CA1205792A - Dimerization of propylene and butene - Google Patents
Dimerization of propylene and buteneInfo
- Publication number
- CA1205792A CA1205792A CA000421308A CA421308A CA1205792A CA 1205792 A CA1205792 A CA 1205792A CA 000421308 A CA000421308 A CA 000421308A CA 421308 A CA421308 A CA 421308A CA 1205792 A CA1205792 A CA 1205792A
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- CA
- Canada
- Prior art keywords
- catalyst
- amine
- temperature
- butene
- nickel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- 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
- C07C2/24—Catalytic processes with metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- B01J29/072—Iron group metals or copper
-
- 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
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/755—Nickel
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
Abstract
ABSTRACT OF THE DISCLOSURE
An improved process, and catalyst therefor, for the dimerization of propylene, butene-1 and butene-2, is disclos-ed. The monomer is contacted with the catalyst at 100-260°C
and a pressure of 3-30 MPa and the dimers formed are separat-ed. The catalyst is prepared by depositing nickel on a zeolite, contacting the nickel with an amine and heat-treat-ing the resultant composition at 260-350°C. The amine may be ammonia, alkylamines in which the alkyl group has 1-6 carbon atoms and piperidine. The process may be used in the manu-facture of hexenes and octenes.
An improved process, and catalyst therefor, for the dimerization of propylene, butene-1 and butene-2, is disclos-ed. The monomer is contacted with the catalyst at 100-260°C
and a pressure of 3-30 MPa and the dimers formed are separat-ed. The catalyst is prepared by depositing nickel on a zeolite, contacting the nickel with an amine and heat-treat-ing the resultant composition at 260-350°C. The amine may be ammonia, alkylamines in which the alkyl group has 1-6 carbon atoms and piperidine. The process may be used in the manu-facture of hexenes and octenes.
Description
~2~
IMER~ATION OF PROP~LENE AND BUTENh The present inven-tion rela-tes to an improved pro-cess for the dimerization of propylene, butene-l and butene-2 and in par-ticular to an improved catalyst for such a process.
Linear olefins are widely used in industry, for example as s-tarting materials in the manufacture of a wide variety of materlals including chemlcals, e.g. plasticizers and biodegradable detergents, chemical intermedlates and polymers. Polymers are normally formed Erom linear olefins having terminal unsaturation viz linear alpha-olefins. Such olefins may ~e used as a comonomer in the manufacture of polyethylene, especially linear low density polyethylene which is a copolymer of ethylene and higher alpha-olefin(s) e.g. butene-l, hexene-l and octene-l. The polyethylene business is very competitive and it is therefore important tha-t the methods used to obtain any comonomers be e~ficient and economic.
A number oE processes are known for the production of oleins by -the dimerization of lower alpha-ole-fins. In such processes, an olefin or mixture of olefins is brought into contact, in a reac-tion zone, wl-th a catalyst that is a metal, a metal oxide or a so-called Zieg]er coordination catalyst. Dimerization processes are operated at elevated temperatures and pressures.
One process for -the dimerlzation of alpha-olefins, using a supported metal catalyst, is that disclosed in Canadian Patent 1 008 ~73 of L. Forni and R. Invernizzi, which issued 1977-04-12. The catalyst is prepared by depositing nickel on a natural or synthetic crystalline zeolite, con-tacting -the deposited nickel with an organic or inorganic base at a temperature of 25~C for at least 3 hours, eliminating excess base and heat-treating the resultant produc-t at 250C.
An improved process for -the dirner.i~ation of propylene, butene-l and butene-2 has now been founcl.
Accordingly the presen~ inven-tion provides a pro-cess or the dimerization oE propylene, butene-l and butene-2 compr.ising contacting a monomer selected from the group con-sistiny oE propylene, butene~l and butene-2, and mixtures of butene-l and butene-2, with a eatalyst at a temperature of lO0-260C and at a pressure of 3-30 MPa, and separating dimers so formecl, said catalyst being selected from the group consisting of:
(a) a catalyst prepared by depositing nickel on a na-tural or synthetic crystalline zeolite, con-tacting the nickel with an amine seleeted from the group consisting of ammonia, alkylamines in which the alkyl group has l-6 carbon atoms and piperidine at a temperature of -20 to 100C, removing excess amine and then heat-treating the resultant composition at a temperature of 260-350C; and (b) a eatalyst prepared by depositing nickel on a natural or synthetic zeoli-te, eontacting the nickel with an amine selected from the group consisting of ammonia, alkylamines in whieh the alkyl group has 1-6 earbon atoms and piperidine at a -temperature of -20 to 300C, and heat-treating the resultant eomposition under vaeuum at a temperature of 260-350C.
The present. invention also provides a eatalyst for an olefin dimeri~ation proeess, said eatalyst being seleeted from the group consisting of:
(a) a catalyst prepared by depositing niekel on a natural or synthetie erystalline ~eol.i-te, eon~
tac-t.ing the ni.ckel with an amine seleetec1 from the group consisting of ammonia, alkylam:ines in whic;h the alkyl group has 1-6 carbon atoms ancl piperidlne at a tempera-ture of -20 to 100C, removing excess amine and then heat-treating the resultant composition at a temperature of 260-350~C; and (b) a catalyst prepared by deposi~ing nickel on a na-tural or synthetic zeolite, contactin~ the nickel ~ith an amine selected from t'ne group consisting of ammonia, alkylamines in ~hich the alXyl group has 1-6 carbon atoms and piperidine at a temperature of -20 to 300C, and heat-treating the resultant composition under vacuum at a temperature of 260-350C.
In a preferrad embodiment of the process and catalyst of the present invention, the amine is ammonia or n-butylamine.
The present invention relates -to the dirnerization of propylene, butene-l and butene-2. The principal products of such a dimerization reaction are hexenes and octenes, respectively, of which the linear olefins are of most interest. Linear olefins in the form o-E, or converted to, linear alpha-olefins may be copolymerized with ethylene.
In the dimeri~ation process propylene, butene-1 or butene-2, or mixtures of butene-l and butene-2 is fed to a reactor containing the dimerization catalyst, especially such catalyst in the form of a fixed bed catalyst. The dimeri7a-tion may be carried out at temperatures of from about 100C
to ~60C, preferably 150-200C, and at pressures of rom about 3-30 MPa, preferably 5-15 MPa and in particular 9-15 MPa.
