Production and separation of 3,3′-, 3,4′- and 4,4′-dimethyl biphenyl isomers

Patent metadata

Field	Value
Publication number	US-10138176-B2
Application number	US-201815886408-A
Country	US
Kind code	B2
Filing date	Feb 1, 2018
Priority date	Feb 1, 2017
Publication date	Nov 27, 2018
Grant date	Nov 27, 2018

Abstract

In a process for producing one or more 3,3′-, 3,4′- and 4,4′-dimethyl biphenyl isomers, a feed comprising toluene is contacted with hydrogen in the presence of a hydroalkylation catalyst under conditions effective to produce a hydroalkylation reaction product comprising (methylcyclohexyl)toluenes. At least part of the hydroalkylation reaction product is dehydrogenated in the presence of a dehydrogenation catalyst under conditions effective to produce a dehydrogenation reaction product comprising a mixture of dimethyl biphenyl isomers. The dehydrogenation reaction product is then separated into at least a first stream containing one or more 3,3′-, 3,4′- and 4,4′-dimethyl biphenyl isomers and at least one second stream comprising one or more 2,X′-dimethyl biphenyl isomers (where X is 2, 3, or 4). The 3,3′-, 3,4′- and 4,4′-dimethyl biphenyl isomers are then separated utilizing selective adsorption.

First claim

The invention claimed is:

1. A process for producing one or more 3,3′-, 3,4′- and 4,4′-dimethyl biphenyl isomers, the process comprising:
(a) contacting a feed comprising toluene with hydrogen in the presence of a hydroalkylation catalyst under conditions effective to produce a hydroalkylation reaction product comprising (methylcyclohexyl)toluenes;
(b) dehydrogenating at least part of the hydroalkylation reaction product in the presence of a dehydrogenation catalyst under conditions effective to produce a dehydrogenation reaction product comprising said dimethyl biphenyl isomers;
(c) separating the dehydrogenation reaction product into at least a first stream comprising one or more 3,3′-, 3,4′- and 4,4′-dimethyl biphenyl isomers and at least one second stream comprising one or more 2,X′-dimethyl biphenyl isomers (where X=2, 3 or 4); and
d) separating the 3,3′-, 3,4′- and 4,4′-dimethyl biphenyl isomers in the first stream, wherein said separation comprises at least one selective adsorption using an adsorbent comprising at least one zeolite, wherein the zeolite structure type comprises BEA, FAU, MFI, MEL, MTW, MOR, LTL, EMT, FER, MAZ, MEI, TON, MWW, EUO, MFS, IMF, MRE, ITN, MTT, MSE or IWV, wherein said zeolite has a largest diffuse along dimension of at least about 4 Angstroms (A).

2. A process according to claim 1 , wherein the separation into at least a first stream and at least one second stream comprises distillation and/or crystallization.

3. A process according to claim 1 , wherein the separation of the 3,3′-, 3,4′- and 4,4′-dimethyl biphenyl isomers in the first stream comprises:
(i) contacting the first stream with a first adsorbent thereby selectively adsorbing at least one of the 3,3′-, 3,4′- and 4,4′-dimethyl biphenyl isomers within the adsorbent;
(ii) withdrawing from said first adsorbent a raffinate stream comprising less selectively adsorbed dimethyl biphenyl isomers; and
(iii) withdrawing from said first adsorbent a first extract stream comprising said selectively adsorbed dimethyl biphenyl isomers.

4. A process according to claim 3 , further comprising:
(i) contacting the raffinate stream with a second adsorbent thereby selectively adsorbing one of the dimethyl biphenyl isomers less selectively adsorbed by the first adsorbent; and
(ii) withdrawing from said second adsorbent a second extract stream comprising a less selectively adsorbed dimethyl biphenyl isomer and a third extract stream comprising said selectively adsorbed dimethyl biphenyl isomer.

5. A process according to claim 3 , further comprising selectively crystallizing one of the 3,3′-, 3,4′- and 4,4′-dimethyl biphenyl isomers from the raffinate stream.

6. A process according to claim 1 , wherein the separation of the 3,3′-, 3,4′- and 4,4′-dimethyl biphenyl isomers in the first stream comprises:
(i) separating by crystallization at least one of the isomers to provide a solid product and a raffinate stream comprising non-crystallizing isomers;
(ii) contacting the raffinate stream with an adsorbent thereby selectively adsorbing at least one of the non-crystallizing isomers within the adsorbent;
(iii) withdrawing from said adsorbent an extract stream comprising the less selectively adsorbed dimethyl biphenyl isomer or isomers; and
(iv) withdrawing from said adsorbent another extract stream comprising said selectively adsorbed dimethyl biphenyl isomer or isomers.

