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1. WO2016153575 - PRODUCTION OF BIPHENYL COMPOUNDS

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[ EN ]

CLAIMS

What is claimed is:

1. A process for producing biphenyl compounds, the process comprising:

(a) contacting a hydroalkylation feed comprising Cn aromatic hydrocarbons with hydrogen in the presence of a hydroalkylation catalyst under conditions effective to produce a hydroalkylation reaction effluent comprising (i) C2n cycloalkylaromatic compounds and (ii) Cn saturated cyclic hydrocarbons, where n is an integer from 6 to 12;

(b) providing at least a portion of the hydroalkylation reaction effluent to a first dehydrogenation zone, therein dehydrogenating at least a portion of the C2n cycloalkylaromatic compounds and at least a portion of the Cn saturated cyclic hydrocarbons in the presence of a first dehydrogenation catalyst under conditions effective to produce a first dehydrogenation reaction product comprising (i) a mixture of C2n biphenyl compounds; (ii) recovered Cn aromatic hydrocarbons; and (iii) unreacted Cn saturated cyclic hydrocarbons;

(c) separating the first dehydrogenation reaction product into (i) a heavy dehydrogenation stream rich in the C2n biphenyl compounds, and (ii) a light dehydrogenation stream rich in the recovered Cn aromatic hydrocarbons and the unreacted Cn saturated cyclic hydrocarbons;

(d) providing at least a portion of the light dehydrogenation stream to a second dehydrogenation zone separate from the first dehydrogenation zone; and

(e) in the second dehydrogenation zone, dehydrogenating at least a portion of the unreacted Cn saturated cyclic hydrocarbons in the presence of a second dehydrogenation catalyst under conditions effective to produce a second dehydrogenation reaction product comprising additional recovered Cn aromatic hydrocarbons.

2. The process of claim 1, further comprising

(f) recycling at least a portion of the second dehydrogenation reaction product such that it forms at least a part of the hydroalkylation feed for the hydroalkylation step (a).

3. The process of claim 2, wherein recycling at least a portion of the second dehydrogenation reaction product comprises

(f-1) purifying the second dehydrogenation reaction product to obtain a purified second dehydrogenation reaction product; and

(f-2) providing at least a portion of the purified second dehydrogenation reaction

product as at least part of the hydroalkylation feed for the hydroalkylation step (a).

4. The process of any one of claims 1-3, wherein:

in step (a),

the Cn aromatic hydrocarbons are selected from the group consisting of benzene, toluene, ethylbenzene, xylene, and diethylbenzene;

the C2n cycloalkylaromatic compounds are selected from the group consisting of cyclohexylbenzene, (methylcyclohexyl)toluene, (ethylcyclohexyl) ethylbenzene, (dimethylcyclohexyl)xylene, and (diethylcyclohexyl) diethylbenzene; and

the Cn saturated cyclic hydrocarbons are selected from the group consisting of cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, and diethylcyclohexane;

in step (b),

the C2n biphenyl compounds are each selected from the group consisting of biphenyl, dimethylbiphenyl, diethylbiphenyl, tetramethylbiphenyl, and tetraethylbiphenyl;

the recovered Cn aromatic hydrocarbons comprise the same compound or compounds as the Cn aromatic hydrocarbons; and

the unreacted Cn saturated cyclic hydrocarbons comprise the same compound or compounds as the Cn saturated cyclic hydrocarbons; and

in step (e),

the additional recovered Cn aromatic hydrocarbons comprise the same compound or compounds as the Cn aromatic hydrocarbons.

5. The process of claim 4, wherein:

in step (a), the Cn aromatic hydrocarbons are toluene, the C2n cycloalkylaromatic compounds are (methylcyclohexyl)toluene, and the Cn saturated cyclic hydrocarbons are methylcyclohexane;

in step (b), the C2n biphenyl compounds are dimethylbiphenyl, the recovered Cn aromatic hydrocarbons are toluene, and the unreacted Cn saturated cyclic hydrocarbons are methylcyclohexane; and

in step (e), the additional recovered Cn aromatic hydrocarbons are toluene.

6. The process of claim 4 or claim 5, further comprising:

(g) contacting at least a portion of the heavy dehydrogenation stream obtained in step (c) with an oxidant under conditions effective to convert at least part of the C2n biphenyl compounds to biphenyl carboxylic acids; and

(h) reacting the biphenyl carboxylic acids with one or more Ci - Ci4 alcohols under conditions effective to produce biphenyl esters.

