AU631168B2 - Enhanced lube yield and vi's from propylene oligomers - Google Patents

Description

AUSTRALIA

Patents Act COMPLETE SPECIFICE 1 IONw

(ORIGINAL)

Class Application Number: Lodged: Complete Specification Lodged: Accepted: Published.

Priority Related Art: Int. Class Applicant(s): Mobil Oil Corporation 150 East 42nd Street, New York, New Yock, UNITED STATES OF AMERICA :Address for Service is: PHILLIPS ORMOf4DE FITZPATRICK Patent and Trade Mark Attorneys 367 Collins Street Melbourne 3000 AUSTRALIA "*"Com~plete Specification for the invention entitled: ENHANCED LUBE YIELD AND VI'S FROM PROL'YLVNE OLIGOMERS Our Ref 159255 POF Code: 1462/1402 The followitig statement is a full description of this invention, including -the best method of performing it known to applicant(s): 6006 iiiri: L i i- -la- ENHANCED LUBE YIELD AND VI'S FROM PROPYLENE OLIGOMERS This application is directed to a composition comprising the oligomerization product of branched internal olefins or blends thereof with alpha olefins to produce improved synthetic lubricants.

Synthetic hydrocarbon lubricants obtained from Friedel-Crafts catalyzed oligomerization of alpha-olefins that are known: U.S. Patent No. 4,469,912. Oligomerization of alpha olefins such as 1-decene using boron trifluoride plus promotor are described in for example U.S. Patent Nos. 3,149,178, 3,763,244, 3,780,128 and 4,469,912. U.S. Patent No. 4,463,201 discloses synthetic lubricating oils prepared by copolymerizing certain olefinic monomers and a third alpha olefin and thereafter dewaxing the polymerization product via a urea addition process.

This invention is directed to a process of making improved synthetic lubricants comprising reacting branched internal olefins with added alpha olefin to produce synthetic lube-range product in increased yield, higher viscosity index (VI) and high quality.

This invention is further directed to a product from the co-oligomerization of an alpha olefin and a lightly branched s'0 olefin product derived from oligomerization of a low molecular weight olefin over a ZSM-5 type zeolite which product is highly V*o suitable as lube base stock.

6 According to the present invention, high quality synthetic oils are provided by reacting an oligomer of a lightly branched internal olefin with an alpha olefin. In the context of this invention highly branched means greater than 2 branches per 12 carbon atoms and lightly branched means from 1 to 2 or less.

o*o Generally speaking, in the prior art this has meant 1 branch per carbon atoms. The resulting lube-range product is formed in *9 9 9 t

I

ILic--- r; F-4596 2increased yield and of considerably higher VI than that produced by oligomerizing branched internal olefins alone. The higher yields and VI's could not be predicted from a combination of properties of the branched and alpha olefins.

The branched internal olefinic oligomers are most advantageously reacted on a substantially equimolar basis with the added alpha olefin.

Propylene is the preferred branched internal olefin oligoinerized to provide C 10 propylene oligomers, preferrably

C

12 oligomers. The branched internal olefinic oligomer may be prepared by any suitable method known in the art. Preferably it is prepared in the presence of an HZSM-5 type catalyst under known oligomerization conditions.

Suitable alpha olefins include alpha olefins having from 6 to 20 carbon atoms such as 1-C 12

I-C

14 and 1-C 16 The first stage or phase of the present process is carried out in the presence of a suitable zeolite catalyst, particularly a S ZSM-5 type zeolite. Preferred for use herein include the crystalline aluminosilicate zeolites having a silica to alumina o20 ratio of at least 12, a Constraint Index of 1 to 12 and acid °0°9 cracking activity of 160 to 200. Representative of the ZSM-S type Sa° zeolites are ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 and o ZSM-38 or their hydrogen forms. ZSM-5 is disclosed and claimed in U.S. Patent No. 3,702,886 and U.S. Patent No. Re. 29,948; ZSM-ll is disclosed and claimed in U.S. Patent No. 3,709,979. Also, see U.S.

Patent No. 3,832,449 for ZSM-12; U.S. Patent No. 4,079,979. Also, S* see U.S. Patent No. 3,832,449 for ZSM-12; U.S. Patent No. 4,076,842 ooo for ZSM-23; U.S. Patent No. 4,016,245 for ZSM-35 and U.S. Patent No.

