WO2000039061A1

WO2000039061A1 - Preparation of alkylated diphenyl oxides

Info

Publication number: WO2000039061A1
Application number: PCT/US1999/030967
Authority: WO
Inventors: Margaret May-Son Wu; Rene B. La Pierre; Gillbert Randy Jersey; Andrew G. Horodysky
Original assignee: Mobil Oil AS
Current assignee: Mobil Oil AS
Priority date: 1998-12-30
Filing date: 1999-12-28
Publication date: 2000-07-06
Anticipated expiration: 2001-06-30
Also published as: AU3342700A; WO2000039061A9

Abstract

A continuous process for the manufacture of alkylated diphenyl compounds such as diphenyl ether and diphenyl sulfides by alkylating a diphenyl compound such as diphenyl ether with an olefinic alkylating agent by passing a continuous flow of the diphenyl compound and the olefin over a solid particulate catalyst which comprises a molecular sieve of the MCM-22 family. The process is flexible. By adjusting feed compositions, products of different compositions and wide range of properties are produced.

Description

Preparation of Al ated Diphenyl Oxides

This invention relates to a method for the manufacture of alkylated diphenyl oxides in a convenient continuous flow process.

This application claims priority of U.S. Provisional Patent Application Serial No. 60/114,245, filed 30 December 1998.

Alkylated diphenyl oxide (ADPO) can be used as high performance synthetic base stocks or as starting material for high performance detergents. Polyphenyl ethers are known for their high temperature properties as noted in "Lubricants and Related Products", Klamann, Verlag Chemie, 1984, pp. 116-121. These products can be used as high performance lubricant base stocks or can be used as starting material for high performance detergents such as the sulfonated ADPO which has been reported as a class of high performance detergent.

The known commercial methods for preparing ADPO use Friedel-Crafts catalysts which are not only hazardous but also expensive, being consumed at stoichiometric rates in the reaction but also require aqueous work-up; the large amounts of catalyst residues also present disposal problems. The use of zeolites such as ultra-stable Y catalysts has been propsed, for example, in U.S. Patent No. 5,552,071 (Rudnick) where zeolites such as USY and MCM-22 are proposed for batch operation. Batch processes are not, however, suitable for large-scale and continuous production. The USY catalyst as disclosed in U.S. Patent No. 5,552,071 deactivates quickly and large amount of catalyst is needed to achieve high conversion. This solid catalyst is usually not easily regenerable when used in this type of process and, as a result, has to be disposed as solid waste. There is therefore a need for a continuous process for the production of ADPOs using solid catalyst with long cycle durations in a continuous, fixed bed reactor. We have now found that the catalysts belong to MCM-22 family of molecular sieves have superior activity and can be used in continuous processes to produce ADPO economically in large scale without generating large volumes of catalyst waste.

According to the presnt invention we therefore provide a continuous process for the manufacture of ADPO by alkylating a diphenyl compound such as diphenyl ether itself with an olefinic alkylating agent by passing a continuous flow of the ether and the olefin under alkylation conditions over a solid particulate catalyst which comprises a molecular sieve of the MCM-22 family, preferably zeolite MCM-22. The process is flexible. By adjusting feed compositions, ADPO of different compositions and wide range of properties are produced.

The diphenyl ether reactant is reacted with the olefinic alkylating agent in the presence of the solid molecular sieve catalyst in a continuous flow process in which the catalyst is held in a fixed bed with the reactants being passed over it under fluid flow conditions. The reactants may be in the liquid, gas or mixed (liquid/gas) phases with liquid phase operation being preferred. The temperatures for the reaction will typically be at least ambient and normally will range up to 400°C although 200°C (reactor inlet) represents a useful practical working maximum. Pressure may range from ambient up to any range within the equipment rating although in most cases autogenous pressure may be suitable. Typically pressures will range up to no more than 3,000 kPa (reactor inlet) to permit the use of conventional low pressure equipment. Space velocity (WHSV) will typically be from 0.1 to 10, more usually from 0.2 to 2.0 hr^"1. The catalyst is maintained in a fixed bed and for this purpose, the catalyst is formulated in the conventional manner into particulate form with a size suitable to maintain an acceptable pressure drop across the fixed bed. The molecular sieve compnent may be formulated into the finished particulate catalyst with binders or matrix materials such as alumina, silica or silica-alumina as is conventional or may be a self-bound catalyst. Particles may be cylindrical, lobed, hollow cylindrical, or other suitable configurations for maintaining bed pressure drop within limits. The aromatic compound which is alkylated is a diphenyl ether or sulfide compound, that is a compound containing at least two aromatic rings linked by an oxygen or sulfur bridge. This class of compounds includes diphenyl ether itself, which is a preferred starting material both from the view point of cost as well as from the properties of the final products as well as diphenylk sulfide. It also includes the substituted diphenyl ethers where the substituents may typically be hydrocarbon substituents such as alkyl, aryl, alkaryl, or aralkyl groups but other substituents such as phenolic hydroxyl, mercapto, halo may also be present. The bridging atoms need not be limited to oxygen or sulfur as in the diphenyl oxides and sulfides and phenoxathins but may also include nitrogen as in the phenothiazines.

