GB2156376A - Oligomerization of propylene - Google Patents
Oligomerization of propylene Download PDFInfo
- Publication number
- GB2156376A GB2156376A GB08407784A GB8407784A GB2156376A GB 2156376 A GB2156376 A GB 2156376A GB 08407784 A GB08407784 A GB 08407784A GB 8407784 A GB8407784 A GB 8407784A GB 2156376 A GB2156376 A GB 2156376A
- Authority
- GB
- United Kingdom
- Prior art keywords
- propylene
- reaction
- psig
- reaction zone
- temperature
- 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.)
- Granted
Links
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 24
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000006384 oligomerization reaction Methods 0.000 title description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 15
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910015900 BF3 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- -1 aluminum alkyl halide Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 230000003606 oligomerizing effect Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
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
- C07C2/14—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
- 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
- C07C2527/1206—Hydrogen fluoride
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Propylene oligomers having from 21 to 48 carbon atoms per molecule are prepared by a process which comprises (a) contacting propylene in a reaction zone with a hydrogen fluoride catalyst; (b) maintaining the temperature in the reaction zone in the range from 20 DEG C to -30 DEG C; and (c) maintaining the pressure in the reaction zone in the range from 0 psig to 400 psig (1 to 29 kg/cm<2>).
Description
SPECIFICATION
Oligomerization of propylene
This invention relates to the manufacture of heavy olefins intended for use in particular as the raw materials for making, for example, surface-active products and lubricating compositions. More specifically, it relates to a process for preparing heavy olefins from propylene. This process is particularly suitable for the manufacture of olefins having from 21 to 48 carbon atoms per molecule.
Several processes are known for making propylene oligomers. These processes consist essentially of subjecting propylene to the action of appropriate catalysts. The average molecular weight of the oligomer depends on the nature of the catalyst and the conditions of temperature and pressure at which the reaction takes place. It is known, for instance, that oligomers having an average carbon chain length of 12 can be obtained by causing propylene to react on a catalyst based on phosphoric acid, at a temperature of 100"C to 250"C approximately, at a pressure from 20 to 100 atmospheres, and that oligomers having an average carbon chain length of about 24 carbon atoms can be obtained by polymerizing propylene in the presence of boron trifluoride, at temperatures of the order of 10 C to 500C, in the liquid phase.
U.S. Patent No. 3,932,553 describes the oligomerization of propylene in the presence of a boron trifluoride catalyst and a small amound of an olefinic diene to provide oligomers having about 15 to 21 carbon atoms.
U.S. Patent No. 4,024,203 describes the oligomerization of lower molecular weight mono alpha olefins utilizing a catalyst composition containing a Bronsted acid, a sulfone, and optionally, a Lewis acid, to provide predominantly dimers and trimers.
U.S. Patent No. 4,041,098 describes a method of oligomerizing straight-chain alpha olefins having from 3 to 14 carbon atoms with a soluble catalyst system comsisting of an aluminum alkyl halide and an organo halide.
According to the present invention, there is provided a process for the production of propylene oligomers having from 21 to 48 carbon atoms per molecule, which comprises (a) contacting propylene in a reaction zone with a hydrogen fluoride catalyst; (b) maintaining the temperature in the reaction zone in the range from 20"C to -30 C; and (c) maintaining the presure in the reaction zone in the range from 0 psig to 400 psig (1 to 29 kg/cm2). Among other factors, this invention is based on the discovery that propylene could successfully be oligomerized in the presence of hydrogen fluoride to provide high molecular weight (Ci21-C48) olefins in high yield and conversions.
The oligomerization reaction is carried out in the presence of a hydrogen fluoride catalyst. Generally, from 1 to 20, and preferably, from 1 to 5, moles of hydrogen fluoride are utilized per mole of propylene.
The reaction proceeds to give generally from 60% to over 85% conversion to the oligomer product, depending in large part on the time of reaction involved. The average reaction times necessary to obtain these conversions generally varies from 1 to 5 hours, the conversion rates increasing generally with time.
The temperature of the reaction is maintained at from 20"C to -30 C, preferably 0 C to -15 C. The reaction pressure is maintained at 0 psig (1 kg/cm2) to 400 psig (29 kg/cm2), preferably 100 psig (8 kg/cm2) to 200 psig (15 kg/cm2).
The oligomerization of propylene is carried out in the usual suitable reactor. This reactor has to be designed to withstand the pressure used and corrosion by hydrogen fluoride. It must have a stirrer and the necessary means of cooling the reaction mixture and discharging the heat liberated by the reaction. It must finally be provided with the device and the additional means making it possible to incorporate the reagents and to withdraw the products from the reaction.
The raw product of the reaction includes gaseous products which consist essentially of propane, the main impurity of the propylene used as raw material, and of hydrogen fluoride. They are extracted from the raw product of the reaction by using the usual suitable means that are well known to the technician.