4,046,839 for ZSM-38. A suitable catalyst is HZSM-S zeolite with :43o030 wt% alumina binder in the form of cylindrical extrudates of 1 to mm. These medium pore shape selective catalysts are sometimes known as porotectosilicates or "pentasil" catrlysts. Especially preferred is ZSM-23 or its hydrogen form. These catalyst may be unmodified or surface modified.

-I W F-4596 3-- A phosphoric acid modified boron trifluoride catalyst is usually used in the process. However, a portion of the BF 3 may be complexed with water. The use of such catalyst with added alpha olefin results in increased process yields as high as 25% with VI's of 135+.

When aqueous phosphoric acid is used as mentioned hereinabove the BF will be at least partially complexed with water.

However, the phosphoric acid must comprise at least 50% or more of the aqueous acid solution. The phosphoric acid may be H 3

PO

4 orthophosphoric or polyphosphoric acids.

The reaction conditions are usually as follows: 0 C to 60 0 C temperature preferably 0 to 40°C; atmospheric to 793 kPa (100 psig) pressure, preferably slightly super atmospheric. The molar ratio of the first stage product to alpha olefin is 1:1.

Generally speaking the oligomer, e.g. a C 12 propylene oligomer is prepared first and thereafter blended and reacted with the added alpha olefin to provide improved lube-range products.

Preferred reactants are an alpha olefin 1-C 6 to 1-C 20 and more preferably 1-C 8 to 1-Gc 8 and medium 0'o molecular weight lightly branched olefin product of a low molecular weight C 3 to C 8 olefin over ZSM-5 type zeolites (optionally surface modified) such as ZSM-5, ZSM-23 and ZSM-5 type zeolites in general or their hydrogen forms. By lightly branched olefin is meant olefins having 2 or less than 2, 1.1-2 branches per 12 methyl groups. The low molecular weight olefins are any suitable

C

3 to C 8 olefin and pr'eferably C 3 to C 4 olcfins.

"o ~Synthetic fluids produced by the process described herein are also highly useful as blending base stocks for high quality "ti 0 lubricants. The use of this process would allow refinery-produced propylene and alpha olefins to be of significant commercial value as an alternative to expensive polymer oils such as 1-decene polymer rs°° oil. Accordingly, the products of this invention can be directly L--lL4-I~-- F-4596 4used as lube range products or can be blended with any suitable lubricating media such as oils of lubricating viscosity including hydrocracked lubricating oils, hydraulic oils, automotive oils, gear oils, transmission fluids, waxes, greases and other forms of lubricant compositions selected from mineral oils, synthetic oils or mixtures thereof. Typical synthetic vehicles include polyisobutylene, polybutenes, hydrogenated polydecenes, polypropylene glycol, polyethylene glycol, trimethylol propane esters, neopentyl and pentaerythritol esters, di(2-ethyl hexyl) sebacate, di(2-ethylbenyl) adiptate, dibutyl phthalate, fluorocarbons, silicate esters, silanes, esters of phosphorus-containing acids liquid ureas, ferrocene derivatives, hydrogenated mineral oils, chain-type polyphenols, silozanes and silicones (polysiloxanes), alkyl-substituted diphenyl ethers typified by a butyl-substituted bis-(p-phenoxy phenyl) ether, phenoxy phenylether, and the like.

EXAMPLES

o The below described examples further illustrate the process of the invention but are not intended in any way to limit the scope 6 00 0oo of the invention.

S° Example 1 A C 1

C

14 oligomer was prepared via HZSM-5 catalysis as follows: A propylene/butylene FCC off gas mixture was passed over a fixed bed of HZSM-5 catalyst at a feed rate of 0.6 grams per gram of catalyst per hour; pressure was 4240 kPa (600 psig); reactor S inlet temperature was 232 0 C (4500F). The resulting mixed oligomers ,oo" were distilled to give a C 11

-C

14 cut.

r^ Example 2 The C 11

C

14 propylene/butylene oligomer prepared as in Example 1 was catalytically oligomerized using BF 3

/H

3 P0 4 ,go catalyst as described below: F-4596 grams of the C 11

-C

14 oligomer was charged to a flask, BF 3 was bubbled in subsurface. After BF3 saturation had occurred, 0.4 gram of 70% H 3

PO

4 was added. Reaction was continued for six hours at room temperature with continued addition of BF 3 The reaction mixture was quenched with water, dried, and distilled to remove lower boiling materials, giving a oligomer yield of 30%. The viscosity index (VI) was 57.

Example 3 Oligomerization, in the same fashion as Example 2, of a 67:33 (wt) blend of the C 11

C

14 propylene oligomer and 1-hexadecene (C 16 gave 61% yield of C 25 oligomer with 117 VI.

