GB2231583A - Process for the production of 1-butene by ethylene dimerization - Google Patents
Process for the production of 1-butene by ethylene dimerization Download PDFInfo
- Publication number
- GB2231583A GB2231583A GB9010592A GB9010592A GB2231583A GB 2231583 A GB2231583 A GB 2231583A GB 9010592 A GB9010592 A GB 9010592A GB 9010592 A GB9010592 A GB 9010592A GB 2231583 A GB2231583 A GB 2231583A
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- United Kingdom
- Prior art keywords
- catalyst
- reactor
- process according
- fluidised bed
- dimerization
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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
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/30—Catalytic processes with hydrides or organic compounds containing metal-to-carbon bond; Metal hydrides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A process for the production of 1-butene from ethylene is carried out in a fluidised bed reactor using a dimerization catalyst which is a titanium alkoxide at a concentration of 140 to 160 ppm, a co-catalyst which is a trialkyl aluminum, the co-catalyst being added into the fluidised bed reactor to give a mol ratio of Al:Ti of 3 to 7, at a reactor temperature of 60 to 80 DEG C and a reactor pressure of 1000 to 5000 kPa. The fluidised bed is comprised of inorganic particles such as ceramic microballs. The process is optimized to give good catalyst selectivity and activity at acceptable conversion rates.
Description
PROCESS FOR THE PRODUCTION OF 1-BUTENE BY ETHYLENE DIMERIZATION
This invention relates to a process for the production of 1-butene by dimeri=in ethylene in a gas phase reactor.
Pioneers of the early olefin polymeri=ation catalysts discovered that one transition metal based system, titanium (IV) alkoxide of the form Ti(OR)4 combined with an alkyl-aluminium. produces butene on contact with ethvlene, rather than the usual high polymers.
Since then, many scientists have studied different catalyst systems and established that 1-butene is always the main reaction product, but small amounts of 2-butenes and higher olefins (C6-C10) can also be formed, depending on the reaction conditions.
Opinions differ concerning the exact nature of the active species, as a variety of species is formed depending on the amount of aluminium alkyl used. According to the latest publications, interaction of excess trialkyl aluminium with titanium alkoxide results in the formation of two complexes with titanium in +3 and -2 oxidation states. These species containing
Ti-C bonds are potentially active ethylene dimerization centres.
It is knows that these centres are unstable and activity of these catalysts in the dimerization process rapidly decreases with time and high temperature. Productivity of the catalyst in the dimeri=ation reaction depends on the At:Ti ratio. See for example J. Pol. Sci. 22, 3027 (1984); J. Expel, Polym. Sci. 29,
M71 (19M4). Adv. Polym. Sci. 15, 91 (1974). J. Pol. Sci. 27, 1069 ( 6! and J. of Cat. 105, 187 (1987).
Other prior art of which the Applicant is aware is divulged in US
Patents 3,879,485, ,969,429, 3,911,042 and 4,101,600.
As 1-butene is not always readily available, there has been a need to develop a process for the production of 1-butene by dimerizing ethylene.
European Patent No. 0215916 to Union Carbide Cerporatio'nn discloses a process for the dimerization of ethylene t 1-butene in the presence of a dimerization catalyst which is a titanium tetraalkoxide and in the presence of a co-catalyst which is a trialkyl aluminium at a reactor temperature of 30 to 115 & and at a rector pressure of up to 7000 kPa. The present invention is an opt imi=at ion of this process.
According to the invention there is provided a process for the production of 1-butene from ethylene in a fluidised bed reactor by dimerizing the ethylene under suitable conditions of temperature and pressure and in the presence of a suitable dimeri;ation catalyst and a suitable co-catalyst wherein: (a) the dimerization catalyst is a titanium alkoxide, preferably
tetraisopropyl titanate or tetraisobutyl titanate: (b) the co-catalyst is a trialkyl aluminium, preferably triethyl
aluminium: (c) the concentration of the dimerization catalyst is 140 to 160
ppm inclusive; (d) the co-catalyst is added into the fluidised bed reactor to alive a mol ratio of Xl:Ti of 3 to 7 inclusive, preferably 4.5 to 5.5 inclusive:: (e) the reactor temperature is from 60 to kOOC inclusive,
preferably approximately OOC: (f) the reactor pressure is from 1000 to 5000 kPa (g) inclusive.
preferably approximately 2500 kPa (g); and (g) the fluidised bed in the reactor is comprised of particles
of a suitable si=e and density of an inorganic material,
which particles are mechanically suitable and chemically
suitable for use in the fluidised bed.
