GB2205853A - A process for the production of octenes - Google Patents
A process for the production of octenes Download PDFInfo
- Publication number
- GB2205853A GB2205853A GB08714023A GB8714023A GB2205853A GB 2205853 A GB2205853 A GB 2205853A GB 08714023 A GB08714023 A GB 08714023A GB 8714023 A GB8714023 A GB 8714023A GB 2205853 A GB2205853 A GB 2205853A
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- Prior art keywords
- process according
- butene
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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
- C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/22—Organic complexes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
N-butenes (especially butene-1) can be dimerised by contacting them with a catalyst comprising a mixture of a fluorine-containing nickel chelate, especially bis (1, 1 min , 1 sec , 5 min , 5 sec , 5 min sec hexa-fluoro-2,4-pentane dionato) nickel, and a partially hydrolysed aluminium hydrocaryl compound, especially tetra isobutyl alumoxane.
Description
A PROCESS FOR THE PRODUCTION OF OCTENES
This invention concerns a method for oligomerising a n-butene
The homogeneous dimerisation of light olefins such as ethylene, propylene and to a lesser extent n-butenes is known. (W. Keim, A. Behr, M. Rbper, Comprehensive
Organometallic Chem. 8,371) The homogeneous reaction is catalysed by a transition metal, usually a nickel derivative activated by a Lewis acid. In most cases the products of such reactions are an isomer mixture in which branched isomers prevail.
We have now discovered a method of oligomensation involving a homogeneous catalyst-system to obtain octenes from a n-butene in good yield in which the product contains a high proportion of linear and mono-branched isomers.
According to this invention a process for oligomerising an n-butene is one wherein the reaction mixture comprises a homogeneous liquid mixture of a fluorine-containing nickel chelate, a partially hydrolysed aluminium alkyl compound and a n-butene. In practice an n-butene is oligomerised using a homogeneous catalyst formed in situ when the n-butene is introduced into the mixture of a fluorine-containing nickel chelate and a partially hydrolysed aluminium hydrocarbyl compound. This method is particularly suitable for producing octenes with high quantities of methyl-heptenes and n-octenes wherein the n-butene is dimerised.
One of the compounds of the catalyst system is a fluorine-containing nickel chelate. A chelate compound is usually a combination of a metal with two or more electron-donating groups which are capable of forming a ring structure. Suitable fluorine-containing nickel chelates are nickel chelates derived from fluorine-containing organic compounds. Suitable fluorie-containing compounds include dicarbonyl compounds of the formula
where R and R' are hydrogen, alkyl, preferably C1 to
C12 alkyl, aryl, preferably phenyl, alkaryl, preferably
C7 to C20 alkaryl, aralkyl, preferably C7 to C20 aralkyl, or halogenated alkyl, aryl, alkaryl or aralkyl, provided that at least one of the groups R and
R' is a fluorinated group. Preferably R and R' are fluorinated alkyl groups.Examples of di-carbonyl-containing nickel chelates are nickel keto aldehyde and preferably nickel diketone. Examples of nickel carbonyl chelates are given by the formula
where R and R' are as given above.
Particularly suitable fluorine-containing nickel chelates are bis (1,1' ,1" trifluoro 2,4-pentanedionato) nickel, bis(1,1',1" tri fluoro 2,4-hexane dionato) nickel, bis(1,1',1",8,8',8" hexafluoro 2,4-octane dionato) nickel, and especially bis(1,1',1",5,5',5" hexafluoro-2,4-pentane dionato) nickel. Generally it is preferred that the hydrocarbyl groups are completely fluorinated.
Other suitable fluorine-containing compounds include hydroxy carbonyl compounds of the formula
carbonyl amine compounds of the formula
glyoxine compounds of the formula
organic disulphide compounds of the formula
hydroxyl amine compounds of the general formula R-S-CH2-CH2-S-R' where R and R' are as defined above in connection with the dicarbonyl compounds.
Suitable aluminium hydrocarbyl compounds which are partially hydrolysed include hydrocarbyl substituted alumoxanes. Such alumoxanes have the generic formula
where R1,R2,R3 and p4 are similar or dissimilar hydrocarbyl groups. Although they may be aryl, alkaryl (e.g. C1 to C20 alkaryl) or aralkyl (e.g. C1 to C20 aralkyl) groups, preferably they are alkyl groups, for example methyl, ethyl, butyl, hexyl or octyl groups.