Based on a linear combination of properties, expected yield and VI for the blend are 50% yield, 91 VI. Thus, the added alpha-olefin enhances yield and VI in excess of that predicted. The added 1-hexadecene increases VI as if it had an effective blending VI of greater than 200 (actual l-C 16 dimer/ trimer VI 101). See Table 1 for summary.

Example 20 In the same manner as in Example 3, VI and yield were determined for C25+ oligomer produced by BF 3 /aq. 11 3

PO

4 S" catalyzed reaction of a C 2 propylene oligomer fraction prepared as in Example 1 using an amine-modifind HZSM-23 catalyst prepared in accordance with Example 7 of U.S. Patent No. 4,160,788; j 25 1-hexadecene; a 67:33 (wt) blend of and As in (I Example 3, the yield and VI of the blend were considerably increased, and were higher than calculated (see Table 2).

Example S Addition of 15% 1-hexadecene to 85% of a C 12 propylene oligomer (as in Example 4) increased oligomer product VI from 104 to 118 (113 calculated).

4 -i- F-4S96 6-- TABLE 1 Enhanced Yield and VI with Added Alpha-Olef in CEais t: BF3y'aq. 1- 3 P0 4 VI of Oligomer 7Sil Pure qLigmoers: 1- 1

-C

14 Propylene Oligomer 57 2. 1-C1 6 90%0 161 Blend: YIELD VI Observed: 61% 117 67%1 33% (2) Calculateda: 50% 91 Effective Blending VT Of 1-C 16 239 0 go[67% (57) 33%V =117) x =239 Calculated assuming linear combination (weight basis) of properties.

0 4 F-4 596 7-- TABLE 2 Enhanced Yield and VI with added Aipha-Olef ins Catalyst:

BF

3 /aq. 11 3 P0 4 2±Yld VofOime Pure Oligmoers:

C

12 Propylene Oligomer 60% 104 (from amine 'HZSM-23) 2. 1-hexadecene 90% 161 Blend: 6 7% 33% (2) observed: Calculated a: Effective Blending VI Of 1-C 16 207 [67%0 (104) 33% x =207 4 49 09 9 9 99 0 o 99 44 0 44 0 *404 99 00 9 990 9900 0 99*4 138] Calculated assuming linear combination (weight basis) of properties.

9 0 9,4 9 0 0 F-4596 8-- Example 6 In the same manner as in Example 4, C 25 oligomers were produced by BF 3

/H

3

PO

4 catalyzed reaction of a C 1 2 or

C

15 lightly branched oligomer fraction prepared as in Example 1, using an amine-modified HZSM-23 catalyst in accordance with Example 7 of U.S. Patent No. 4,160,788; and various alpha-olefins (see Table 3) in varying amounts. As in Fxample 4, the viscosity index (VI) of the co-oligomer is considerably increased over the VI of the branched olefin homo-oligomer and is higher than expected from linear blending of branched olefin and alpha olefin homo-oligomers.

This example illustrates: 1.1 to 2.0 branch ZSM-23 oligomer 1-C 1 0 1-C 16 alpha olefin to 50% alpha olefin uses BPF H 3 P0 4 catalyst Example 7 A mixture of 33 weight parts of a C 12 ZSM-23 derived propylene oligomer with 1.6 methyl branches per C 1 2 prepared in accordance with Example 6 was co-oligomerized with 67 weight parts 1-decone using the following procedure: A mixture of 670 grams 1-decene, 330 grams branched C12+, and 7.2 grams of n-propanol was pumped into a reactor at 25 to 301C and atmospheric pressure over four hours. A continuous subsurface

BF

3 flow was maintained. After ompletlon of the addition, the S 25 reactor was held at 20 to 25 0 C for an additional two hours. After Io', caustic wash and stripping at low pressure, the fraction of the product boiling above 399 0 C (750°F) (84% yield) was hydrogenated at 185oC using a Ni-kieselguhr catalyst. Properties of the hydrogenated lube-range oligomer were: VI 128; pour point -54C kinematic viscosity at 100C k S.3 nin/s.