The catalyst for the dimerization proce~s may be prepared by depositing nickel on a natural or synthetic crystalline zeolite. Natural zeoli-tes include those describ-ed in Kirk-Othmer "Encyclopedia o~ Chemical TechnolocJy" 1st Ed. Vol. 1~ p 295 et seq and in the aEoremen~ioned Canadian Patent 1 008 473. 5ynthetic zeolites are commorlly known as molecular sieves. Techniques for depositing nickel on the æeolites are al~o known and include the use of ion-exchange methods. For instance a zeolite of a suitable particle size is brought into contact with an aqueous solu-tion o~ a nickel salt a-t ambien-t temperature (about 20C), for example a solution of nickel chloride, nickel nltrate or the like. The zeolite is then washed with deionized ~ater until free of the anion o~ the nickel salt and dr:ied. The use oE ion exchange techniques is further described in the aforementioned Canadian Paten-t 1 008 473.
The zeolite having nickel deposited thereon (nickel/zeolite) is contacted with an amine selec~ed from the group consisting o~ ammonia, alkylamines and piperidine. The alkylam~nes may have alkyl groups with 1-6 carbon atoms, especially four carbon atoms. The preferred amines are ammonia and n-butylamine. The nickel/zeolite may be contact-ed with the amine over a range of tempera-tures e.g. -20 to 300~C and especially 0 to 50C. The contact may be solid~
liquid contact or solid~gas contact.
If the amine is gaseous or has a high vapour pressure under ambient conditions, or at a elevated temperature, the gaseous amine may be contacted with nickel/zeolite. Preferably the amine is diluted wlth an inert gas, for example, nitrogen.
If the amine is liquid, inert gas may ~e passed through the liquid amine and then brought into contact with the nickel/zeolite. Alternatively, amine, especially a pre-determined or controlled amount of amine, may be brought into contact with nickel/zeolite by diffusion under vacuum.
The amine-treated nickel/zeolite is then treated to remove excess amine. Excess amine is preerably removed at a temperature of less than about 300~C, the particular tempera-ture used depending on the amine and the method used to remove excess amine. The excess amine may be removed by passing an inert gas, especially nitrogen, over the amine--treated nickel/ ~eolite for a period of time. The aminecontent of the gas that has been passed over the zeolite may , , ~
, :~
3%
be monl-tored to determine when excess amine has heen removed.
~hen excess ami~e is removed using inert gas, a preferred temperature is ambient temperatllre (about 20C).
Alternatively a vacuum may be used to remove excess alnine in which event an elevated -temperature is preferred.
After the excess a~line has been removed, the amine--treated nickel/zeoli-te is activated by hea-ting -to a tempera-ture of 2~0-3~C, especially 270-320C, for at least 30 minutes, preferably Eor at least one hour. The activation may be carried out in -the presence o-f an inert ~as~ ~lterna--tively the amine-treated nickel/zeolite may be activated under vacuum. If so, -the removal of amine and activation of the amine-treated nic~el/zeolite may be carried out simultaneously.
The process conditions, including method of catalyst preparation, dimerization temperature and pressure, and reaction time may affect the nature of the products obtained in the process. For example the process conditions may affect -the amount oE a particular, especially desired, reaction product, for example, the amount oE linear hexene and octene. Moreover the process may be operated as a relatively low yield, high selectivity process or aa a higher yield, lower selectivity process, selectivity being the forma-tion of a particular desired dimerization product. The actual process conditions used afect the distribution of the products formed, as will be apparent -from the examples hereinafter.
The dimerization process of the present invention may be used for the manufacture of hexenes and octenes, especially linear he~enes and linear octenes. The latter two oleins may be isomerized to hexene-1 and octene-l, respec-tively, and used as comonomers in the manufacture of polyethylene.
The present invention is iLlustrated by t~le follo~-iny examples in which the catalys-ts were prepared usiny Method A, Method ~ or Method C as ollows.
~ethod A: Nlckel was deposi~ed on a zeoli-te viz. 13X
molecular sieve having a ~0-80 Tyler* rnesh size, obtained from t~e Linde Division of Union Carbide Corporation, from an aqueous solu-tion of nickel nitrate using ion exchange techniques. rl~e pH of the aqueous solution was 5.5. The nic~cel/zeoli~e obtained was washed thoroughly with deionized wa-ter until the washings obtained were ree of nitra-te anion and then ~ried in an oven at 120C for one hourv The catalyst nickel/zeolite precursor thus obtained was treated with amine at ambient temperature by passing a mixture of amine and nitrogen through a bed of the catalyst precursor.
Excess amine was then removed by purging with nitrogen at ambient -temperature or two hours. Subsequently the amine-treated catalyst precursor was heated to the activation temperature and main-tained at that temperature for one hour;
the flow of nitrogen was maintained during such activation.
Method B: The catalyst precursor was prepared by the method descrihed in Method A. After having heen dried at 120C for one hour, as descrihed in ~ethod A, 30 g of the precursor were contac-ted with a mixture of amine(lO ml/minute) and nitrogen(750 ml/minute) at ambient temperature for a ~eriod of three hours. The precursor was then contacted with nitrogen (750 ml/minute) for a further two hours. The amine-treated catalyst precursor was then heated, under vacuum, to the activation temperature and maintained at that temperature for one hour.
Method C: 50 g of the catalyst precursor were prepared by the method descrihed in Method A excep-t tha-t the precursor was dried at 300C for two hours under vacuum. 3.8 g of amine, which had heen degassed, was -then allowed to diffuse to the catalyst precursor, under vacuum and at 300C, over a period of three hours; the catalyst precursor was continuous-ly shaken to facilitate contact of amine and catalyst precursor. ~ny excess amine was removed, and the catalys-t activated, hy continuing to -treat the amine-lrea-ted catalyst *denotes trade mark.
precursor under vacuum at 300C Eor a fu-rther period o~ one hour.
