Production of biphenyl compounds

Patent metadata

Field	Value
Publication number	US-9708230-B2
Application number	US-201514976983-A
Country	US
Kind code	B2
Filing date	Dec 21, 2015
Priority date	Mar 25, 2015
Publication date	Jul 18, 2017
Grant date	Jul 18, 2017

Abstract

In a process for producing biphenyl compounds, a C n aromatic hydrocarbon may be hydroalkylated to give C 2n cycloalkylaromatic compounds and byproduct C n saturated cyclic hydrocarbons. The C 2n cycloalkylaromatic compounds are dehydrogenated to provide the biphenyl compounds. The C n saturated cyclic hydrocarbons may also be dehydrogenated back to the corresponding C n aromatic hydrocarbon, which may be recycled to provide additional feed. Although both the intermediate C 2n cycloalkylaromatic compounds and the byproduct C n saturated cyclic hydrocarbons should be dehydrogenated, at least part of the dehydrogenation of the C n saturated cyclic hydrocarbons should take place in the absence of C 2n or greater hydrocarbons. Thus, dehydrogenation of the byproduct C n saturated cyclic hydrocarbons should take place at least in part separately from dehydrogenation of the C 2n cycloalkylaromatic compounds.

First claim

What is claimed is:

1. A process for producing biphenyl compounds, the process comprising:
(a) contacting a hydroalkylation feed comprising C n aromatic hydrocarbons with hydrogen in the presence of a hydroalkylation catalyst under conditions effective to produce a hydroalkylation reaction effluent comprising (i) C 2n cycloalkylaromatic compounds and (ii) C n saturated cyclic hydrocarbons, wherein 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 C 2n cycloalkylaromatic compounds and at least a portion of the C n 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 C 2n biphenyl compounds; (ii) recovered C n aromatic hydrocarbons; and (iii) unreacted C n saturated cyclic hydrocarbons;
(c) separating the first dehydrogenation reaction product into (i) a heavy dehydrogenation stream rich in the C 2n biphenyl compounds, and (ii) a light dehydrogenation stream rich in the recovered C n aromatic hydrocarbons and the unreacted C n 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 C n saturated cyclic hydrocarbons in the presence of a second dehydrogenation catalyst under conditions effective to produce a second dehydrogenation reaction product comprising additional recovered C n aromatic hydrocarbons;
wherein:
in step (a),
the C n aromatic hydrocarbons are selected from the group consisting of benzene, toluene, ethylbenzene, xylene, and diethylbenzene;
the C 2n cycloalkylaromatic compounds are selected from the group consisting of cyclohexylbenzene, (methylcyclohexyl)toluene, (ethylcyclohexyl) ethylbenzene, (dimethylcyclohexyl)xylene, and (diethylcyclohexyl) diethylbenzene; and
the C n saturated cyclic hydrocarbons are selected from the group consisting of cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, and diethylcyclohexane;
in step (b),
the C 2n biphenyl compounds are each selected from the group consisting of biphenyl, dimethylbiphenyl, diethylbiphenyl, tetramethylbiphenyl, and tetraethylbiphenyl;
the recovered C n aromatic hydrocarbons comprise the same compound or compounds as the C n aromatic hydrocarbons; and
the unreacted C n saturated cyclic hydrocarbons comprise the same compound or compounds as the C n saturated cyclic hydrocarbons; and
in step (e),
the additional recovered C n aromatic hydrocarbons comprise the same compound or compounds as the C n aromatic hydrocarbons; and
wherein the dehydrogenating (e) takes place in the presence of less than about 5.0 wt % C 2n or higher 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 claim 1 , wherein:
in step (a), the C n aromatic hydrocarbons are toluene, the C 2n cycloalkylaromatic compounds are (methylcyclohexyl)toluene, and the C n saturated cyclic hydrocarbons are methylcyclohexane;
in step (b), the C 2n biphenyl compounds are dimethylbiphenyl, the recovered C n aromatic hydrocarbons are toluene, and the unreacted C n saturated cyclic hydrocarbons are methylcyclohexane; and
in step (e), the additional recovered C n aromatic hydrocarbons are toluene.