After being freed from gas, the oligomer obtained still contains fluoride components derived from the hydrogen fluoride. These compounds can be eliminated by means of the usual processes, such as fractional distillation.
In the process of the present invention, it has been found that the average molecular weight of the olefins formed by the oligomerization of the propylene is higher, other things being equal, the lower the temperature used. The invention makes it possible in particular to prepare oligomers with an average number of carbon atoms per molecule of 21 to 48, by performing the reaction at a temperature between 20"C and -30 C With regard to product distribution the average carbon number varied from C48 at -30 C to C27-3D at +10 C. On the average, one propylene unit is added for each 6"C decrease in temperature. The optimum temperature range for C33 39 oligomer is 0 C to -150C.
The following Examples are provided to illustrate the invention. In these Examples, the pressure in the reaction vessel was atmospheric, i.e. 0 psig (1 kg/cm2).
Examples
Example I
To a 1000 ml polypropylene bottle equipped with a stirrer, thermowell, condenser, gas inlet tube and
sample port, was added 250 ml (12.5 moles) of hydrogen fluoride. The reaction vessel was immersed in
an acetone- ice bath. The mixture was rapidly stirred while bubbling propylene into the reactor and
maintaining the temperature at about 10 C. Samples were taken for analysis at 1-hour intervals. The re
sults are shown in Table 1.
Table 1
Time, Conversion to Average
Hours Material > C18. Carbon No.
1 61e 24
2 708 27
3 768 30
4 86% 36
Example 2
The procedure of Example 1 was followed, except that the reactor temperature was maintained at
about 0 C. Samples were taken for analysis at 1-hour intervals. The results are shown in Table 2.
Table 2
Time, Conversion to Average
Hours Material > C18 Carbon No.
1 89% 27
2 894 30
Example 3
The procedure of Example 1 was followed, except that the reactor temperature was maintained at
about -15 C. Samples were taken for analysis at 1-hour intervals. The results are shown in Table 3.
Table 3
Time, Conversion to Average
Hours Material > C18 Carbon No.
1 83% 30
2 88% 33
3 93two 39
Claims (5)
1. A process for the preparation of propylene oligomers having from 21 to 48 carbon atoms per molecule which comprises:
(a) contacting propylene in a reaction zone with a hydrogen fluoride catalyst;
(b) maintaining the temperature in the reaction zone in the range from 20"C to -30 C; and
(c) maintaining the pressure in the reaction zone in the range from 0 psig to 400 psig (1 to 29 kg/cm2).
2. A process according to Claim 1, wherein the reaction is carried out at a temperature of from 0 C to 1500.
3. A process according to Claim 1 or 2, wherein the reaction is carried out at a presssure in the range from 100 psig to 200 psig (8 to 15 kg/cm2).
4. A process according to any preceding claim, wherein the reaction zone reaction conditions are maintained for a time sufficient to yield at least 60% conversion of the propylene to propylene oligomers.
5. A process for the preparation of propylene oligomers substantially as described in any one of the foregoing Examples.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08407784A GB2156376B (en) | 1984-03-26 | 1984-03-26 | Oligomerization of propylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08407784A GB2156376B (en) | 1984-03-26 | 1984-03-26 | Oligomerization of propylene |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8407784D0 GB8407784D0 (en) | 1984-05-02 |
| GB2156376A true GB2156376A (en) | 1985-10-09 |
| GB2156376B GB2156376B (en) | 1988-05-05 |
Family
ID=10558683
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08407784A Expired GB2156376B (en) | 1984-03-26 | 1984-03-26 | Oligomerization of propylene |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2156376B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB700616A (en) * | 1950-07-04 | 1953-12-09 | Standard Oil Co | Improvements in or relating to propylene polymerization with hf-bf |
| EP0004804A1 (en) * | 1978-03-28 | 1979-10-17 | Rhone-Poulenc Industries | Process for the dimerisation of olefins with 8-20 carbon atoms and dimers of olefins so obtained |
| GB1581199A (en) * | 1977-07-18 | 1980-12-10 | Anic Spa | Preparation of oligomers of alpha-olefins |
-
1984
- 1984-03-26 GB GB08407784A patent/GB2156376B/en not_active Expired
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB700616A (en) * | 1950-07-04 | 1953-12-09 | Standard Oil Co | Improvements in or relating to propylene polymerization with hf-bf |
| GB1581199A (en) * | 1977-07-18 | 1980-12-10 | Anic Spa | Preparation of oligomers of alpha-olefins |
| EP0004804A1 (en) * | 1978-03-28 | 1979-10-17 | Rhone-Poulenc Industries | Process for the dimerisation of olefins with 8-20 carbon atoms and dimers of olefins so obtained |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2156376B (en) | 1988-05-05 |
| GB8407784D0 (en) | 1984-05-02 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19940326 |