JPH02229890A - Manufacture of lubricating oil with higher yield and viscosity index from propylene oligomer - Google Patents

Abstract

PURPOSE: To obtain a lubricating oil with a high viscosity index in a high yield by reacting an oligomer prepd. on a specific zeolite with an α-olefin, removing low-boiling substances from the resultant product, and hydrogenating the resultant compound.

CONSTITUTION: A 3-8C (pref. 3-4C) olefin (mixture) is oligomerized on ZSM-5 zeolite to give a lightly branched olefin product having a medium mol.wt. The product is co-oligomerized with an equimolar amt. of a 6-20C α-olefin (mixture) (pref. 1-decene, 1-dodecene, 1-butyldecene, or 1-hexadecene) in a suitable reaction solvent in the presence of a catalytic amt. of an aq. BF₃/H₃PO₄ soln. The resultant product is freed from low-boiling substances and is hydrogenated to give the objective lubricating oil.

COPYRIGHT: (C)1990,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The object of this application is to provide compositions consisting of the products obtained by oligomerizing branched internal olefins or blends thereof with α-olefins in order to produce improved synthetic lubricating oils. It is directed towards.

Synthetic hydrocarbon lubricants obtained from Friedel-Crafts catalytic oligomerization of σ-olefins are described in U.S. Pat.
, 469,912. Oligomerization of a-olefins such as l-decene using boron trifluoride and promoters is described, for example, in U.S. Pat.
No. 9,178, No. 3,763,244, No. 3,780
, No. 128 and No. 4,469,912. U.S. Pat. No. 4,463,201 discloses a synthetic lubricating oil obtained by copolymerizing certain olefin monomers with tertiary a-olefins and then de-stallizing the polymerized product by a urea addition process. There is.

The present invention is directed to a process for reacting branched internal olefins with added alpha-olefins to produce synthetic lubricant range products in high yield, high viscosity index (VI), and high quality. .

The present invention further provides a lightly branched olefin product obtained by oligomerization of (I) an alpha-olefin and (b) a low molecular weight solenoid over a ZSM-5 type zeolite; The aim is to create products that are highly suitable as base materials for lubricants.

In accordance with the present invention, high quality synthetic oils are provided by reacting oligomers of lightly branched internal olefins with σ-olefins. In connection with this invention, “
``Highly branched'' refers to molecules with two or more branches per 12 carbon atoms, and ``slightly branched''.
means the number of branches is 1 to 2 or less. Generally speaking, this corresponds to 20 carbon atoms in conventional technology.
This meant that each branch had one branch. The resulting lubricating oil range products are formed in higher yields and with significantly higher viscosity indices than those obtained by oligomerizing branched internal olefins alone. The higher yield and viscosity index could not be predicted from the combination of branched and σ-olefin properties.

Branched internal olefin oligomers have an added σ
- most advantageously reacts with the olefin in substantially equimolar proportions.

Propylene is oligomerized to C. . 3 propylene
Preferred internal olefins provide oligomers, preferably C14+ oligomers. Branched internal olefin oligomers can be made by any suitable method known in the art. Preferably, it is prepared under known oligomerization conditions}iZsM.5
prepared in the presence of type catalysts.

Suitable α-olefins include a-olefins having 6 to 20 carbon atoms;
Olefins, e.g. 1-C+i, 1-C14, 1-C
There is ts.

The first step or phase of the process of the invention is carried out in the presence of a suitable zeolite catalyst, in particular a ZSM zeolite. Preferred for use herein are crystalline aluminosilicate zeolites having a silica to alumina ratio of at least 12, a restraint index of 1 to 12, and an acid decomposition activity of 160 to 200. A typical example of ZSM-5 type zeolite is
ZSM-5, ZSM-1 1, ZSM-1 2
, ZSM-22, ZSM-23, ZSM-35, ZSM
-38 or their hydrogen forms. ZSM-5 is disclosed and claimed in US Pat. No. 3,702,186, Reissue No. 29,948. ZSM-11 is disclosed in No. 3,709,979 and is claimed as a patent. Similarly, for ZSM-12, U.S. Patent Nos. 3,832,449 and 4,709,979, and for ZSM-234m, U.S. Pat.
Regarding zSM-3 5, see No. 4,016,245;z
sM-38J: Please refer to No. 4,046,839 for details. A suitable catalyst is H with 35% by weight binder in the form of cylindrical extrudates of 1 to 5 IIWl.
It is a ZSM-5 type zeolite. These medium-pore selective catalysts are often known as borotectate or "bentasil" catalysts. Particularly preferred is ZSM-23 or its hydrogen derivative. These catalysts are used unmodified or after surface modification.

