP87110203A patent/EP0254956A3/de not_active Withdrawn
- 1987-07-23 CN CN198787105326A patent/CN87105326A/zh active Pending
- 1987-07-28 NO NO873160A patent/NO873160L/no unknown
- 1987-07-28 US US07/078,508 patent/US4837372A/en not_active Expired - Fee Related
- 1987-07-29 CA CA000543270A patent/CA1286322C/en not_active Expired - Fee Related
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107001186A (zh) * | 2014-11-14 | 2017-08-01 | 巴斯夫欧洲公司 | 通过正丁烯脱氢制备1,3‑丁二烯且提供含有丁烷和2‑丁烯的料流的方法 |
Also Published As
Publication number | Publication date |
---|---|
NO873160D0 (no) | 1987-07-28 |
CA1286322C (en) | 1991-07-16 |
EP0254956A3 (de) | 1988-08-03 |
EP0254956A2 (de) | 1988-02-03 |
NO873160L (no) | 1988-02-01 |
US4837372A (en) | 1989-06-06 |
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