7. The process of any one of claims 1-3, wherein n is an integer from 7 to 11, and further wherein:

(I) the hydroalkylation feed in step (a) further comprises one or more Cn+i - Ci2 aromatic hydrocarbons;

(II) the hydroalkylation reaction effluent in step (a) further comprises (iii) one or more C2n+2 - C24 cycloalkylaromatic compounds and (iv) one or more Cn+i - Ci2 saturated cyclic hydrocarbons;

(III) at least a portion of the one or more C2n+2 - C24 cycloalkylaromatic compounds and at least a portion of the one or more Cn+i - Ci2 saturated cyclic hydrocarbons are dehydrogenated in the first dehydrogenation zone in step (b) along with the portion of the C2n cycloalkylaromatic compounds and the portion of the Cn saturated cyclic hydrocarbons, such that the first dehydrogenation reaction product in step (b) further comprises (iv) a mixture of C2n+2 - C24 biphenyl compounds; (v) one or more recovered Cn+i - Ci2 aromatic hydrocarbons; and (vi) unreacted Cn+i - Ci2 saturated cyclic hydrocarbons; and

(IV) the light dehydrogenation stream in step (c) further comprises at least a portion of the one or more recovered Cn+i - Ci2 aromatic hydrocarbons and at least a portion of the unreacted Cn+i - Ci2 saturated cyclic hydrocarbons.

8. The process of any one of claims 1-3, wherein n is an integer from 6 to 10, and further wherein:

(I) the hydroalkylation feed in step (a) further comprises one or more Cn+i - Cn aromatic hydrocarbons;

(II) the hydroalkylation reaction effluent in step (a) further comprises (iii) one or more

C2n+2 - C22 cycloalkylaromatic compounds and (iv) one or more Cn+i - Cn saturated cyclic hydrocarbons;

(III) at least a portion of the one or more C2n+2 - C22 cycloalkylaromatic compounds and at least a portion of the one or more Cn+i - Cn saturated cyclic hydrocarbons are dehydrogenated in the first dehydrogenation zone in step (b) along with the portion of the C2n cycloalkylaromatic compounds and the portion of the Cn saturated cyclic hydrocarbons, such that the first dehydrogenation reaction product in step (b) further comprises (iv) a mixture of C2n+2 - C22 biphenyl compounds; (v) one or more recovered Cn+i - Cn aromatic

hydrocarbons; and (vi) unreacted Cn+i - Cn saturated cyclic hydrocarbons; and

(IV) the light dehydrogenation stream in step (c) further comprises at least a portion of the one or more recovered Cn+i - Cn aromatic hydrocarbons and at least a portion of the unreacted Cn+i - Cn saturated cyclic hydrocarbons.

9. The process of any one of the foregoing claims, wherein the at least a portion of the light dehydrogenation stream provided to the second dehydrogenation zone in step (d) comprises less than 1.0 wt% C2n or higher hydrocarbons.

10. The process of any one of the foregoing claims, wherein the rate of conversion of the unreacted Cn saturated cyclic hydrocarbons to the additional recovered Cn aromatic hydrocarbons in step (e) is at least about 90%.

11. The process of any one of the foregoing claims, wherein either or both of the first and second dehydrogenation catalysts of steps (b) and (e), respectively, comprises an element or compound thereof selected from group 10 of the Periodic Table of Elements.

12. The process of any one of the foregoing claims, wherein the dehydrogenating (e) takes place in the presence of less than 1.0 wt% C2n or higher hydrocarbons.

13. A process for producing biphenyl compounds, the process comprising:

(a) contacting a hydroalkylation feed comprising at least one Cn aromatic hydrocarbon with hydrogen in the presence of a hydroalkylation catalyst under conditions effective to produce a hydroalkylation reaction effluent comprising (i) a C2n cycloalkylaromatic compound and (ii) a Cn saturated cyclic hydrocarbon, where n is an integer from 6 to 12;

(b) separating the hydroalkylation reaction effluent into (i) a heavy hydroalkylation effluent rich in the C2n cycloalkylaromatic compound and (ii) a light hydroalkylation effluent rich in the Cn saturated cyclic hydrocarbon;

(c) providing at least a portion of the heavy hydroalkylation effluent to a first dehydrogenation zone and therein dehydrogenating at least a portion of the C2n cycloalkylaromatic compound in the presence of a first dehydrogenation catalyst under conditions effective to produce a heavy dehydrogenation reaction product comprising a mixture of C2n biphenyl compounds; and

(d) providing at least a portion of the light hydroalkylation effluent to a second dehydrogenation zone separate from the first dehydrogenation zone, and therein

dehydrogenating at least a portion of the Cn saturated cyclic hydrocarbon in the presence of a second dehydrogenation catalyst under conditions effective to produce a light dehydrogenation reaction product comprising recovered Cn aromatic hydrocarbon.