By "mechanically suitable" there is meant that the particles must tlale t suitable shape. the particles must be substantially uniform in size. and the particles must have a low degree of ìriabilit.
By "chemically suitable" there is meant that the particles must be inert, and the particles must be substantially free of substances which can poison the catalyst or co-catalyst.
Preferably, the particles should not absorb 1-butene and other olefins to any great extent.
The particles may be for example ceramic microballs or silica beads.
The dimeri=ation catalyst and/or the co-catalvst may be used supported on a solid inorganic support.
The process of the invention is a process for the production of 1-butene in a fluidized bed reactor by selectively dimerizing ethylene to 1-butene.
The process of the invention, using a continuous fluidized bed reactor, will now be described in general terms. Ethvlene is compressed and fed into the reactor continuously. The dimerization catalyst. when it is a liquid, is fed into the fluidized bed above the distribution plate, through an injection tube. The dimeriation catalyst, when it is in powder form, i.e.
the catalyst is supported on a solid inorganic support, is fed into the fluidized bed. The co-catalvst is fed into the reactor through an injection tube situated above the distribution plate.
The gas phase composition in the fluidized bed reactor is monitored by an in-line gas chromatograph every 10 to 15 minutes.
The most important process variable. the molar ratio of e:Ti is adjusted according to dimerization selectivity for 1-butene.
The temperature and pressure in the reactor are automatically controlled at process conditions. The heat of reaction is removed outside the reactor by cooling the cycle gas stream for recycling it into the ethylene feed.
The process is carried out in a fluidized bed reactor where the fluidized bed is comprised of particles of a suitable size and density of an inorganic material, which particles are mechanically suitable and chemically suitable for use in the fluidized bed.
As stated above, by "mechanically suitable" there is meant that the particles must have a suitable shape, preferably substantially spherical, the particles must be substantially uniform in size, and the particles must have a low degree of friability so that they do not erode in the harsh conditions of the fluidized bed.
Further, as stated above, by "chemically suitable" there is meant that the particles must be inert i.e. they must not interfere with the reactions which proceed in the fluidized bed and must not be corroded by the conditions in the fluidized bed. and the particles must be substantially free of substances such as heavy metals or transition metals which can poison the catalyst or co-catalyst. Preferably, the particles must also not absorb l-butene or any olefin to any great extent.
The particles for use in the fluidized bed may be for example ceramic microballs or silica beads.
The particles must be of a suitable size and density for use in the fluidized bed.
Thus, the particles preferably have a size of 800 to 1200 microns inclusive, and a bulk density of from 400 to 500 kg/cm3 inclusive.
As stated above. the particles may be or example ceramic
microballs. In this case, the ceramic microballs may have the
following characteristics:
True particle density g/cm3 0,60-0,80
Bulk density g/cm3 0,40-0,50
Packing factor o/o
Strength at 1500 psi (10,3 mpa), 7e survivors by volume 90
Softening temperature oC 1200.
The use of particles for the fluidized bed as described above have certain advantages over the use of granular polyethylene.
Firstly, the particles generally have a lower degree of absorption of 1-butene and other olefins which improves the efficiency of the process. Secondly, the particles may have a longer life expectancy.
When using a fluidized bed comprised of particles as described above, the dimerization catalyst and the co-catalyst may either be used in the form of a liquid, e.g. the dimerization catalyst which is preferably tetra-isopropyl-titanate, may be introduced into the fluidized bed reactor as a 20% solution in isopentane and the co-catalyst which is trialkyl aluminium, may be introduced into the fluidized bed reactor as a 20d solution in isopentane, or the catalyst and co-catalyst may be used supported on a solid inorganic support as described in more detail below.
The dimerization catalyst and the co-catalyst may be utilized in a form where the catalyst, or the co-catalyst or both the catalyst and co-catalyst are supported on a solid inorganic support. In other words, the catalyst and/or co-catalyst are introduced in a powder form into the fluidized bed.
Preferably, both the catalyst and the co-catalyst, i.e. the titanium alkoxide and the trialkyl aluminium are both supported on the same solid inorganic support. The solid inorganic support must have a suitable particle size distribution and surface area.
