Aromatic compositions and methods for obtaining them

Patent metadata

Field	Value
Publication number	US-10710945-B2
Application number	US-201615753023-A
Country	US
Kind code	B2
Filing date	Aug 3, 2016
Priority date	Sep 25, 2015
Publication date	Jul 14, 2020
Grant date	Jul 14, 2020

Abstract

Aromatic compositions useful in various applications, such as aromatic fluid solvents and high temperature heat transfer fluids, are provided herein. Also provided are advantageous methods for obtaining the aromatic compositions, utilizing hydroalkylation of precursor aromatic hydrocarbons such as benzene, toluene, xylene, and the like. Particularly preferred aromatic compositions include one or more of cycloalkylaromatic, dicycloalkylaromatic, biphenyl, terphenyl, and diphenyl oxide compounds. The aromatic compositions may be blended with an aromatic solvent or other aromatic fluid comprising one or more of alkylnaphthalenes, alkylbenzenes, and naphthalene, e.g., to form a useful aromatic fluid solvent, or the aromatic compositions may be utilized as high temperature heat transfer fluids (with or without additional blend components).

First claim

We claim:

1. A process comprising:
(a) obtaining a first aromatic composition from one or more precursor aromatic hydrocarbons, wherein the first aromatic composition comprises one or more of: (i) one or more cycloalkylaromatic compounds; (ii) one or more dicycloalkylaromatic compounds; (iii) one or more biphenyl compounds; and (iv) one or more terphenyl compounds; and
(b) blending the first aromatic composition with a second aromatic composition comprising 8-18 wt % 1-methylnaphthalene, 21-31 wt % 2-methylnaphthalene, 0.1 to 5 wt % 2-ethylnaphthalene, 13-23 wt % dimethyl naphthalene, 2-12 wt % trimethylnaphthalene, 0-15 wt % alkylbenzenes, and 0-15 wt % naphthalene, thereby forming a blended aromatic fluid composition;
wherein obtaining the first aromatic composition comprises one of:
(a-1) contacting a hydroalkylation feed comprising the one or more aromatic hydrocarbons with hydrogen in the presence of a MCM-22 hydroalkylation catalyst so as to produce a hydroalkylation reaction effluent comprising (i) the one or more cycloalkylaromatic compounds and (ii) the one or more dicycloalkylaromatic compounds; and
(a-2) contacting a transalkylation feed comprising the one or more aromatic hydrocarbons with a precursor cycloalkylaromatic compound in the presence of a transalkylation catalyst comprising zeolite beta, zeolite Y, Ultrastable Y (USY), Dealuminated Y (Deal Y), mordenite, ZSM-3, ZSM-4, ZSM-18, ZSM-20, or mixtures thereof, so as to produce a transalkylation reaction effluent comprising the one or more cycloalkylaromatic compounds and the one or more dicycloalkylaromatic compounds.

2. The process of claim 1 , wherein the first aromatic composition comprises the one or more biphenyl compounds and/or the one or more terphenyl compounds, and further wherein obtaining the first aromatic composition further comprises dehydrogenating at least a portion of the hydroalkylation reaction effluent or the transalkylation reaction effluent, thereby obtaining the one or more biphenyl compounds and/or the one or more terphenyl compounds.

3. The process of claim 1 , wherein the first aromatic composition comprises the one or more cycloalkylaromatic compounds and/or the one or more dicycloalkylaromatic compounds.

4. The process of claim 1 , wherein the first aromatic composition comprises each of the one or more cycloalkylaromatic compounds; the one or more dicycloalkylaromatic compounds; the one or more biphenyl compounds; and the one or more terphenyl compounds; and further wherein obtaining the first aromatic composition further comprises dehydrogenating a portion of the hydroalkylation reaction effluent or the transalkylation reaction effluent.

5. The process of claim 1 , wherein: (i) the precursor aromatic hydrocarbons are each independently selected from the group consisting of benzene and C 7 to C 12 alkylbenzenes; (ii) the cycloalkylaromatic compounds are each independently selected from the group consisting of cyclohexylbenzene, methylcyclopentylbenzene, and C 13 to C 24 alkyl-substituted cyclohexylbenzenes; (iii) the dicycloalkylaromatic compounds are each selected from dicyclohexylbenzene and C 19 to C 36 alkyl-substituted dicyclohexylbenzenes; (iv) the biphenyl compounds are each independently selected from biphenyl and C 13 to C 24 alkyl-substituted biphenyl; and (v) the terphenyl compounds are each independently selected from terphenyl and C 19 to C 36 alkyl-substituted terphenyls.