i TABLE 3 ZSM-23 Derived Olefin o(-olefin -9.(-Oefin C 12 Content so 50

'-CIO

I-Cl 4 1-Cl 4

'-CIO

Methyl Branches 1.1 1.1 1.1 1.1 Li ill 124 (123) 124(118) 125(121) 118 132(124) 105 121(116) 108 121k(121) 104 120(112) S. 8cS 6.4 6.2 7.7 6.4 5.2 7.1 5.8 7.1 EZS+ Oligomer Properties 0. Kinematic vi Vis-cosity Pour Point, C 100% The number in parentheses is VI calculate( olefin aipha-olef in. Aipha-olefin VI: 1-C 1 6 =160 I assuming linear combination of VI of branched 1-Cl 0 135; 1-C 12 140; 1-C 14 150; F-4596 Example 8 In a manner similar to the previous example, a mixture of 1-C10, 25% 1.6 branch C12+ ZSM-23 derived propylene oligomer was co-oligomer was co-oligomer was co-oligomerized. After removal of low-boling components and hydrogenation, the properties of the lube-range oligomer were: VI 133; pour point (-54°C (-650F); kinematic viscosity at 100°C 5.4 mm 2 flash point 232 0

C

(4500F).

Examples 7 and 8 clearly illustrate that a high-quality lube base stock can be made by the specified co-oligomerization process.

The present invention uses as the major component an inexpensive propylene oligomer instead of an alpha olefinic oligomer and surprisingly produces lube-range product in increased yield with significantly higher VI's than was predictable from a combination of properties of alpha olefins and branched internal olefins (propylene oligomers). Tables 1, 2, and 3 provide data clearly showing the Simproved yield and higher VI's obtainable by use of the novel process embodied herein.

0".20 Although the present invention has been described with S"ooo preferred embodiments, it is to be understood that modifications and I variations may be resorted to, without departing from the spirit and scope of this invention, as those skilled in the art will readily understand. Such modifications and variations are considered to be within the purview and scope of the appended claims.

4O 11*L1a

LL

Claims (15)

1. A process for preparing synthetic lube range products comprising oligomerizing a to1ecu~ela&i0t C3 to C 8 olefin or mixture thereof over a zeolite of the ZSM-5 family to form a merdmusaoEula we lightly branched olefinic product, co-oligomerizing the product of in substantially equimolar amounts with an alpha olefin or a mixture of alpha olefins in the presence of catalytic amounts of BF 3 /aq 1 3 P0 4 in a suitable reaction medium and thereafter removing low boiling materials from and hydrogenating the product of (2)

2. The process of claim 1 wherein the alpha-olefin is a C 6 to C20 alpha olefin or mixture thereof.

3. The process of claim 1 or 2 wherein the alpha-olefin is a C 8 to (18 alpha-olefin or mixture thereof.

4. The process of any of the preceding claims wherein the alpha-olefin is selected from l-decene, 1-dodecene, 1-butyldecene, 1-hexadecene and mixtures thereof. .i

5. The process of any of the preceding claims wherein the low molecular weight olefin is a C 3 to C 4 olefin or mixture f 4, thereof. I,

6. The process of any one of the preceding claims wherein the lightly branched olefinic product is a C 11 to C14 propylene/butylene oligomer.

7. The process of any of the preceding claims wherein the lightly branched olefinic product is a C11 to Ci. propylene S* oligomer.

8. The process of any of the preceding claims wherein the olefinic product is a C15 propylene oligomer.

9. The process of any of the preceding claims wherein the zeolite of the ZSM-5 family is selected from ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-3S and ZSM-38 or their hydrogen forms.

The process of any of the preceding claims wherein the reaction is carried out at a temperature of from to 60 C and at pressure from atmospheric to 793 kPa, and a molar ratio of product of step to added olefin of 1 to 1.

11. A synthetic lube range product prepared by contacting under oligomerization conditions for a time sufficient, a lightly branched olefinic product, prepared from a low molecular weight C3 to C 8 olefin or mixture thereof in the presence of a zeolite of the ZSM-5 family, and added alpha-olefin or mixture of alpha-olefins in substantially equimolar amounts in the presence of catalytic amounts of BF 3 /aq H 3 PO 4 in a suitable reaction medium.

12. The product of claim 11 wherein the added alpha-olefin is selected from C 6 to C20 alpha-olefins or mixtures thereof.

13. The product of claim 11 or 12 wherein the zeolite of the ZSM-5 Family is selected from ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 and ZSM-38 or their hydrogen forms.

14. A process according to claim 1 substantially as hereinbefore described with reference to any one of Examples 1 to 8. A product according to claim 11 substantially as hereinbefore described with reference to any one of Examples 2 to 8. DATED:

15 September 1992 PHILLIPS ORMONDE FITZPATRICK Attorneys for: PORATION MOBIL OIL CORPORATION D< 12 L i -I