The solid inorganic support preferably has a particle size
distribution as follows:
Maximum percentage by weight of particles retained on a 60
mesh screen: 0.05 Maximum percentage by weight of particles retained on a 100
mesh screen: 25% axium percentage of particles passing through a 325 mesh
screen: 5%
and a surface area, after 3 hours at 6000C, of 280 to 360 area,
m/g inclusive.
The loading of the catalyst, i.e. the titanium alkoxide on to the inorganic support is preferably 3,5-5%, more preferably 4,5% m/m
Ti to dry inorganic support. The molar ratio A:Ti is preferably 3-7 depending on the quality of the ethylene feed stream, more preferably 5 t 0,5, i.e. 4,5 to 5,5.
A suitable solid inorganic support may be for example Davison
Silica 959.
The supported catalyst or co-catalyst may be prepared as follows.
The dry inorganic support is immersed in a solution containing the catalyst in a solvent such as isopentane, at a concentration that will allow a loading of 3,5-5 Ti m/m to dry inorganic support. The slurry is mixed for a short time, preferably 30 minutes. to ensure uniform distribution of the solution in the dry inorganic support. The impregnated support is then dried.
usually in the same vessel with continuous mixing at temperatures between 500C and 900C preferably 850C. The dry supported catalyst is then treated with a solution of the co-catalyst in a suitable solvent such as isopentane, to ensure a molar ratio of t:Ti of 3-7. The supported catalyst is then dried at temperatures between 50CC and 80 C, preferably 700C.
The use of a supported catalyst and/or co-catalyst has several advantages over the use of the catalyst and/or co-catalyst in liquid form. Firstly. by using a solid catalyst/co-catalyst, there is no saturation of the fluidized bed with a liquid which means that it is easier to tailor the amount of residual catalyst left behind in the fluidized bed. Secondly, surface area contact between the catalyst 'co-catalyst and the gas phase is improved.
Thirdly it is easier to maintain a constant ratio of At:Ti.
Fourthly, the catalyst is better protected against poisoning.
Finally. the supported catalyst is more stable and thus can be kept for longer periods.
The use of a supported catalyst/co-catalyst may have certain disadvantages. The catalyst/co-catalyst may be entrained in the gas phase and carried over into the cooling system. However, this problem can be prevented by the introduction of a filter upstream of the cooler with a blowback system.
To achieve high catalyst activity and selectivity at acceptable conversion rates, the process variables, e.g. the reactor temperature. the reactor pressure and the concentration of dimerization catalyst were experimented with to optimize the process. The process variables were changed one at a time
Each time once the reaction in the fluidised bed had stabilised.
the regime was maintained for a suitable period of up to 50 hours and as samples were taken every 2 to 3 hours and analysed.
Further the process as a whole was monitored. From this information the process selectivity and catalyst activity was calculated.
Thus according to the invention the process is carried out under the following reaction conditions:
Reactor temperature OC 60-80, preferably 70
Reactor pressure kPa(g) 1000-5000, preferably 2500
Concentration of dimerization
catalyst ppm 150 T 10 A:Ti mol ratio 3-7, preferably 5 - 0,5
Mass balance calculations during the process show a selectivity of dimeri=ation to 1-butene of 95-98 A typical gas composition is as follows: 1-butene 96,3% trans-2-butene 0,5 cis-2-butene 0,2 hexene 0,64% ethylene 2,3% isopentane 0,05%
The catalyst yield is 10 000 to 14 000 gr butenejgr Ti.
It can be seen that the process of the invention provides a high yield of 1-butene which may then be used, for example. for the production of linear low density polyethylene.
Claims (1)
1.
A process for the production of 1-butene from ethylene in a fluidized bed reactor by dimerizing the ethylene under suitable conditions of temperature and pressure and in the presence of a suitable dimerization catalyst and a suitable co-catalyst wherein: (a) the dimerization catalyst is a titanium alkoxide; (b) the co-catalyst is a trialkyl aluminium; (c) the concentration of the dimerization catalyst is 140 to 160 ppm inclusive; (d) the co-catalyst is added into the fluidised bed reactor to
ive a mol ratio of Al:Ti of 3 to 7 inclusive; (e) the reactor temperature is from 60 to OOC inclusive: (f) the reactor pressure is from 1000 to 5000 kPa (g) inclusive:
and the fluidised bed in the reactor is comprised of particles
of a suitable size and density of an inorganic material.
which particles are mechanically suitable and chemically
suitable for use in the fluidised bed.
2.
A process according to claim 1 wherein the dimerization catalyst is tetraisocropyl titanate.