The alkylating agent is an olefinic alkylating agent, normally a hydrocarbon olefin although substituted olefins may also be used. For superior lubricating peroperties, the longer chain alkyl groups are preferred in the final product, typically from at least eight carbon atoms and preferably at least 10 carbon atoms in order to confer good lubricating performance and good oil solubility characteristics in paraffmic type lubricant materials. For this purpose, olefins of at least eight carbons are preferred although less than eight carbons such as hexene-1 may be used in a similar way. Olefins such as octene, decene, dodecene, tetradecene, hexadecene and octadecene are therefore preferred since olefins of more than 18 carbon atoms do not confer improved solubility or lubricant performance characteristics while tending to cause a deterioration in low temperature viscometrics. The alpha olefins, conveniently available commercially, typically from the ethylene growth reaction, are preferred since they produce alkyl substituents on the aromatic rings which are linear beyond the point of ring attachment and with only a methyl branch at the point of attachment. Thus, the preferred olefinic alkylating agents for alkylated diphenyl ethers which are to be used as lubricants are octene-1 , decene-1 , dodecene-1 , tetradecene-1 , hexadecene-1 and octadecene-1. Longer chain olefins such as the long chain olefins sold commercially as "Gulftene" (™) may be used if desired, for example, for the manufacture of intermediates where a long alkyl chain is required. The ratio between the diphenyl ether and the alkylating agent is typically from 1 :10 to 10:1 molar although considerable excesses of either reactant may be tolerated, especially of the olefin. Normally, ratios between 1 :5 and 5:1 molar are useful. Depending on the ratio, the degree of alkylation may be varied although for lubricant purposes, monoalkylation has been found to provide superior results, as described in U.S. 5,552,071. Ratios between 1 :2 and 2:1 molar will be most commonly used.

The alkylation reaction is carried out in the presence of a particulate catalyst which comprises a molecular sieve of the MCM-22 family, preferably zeolite MCM-22. The MCM-22 family comprises the molecular sieve materials MCM-22, MCM-56 and MCM-49. MCM-22 is described in U.S. Patents Nos. 4,954,325 and 5,100,534 and 5,103,066; MCM-49 and MCM-56 are described in U.S. Patents Nos. 5,362,697; 5,453,554; 5,557,024; 5,827,491 ; 5,362,697 and 5,536,894, to which reference is made for a description of these molecular sieves, their properties and methods for their manufacture.

The MCM-22 family catalyst is a solid, long-lasting, highly productive and regenerable catalyst for producing ADPO class compounds. These type of catalysts has much higher productivity and longer catalyst life time than previous reported USY or other zeolites. They are highly suitable for use in the fixed-bed, continuous operation characteristic of the present manufacturing process.

Example 1 Two grams of a self-bound MCM-22 catalyst crushed and sized to 24/60 mesh size from 3mm extrudate was loaded into a continuous fixed bed reactor of 12mm inside- diameter. The catalyst was purged with nitrogen at 200°C for 16 hours. A mixture of 42.9% diphenyl oxide and 57.1 % 1-hexadecene of 1/1 molar ratio was fed through the reactor (Table 1 ). After adjustment of reaction conditions, reactor temperature was set at 175°C and total liquid feed rate at 4 gram/hour. After a brief line-out time (L05 run in Table 1), the catalyst activity remained constant for 180 hours (run MB5 to MB13). The reaction was terminated while the catalyst was still fully active. During this time, the conversion for the total feed was 83%, for 1-hexadecene 96% and diphenyl oxide 66%. Selectivity to alkylated diphenyl oxide was >95%. The results are shown in Table 1 below.

