Dealklylation and transalkylation of mixed phenols to make cresols

Patent metadata

Field	Value
Publication number	US-11485694-B2
Application number	US-201917258337-A
Country	US
Kind code	B2
Filing date	Feb 4, 2019
Priority date	Feb 4, 2019
Publication date	Nov 1, 2022
Grant date	Nov 1, 2022

Abstract

Processes of producing cresols from a phenols containing feed are described. The processes involve a combination of dealkylation and transalkylation processes. The dealkylation process converts the heavy alkylphenols in an alkylphenols stream to phenol and olefins. The olefins produced in the dealkylation process are separated out. The methylphenols, which are not converted in the dealkylation process, and phenol react in the transalkylation process to generate cresols.

First claim

What is claimed is:

1. A process of producing cresols from a phenols containing feed comprising:
introducing the phenols containing feed stream into a first separation zone;
separating the phenol containing feed stream in the first separation zone into at least a phenol stream comprising phenol, an alkylphenol stream comprising heavy methyl phenols and heavy alkylphenols, and a cresols stream comprising cresols, wherein the heavy alkylphenols comprise alkylphenols having alkyl groups containing 2 or more carbon atoms;
dealkylating the heavy alkylphenols in the alkylphenols stream in a dealkylation reaction zone in the presence of a dealkylation catalyst under dealkylation conditions to produce cresols, phenol, heavy methyl phenols, and olefins forming a dealkylation effluent stream comprising the phenol, the cresols, the heavy methyl phenols, and the olefins;
separating the dealkylation effluent stream in a dealkylation separation zone into at least an olefin stream comprising the olefins, and a second stream comprising the phenol, the cresols, and the heavy methyl phenols;
introducing the phenol stream from the first separation zone and the second stream from the dealkylation separation zone to the transalkylation reaction zone;
transalkylating the phenol and the heavy methyl phenols in the second stream and the phenol in the phenol stream from the first separation zone in a, transalkylation reaction zone in the presence of a transalkylation catalyst under transalkylation conditions to produce additional cresols forming a transalkylation effluent stream comprising the additional cresols, unreacted phenol, unreacted heavy alkylphenols, and unreacted heavy methyl phenols; and
recovering the cresols stream and optionally the olefin stream, or at least a portion of the phenol stream, or both.

2. The process of claim 1 further comprising:
recycling the transalkylation effluent stream to the first separation zone.

3. The process of claim 1 wherein separating the phenols containing feed stream comprises separating a phenol stream comprising phenol and alkylphenols from the phenols containing feed stream by extraction.

4. The process of claim 3 further comprising:
fractionating the phenols containing feed stream before separating the extracted stream.

5. The process of claim 3 further comprising:
fractionating the extracted phenol stream into at least the phenol stream, the alkylphenol stream, and the cresols stream.

6. The process of claim 4 wherein fractionating the phenols containing feed stream comprises:
fractionating the phenols containing feed stream into a stream comprising components having a boiling below 245° C. and a stream comprising components having a boiling point above 245° C. further comprising one or more of:
recovering naphthols from the stream comprising components having a boiling above 245° C.;
hydroprocessing the stream comprising components having a boiling above 245° C.; or
dealkylating at least a portion of the stream comprising components having a boiling point above 245° C. to form a dealkylated stream and transalkylating at least a portion of the dealkylated stream.

7. The process of claim 5 further comprising purifying the cresols stream.

8. The process of claim 1 wherein separating the dealkylation effluent stream comprises:
fractionating the dealkylation effluent stream into at least the olefin stream and the second stream.

9. The process of claim 1 further comprising:
passing fresh phenol to the transalkylation reaction zone.

10. The process of claim 1 wherein the dealkylation reaction conditions comprise at least one of: a temperature in a range of 100-700° C.; a pressure in a range of 1-5 MPa(a); or a WHSV of 1-5 h −1 .

11. The process of claim 1 wherein the transalkylation reaction conditions comprise at least one of: a temperature in a range of 50-700° C.; a pressure in a range of 100 kPa(a) to 6 MPa(a); or a WHSV in a range of 0.1-20 h −1 .