_ample I
A tubular reactor was charged with catalyst and heated in an inert atmosp'nere (nitrogen) to a pre-selected -temperature. Propylene was passed throuc~h the reactor. The products obtained were analyzed by on-line ~as chromatography and by gas chromatography/mass spec-troscopy techniques.
A series of runs were carried out us:ing catalysts prepared at different activation -temperatures. Further experimental details and the results obtained are given in TABLE I.
In the Tables hereinafter, "Conversion" is the amount of oligomerization product expressed as a percen-tage of the monomer fed to -the catalyst, "Selectivity" is the amount o dimerization product expressed as a percentage of the oligomerization product and "Linearity" i5 the amount of the dimerization product.
Example I illustrates that significantly higher conversion is obtained in the dimerization of propylene when catalysts and processes of the present invention are used.
xample II
The procedure of Example I was repeated using butene as the monomer instead of propylene. Butene-l was used in all runs except Run 10 in which butene-2 was used.
Further experimental details and the results obtained are given in TABLE II.
Example II illustrates that signi~icantly higher conversion is ob-tained in the dimeriæation of butene, even at reduced hold-up time, wl~en catalyst and processes of -the present invention are used. The example also illustrates effects of amine type and process conditions.
Example III
~ sing the procedure of Example I, a series oE runs were carried out to show the efEect oE the amine used in the treatmen-t o~ the nic~el. F'urther experimen-tal details and ~2~ ;7~2 -the results obtained are given in Table :[II.
Example lIt iLlustrates the effects of the use oE
diferent amines in the dimerization of propylene using a process of the present invent:ion, in comparison to the use of a catalyst that had no-t beerl treated wi-th amine.
Ex _ple IV
Using the procedure o* Example I, a series of runs were carried out to show the eEect o varying the tempera-ture and hold-up time in the dimerization reactor. Further experimental details and -the results obtained are given in TABLE IV.
Example IV shows the effect of process conditions on the dimeriæation oE propylene using a process of the present invention. Process conditions may have a siyni*icant effect on conversion, as shown for example by Runs 23-25 and Run 20 of Example III.
7~t~
g TARLE I
Run No.* ~ 2__ _ __3____ _ _4 Ca-talyst A ~ A A
Methocl Amine NH3 N~13 N~13 NH3 Activation 270 300 350 250 Temperature(C) Reaction 5 5 5 5 Pressure(MPa) Reaction 120 150 150 150 Temperature(C) Hold-up Time 6 5 5 6 (min.) Products (%) Unreacted 43.5 25.5 39.l 79.4 Monomer Methyl- 25.l 21.4 20.3 7.5 pentenes Hexenes 33.2 31.4 28.9 lO.8 Dime-thyl- 0.8 l.0 0.8 0.3 butenes ~onenes 8.0 14.3 lO.5 2.l Dodecenes 2.7 5.6 l.3 0.8 Conversion (%)56.5 74.5 60.9 20.6 Selectivity to 85 73 81 86 C6 olefins (g6) I~inearity in 55 58 58 57 C~ olefins (~) *Runs 4 ancl 6 are comparative runs.
Table I (continued) Run No.* _ _ _ ___ _ 5_ _ 6 Catalyst C A
Me t:hod Amine nBuNH2 nBuNH2 Activation 300 250 Temperature(C) Reaction 5 5 Pressure(MPa) Reaction 150 150 Temperature(C) Hold-up Time 6 6 (mln. ) Products (%) Unreacted 39.3 80.7 Monomer Methyl- 20.1 7.5 pentenes ~exenes 8.5 10.3 Dimethyl- 0.8 0.3 butenes Nonenes 10.1 1.5 Dodecenes 1.4 0.3 Conversion (%)60.719.3 Selectivity to81 91 C6 olefins (%) Linearity in 58 57 C6 olefins (~) *Runs 4 and 6 are comparative runs.
,~
7~
TABLE II
Run No. k __ _ _ ___ _ __ 7_ _ _8 ___ _ 9 _ _ **
Catalyst Method A A A B
Amine nBuNH2 nBuNIl2 nBuNH2 nBuNH2 Activation 230 250 300 300 Temperature(C) Reac-tion 5 5 5 5 Pressure(ME'a) Reaction 170 170 170 180 Temperature(C) Hold-up Time 30 30 10 10 (min.) Products(%) Butene-l 11.3 11.4 7.6 13.6 Butene-2 83.6 83.9 71.3 52.6 Branched C8 2.1 4.6 9.0 15.6 olefins Linear C8 2O8 5.6 8.5 12.2 olefins Dodecenes 0.2 0.9 2.8 6.0 Conversion(%) 5.1 11.1 21.1 33.8 Selectivity to C8 olefins (%)96 92 83 82 Linearity in C8 olefins (%)57 55 ~7 *Runs 7, 8 and 11 are comparative runs.
**olefin was butene-2.
TABLE II ~con-tinued) Run No.* 11 12 13 14 15 ___ ____ _ _ __ __ __.____ ._ ____ _ _ _ ~_ _ Catalyst Method A A A A B
Amine NH3 NH3 NH3Me2~H Me3N
Activatlon 250 270 300 300 270 Temperature(C) Reaction 5 5 5 5 5 Pressure(MPa) Reaction 1.70 170 150 170 170 Temperature(~C~
Hold-up Time 10 lO 5 10 10 (min.) Products(%) Butene-l 8.3 8.2 6.5 7.3 7.5 Butene-2 72.968.2 81.670.6 77.1 Branched C88.0 9.8 5.4 9.3 6.7 olefins Linear C8 7-7 9.6 5.6 9.0 6.8 olefins Dodecenes 3.3 3.7 1.2 3.7 1.8 Conversion(%)18.823.6 11.922.1 15.4 Selectivity to C8 ole ins (%) 82 82 90 83 88 Linearity in C8 olefins (%)49 ~7 51 49 50 *Runs 7, 8 and 11 are comparative runs.