Typically, boron trifluoride catalysts modified with phosphoric acid are used in this process. However, some of BF may form complexes with water. When such catalysts are used with added alpha-olefins, the resulting viscosity index is greater than 135 and process yields are increased by as much as 25%.

As mentioned above, using an aqueous solution of phosphoric acid;
is at least partially complexed with water. However, the phosphoric acid must consist of at least 50% or more aqueous acid. Phosphoric acid is H,
Either PO orthophosphoric acid or polyphosphoric acid may be used.

Reaction conditions are typically as follows: Temperature ranges from 10°C to 6Q'O, preferably 0°C to 40°C; pressure ranges from atmospheric to 793 KPJ (!00 psig).
range, preferably 1 to slightly above atmospheric pressure.

The molar ratio of the first stage product to σ-olefuin is l:
It is 1.

Generally speaking, an oligomer, such as a C+t propylene oligomer, is first prepared and then blended with an added a-olefin and reacted to produce an improved lubricating oil range of products.

Preferred reactants include (a) α of 1-Cs to 1-Cxo;
-olefin, more preferably 1-C, to 1-C+s
A-olefin and 0) low molecular weight C3-C olefin are processed into ZSM-5 type zeolites (with optional surface modification), such as ZSM-5, ZSM-23, generally are medium molecular weight, lightly branched olefin products reacted on ZSM-5 type zeolites or their hydrogen forms. What is a slightly branched olefin?
It refers to olefins in which the number of branches per 12 methyl groups is 2 or less than 2, for example from 1.1 to 2. The low molecular weight solute olefin is a C3-C■ olefin, preferably a C3-
Any suitable C4 olefin may be used.

Synthetic fluids produced by the methods described herein are also extremely useful as raw materials for blending high quality lubricating oils. Using this method, it is possible to make propylene and alpha-olefins produced in refineries extremely commercially valuable as replacements for expensive polymer oils such as 1-decene polymers. Therefore, the product of this invention can be used directly as a product in the lubricating oil range or in other suitable lubricants such as hydrolyzed lubricating oils, hydraulic fluid oils, motor oils, gear oils, transmission oils, etc. It may also be blended with any suitable lubricating medium, including other types of lubricating compositions selected from commercial fluids, waxes, greases, and mineral oils, synthetic oils, or mixtures thereof. Typical synthesis vehicles include polyisobutylene, polybutene, hydrogenated polydecene, polypropylene glycol, polyethylene glycol, trimethylolpropane ester, neopentylene and betaerythritol ester,
Di(2-ethylhexyl) sebacic acid ester, di(2-ethylhexyl) sebacic acid ester,
-ethylbenzyl) adipate, dibutyl heptatarate, full-grained hydrocarbons, silicic acid esters, silanes, esters of phosphorus-containing acidic liquid urea, ferrocene derivatives, hydrogenated I; mineral oil, chain-type polyphenols, siloxanes and silicone (polysiloxane), alkyl-substituted di-7enyl ether, e.g. butyl-substituted bis-(p-
(7) ether, phenoxy phenyl ether, etc.

EXAMPLES The examples described below are intended to explain the method of the invention more specifically, but are not intended to limit the scope of the invention in any way.

Example l Through the catalytic action of HZSM-5, C11~
A C14 oligomer was prepared: A propylene/butylene gas mixture coming from an FCC was passed over a fixed bed of HZSM-5 catalyst at a feed rate of 0.6 section/g catalyst for 71 hours. The pressure was 4,240 KPa (600 psig) and the temperature at the reactor inlet was 232°C! (4 5 0'F). The obtained mixed oligomer was distilled to give C11-C.
A fraction was obtained.