12. The process of claim 1 further comprising introducing one or more of: a water or steam stream, a hydrogen stream, or a benzene stream to the dealkylation reaction zone.

13. The process of claim 1 wherein the phenols containing feed stream comprises one or more of: a coal tar feed stream, light oil, or a bio-oil feed stream.

14. A process of producing cresols from a phenols containing feed comprising:
introducing a phenols containing feed stream into a first separation zone;
separating the phenols containing feed stream in the first separation zone into at least a phenol stream comprising phenol, an alkylphenol stream comprising heavy methyl phenols and heavy alkylphenols, and a cresols stream comprising cresols, wherein the heavy alkylphenols comprise alkylphenols having alkyl groups containing 2 or more carbon atoms;
dealkylating the heavy alkylphenols in the alkylphenols stream in a dealkylation reaction zone in the presence of a dealkylation catalyst under dealkylation conditions to produce cresols, phenol, heavy methyl phenols, and olefins forming a dealkylation effluent stream comprising the phenol, the cresols, the heavy methyl phenols, and the olefins;
separating the dealkylation effluent stream in a dealkylation separation zone into at least an olefin stream comprising the olefins, and a second stream comprising the phenol, the cresols, and the heavy methyl phenols;
introducing the phenol stream from the first separation zone and the second stream from the dealkylation separation zone to the transalkylation reaction zone;
transalkylating the phenol and the heavy methyl phenols in the second stream and the phenol in the phenol stream in a transalkylation reaction zone in the presence of a transalkylation catalyst under transalkylation conditions to produce additional cresols forming a transalkylation effluent stream comprising the additional cresols, unreacted phenol, unreacted heavy alkylphenols, and unreacted methyl phenols;
recycling the transalkylation effluent stream to the first separation zone; and
recovering the cresols stream and one or more of: at least a portion of the phenol stream, or the olefins stream.

15. The process of claim 14 wherein separating the phenols containing feed stream comprises:
separating an extracted phenol stream comprising phenol and alkylphenols from the phenols containing feed stream by extraction;
fractionating the extracted phenol stream into at least the phenol stream, the alkylphenol stream, and the cresols stream; and
optionally, fractionating the phenols containing feed stream before extracting the extracted phenol stream.

16. The process of claim 14 wherein the dealkylation reaction conditions comprise at least one of: a temperature in a range of 100-700° C.; a pressure in a range of 1-5 MPa(a); or a WHSV of 1-5 h −1 .

17. The process of claim 14 wherein the transalkylation reaction conditions comprise at least one of: a temperature in a range of 50-700° C.; a pressure in a range of100 kPa(a) to 6 MPa(a); or a WHSV of 0.1-20 h −1 .

18. The process of claim 1 wherein the dealkylation catalyst comprises silica alumina, zeolites, gamma alumina, chromium oxide, other oxides or mixed oxides, or combinations thereof, and wherein the transalkylation catalyst comprises zeolites, acidic clay, silica alumina, acidic resins, and mixed metal oxides.

19. The process of claim 14 wherein the dealkylation catalyst comprises silica alumina, zeolites, gamma alumina, chromium oxide, other oxides or mixed oxides, or combinations thereof, and wherein the transalkylation catalyst compris

Assignees

• China Petroleum & Chem Corp
• Uop Llc

Inventors

• Zhang Shuguang
• Zhou Lubo

Classifications

• C07C37/006

  from the petroleum industry · CPC title

• C07C37/50

  by reactions decreasing the number of carbon atoms (C07C37/04, C07C37/045, C07C37/055, C07C37/08 take precedence) · CPC title

• C07C37/007

  from the tar industry · CPC title

• C07C37/48 Primary

  by exchange of hydrocarbon groups, which may be substituted, from the same of other compounds, e.g. transalkylation · CPC title

• C07C39/07

  containing only methyl groups, e.g. cresols, xylenols · CPC title