.~
7~
TABL:E III
Run No. _ _ __ 16 _ _ :17* 18 Catalyst Method A B A
Amine Piperidine nBuNH2 Me2NFI
Actlvation 300 300 270 Temperature~r'C) Reaction 15 5 5 Pressure(MPa) Reaction 180 150 150 Temperature(~C) Hold-up Time 6 6 5 (min.) Products(~) Unreacted27.2 39.3 86.5 Monomer Methyl- 26.4 20.1 5.7 pentenes Hexenes 33.5 28.5 6.7 Dimethyl l.l 0.8 0.1 butenes Nonenes 10.5 lO.l 1.1 Dodecenes1.2 1.4 0 Conversion(%)72.860.7 13.5 Selectivity to 84 81 92 C6 olefins (~) Linearity in56 58 54 C6 olefins (~) *Run 17 is identical -to Run 5.
~2~i7~
TABLE III (contlrlued) Run No. __ 19* __ _ 20 _ _ 21 22*
Catalyst B B B B
Method Amine NH3 Me3N MeNH2 ~one Activation 300 270 300 300 Temperature(~C) Reaction 5 5 5 5 Pressure(MPa) Reaction 150 180 150 150 Temperature(C) Hold-up Time 5 6 5 6 (min.) Products(%) Unreac-ted25.5 87.3 60.6 94.0 Monomer Methyl- 21.4 5.5 12.6 3.0 pentenes Hexenes 31.4 6.5 19.2 3.2 Dimethyl- 1.0 0.2 0.6 0.1 butenes Nonenes 14.3 1.0 5.6 0.6 Dodecenes5.6 0 1.5 0 Conversion(%)74.512.7 39.4 6.0 Selectivity 73 92 82.5 91 C6 olefins (%) Linearity in58 55 59 48 C6 olefins *Run 19 iB identical to Run 2.
Run 22 i8 a comparative run.
3~
TABLE IV
_un No.* _ _ __ _ _ __23 24 _ 25 _ 26* _ _ 27 Catalyst B B B A A
Method Amine Me3N Me3NMe3~ ~H3 ~13 Activation 270 270 270 350 350 Temperature(C) Reaction 5 10 15 5 15 Pressure(MPa) Reaction 200 200 200 150 150 Temperature(C) Hold-up Time 6 6 6 5 (min.) Products(%) Unreacted 8008 59.5 43.7 39.1 54.4 Monomer Methyl- 6.9 12.6 19.3 20.3 14.7 pentenes Hexenes 9.2 18.2 27.0 28.9 22.0 Dimethyl- 0.3 0.6 0.9 0.8 0.7 butenes Monenes 2.0 5.3 7.1 10.5 7.1 Dodecenes 0.3 2.0 2.1 1.3 1.0 Conversion(~)19.240.5 56.3 60.9 45.6 Selectivity to88 86 84 81 82 C6 olefins t~) Linearity i.n 56 58 57 58 59 C6 olefins (~) Vol. Productivity of8.015.8 23.4 27.7 114.4 linear C olefins ( g/l/min-6 ) *Run 26 is identical to Run 3.
~5~
TABLE IV (continued) Run o.__ _ _ __ __ _ _ 28* 29 _ _ 30 __ 31*
Catalyst B B B B
Method Amine NH3 NH3 Me3N Me3~
Activation 300 300 270 270 Temperature(C) Reaction 5 5 5 5 Pressure(MPa) Reaction 150 150 150 180 Temperature(C) Hold-up Time 5 1 6 6 (min. ) Products~%) 25.5 84.8 96.4 87.3 Monomer Methyl- 21.4 5.4 1.6 5.5 pentenes Hexenes 31.4 7.8 2.0 6.5 Dimethyl- 1.0 002 0 0~2 butenes 14.3 1.3 0.1 1.0 Dodecenes 5.6 0.2 0 0 Conversion(%) 74.5 15.2 3.6 12.7 Selectivity to 73 90 97 92 C6 olefins (%) Linearity in 58 54 56 55 C6 olefins (%) Vol. Productivity of 32~7 40.6 1.7 5.6 linear C olefins ( g/l/min6 ) *Runs 28 and 31 are identical to Runs 2 and 20, respectively , ,,
IMER~ATION OF PROP~LENE AND BUTENh The present inven-tion rela-tes to an improved pro-cess for the dimerization of propylene, butene-l and butene-2 and in par-ticular to an improved catalyst for such a process.
Linear olefins are widely used in industry, for example as s-tarting materials in the manufacture of a wide variety of materlals including chemlcals, e.g. plasticizers and biodegradable detergents, chemical intermedlates and polymers. Polymers are normally formed Erom linear olefins having terminal unsaturation viz linear alpha-olefins. Such olefins may ~e used as a comonomer in the manufacture of polyethylene, especially linear low density polyethylene which is a copolymer of ethylene and higher alpha-olefin(s) e.g. butene-l, hexene-l and octene-l. The polyethylene business is very competitive and it is therefore important tha-t the methods used to obtain any comonomers be e~ficient and economic.
A number oE processes are known for the production of oleins by -the dimerization of lower alpha-ole-fins. In such processes, an olefin or mixture of olefins is brought into contact, in a reac-tion zone, wl-th a catalyst that is a metal, a metal oxide or a so-called Zieg]er coordination catalyst. Dimerization processes are operated at elevated temperatures and pressures.
One process for -the dimerlzation of alpha-olefins, using a supported metal catalyst, is that disclosed in Canadian Patent 1 008 ~73 of L. Forni and R. Invernizzi, which issued 1977-04-12. The catalyst is prepared by depositing nickel on a natural or synthetic crystalline zeolite, con-tacting -the deposited nickel with an organic or inorganic base at a temperature of 25~C for at least 3 hours, eliminating excess base and heat-treating the resultant produc-t at 250C.
An improved process for -the dirner.i~ation of propylene, butene-l and butene-2 has now been founcl.
Accordingly the presen~ inven-tion provides a pro-cess or the dimerization oE propylene, butene-l and butene-2 compr.ising contacting a monomer selected from the group con-sistiny oE propylene, butene~l and butene-2, and mixtures of butene-l and butene-2, with a eatalyst at a temperature of lO0-260C and at a pressure of 3-30 MPa, and separating dimers so formecl, said catalyst being selected from the group consisting of:
(a) a catalyst prepared by depositing nickel on a na-tural or synthetic crystalline zeolite, con-tacting the nickel with an amine seleeted from the group consisting of ammonia, alkylamines in which the alkyl group has l-6 carbon atoms and piperidine at a temperature of -20 to 100C, removing excess amine and then heat-treating the resultant composition at a temperature of 260-350C; and (b) a eatalyst prepared by depositing nickel on a natural or synthetic zeoli-te, eontacting the nickel with an amine selected from the group consisting of ammonia, alkylamines in whieh the alkyl group has 1-6 earbon atoms and piperidine at a -temperature of -20 to 300C, and heat-treating the resultant eomposition under vaeuum at a temperature of 260-350C.