Reversing 1 The C11-C11 propylene/butylene oligomer prepared in Example 1 was catalytically oligomerized using a BF3/H3PO4 catalyst as follows: 50 g of C11-C14 oligomer was charged to a flask; BF was bubbled on the inner layer surface. After completely saturating the BF, 0.4 g of 70% H, P04 was added. The reaction was continued at room temperature for 6 hours while continuously adding BF. The reaction mixture was quenched with water, dried and distilled to remove low boiling materials.
C! 1 oligomer was obtained with a yield of 30%. Viscosity index (V
1) was 57.

Example 3 Globylene with %Cll to C14 in the same manner as in Example 2
67:33 of oligomer and 1-hexadecene (C+a)
A blend of (Ii quantitative ratio) was oligomerized to obtain a Czs+ oligomer having a viscosity index of 117 in a yield of 61%. The yield and viscosity index of the blend predicted assuming a linear combination of physical properties were 50% and 91, respectively. The added α-olefin thus gave higher yields and viscosity indexes that exceeded the predicted values.

The added 1-hexadecene was 200% (actual 1
-C+a- Dimer/Trimer Viscosity Index 161) Increase the viscosity index as if it had a greater effective blend viscosity index. See Table 1 for a summary.

Example 4 Similarly to Example 3, (a) U.S. Pat.
A C.I. ! *Propylene oligomer fraction; (b) 1-hexadecene; (cXa) and (b)
A blend of 67:33 (weight ratio): BF, /H,P
The viscosity index and yield of C, s+ oligomers produced by reaction using an O4 aqueous solution catalyst were determined. Example 3
As in the case, the yield and viscosity index of the blend increased considerably and were higher than the calculated values (see Table 2).

Example 5 85% CI2 brobylene oligomer with 15% 1-
Upon addition of hexadecene, the viscosity index of the oligomeric product increased from 104 to 118 (calculated 113).

Pure oligomer; 1. C,,~C11 propylene oligomer = 57 2.1-C+s-i 6z CZS+Yield 30% 90% Blend:
Revenue! Observed value: 61% 67% (1) + 33% (2) Calculated value: 50% 1-c,. The effective value of L/7 de Vl-239 [67% (5
7) +33% (X) = 1171X-239 Note) Calculated value assuming a linear combination of physical properties (based on weight).

■I 9l Yield increased by added α-olefin and VI catalyst: BF3/I-{3PO. Aqueous solution pure oligomer 2 C21 yield oligomer V11
．． C+z” propylene ground sesame 60%
104 (from amine/HZSM-23 catalyst) 2.1-hexadecene 90%
161 blend: Observed value: 75% 67% (+) + 33% (2) Calculated value: 70% i-c. , the effective blend VI = 207 [67% (+0
4) +33% (I) - 1381Xζ207 Note) Total 1i value assuming a linear combination of physical properties (based on weight).

? Example 6 As in Example 4, (!) U.S. Patent No. 4,160
, No. 788, amine-modified HZS according to Example 7 of
Fractions of lightly branched oligomers of C-+■ or C-1 prepared as in Example 1 using M-23 catalyst and (b) various α-
B F s/H 3P with olefins (see Table 3)
Czs+ oligomers were produced by O a catalytic reaction. As in Example 4, the viscosity index (V1) of the cooligomer increases considerably over the Vl of the homooligomer of branched olefins, and the viscosity index (V1) of the cooligomer increases considerably over the Vl of the homooligomer of branched olefins, and It is higher than the predicted value assuming deing (linexr blsndiB) and! 20 This example illustrates the following: degree of branching 1
．． Oligomer-1-C.1 derived from ZSM-23 catalytic power 1 of 1 to 2.0. ．． is BF3/HsPO,M [1-
Clg's σ-olefins (α-olefins included)
~50%).