The particularly preferred alkyl groups are branched alkyl groups, for example isobutyl or isopentyl groups.
In general R1 ,R2,R3 and R4 will be identical, for example isobutyl groups viz
tetraisobutyl aluminium
oxane
Of the n-butenes, butene-l is preferred but one can use cis-2-butene or trans-2-butene if desired.
The ratio of fluorine-containing nickel chelate to partially hydrolysed aluminium hydrocarbyl compound can vary but in general the ratio is such that the mole ratio of aluminium to nickel varies between 1:1 and 10:1, preferably between 1:1 and 2:1.
In the process of the invention it is usual for the fluorine-containing nickel chelate to be introduced into the reactor under an inert atmosphere. The n-butene is then introduced into the reactor followed by the hydrolysed aluminium hydrocarbyl compound, usually dissolved in an inert solvent, for example hexane or heptane.
The temperature at which the oligomerisation occurs can vary, but usually the temperature is between 200C and 140"C, preferably between 300C and 800C. The pressure employed in performing the method of the invention should be sufficient to maintain the butene in the liquid phase at the operating temperature and preferably 2 to 30 bars absolute.
The process is usually operated so that the ratio of the moles of n-butene to moles of nickel in the catalyst is at least 100:1, preferably between 300:1 and 2000:1.
The time of reaction is usually between 1 and 10 hours, preferably between 4 and 6 hours.
The reaction can be terminated by the addition of an aqueous acid, e.g. aqueous sulphuric acid solution.
It is found that by using the process of this invention the dimer product, namely octene is mainly composed of methyl-substituted heptenes and n-octenes. This compares with other known processes where up to 32% dimethyl hexenes are produced, only 108 n-octene and 588 methyl heptene.
Example
Into a well dried and argon flushed autoclave containing bis (1,1' ,1",5,5' ,S hexafluoro 2,4 pentadionato) nickel, 200 g. of a n-butene was charged at 100C. Subsequently a solution of tetra isobutyl aluminium oxane in heptane was introduced and the reaction was allowed to proceed for 5 hours. The reaction was terminated by the addition of 10 cc of aqueous sulphuric acid solution and the reaction mixture was analysed by gas chromatography after hydrogenation.
The following table shows the olefin dimerised, the' mole radio of olefin to nickel, the mole ratio of aluminium to nickel and the temperature of reaction.
The table also gives the weight per cent conversion, the selectivity (weight per cent of octenes and dodecenes) and the amounts of the octene isomers. Selectivity, WT% C8 = Isomers, WT%
Mole Olef./ Mole Al T Conversion
Run Olefin Mole Ni Mole Ni C WT% C8= C12= 3-br 2-br 1-br Linear 1 C4=-1 415 1.5 40 67 78 22 0.3 4.0 67.5 30 2 C4=-2tr 415 1.5 40 47 87 13 0.3 1.5 74.7 23.5 3 C4=-1 12,470 25 40 0 4 " 1,870 5 40 12 90 0 0.0 4.5 48.6 46.9 5 " 1,880 5 70 30 88 10 0.3 10.9 54.2 34.6 6 " 1,809 5 120 21 90 10 0.0 5.6 47.3 47.1 7 " 406 1.5 70 65 76 19 1.5 3.7 58.1 36.7 8 " 404 5 70 19 74.5 17.4 0.0 10.3 48.4 41.3 9 " 1,836 1.5 70 43 71 22 0.0 2.7 39.7 57.6 10 C4=-2tr 1,862 1.5 70 13 84.0 11.5 0.0 1.5 81.1 17.4 11 C4=-1 415 1.5 120 62.5 78 21 0.6 4.3 56.4 38.7 12 " 1,791 10 70 2.5 73 20 6.8 3.2 37.8 52.2
Notes C4=-1, butene-1
C4=-2tr, trans butene-2 C4=-2 cis, cis butene-2
C8=, octene, C12=, dodecene 1-br, 2-br, 3-br, one branch, two branches and three branches It can be seen from the Table that high ratios of aluminium to nickel produce very low conversions and that best results are achieved with mole ratios of 1.5:1. It is also seen that with this preferred mole ratio of 1.5 there is little difference in varying the temperature from 40C to 700C.