The present. invention also provides a eatalyst for an olefin dimeri~ation proeess, said eatalyst being seleeted from the group consisting of:
(a) a catalyst prepared by depositing niekel on a natural or synthetie erystalline ~eol.i-te, eon~
tac-t.ing the ni.ckel with an amine seleetec1 from the group consisting of ammonia, alkylam:ines in whic;h the alkyl group has 1-6 carbon atoms ancl piperidlne at a tempera-ture of -20 to 100C, removing excess amine and then heat-treating the resultant composition at a temperature of 260-350~C; and (b) a catalyst prepared by deposi~ing nickel on a na-tural or synthetic zeolite, contactin~ the nickel ~ith an amine selected from t'ne group consisting of ammonia, alkylamines in ~hich the alXyl group has 1-6 carbon atoms and piperidine at a temperature of -20 to 300C, and heat-treating the resultant composition under vacuum at a temperature of 260-350C.
In a preferrad embodiment of the process and catalyst of the present invention, the amine is ammonia or n-butylamine.
The present invention relates -to the dirnerization of propylene, butene-l and butene-2. The principal products of such a dimerization reaction are hexenes and octenes, respectively, of which the linear olefins are of most interest. Linear olefins in the form o-E, or converted to, linear alpha-olefins may be copolymerized with ethylene.
In the dimeri~ation process propylene, butene-1 or butene-2, or mixtures of butene-l and butene-2 is fed to a reactor containing the dimerization catalyst, especially such catalyst in the form of a fixed bed catalyst. The dimeri7a-tion may be carried out at temperatures of from about 100C
to ~60C, preferably 150-200C, and at pressures of rom about 3-30 MPa, preferably 5-15 MPa and in particular 9-15 MPa.
The catalyst for the dimerization proce~s may be prepared by depositing nickel on a natural or synthetic crystalline zeolite. Natural zeoli-tes include those describ-ed in Kirk-Othmer "Encyclopedia o~ Chemical TechnolocJy" 1st Ed. Vol. 1~ p 295 et seq and in the aEoremen~ioned Canadian Patent 1 008 473. 5ynthetic zeolites are commorlly known as molecular sieves. Techniques for depositing nickel on the æeolites are al~o known and include the use of ion-exchange methods. For instance a zeolite of a suitable particle size is brought into contact with an aqueous solu-tion o~ a nickel salt a-t ambien-t temperature (about 20C), for example a solution of nickel chloride, nickel nltrate or the like. The zeolite is then washed with deionized ~ater until free of the anion o~ the nickel salt and dr:ied. The use oE ion exchange techniques is further described in the aforementioned Canadian Paten-t 1 008 473.
The zeolite having nickel deposited thereon (nickel/zeolite) is contacted with an amine selec~ed from the group consisting o~ ammonia, alkylamines and piperidine. The alkylam~nes may have alkyl groups with 1-6 carbon atoms, especially four carbon atoms. The preferred amines are ammonia and n-butylamine. The nickel/zeolite may be contact-ed with the amine over a range of tempera-tures e.g. -20 to 300~C and especially 0 to 50C. The contact may be solid~
liquid contact or solid~gas contact.
If the amine is gaseous or has a high vapour pressure under ambient conditions, or at a elevated temperature, the gaseous amine may be contacted with nickel/zeolite. Preferably the amine is diluted wlth an inert gas, for example, nitrogen.
If the amine is liquid, inert gas may ~e passed through the liquid amine and then brought into contact with the nickel/zeolite. Alternatively, amine, especially a pre-determined or controlled amount of amine, may be brought into contact with nickel/zeolite by diffusion under vacuum.
The amine-treated nickel/zeolite is then treated to remove excess amine. Excess amine is preerably removed at a temperature of less than about 300~C, the particular tempera-ture used depending on the amine and the method used to remove excess amine. The excess amine may be removed by passing an inert gas, especially nitrogen, over the amine--treated nickel/ ~eolite for a period of time. The aminecontent of the gas that has been passed over the zeolite may , , ~
, :~
3%
be monl-tored to determine when excess amine has heen removed.
~hen excess ami~e is removed using inert gas, a preferred temperature is ambient temperatllre (about 20C).
Alternatively a vacuum may be used to remove excess alnine in which event an elevated -temperature is preferred.
After the excess a~line has been removed, the amine--treated nickel/zeoli-te is activated by hea-ting -to a tempera-ture of 2~0-3~C, especially 270-320C, for at least 30 minutes, preferably Eor at least one hour. The activation may be carried out in -the presence o-f an inert ~as~ ~lterna--tively the amine-treated nickel/zeolite may be activated under vacuum. If so, -the removal of amine and activation of the amine-treated nic~el/zeolite may be carried out simultaneously.
The process conditions, including method of catalyst preparation, dimerization temperature and pressure, and reaction time may affect the nature of the products obtained in the process. For example the process conditions may affect -the amount oE a particular, especially desired, reaction product, for example, the amount oE linear hexene and octene. Moreover the process may be operated as a relatively low yield, high selectivity process or aa a higher yield, lower selectivity process, selectivity being the forma-tion of a particular desired dimerization product. The actual process conditions used afect the distribution of the products formed, as will be apparent -from the examples hereinafter.
The dimerization process of the present invention may be used for the manufacture of hexenes and octenes, especially linear he~enes and linear octenes. The latter two oleins may be isomerized to hexene-1 and octene-l, respec-tively, and used as comonomers in the manufacture of polyethylene.
The present invention is iLlustrated by t~le follo~-iny examples in which the catalys-ts were prepared usiny Method A, Method ~ or Method C as ollows.