? Example 7 C derived from ZSM-23 catalyst with a methyl branching technique of 1.6 per 01 ■ prepared according to Example 6
6 parts by weight of a mixture of propylene oligomers of I2+
Cooligomerized using 7 parts by weight of 1-decene and the following procedure: 670 g of 1-decene, 330 g of branched CI2
+ a mixture of oligomers and 7.2 g of globanol,
The reactor was charged at 25-30°C under atmospheric pressure for 4 hours at a time. A continuous BF and flow on the inner layer surface was maintained. BF,
After the addition of
Maintained at °C. After caustic washing and low pressure stripping, seven fractions of the product boiling above 399°C (750°F) were hydrogenated at 185°C using a Ni-diatomaceous earth catalyst. The properties of the oligomers in the hydrogenated lubricating oil range were as follows: Vl-128; pour point = -65°F; kinematic viscosity (100°C!) = 5. 3 B2/s. clearly show that improved yields and higher Ml can be obtained by using the novel method embodied herein.

Although the present invention has been described in terms of preferred embodiments, it will be readily apparent to those skilled in the art that modifications and variations may be made without departing from the spirit and scope of the invention. should be understood. Such modifications and variations are considered to be within the scope of the appended claims.

(,?}4 Implementation fi8 Similar to the previous example, 75% of 1-C+a and 25% of
A mixture of propylene oligomers derived from a ZSM-23 catalyst with a degree of branching of 1.6 and C+x+ was oligomerized. The properties of the lubricating oil range oligomers obtained after removal of low boiling components and hydrogenation were as follows: Ml-133; pour point -54°C (-65°F); kinematic viscosity. (100℃)=5.4mm”/s; flash point -232
”C (450°F).

Examples 7 and 8 clearly demonstrate that high quality lubricant raw materials can be produced by special cooligomerization methods.

Claims (1)

[Claims] 1. (1) Oligomerization of low molecular weight C_3 to C_■ olefins or mixtures thereof over ZSM-5 group zeolites to produce lightly branched olefin products with medium molecular weight. (2) the product of (1) in substantially equimolar amounts with an α-olefin, or a mixture of α-olefins, in the presence of a catalytic amount of an aqueous BF_3/H_3PO_4 solution in a suitable reaction medium; cooligomerization, and (3) thereafter removing low boilers from the product of (2) and hydrogenating. 2. The method according to claim 1, wherein the α-olefin is an α-olefin of C_■ to C_2_0 or a mixture thereof. 3. The method according to claim 1 or 2, wherein the α-olefin is an α-olefin of C_■ to C_1_■ or a mixture thereof. 4, α-olefin is 1-decene, 1-dodecene, 1
-butyldecene, 1-hexadecene and mixtures thereof. 5. The method according to any one of claims 1 to 4, wherein the low molecular weight olefin is a C_3 to C_4 olefin or a mixture thereof. 6. The slightly branched olefin product is C_1_1
-C_1_4 propylene/butylene oligomer. The method according to any one of claims 1 to 5. 7. The slightly branched olefin product is C_1_1
The method according to any one of claims 1 to 6, which is a propylene oligomer of ~C_1_4. 8. A process according to any one of claims 1 to 7, wherein the olefin product is a C_1_5 propylene oligomer. 9.ZSM-5 group zeolite is ZSM-5, ZSM-
11, ZSM-12, ZSM-22, ZSM-23, Z
9. A method according to any one of claims 1 to 8, wherein the method is selected from SM-35, ZSM-38 or their hydrogen forms. 10. Temperature from -10℃ to 60℃, atmospheric pressure to 793KP■
10. A process according to claim 1, wherein the reaction is carried out at a pressure of 1:1 and a molar ratio of the product of step (1) to the added olefin of 1:1. 11. A lightly branched olefin product prepared from low molecular weight C_3 to C_■ olefins or mixtures thereof in the presence of a ZSM-5 group zeolite and a catalytic amount of BF_3/ in a suitable reaction medium. A synthetic lubricating oil range of products prepared by contacting an α-olefin or a mixture of α-olefins added in substantially equimolar amounts in the presence of H_3PO_4 under oligomerization conditions for a sufficient period of time. 12. The α-olefin added is C_■～C_2_0
12. The product of claim 11, wherein the product is selected from α-olefins or mixtures thereof. 13.ZSM-5 group zeolite is ZSM-5, ZSM
-11, ZSM-12, ZSM-22, ZSM-23,
13. The method according to claim 11 or 12, wherein the method is selected from ZSM-35, ZSM-38 or their hydrogen forms.