5. The process of claim 1 , 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 C 2n biphenyl compounds to biphenyl carboxylic acids; and
(h) reacting the biphenyl carboxylic acids with one or more C 1 -C 14 alcohols under conditions effective to produce biphenyl esters.

6. The process of claim 1 , wherein n is an integer from 7 to 11, and further wherein:
(I) the hydroalkylation feed in step (a) further comprises one or more C n+1 -C 12 aromatic hydrocarbons;
(II) the hydroalkylation reaction effluent in step (a) further comprises (iii) one or more C 2n+2 -C 24 cycloalkylaromatic compounds and (iv) one or more C n+1 -C 12 saturated cyclic hydrocarbons;
(III) at least a portion of the one or more C 2n+2 -C 24 cycloalkylaromatic compounds and at least a portion of the one or more C n+1 -C 12 saturated cyclic hydrocarbons are dehydrogenated in the first dehydrogenation zone in step (b) along with the portion of the C 2n cycloalkylaromatic compounds and the portion of the C n saturated cyclic hydrocarbons, such that the first dehydrogenation reaction product in step (b) further comprises (iv) a mixture of C 2n+2 -C 24 biphenyl compounds; (v) one or more recovered C n+1 -C 12 aromatic hydrocarbons; and (vi) unreacted C n+1 -C 12 saturated cyclic hydrocarbons; and
(IV) the light dehydrogenation stream in step (c) further comprises at least a portion of the one or more recovered C n+1 -C 12 aromatic hydrocarbons and at least a portion of the unreacted C n+1 -C 12 saturated cyclic hydrocarbons.

7. The process of claim 1 , wherein n is an integer from 6 to 10, and further wherein:
(I) the hydroalkylation feed in step (a) further comprises one or more C n+1 -C 11 aromatic hydrocarbons;
(II) the hydroalkylation reaction effluent in step (a) further comprises (iii) one or more C 2n+2 -C 22 cycloalkylaromatic compounds and (iv) one or more C n+1 -C 11 saturated cyclic hydrocarbons;
(III) at least a portion of the one or more C 2n+2 -C 22 cycloalkylaromatic compounds and at least a portion of the one or more C n+1 -C 11 saturated cyclic hydrocarbons are dehydrogenated in the first dehydrogenation zone in step (b) along with the portion of the C 2n cycloalkylaromatic compounds and the portion of the C n saturated cyclic hydrocarbons, such that the first dehydrogenation reaction product in step (b) further comprises (iv) a mixture of C 2n+2 -C 22 biphenyl compounds; (v) one or more recovered C n+1 -C 11 aromatic hydrocarbons; and (vi) unreacted C n+1 -C 11 saturated cyclic hydrocarbons; and
(IV) the light dehydrogenation stream in step (c) further comprises at least a portion of the one or more recovered C n+1 -C 11 aromatic hydrocarbons and at least a portion of the unreacted C n+1 -C 11 saturated cyclic hydrocarbons.

8. The process claim 1 , 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 % C 2n or higher hydrocarbons.

9. The process of claim 1 , wherein the rate of conversion of the unreacted C n saturated cyclic hydrocarbons to the additional recovered C n aromatic hydrocarbons in step (e) is at least about 90%.

10. The process of claim 1 , 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.

11. The proc

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Salciccioli Michael
• Dakka Jihad M
• Sangar Neeraj
• Decaul Lorenzo C
• Kheir Ali A

Classifications

• C07C2521/08

  Silica · CPC title

• C07C2/74 Primary

  by addition with simultaneous hydrogenation · CPC title

• C07C5/367

  Formation of an aromatic six-membered ring from an existing six-membered ring, e.g. dehydrogenation of ethylcyclohexane to ethylbenzene · CPC title

• C07C2523/42

  Platinum · CPC title

• C07C67/08

  by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds · CPC title