~ethod A: Nlckel was deposi~ed on a zeoli-te viz. 13X
molecular sieve having a ~0-80 Tyler* rnesh size, obtained from t~e Linde Division of Union Carbide Corporation, from an aqueous solu-tion of nickel nitrate using ion exchange techniques. rl~e pH of the aqueous solution was 5.5. The nic~cel/zeoli~e obtained was washed thoroughly with deionized wa-ter until the washings obtained were ree of nitra-te anion and then ~ried in an oven at 120C for one hourv The catalyst nickel/zeolite precursor thus obtained was treated with amine at ambient temperature by passing a mixture of amine and nitrogen through a bed of the catalyst precursor.
Excess amine was then removed by purging with nitrogen at ambient -temperature or two hours. Subsequently the amine-treated catalyst precursor was heated to the activation temperature and main-tained at that temperature for one hour;
the flow of nitrogen was maintained during such activation.
Method B: The catalyst precursor was prepared by the method descrihed in Method A. After having heen dried at 120C for one hour, as descrihed in ~ethod A, 30 g of the precursor were contac-ted with a mixture of amine(lO ml/minute) and nitrogen(750 ml/minute) at ambient temperature for a ~eriod of three hours. The precursor was then contacted with nitrogen (750 ml/minute) for a further two hours. The amine-treated catalyst precursor was then heated, under vacuum, to the activation temperature and maintained at that temperature for one hour.
Method C: 50 g of the catalyst precursor were prepared by the method descrihed in Method A excep-t tha-t the precursor was dried at 300C for two hours under vacuum. 3.8 g of amine, which had heen degassed, was -then allowed to diffuse to the catalyst precursor, under vacuum and at 300C, over a period of three hours; the catalyst precursor was continuous-ly shaken to facilitate contact of amine and catalyst precursor. ~ny excess amine was removed, and the catalys-t activated, hy continuing to -treat the amine-lrea-ted catalyst *denotes trade mark.
precursor under vacuum at 300C Eor a fu-rther period o~ one hour.
_ample I
A tubular reactor was charged with catalyst and heated in an inert atmosp'nere (nitrogen) to a pre-selected -temperature. Propylene was passed throuc~h the reactor. The products obtained were analyzed by on-line ~as chromatography and by gas chromatography/mass spec-troscopy techniques.
A series of runs were carried out us:ing catalysts prepared at different activation -temperatures. Further experimental details and the results obtained are given in TABLE I.
In the Tables hereinafter, "Conversion" is the amount of oligomerization product expressed as a percen-tage of the monomer fed to -the catalyst, "Selectivity" is the amount o dimerization product expressed as a percentage of the oligomerization product and "Linearity" i5 the amount of the dimerization product.
Example I illustrates that significantly higher conversion is obtained in the dimerization of propylene when catalysts and processes of the present invention are used.
xample II
The procedure of Example I was repeated using butene as the monomer instead of propylene. Butene-l was used in all runs except Run 10 in which butene-2 was used.
Further experimental details and the results obtained are given in TABLE II.
Example II illustrates that signi~icantly higher conversion is ob-tained in the dimeriæation of butene, even at reduced hold-up time, wl~en catalyst and processes of -the present invention are used. The example also illustrates effects of amine type and process conditions.
Example III
~ sing the procedure of Example I, a series oE runs were carried out to show the efEect oE the amine used in the treatmen-t o~ the nic~el. F'urther experimen-tal details and ~2~ ;7~2 -the results obtained are given in Table :[II.
Example lIt iLlustrates the effects of the use oE
diferent amines in the dimerization of propylene using a process of the present invent:ion, in comparison to the use of a catalyst that had no-t beerl treated wi-th amine.
Ex _ple IV
Using the procedure o* Example I, a series of runs were carried out to show the eEect o varying the tempera-ture and hold-up time in the dimerization reactor. Further experimental details and -the results obtained are given in TABLE IV.
Example IV shows the effect of process conditions on the dimeriæation oE propylene using a process of the present invention. Process conditions may have a siyni*icant effect on conversion, as shown for example by Runs 23-25 and Run 20 of Example III.
7~t~
g TARLE I
Run No.* ~ 2__ _ __3____ _ _4 Ca-talyst A ~ A A
Methocl Amine NH3 N~13 N~13 NH3 Activation 270 300 350 250 Temperature(C) Reaction 5 5 5 5 Pressure(MPa) Reaction 120 150 150 150 Temperature(C) Hold-up Time 6 5 5 6 (min.) Products (%) Unreacted 43.5 25.5 39.l 79.4 Monomer Methyl- 25.l 21.4 20.3 7.5 pentenes Hexenes 33.2 31.4 28.9 lO.8 Dime-thyl- 0.8 l.0 0.8 0.3 butenes ~onenes 8.0 14.3 lO.5 2.l Dodecenes 2.7 5.6 l.3 0.8 Conversion (%)56.5 74.5 60.9 20.6 Selectivity to 85 73 81 86 C6 olefins (g6) I~inearity in 55 58 58 57 C~ olefins (~) *Runs 4 ancl 6 are comparative runs.
Table I (continued) Run No.* _ _ _ ___ _ 5_ _ 6 Catalyst C A
Me t:hod Amine nBuNH2 nBuNH2 Activation 300 250 Temperature(C) Reaction 5 5 Pressure(MPa) Reaction 150 150 Temperature(C) Hold-up Time 6 6 (mln. ) Products (%) Unreacted 39.3 80.7 Monomer Methyl- 20.1 7.5 pentenes ~exenes 8.5 10.3 Dimethyl- 0.8 0.3 butenes Nonenes 10.1 1.5 Dodecenes 1.4 0.3 Conversion (%)60.719.3 Selectivity to81 91 C6 olefins (%) Linearity in 58 57 C6 olefins (~) *Runs 4 and 6 are comparative runs.