Claims (13)
1. A process for oligomerising an n-butene wherein the reaction mixture comprises a homogeneous liquid mixture of a fluorine-containing nickel chelate, a partially hydrolysed aluminium alkyl compound and an n-butene.
2. A process for oligomerising an n-butene which comprises oligomerising n-butene using a homogeneous catalyst formed in situ from a fluorine containing nickel chelate and a partially hydrolysed aluminium alkyl compound.
3. A process according to either of claims 1 and 2 wherein the nickel chelate is a dicarbonyl compound of the formula
where R and R are hydrogen, alkyl, aryl, alkaryl, aralkyl or halogenated alkyl, aryl, alkaryl or aralkyl, provided that at least one of the groups R and R' is a fluorinated group.
4. A process according to claim 3 wherein R and
R' are fluorinated alkyl groups.
5. A process according to claim 4 wherein the fluorine-containing nickel chelate is bis(1,1',1",5',5",5"' hexa fluoro-2,4-pentane dionato) nickel.
6. A process according to any one of the preceding claims wherein the partially hydrolysed aluminium hydrocarbyl compound is a hydrocarbyl substituted alumoxane of the formula
where R, R, R and R4 are similar or dissimilar hydrocarbyl groups.
7. A process according to claim 6 wherein
R, R, R and R4 are C1 to C10 alkyl groups.
8. A process according to claim 6 wherein R ,R2 ,R3 and R4 are all t-butyl groups.
9. A process according to any one of the preceding claims wherein the n-butene is butene-1.
10. A process according to any one of the preceding claims wherein the mole ratio of aluminium to nickel is between 1:1 and 10:1.
11. A process according to any one of the preceding claims wherein the temperature of oligomerisation is between 300C and 80"C.
12. A process according to any one of the preceding claims wherein the pressure under which the reaction occurs is between 2 and 30 bars.
13. A process according to any one of the preceding claims, wherein the mole ratio of n-butene to nickel in the catalyst is between 300:1 and 2000:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08714023A GB2205853A (en) | 1987-06-16 | 1987-06-16 | A process for the production of octenes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08714023A GB2205853A (en) | 1987-06-16 | 1987-06-16 | A process for the production of octenes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB8714023D0 GB8714023D0 (en) | 1987-07-22 |
| GB2205853A true GB2205853A (en) | 1988-12-21 |
Family
ID=10618976
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08714023A Withdrawn GB2205853A (en) | 1987-06-16 | 1987-06-16 | A process for the production of octenes |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2205853A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000073249A1 (en) * | 1999-06-02 | 2000-12-07 | Chevron Phillips Chemical Company Lp | Process for dimerizing olefins |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1124123A (en) * | 1965-02-12 | 1968-08-21 | Sentralinst For Ind Forskning | Production of olefines |
| GB1151550A (en) * | 1965-09-06 | 1969-05-07 | Scholven Chemie Ag | Process for Dimerizing Lower Alpha-Olefins |
| GB1216885A (en) * | 1967-01-11 | 1970-12-23 | Inst Francais Du Petrole | New organometallic complexes |
| GB1282305A (en) * | 1969-05-01 | 1972-07-19 | Exxon Research Engineering Co | Oligomerization and cooligomerization process |
-
1987
- 1987-06-16 GB GB08714023A patent/GB2205853A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1124123A (en) * | 1965-02-12 | 1968-08-21 | Sentralinst For Ind Forskning | Production of olefines |
| GB1151550A (en) * | 1965-09-06 | 1969-05-07 | Scholven Chemie Ag | Process for Dimerizing Lower Alpha-Olefins |
| GB1216885A (en) * | 1967-01-11 | 1970-12-23 | Inst Francais Du Petrole | New organometallic complexes |
| GB1282305A (en) * | 1969-05-01 | 1972-07-19 | Exxon Research Engineering Co | Oligomerization and cooligomerization process |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000073249A1 (en) * | 1999-06-02 | 2000-12-07 | Chevron Phillips Chemical Company Lp | Process for dimerizing olefins |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8714023D0 (en) | 1987-07-22 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |