Methods and systems for converting hydrocarbons

Patent metadata

Field	Value
Publication number	US-10513475-B2
Application number	US-201715839974-A
Country	US
Kind code	B2
Filing date	Dec 13, 2017
Priority date	Dec 14, 2016
Publication date	Dec 24, 2019
Grant date	Dec 24, 2019

Abstract

Methods and systems for converting hydrocarbons including exposing a portion of a hydroperoxide-containing feed including tert-butyl hydroperoxide to a solid deperoxidation catalyst under decomposition conditions to form an oxidation effluent comprising tert-butyl alcohol, wherein the solid deperoxidation catalyst comprises a manganese oxide octahedral molecular sieve, are provided herein. Further methods and systems for converting the oxidation effluent to an alkylation product are also provided herein.

First claim

The invention claimed is:

1. A method for converting hydrocarbons, comprising:
an oxidizing step comprising exposing a portion of a hydroperoxide-containing feed comprising tert-butyl hydroperoxide to a solid deperoxidation catalyst under decomposition conditions to form an oxidation effluent comprising tert-butyl alcohol, wherein the decomposition conditions comprise a temperature of about 50° C. to about 170° C. and a pressure of about 10 psig to about 500 psig, wherein the solid deperoxidation catalyst comprises a manganese oxide octahedral molecular sieve, wherein the manganese oxide octahedral molecular sieve comprises a MnO 6 octahedra which share edges to form a tunnel structure, wherein the oxidizing step further comprises exposing an isoparaffin-containing feed comprising isobutane to oxidation conditions in the presence of oxygen to form the hydroperoxide-containing feed, wherein at least about 10 wt % of the isobutane in the isoparaffin-containing feed is converted to tert-butyl alcohol, and the isoparaffin-containing feed optionally comprises at least about 80 wt % isobutane relative to a weight of the isoparaffin-containing feed, wherein the oxidation conditions comprise a temperature of about 100° C. to about 200° C. and a pressure of about 200 psig to about 1000 psig;
a dehydrating and/or dimerizing step comprising directly exposing a portion of the oxidation effluent to a first solid acid catalyst under dehydrating and/or dimerizing conditions to form an isoolefin-containing effluent comprising 2,4,4-trimethylpent-1-ene and/or 2,4,4-trimethylpent-2-ene, wherein at least about 70 wt % of tert-butyl alcohol is converted to 2,4,4-trimethylpent-1-ene and/or 2,4,4-trimethylpent-2-ene; and
a hydrogenating step comprising directly exposing a portion of the isoolefin-containing effluent to a second solid acid catalyst and hydrogen under hydrogenation conditions to form an alkylation effluent comprising a C 8 fraction comprising at least 50 wt % of 2,3,4-, 2,3,3- and 2,2,4-trimethylpentane having an octane rating, as determined by (RON+MON)/2, of at least about 90, relative to a weight of the C 8 fraction, wherein the first solid acid catalyst and the second solid acid catalyst are the same or different.

2. The method of claim 1 , wherein at least about 70% of the tert-butyl hydroperoxide is converted to tert-butyl alcohol and/or the solid deperoxidation catalyst has a selectivity of at least about 70% for conversion of tert-butyl hydroperoxide to tert-butyl alcohol.

3. The method of claim 1 , wherein at least about 90% of the tert-butyl hydroperoxide is converted to tert-butyl alcohol and/or the solid deperoxidation catalyst has a selectivity of at least about 90% for conversion of tert-butyl hydroperoxide to tert-butyl alcohol.

4. The method of claim 1 , wherein the tunnel structure is 2×2 tunnel structure or 3×3 tunnel structure.

5. The method of claim 1 , wherein the solid deperoxidation catalyst is selected from the group consisting of OMS-2, Nb-OMS-2, K-OMS-2, OMS-1, amorphous manganese oxide and a combination thereof.

6. The method of claim 1 , wherein the oxidation effluent comprises a molar ratio of isobutane to tert-butyl alcohol of about 0:1 to about 2:1.

7. The method of claim 1 , wherein a portion of the oxidation effluent further comprises water, one or more oxygenates, or a combination thereof, and the one or more oxygenates optionally comprises water, methanol, an ester, acetone, or a combination.

8. The method of claim 7 , wherein the ratio by weight of tert-butyl alcohol to methanol in the oxidation effluent is from about 10:1 to about 25:1, the ratio by weight of tert-butyl alcohol to acetone is from about 4:1 to about 20:1, or both.

9. The method of claim 1 , further comprising one or more of:
exposing an n-paraffin-containing feed comprising n-butane to a bifunctional acid catalyst to form the isoparaffin-containing feed via isomerization;
separating a portion of n-butane and/or isobutane from the alkylation effluent to form a first recycle stream;
separating a portion of n-butane and/or isobutane from the oxidation effluent to form a second recycle stream; and
recycling a portion of the first recycle stream and/or the second recycle stream to the n-paraffin-containing feed and/or the isoparaffin-containing feed.

10. The method of claim 1 , wherein the first and/or second solid acid catalyst comprises a zeolite, a mixed metal oxide, or a combination thereof.

11. The method of claim 1 , wherein the first and/or second solid acid catalyst comprises a crystalline microporous material of the MWW framework topology selected from the group consisting of MCM-22, PSH-3, SSZ-25, ERB-1, ITQ-1, ITQ-2, MCM-36, MCM-49, MCM-56, EMM-10, EMM-12, EMM-13, UZM-8, UZM-8HS, UZM-37, MIT-1, and a mixture thereof.

12. The method of claim 1 , wherein the first and/or second solid acid catalyst comprises a mixed metal oxide based on oxides of Fe/W/Zr, W/Zr, Ce/W/Zr, Cu/W/Zr, Mn/W/Zr, or a combination thereof.

13. The method of claim 1 , wherein the first and/or second solid acid catalyst further comprises an inorganic oxide binder, optionally wherein, the inorganic oxide binder comprises alumina, silica or a combination thereof.

14. The method of claim 1 , wherein the dehydrating and/or dimerizing conditions comprise a temperature about 100° C. to about 210° C.

Assignees

• Exxonmobil Res & Eng Co

Inventors

• Liu Sophie
• Dakka Jihad M
• Nandi Partha
• Yacob Sara
• Nizami Quddus A
• Bai Chuansheng

Classifications

• C07C31/125

  containing five to twenty-two carbon atoms · CPC title

• C10G69/126

  polymerisation, e.g. oligomerisation · CPC title

• C07C5/2702

  Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously · CPC title

• C10G50/00

  Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation · CPC title

• C07C5/03

  of non-aromatic carbon-to-carbon double bonds · CPC title