,~
7~
TABLE II
Run No. k __ _ _ ___ _ __ 7_ _ _8 ___ _ 9 _ _ **
Catalyst Method A A A B
Amine nBuNH2 nBuNIl2 nBuNH2 nBuNH2 Activation 230 250 300 300 Temperature(C) Reac-tion 5 5 5 5 Pressure(ME'a) Reaction 170 170 170 180 Temperature(C) Hold-up Time 30 30 10 10 (min.) Products(%) Butene-l 11.3 11.4 7.6 13.6 Butene-2 83.6 83.9 71.3 52.6 Branched C8 2.1 4.6 9.0 15.6 olefins Linear C8 2O8 5.6 8.5 12.2 olefins Dodecenes 0.2 0.9 2.8 6.0 Conversion(%) 5.1 11.1 21.1 33.8 Selectivity to C8 olefins (%)96 92 83 82 Linearity in C8 olefins (%)57 55 ~7 *Runs 7, 8 and 11 are comparative runs.
**olefin was butene-2.
TABLE II ~con-tinued) Run No.* 11 12 13 14 15 ___ ____ _ _ __ __ __.____ ._ ____ _ _ _ ~_ _ Catalyst Method A A A A B
Amine NH3 NH3 NH3Me2~H Me3N
Activatlon 250 270 300 300 270 Temperature(C) Reaction 5 5 5 5 5 Pressure(MPa) Reaction 1.70 170 150 170 170 Temperature(~C~
Hold-up Time 10 lO 5 10 10 (min.) Products(%) Butene-l 8.3 8.2 6.5 7.3 7.5 Butene-2 72.968.2 81.670.6 77.1 Branched C88.0 9.8 5.4 9.3 6.7 olefins Linear C8 7-7 9.6 5.6 9.0 6.8 olefins Dodecenes 3.3 3.7 1.2 3.7 1.8 Conversion(%)18.823.6 11.922.1 15.4 Selectivity to C8 ole ins (%) 82 82 90 83 88 Linearity in C8 olefins (%)49 ~7 51 49 50 *Runs 7, 8 and 11 are comparative runs.
.~
7~
TABL:E III
Run No. _ _ __ 16 _ _ :17* 18 Catalyst Method A B A
Amine Piperidine nBuNH2 Me2NFI
Actlvation 300 300 270 Temperature~r'C) Reaction 15 5 5 Pressure(MPa) Reaction 180 150 150 Temperature(~C) Hold-up Time 6 6 5 (min.) Products(~) Unreacted27.2 39.3 86.5 Monomer Methyl- 26.4 20.1 5.7 pentenes Hexenes 33.5 28.5 6.7 Dimethyl l.l 0.8 0.1 butenes Nonenes 10.5 lO.l 1.1 Dodecenes1.2 1.4 0 Conversion(%)72.860.7 13.5 Selectivity to 84 81 92 C6 olefins (~) Linearity in56 58 54 C6 olefins (~) *Run 17 is identical -to Run 5.
~2~i7~
TABLE III (contlrlued) Run No. __ 19* __ _ 20 _ _ 21 22*
Catalyst B B B B
Method Amine NH3 Me3N MeNH2 ~one Activation 300 270 300 300 Temperature(~C) Reaction 5 5 5 5 Pressure(MPa) Reaction 150 180 150 150 Temperature(C) Hold-up Time 5 6 5 6 (min.) Products(%) Unreac-ted25.5 87.3 60.6 94.0 Monomer Methyl- 21.4 5.5 12.6 3.0 pentenes Hexenes 31.4 6.5 19.2 3.2 Dimethyl- 1.0 0.2 0.6 0.1 butenes Nonenes 14.3 1.0 5.6 0.6 Dodecenes5.6 0 1.5 0 Conversion(%)74.512.7 39.4 6.0 Selectivity 73 92 82.5 91 C6 olefins (%) Linearity in58 55 59 48 C6 olefins *Run 19 iB identical to Run 2.
Run 22 i8 a comparative run.
3~
TABLE IV
_un No.* _ _ __ _ _ __23 24 _ 25 _ 26* _ _ 27 Catalyst B B B A A
Method Amine Me3N Me3NMe3~ ~H3 ~13 Activation 270 270 270 350 350 Temperature(C) Reaction 5 10 15 5 15 Pressure(MPa) Reaction 200 200 200 150 150 Temperature(C) Hold-up Time 6 6 6 5 (min.) Products(%) Unreacted 8008 59.5 43.7 39.1 54.4 Monomer Methyl- 6.9 12.6 19.3 20.3 14.7 pentenes Hexenes 9.2 18.2 27.0 28.9 22.0 Dimethyl- 0.3 0.6 0.9 0.8 0.7 butenes Monenes 2.0 5.3 7.1 10.5 7.1 Dodecenes 0.3 2.0 2.1 1.3 1.0 Conversion(~)19.240.5 56.3 60.9 45.6 Selectivity to88 86 84 81 82 C6 olefins t~) Linearity i.n 56 58 57 58 59 C6 olefins (~) Vol. Productivity of8.015.8 23.4 27.7 114.4 linear C olefins ( g/l/min-6 ) *Run 26 is identical to Run 3.
~5~
TABLE IV (continued) Run o.__ _ _ __ __ _ _ 28* 29 _ _ 30 __ 31*
Catalyst B B B B
Method Amine NH3 NH3 Me3N Me3~
Activation 300 300 270 270 Temperature(C) Reaction 5 5 5 5 Pressure(MPa) Reaction 150 150 150 180 Temperature(C) Hold-up Time 5 1 6 6 (min. ) Products~%) 25.5 84.8 96.4 87.3 Monomer Methyl- 21.4 5.4 1.6 5.5 pentenes Hexenes 31.4 7.8 2.0 6.5 Dimethyl- 1.0 002 0 0~2 butenes 14.3 1.3 0.1 1.0 Dodecenes 5.6 0.2 0 0 Conversion(%) 74.5 15.2 3.6 12.7 Selectivity to 73 90 97 92 C6 olefins (%) Linearity in 58 54 56 55 C6 olefins (%) Vol. Productivity of 32~7 40.6 1.7 5.6 linear C olefins ( g/l/min6 ) *Runs 28 and 31 are identical to Runs 2 and 20, respectively , ,,
Claims (22)
1. A process for the dimerization of propylene, butene-1 and butene-2 comprising contacting a monomer selected from the group consisting of propylene, butene-1 and butene-2, and mixtures of butene-1 and butene-2, with a catalyst at a temperature of 100-260°C and at a pressure of 3-30 MPa, and separating dimers so formed, said catalyst being selected from the group consisting of:
(a) a catalyst prepared by depositing nickel on a natural or synthetic crystalline zeolite, con-tacting the nickel with an amine selected from the group consisting of ammonia, alkylamines in which the alkyl group has 1-6 carbon atoms and piperidine at a temperature of -20 to 100°C, removing excess amine and then heat-treating the resultant composition at a temperature of 260-320°C; and (b) a catalyst prepared by depositing nickel on a natural or synthetic zeolite, contacting the nickel with an amine selected from the group consisting of ammonia, alkylamines in which the alkyl group has 1-6 carbon atoms and piperidine at a temperature of -20 to 300°C, and heat-treating the resultant composition under vacuum at a temperature of 260-320°C..