6. The process of claim 1 , wherein: (i) the precursor aromatic hydrocarbons comprise one or more of benzene, toluene, and xylene; (ii) the cycloalkylaromatic compounds comprise one or more of cyclohexylbenzene, methylcyclopentylbenzene, (methylcyclohexyl)toluene, and (dimethylcyclohexyl)-xylene; (iii) the dicycloalkylaromatic compounds comprise one or more of dicyclohexylbenzene, di(methylcyclohexyl)toluene, and di(dimethylcyclohexyl)-xylene; (iv) the biphenyl compounds comprise one or more of biphenyl, dimethylbiphenyl, and tetramethylbiphenyl; and (v) the terphenyl compounds comprise one or more of terphenyl, trimethylterphenyl, and hexamethylterphenyl;
wherein each of the aforementioned phenyl compounds comprises at most one methyl substitution per phenyl ring.

7. The process of claim 1 , wherein: (i) the precursor aromatic hydrocarbons comprise benzene, (ii) the cycloalkylaromatic compounds comprise cyclohexylbenzene and methylcyclopentylbenzene, (iii) the dicycloalkylaromatic compounds comprise dicyclohexylbenzene, (iv) the biphenyl compounds comprise biphenyl, and (v) the terphenyl compounds comprise m-terphenyl and o-terphenyl.

8. The process of claim 1 , wherein the first aromatic composition comprises methylcyclopentylbenzene.

9. The process of claim 1 , wherein: (i) the precursor aromatic hydrocarbons comprise toluene, (ii) the cycloalkylaromatic compounds comprise (methylcyclohexyl)toluene, (iii) the dicycloalkylaromatic compounds comprise di(methylcyclohexyl)toluene, (iv) the biphenyl compounds comprise dimethylbiphenyl, and (v) the terphenyl compounds comprise trimethylterphenyl.

10. The process of claim 1 , wherein the first aromatic composition comprises one or more of dimethylbiphenyl, m-terphenyl, o-terphenyl, m-trimethylterphenyl, and o-trimethylterphenyl.

11. A process comprising:
a) hydroalkylating benzene by contacting a feed comprising the one or more aromatic hydrocarbons with hydrogen in the presence of a MCM-22 hydroalkylation catalyst to form a hydroalkylation reaction effluent comprising cyclohexylbenzene, dicyclohexylbenzene, and methylcyclopentylbenzene;
b) oxidizing at least a portion of the hydroalkylation reaction effluent, forming an oxidation reaction effluent comprising cyclohexylbenzene hydroperoxide;
c) optionally, dehydrogenating an additional portion of the hydroalkylation reaction effluent, forming a dehydrogenation reaction effluent comprising one or more of biphenyl and terphenyl (including m-terphenyl, o-terphenyl, and p-terphenyl);
d) cleaving at least a portion of the oxidation reaction effluent, forming a cleavage reaction product comprising cyclohexanone and phenol;
e) optionally, dehydrating at least a portion of the cleavage reaction product, forming a dehydration reaction effluent comprising diphenyl oxide;
f) forming a first aromatic composition from one or more of: (i) a further portion of the hydroalkylation reaction effluent comprising one or more of cyclohexylbenzene, dicyclohexylbenzene, and methylcyclopentylbenzene; (ii) a further portion of the dehydrogenation reaction effluent comprising biphenyl and/or terphenyl; and (iii) a portion of the dehydration reaction effluent comprising diphenyl oxide; and
g) blending the first aromatic composition with a second aromatic composition comprising 8-18 wt % 1-methylnaphthalene, 21-31 wt % 2-methylnaphthalene, 0.1 to 5 wt % 2-ethylnaphthalene, 13-23 wt % dimethyl naphthalene, 2-12 wt % trimethylnaphthalene, 0-15 wt % alkylbenzenes, and 0-15 wt % naphthalene.

12. The process of claim 11 , wherein the first aromatic composition is formed from the further portion of the hydroalkylation reaction effluent, and further wherein the further portion of the hydroalkylation reaction effluent comprises methylcyclopentylbenzene, such that the first aromatic composition comprises methylcyclopentylbenzene.

13. The process of claim 12 , wherein the further portion of the hydroalkylation reaction effluent further comprises cyclohexylbenzene, such that the first aromatic composition further comprises cyclohexylbenzene.

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Xu Teng
• Davis Stephen M

Classifications

• C09K5/10

  Liquid materials · CPC title

• C07C407/00

  Preparation of peroxy compounds · CPC title

• C07C45/53

  of hydroperoxides · CPC title

• C07C37/08

  by decomposition of hydroperoxides, e.g. cumene hydroperoxide · CPC title

• C07C2/74

  by addition with simultaneous hydrogenation · CPC title