Table 1

ADPO from DPO and 1-C16 (1/1 molar), MCM-22

Run no MB1* MB2 MB3 MB4 L05 MB5 MB6

Duration, hrs. 1 2 15.5 8 16.5 6.5 17

Temp. C 150 150 150 150 175 175 175

WHSV. g/g/hr 11 11 2 2 2 2 2

Material 89 96 88 102 98 100 95 balance

Product composition by gc, wt%

Light ends 0.0 0.9 0.4 0.2 0.2 0.1 0.2 0.1

DPO 23.6 36.4 26.6 26.6 19.3 16.0 14.9 15.0

C16= 52.8 45.2 28.3 29.5 12.1 4.6 2.8 2.7

MADPO 15.3 16.4 39.5 40.0 56.4 61.9 61.0 62.4

DADPO 8.3 1.2 5.1 3.7 11.4 16.3 19.3 18.8

Others 0.0 0.0 0.0 0.0 0.6 0.5 1.0 1.0

%Conv. 24 18 45 44 68 79 82 82

% DPO Conv. 52 19 40 40 57 64 66 66

% C16 Conv. 20 24 52 50 79 92 95 96

% ADPO 87 96 97 97 97 96 96 97

Select.

% Mono- 65 93 89 91 83 79 76 77

ADPO

%Di-ADPO 35 7 11 9 17 21 24 23

Others 0 0 0 0 1 1 1 1

MADPO - mono-alkylated diphenyl oxide DADPO - di-alkylated diphenyl oxide Table 1 (cont'd)

Run no MB7 MB8 MB9 MB10 MB11 MB12 MB13

Duration, hrs. 6.5 17 23 25.25 24 24.5 19.75

Temp., C 175 175 175 175 175 175 175

WHSV, g/g/hr 2 2 2 2 2 2 2

Material 99 94 96 98 97 97 96 balance

Product composition by gc, wt% light end 0.1 0.4 0.1 0.2 0.1 0.1 0.0

DPO 15.0 15.4 15.5 14.9 14.9 14.9 13.3

C16= 2.7 2.8 2.7 2.9 2.9 2.6 1.8

MADPO 62.4 60.9 61.0 60.8 61.1 61.5 58.5

DADPO 18.8 19.9 19.5 19.6 19.2 19.6 23.8

Others 1.0 0.0 0.6 0.9 1.0 0.7 2.0

% Total Conv. 82 81 82 82 82 82 85

% DPO Conv. 66 65 65 67 67 67 70

% C16 Conv. 96 95 96 95 95 96 97

% ADPO 97 96 95 95 95 96 97

Select.

% mono- 77 75 76 76 76 76 71

ADPO

%Di-ADPO 23 25 24 24 24 24 28

Others 1 0 1 1 1 1 2 Example 2

This was carried our in a similar manner to Example 1 , except a USY catalyst (Englehard) was charged into the fixed bed reactor (Table 2). As these data demonstrated that the total conversion by the USY catalyst was never higher than 10%.

These two examples clearly demonstrate that MCM22 is a much preferred catalyst than USY for ADPO production.

Table 2

ADPO from DPO and 1-C16 (1/1 molar), USY

Run no Starting MB1 MB2 MB3 L04 MB4 mixture

Duration, hrs. 22 25 24 24 24

Temperature, C 175 175 175 200 200

WHSV, g/g/hr 1 1 1 1

Material balance 89 97 97 96

Product composition by gc, wt%

Light ends 0 0.409 0.426 0.542 0.431 0.497

DPO 42.9 39.505 41.383 41.638 41.703 41.549

C16= 57.1 53.248 57.498 57.863 57.334 56.291

Unknown 0.257 0.119 0.077 0.113 0.159

MADPO 6.753 0.944 0.376 0.796 1.943

DADPO 0.176 0 0 0 0.002

% Total Conversion 7 1 0 1 2

% ADPO Selectivity 96 84 75 83 90

% mono-ADPO 97 100 100 100 100

%di-ADPO 3 0 0 0 0

% Uknown 1 Selecti\ tity 4 11 15 12 7

(*) - gc wt% were calculated by sim-dist. method MADPO - mono-alkylated diphenyl oxide DADPO - di-alkylated diphenyl oxide Example 3

In a flask, 90 gram 1-hexadecene and 82 gram DPO (molar ratio of DPO/1-C16 was 1.2) were mixed and heated to 200°C under nitrogen atmosphere. 1.72 gram of a MCM-22 catalyst (αushed powder of the self-bound catalyst, 1 wt% of total feed) was added. Samples were taken after two hours and analyzed on gc (Table 3). The data showed that the reaction was complete after 4 hours of reaction time.