(a) a catalyst prepared by depositing nickel on a natural or synthetic crystalline zeolite, con-tacting the nickel with an amine selected from the group consisting of ammonia, alkylamines in which the alkyl group has 1-6 carbon atoms and piperidine at a temperature of -20 to 100°C, removing excess amine and then heat-treating the resultant composition at a temperature of 260-320°C; and (b) a catalyst prepared by depositing nickel on a natural or synthetic zeolite, contacting the nickel with an amine selected from the group consisting of ammonia, alkylamines in which the alkyl group has 1-6 carbon atoms and piperidine at a temperature of -20 to 300°C, and heat-treating the resultant composition under vacuum at a temperature of 260-320°C..
2. The process of Claim 1 in which the monomer is propylene.
3. The process of Claim 1 in which the monomer is butene-1.
4. The process of Claim 1 in which the monomer is butene-2.
5. The process of Claim 1 in which the monomer is a mixture of butene-1 and butene-2.
6. The process of Claim 1 in which the dimerization process is carried out at a temperature of 150-200°C.
7. The process of Claim 6 in which the dimeriza-tion process is carried out at a pressure of 5-20 MPa.
8. The process of Claim 5 in which the activation temperature of the catalyst is 270-320°C.
9. The process of any one of Claim 2, Claim 3 and Claim 4 in which the amine is ammonia.
10. The process of any one of Claim 2, Claim 3 and Claim 4 in which the amine is alkylamine.
11. The process of any one of Claim 2, Claim 3 and Claim 4 in which the amine is piperidine.
12. The process of any one of Claim 2, Claim 3 and Claim 4 in which the amine is methylamine.
13. The process of any one of Claim 2, Claim 3 and Claim 4 in which the amine is butylamine.
14. A catalyst for an olefin dimerization process, said catalyst being selected from the group consisting of (a) a catalyst prepared by depositing nickel on a natural or synthetic crystalline zeolite, con-tacting the nickel with an amine selected from the group consisting of ammonia, alkylamines in which the alkyl group has 1-6 carbon atoms and piperidine at a temperature of -20 to 100°C, removing excess amine and then heat-treating the resultant composition at a temperature of 260-320°C; and (b) a catalyst prepared by depositing nickel on a natural or synthetic zeolite, contacting the nickel with an amine selected from the group consisting of ammonia, alkylamines in which the alkyl group has 1-6 carbon atoms and piperidine at a temperature of -20 to 300°C, and heat-treating the resultant composition under vacuum at a temperature of 260-320°C.
15. A catalyst of claim 14 in which the activation temperature is 270-320°C.
16. A catalyst of Claim 14 in which the catalyst is (a).
17. A catalyst of Claim 14 in which the catalyst is (b).
18. The catalyst of any one of Claim 15, Claim 16 and Claim 17 in which the amine is ammonia.
19. The catalyst of any one of Claim 15, Claim 16 and Claim 17 in which the amine is alkylamine.
20. The catalyst of any one of Claim 15, Claim 16 and Claim 17 in which the amine is piperidine.
21. The catalyst of any one of Claim 15, Claim 16 and Claim 17 in which the amine is methylamine.
22. The catalyst of any one of Claim 15, Claim 16 and Claim 17 in which the amine is butylamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000421308A CA1205792A (en) | 1983-02-10 | 1983-02-10 | Dimerization of propylene and butene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000421308A CA1205792A (en) | 1983-02-10 | 1983-02-10 | Dimerization of propylene and butene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1205792A true CA1205792A (en) | 1986-06-10 |
Family
ID=4124536
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000421308A Expired CA1205792A (en) | 1983-02-10 | 1983-02-10 | Dimerization of propylene and butene |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1205792A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0311310A1 (en) * | 1987-10-07 | 1989-04-12 | Mobil Oil Corporation | Olefin oligomerization |
| US4870038A (en) * | 1987-10-07 | 1989-09-26 | Mobil Oil Corporation | Olefin oligomerization with surface modified zeolite catalyst |
| EP0408153A2 (en) * | 1989-07-13 | 1991-01-16 | Shell Internationale Researchmaatschappij B.V. | Preparation and use of metal-containing zeolitic catalysts |
| US5026933A (en) * | 1987-10-07 | 1991-06-25 | Mobil Oil Corporation | Olefin oligomerization with surface modified zeolite catalyst |
| US8129572B2 (en) | 2006-06-07 | 2012-03-06 | Basf Se | Process for codimerizing olefins |
-
1983
- 1983-02-10 CA CA000421308A patent/CA1205792A/en not_active Expired
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0311310A1 (en) * | 1987-10-07 | 1989-04-12 | Mobil Oil Corporation | Olefin oligomerization |
| US4870038A (en) * | 1987-10-07 | 1989-09-26 | Mobil Oil Corporation | Olefin oligomerization with surface modified zeolite catalyst |
| US5026933A (en) * | 1987-10-07 | 1991-06-25 | Mobil Oil Corporation | Olefin oligomerization with surface modified zeolite catalyst |
| EP0408153A2 (en) * | 1989-07-13 | 1991-01-16 | Shell Internationale Researchmaatschappij B.V. | Preparation and use of metal-containing zeolitic catalysts |
| EP0408153A3 (en) * | 1989-07-13 | 1991-03-20 | Shell Internationale Research Maatschappij B.V. | Preparation and use of metal-containing zeolitic catalysts |
| US8129572B2 (en) | 2006-06-07 | 2012-03-06 | Basf Se | Process for codimerizing olefins |
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