3.
Focess according to claim 1 wherein the dimerization catalyst is tetraisoutyl titanate.
4.
A process according to any one of claims 1 to 3 wherein the dimerization catalyst is used supported on a solid inorganic support.
5.
A process according to any one of claims 1 to 4 wherein the co-catalyst is triethyl aluminium.
6.
A process according to any one of claims 1 to 5 wherein the co-catalyst is used supported on a solid inorganic support.
I.
A process according to any one of claims 1 to 6 wherein the co-catalyst is added into the fluidised bed reactor to give a mol ratio of Al:Ti of A,4 to 5,5 inclusive.
A process according to any one of claims 1 to 7 wherein the reactor temperature is approximately 700C.
O.
A process according to any one of claims 1 to 5 wherein the reactor pressure is approximately 2500 kPa (g).
10.
A process according to any one of claims 1 to 9 wherein the fluidised bed is comprised of ceramic microballs.
11.
A process according to any one of claims 1 to 9 wherein the fluidised bed is comprised of silica beads.
12.
A process according to claim 1 substantially as herein described.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB898910935A GB8910935D0 (en) | 1989-05-12 | 1989-05-12 | Process for the production of 1-butene by ethylene dimerisation |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB9010592D0 GB9010592D0 (en) | 1990-07-04 |
| GB2231583A true GB2231583A (en) | 1990-11-21 |
| GB2231583B GB2231583B (en) | 1992-12-23 |
Family
ID=10656634
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB898910935A Pending GB8910935D0 (en) | 1989-05-12 | 1989-05-12 | Process for the production of 1-butene by ethylene dimerisation |
| GB9010592A Expired - Lifetime GB2231583B (en) | 1989-05-12 | 1990-05-11 | Process for the production of 1-butene by ethylene dimerization |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB898910935A Pending GB8910935D0 (en) | 1989-05-12 | 1989-05-12 | Process for the production of 1-butene by ethylene dimerisation |
Country Status (2)
| Country | Link |
|---|---|
| GB (2) | GB8910935D0 (en) |
| ZA (1) | ZA903617B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160002124A1 (en) * | 2014-07-04 | 2016-01-07 | IFP Energies Nouvelles | Catalytic composition and process for the selective dimerization of ethylene to 1-butene |
| KR20190127811A (en) * | 2017-03-14 | 2019-11-13 | 사우디 아라비안 오일 컴퍼니 | Ethylene Oligomerization Process to Prepare Alpha-olefins |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1986005500A1 (en) * | 1985-03-22 | 1986-09-25 | Union Carbide Corporation | Process for simultaneously dimerizing ethylene and copolymerizing ethylene with the dimerized product |
-
1989
- 1989-05-12 GB GB898910935A patent/GB8910935D0/en active Pending
-
1990
- 1990-05-11 GB GB9010592A patent/GB2231583B/en not_active Expired - Lifetime
- 1990-05-11 ZA ZA903617A patent/ZA903617B/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1986005500A1 (en) * | 1985-03-22 | 1986-09-25 | Union Carbide Corporation | Process for simultaneously dimerizing ethylene and copolymerizing ethylene with the dimerized product |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160002124A1 (en) * | 2014-07-04 | 2016-01-07 | IFP Energies Nouvelles | Catalytic composition and process for the selective dimerization of ethylene to 1-butene |
| US9931622B2 (en) * | 2014-07-04 | 2018-04-03 | IFP Energies Nouvelles | Catalytic composition and process for the selective dimerization of ethylene to 1-butene |
| KR20190127811A (en) * | 2017-03-14 | 2019-11-13 | 사우디 아라비안 오일 컴퍼니 | Ethylene Oligomerization Process to Prepare Alpha-olefins |
| JP2020514353A (en) * | 2017-03-14 | 2020-05-21 | サウジ アラビアン オイル カンパニー | Process for ethylene oligomerization to produce alpha olefins |
| KR102266927B1 (en) | 2017-03-14 | 2021-06-21 | 사우디 아라비안 오일 컴퍼니 | Ethylene Oligomerization Process for Making Alpha-Olefins |
Also Published As
| Publication number | Publication date |
|---|---|
| GB9010592D0 (en) | 1990-07-04 |
| ZA903617B (en) | 1991-02-27 |
| GB2231583B (en) | 1992-12-23 |
| GB8910935D0 (en) | 1989-06-28 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19940511 |