7. A process according to claim 1 , further comprising contacting the second stream comprising one or more 2,X′-dimethyl biphenyl isomers (where X=2, 3 or 4) with a hydrogenation catalyst under conditions effective to produce one or more methylcyclohexyl toluene isomers; contacting the said methylcyclohexyl toluene isomers with a transalkylation catalyst under conditions effective to modify the methylcyclohexyl toluene isomer distribution; and contacting the said modified methylcyclohexyl toluene isomer distribution with a dehydrogenation catalyst so as to provide one or more 3,3′-, 3,4′- and/or 4,4′-dimethyl biphenyl isomers.

8. A process according to claim 3 , further comprising contacting any one or more of the raffinate streams with a hydrogenation catalyst under conditions effective to produce one or more methylcyclohexyl toluene isomers, contacting the said methylcyclohexyl toluene isomers with a transalkylation catalyst under conditions effective to modify the methylcyclohexyl toluene isomer distribution and contacting the said modified methylcyclohexyl toluene isomer distribution with a dehydrogenation catalyst so as to provide one or more 3,3′-, 3,4′- and/or 4,4′-dimethyl biphenyl isomers.

9. A process according to claim 4 , further comprising contacting one or more of the extract streams from the first and/or second adsorbent with a hydrogenation catalyst under conditions effective to produce one or more methylcyclohexyl toluene isomers, contacting the said methylcyclohexyl toluene isomers with a transalkylation catalyst under conditions effective to modify the methylcyclohexyl toluene isomer distribution and contacting the said modified methylcyclohexyl toluene isomer distribution with a dehydrogenation catalyst so as to provide one or more 3,3′-, 3,4′- and/or 4,4′-dimethyl biphenyl isomers.

10. A process according to claim 3 , further comprising contacting at least part of the raffinate stream with an isomerization catalyst under conditions effective to produce a mixture of isomers comprising the previously extracted dimethyl biphenyl isomer(s).

11. A process according to claim 4 , further comprising contacting at least part of one or more of the extract streams with an isomerization catalyst under conditions effective to produce a mixture of isomers comprising the previously extracted dimethyl biphenyl isomer(s).

12. A process according to claim 1 , wherein the selective adsorption is performed in the presence of one or more solvents.

13. A process according to claim 12 , wherein the solvent comprises an aromatic hydrocarbon, a saturated hydrocarbon or combinations thereof.

14. A process according to claim 1 , wherein the first stream comprising the 2,X′-DMBP isomers, where X=2, 3 or 4, further comprises one or more of cyclopentadienyl toluenes (CPDTs), 4-methylcyclohexyl toluenes (4,X′-MCHTs), 3-methylcyclohexyl toluenes (3,X′-MCHTs), 2-methylcyclohexyl toluenes (2,X′-MCHT), ethyl- or dimethyl-cyclopentyl toluenes (CPTs), 1-methylcyclohexyl toluenes (1,X′-MCHTs) and dimethyl bicyclohexanes (DMBCHs).

15. A process according to claim 1 , wherein the dehydrogenation product which is separated into at least a first stream comprising one or more 3,3′-, 3,4′- and 4,4′-dimethyl biphenyl isomers and at least one second stream comprising one or more 2,X′-dimethyl biphenyl isomers (where X=2, 3 or 4) comprises 5-50% by weight 3,3′-isomer, 5-80% by weight 3,4′-isomer and 5-90% by weight 4,4′-isomer based on the total weight of the three isomers.

16. A process according to claim 1 , wherein the dehydrogenation product which is separated into at least a first stream comprising one or more 3,3′-, 3,4′- and 4,4′-dimethyl biphenyl isomers and at least one second stream comprising one or more 2,X′-dimethyl biphenyl isomers (where X=2, 3 or 4) comprises 10-40% by weight 3,3′-isomer, 20-70% by weight 3,4′-isomer and 5-30% by weight 4,4′-isomer based on the total weight of the three isomers.

17. A process according to claim 1 , wherein the dehydrogenation product which is separated into at least a first stream comprising one or more 3,3′-, 3,4′- and 4,4′-dimethyl biphenyl isomers and at least one second stream comprising one or more 2,X′-dimethyl biphen

Assignees

• Exxonmobil Res & Eng Co

Inventors

• Lanci Michael P
• Paek Changyub
• Dorsi Catherine M

Classifications

• C07C2/74 Primary

  by addition with simultaneous hydrogenation · CPC title

• C07C5/2732

  Catalytic processes · CPC title

• B01J20/28007

  with size in the range 1-100 nanometers, e.g. nanosized particles, nanofibers, nanotubes, nanowires or the like (carbon nanostructures B01J20/205) · 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

• C07C7/13 Primary

  by molecular-sieve technique · CPC title