Table 3

ADPO from DPO and 1-C16 (1.2/1 molar), MCM-22, 200°C

Run no Feed 1 distilled Pdt

Time, hrs. 0 2 7.5

Product composition by gc, wt%

Light ends 0.0 0.1 0.1 0.1 0.1 0.1

DPO 45.6 22.0 18.6 18.3 18.2 0.0

C16= 54.2 6.4 2.8 2.3 2.4 0.0

MADPO 0.0 58.4 62.2 60.8 60.6 76.8

Unknown 0.0 0.5 0.0 0.7 0.7 0.0

DADPO 0.0 12.4 14.8 16.5 16.9 21.9

Others 0.2 0.2 1.2 1.3 1.3 1.3

100.0 100.0 100.0 100.0 100.0 100.2

% Total 0 72 79 79 79 79 Conv.

% DPO 52 59 60 60 100 Conv.

% C16 Conv. 88 95 96 96 100

% ADPO 0 99 98 97 97 97 Select.

% mono- 0 82 81 79 79 78 ADPO

% Di-ADPO 0 18 19 21 21 22 Example 4

This was carried out similarly to Example 3, except 100 gram 1-hexadecene and 152 gram DPO (molar ratio of DPO/1-C16 was 2) and 1.26 gram of MCM-22 catalyst (0.5 wt%) were charged into the reactor. The results (Table 4) showed that the reaction was complete after 6 hours of reaction. This example also demonstrated that the product properties and the composition of ADPO can be controlled by adjusting feed composition.

Table 4

ADPO from DPO and 1-C16 (2.0/1 molar ratio), MCM-22, 200°C

Run No. Feed 1 2 3 4 Final

Pdt

Time, hrs 2 4 6 7.5

Product comn by gc, wt%

Light ends 0 0.008 0.013 0.01 0.02 0

DPO 60.3 41.921 34.639 34.094 34.451 0.655

C16= 39.7 9.58 2.356 1.742 1.355 0

Unknown 0 0.046 0.584 0 0 0

MADPO 0 44.888 54.813 55.548 55.429 85.841

DADPO 0 3.497 7.505 8.526 8.659 13.382

Others 0 0.06 0.06 0.081 0.086 0.122

% Total Conv. 0 48 63 64 64 99

% DPO Conv. 30 43 43 43 99

% C16 Conv. 76 94 96 97 100

% ADPO Selec 100 99 100 100 100

% mono- 93 88 87 86 87 ADPO

% Di-ADPO 7 12 13 14 13 Example 5

Under the similar reaction conditions of Example 4, 3-5 wt% of USY catalyst was needed to achieve >80% conversion within 8 hours of reaction time.

The product properties of Example 1 to 4 together with USY products are summarized in Table 5 below.

Table 5

ADPO Product Properties

Example 1 Example 3 Example 4 Example 5

Catalyst MCM-22 MCM-22 MCM-22 USY

Molar ratio of DPO/CK 1.0 1.2 2.0 1.0

Temp, C 175 175 200 200

Fixed bed batch batch batch run wt% catalyst charge — 1 0.5 3-5

% Total conv. 76 79 64 80

% 1-C16 conv. 96 96 97 --

%DPO conv. 67 60 43 —

% Mono-ADPO 76 79 86 97

% Di-ADPO 24 21 14

%Di-ADPO after distilla 32 22 13 3

Lube properties

V100°C, cS 6.0 5.55 4.86 4.44

V40C, cS 36.27 34.16 27.14 23.62

VI 109 98 100 96

Pour point, C -41 -50 -40 -50

Claims

CLAIMS:

1. A continuous process for the manufacture of alkylated diphenyl compounds by alkylating a diphenyl compound with an olefinic alkylating agent by passing a continuous flow of the diphenyl compound and the olefin over a solid particulate catalyst which comprises a molecular sieve of the MCM-22 family under alkylation conditions.

2. A process according to 1 in which the diphenyl compound comprises diphenyl ether.

3. A process according to 1 in which the alkylating agent comprises an olefin of 8 to 18 carbon atoms.

4. A process according to 3 in which the olefin comprises an alpha olefin of 8 to 18 carbon atoms.

5. A process according to 1 in which the molecular sieve comprises zeolite MCM- 22.

6. A process according to 1 in which the reaction is carried out at a temperature from ambient to 200°C

7. A process according to 1 in which the reaction is carried out under a pressure from ambient to 3,000 kPa.

8. A process according to 1 in which the molar ratio of the diphenyl compound to the alkylating agent is from 1 :2 to 2:1.

9. A process according to I in which the diphenyl compound comprises diphenyl ether and the olefinic alkylating agent comprises a Cio to d-» 1 -olefin.

10. A process according to 9 in which the 1 -olefin comprises 1 -tetradecene or 1 -hexadecene.