14. The process of claim 13, further comprising:

(e) recycling at least a portion of the light dehydrogenation reaction product of step (d) such that it forms at least a part of the hydroalkylation feed in step (a).

15. The process of claim 14, wherein recycling at least a portion of the light dehydrogenation reaction product comprises:

(e-1) purifying the light dehydrogenation reaction product to obtain a purified light dehydrogenation reaction product; and

(e-2) providing at least a portion of the purified light dehydrogenation reaction product as at least part of the hydroalkylation feed in step (a).

16. The process of any one of claims 13-15, wherein:

in step (a),

the Cn aromatic hydrocarbon is selected from the group consisting of benzene, toluene, ethylbenzene, xylene, and diethylbenzene;

the Cn cycloalkylaromatic compound is selected from the group consisting of cyclohexylbenzene, (methylcyclohexyl)toluene, (ethylcyclohexyl)ethylbenzene,

(dimethylcyclohexyl)xylene, (diethylcyclohexyl)diethylbenzene, and mixtures thereof; and the Cn saturated cyclic hydrocarbon is selected from the group consisting of cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, and mixtures thereof;

in step (c), the C2n biphenyl compounds are each selected from the group consisting of biphenyl, dimethylbiphenyl, diethylbiphenyl, tetramethylbiphenyl, tetraethylbiphenyl, and mixtures thereof; and

in step (d), the recovered Cn aromatic hydrocarbon comprises the same compound or compounds as the Cn aromatic hydrocarbon.

17. The process of claim 16, wherein:

in step (a), the Cn aromatic hydrocarbon is toluene; the Cn cycloalkylaromatic compound is (methylcyclohexyl)toluene; and the Cn saturated cyclic hydrocarbon is methylcyclohexane;

in step (c), the C2n biphenyl compounds are dimethylbiphenyl; and

in step (d), the recovered Cn aromatic hydrocarbon is toluene.

18. The process of claim 16 or claim 17, further comprising:

(f) contacting at least a portion of the heavy dehydrogenation reaction product of step (c) with an oxidant under conditions effective to convert at least part of the C2n biphenyl compounds to biphenyl carboxylic acids; and

(g) reacting the biphenyl carboxylic acids with one or more Ci to Ci4 alcohols under conditions effective to produce biphenyl esters.

19. The process of any of claims 13-15, wherein n is an integer from 7 to 11, and further wherein:

(I) the hydroalkylation feed in step (a) further comprises one or more Cn+i - Ci2 aromatic hydrocarbons;

(II) the hydroalkylation reaction effluent in step (a) further comprises (iii) one or more C2n+2 - C24 cycloalkylaromatic compounds and (iv) one or more Cn+i - Ci2 saturated cyclic hydrocarbons;

(III) the light hydroalkylation effluent in step (b) further comprises at least a portion of the one or more Cn+i - Ci2 saturated cyclic hydrocarbons; and

(IV) at least a portion of the one or more Cn+i - Ci2 saturated cyclic hydrocarbons are dehydrogenated in the second dehydrogenation zone in step (d) along with said at least a portion of the Cn saturated cyclic hydrocarbon.

20. The process of any of claims 13-15, wherein n is an integer from 6 to 10, and further wherein:

(I) the hydroalkylation feed in step (a) further comprises one or more Cn+i - Cn aromatic hydrocarbons;

(II) the hydroalkylation reaction effluent in step (a) further comprises (iii) one or more C2n+2 - C24 cycloalkylaromatic compounds and (iv) one or more Cn+i - Cn saturated cyclic hydrocarbons;

(III) the light hydroalkylation effluent in step (b) further comprises at least a portion of the one or more Cn+i - Cn saturated cyclic hydrocarbons; and

(IV) at least a portion of the one or more Cn+i - Cn saturated cyclic hydrocarbons are dehydrogenated in the second dehydrogenation zone in step (d) along with said at least a portion of the Cn saturated cyclic hydrocarbon.

21. The process of any one of claims 13-20, wherein the light hydroalkylation effluent in step (b) comprises less than 0.1 wt% C2n or greater hydrocarbons.

22. The process of any one of claims 13-21, wherein the rate of conversion of the Cn saturated cyclic hydrocarbon to recovered Cn aromatic hydrocarbon in step (d) is at least about 90%.

23. The process of any one of claims 13-22, wherein either or both of the first and second dehydrogenation catalysts of steps (c) and (d), respectively, comprises an element or compound thereof selected from group 10 of the Periodic Table of Elements.

24. The process of any one of claims 13-23, wherein the at least a portion of the Cn saturated cyclic hydrocarbon is dehydrogenated in the presence of less than 1.0 wt% C2n or higher hydrocarbons.