Hydrocarbon conversion

Patent metadata

Field	Value
Publication number	US-9963406-B2
Application number	US-201615240666-A
Country	US
Kind code	B2
Filing date	Aug 18, 2016
Priority date	Sep 25, 2015
Publication date	May 8, 2018
Grant date	May 8, 2018

Abstract

The invention relates to the conversion of paraffinic hydrocarbon to oligomers of greater molecular weight and/or to aromatic hydrocarbon. The invention also relates to equipment and materials useful in such conversion, and to the use of such conversion for, e.g., natural gas upgrading. Corresponding olefinic hydrocarbon is produced from the paraffinic hydrocarbon in the presence of a dehydrogenation catalyst containing a catalytically active carbonaceous component. The corresponding olefinic hydrocarbon is then converted by oligomerization and/or dehydrocyclization in the presence of at least one molecular sieve catalyst.

First claim

The invention claimed is:

1. A process for producing aromatics, comprising:
(a) providing a feed which comprises ≥1 wt. % of a first hydrocarbon and further comprises a second hydrocarbon, wherein (i) the first hydrocarbon comprises C n+ paraffinic hydrocarbon, (ii) the second hydrocarbon comprises C m− hydrocarbon, (iii) n is a positive integer ≥2 and m is a positive integer ≤n−1, and (iv) the feed has a first hydrocarbon:second hydrocarbon molar ratio in the range of from 0.001 to 100;
(b) providing a first multi-component catalyst, the first catalyst having dehydrogenation functionality and comprising (i) ≥10 wt. % of at least one inorganic oxide component having a surface area ≥10 m 2 /g and a pore volume ≥0.1 ml/g, (ii) ≥0.01 wt. % of at least one catalytically active carbonaceous component, and (iii) ≥0.05 wt. % of at least one element selected from Groups 5-11 of the Periodic Table;
(c) providing a second multi-component catalyst, the second catalyst having dehydrocyclization functionality and comprising ≥10 wt. % of a molecular sieve component and ≥0.005 wt. % of a dehydrogenation component comprising at least one element selected from Groups 3 to 13 of the Periodic Table;
(d) reacting the feed in the presence of the first catalyst under catalytic dehydrogenation conditions effective for dehydrogenating ≥10 wt. % of the C n+ paraffinic hydrocarbon of the feed's first hydrocarbon to produce a first product comprising corresponding olefinic hydrocarbon, C m− hydrocarbon, and molecular hydrogen; and
(e) reacting ≥10 wt. % of the first product's corresponding olefinic hydrocarbon in the presence of the second catalyst under catalytic dehydrocyclization conditions to produce a second product comprising aromatics and additional molecular hydrogen.

2. The process of claim 1 , wherein the first catalyst's inorganic oxide component comprises silica and/or alumina.

3. The process of claim 1 , wherein the first catalyst's catalytically active carbonaceous component (i) comprises ≥90 wt. % of carbon and/or carbide, and (ii) has the morphology of one or more of (A) one or more graphene layers, (B) a plurality of nanotubes, and (C) a plurality of nanofibers.

4. The process of claim 1 , wherein component (iii) of the first catalyst comprises one or more metals selected from V, Cr, Mn, Fe, Co, Ni, Pt, Pd, Ru, Au, Mo, and Rh.

5. The process of claim 1 , wherein the second catalyst comprises ≥20 wt. % of the molecular sieve component and ≥0.1 wt. % of the dehydrogenation component.

6. The process of claim 1 , wherein the second catalyst's molecular sieve component comprises one or more of MCM-22, ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, and ZSM-48.

7. The process of claim 1 , wherein the second catalyst's dehydrogenation component comprises two or more of Ga, Zn, Cu, Re, Mo, W, La, Fe, Ag, Pt, and Pd.

8. The process of claim 1 , wherein n=2 and m=1.

9. The process of claim 1 , wherein:
(i) the feed's first hydrocarbon is a mixture of ethane, propane, and butanes;
(ii) the feed's second hydrocarbon comprises methane;
(iii) the feed comprises 10 wt. % to 40 wt. % of the ethane, 20 wt. % to 50 wt. % of the propane, and 20 wt. % to 50 wt. % of the butanes;
(iv) the feed has a first hydrocarbon:second hydrocarbon molar ratio in the range of from 0.01 to 0.05; and
(v) the feed comprises ≤1 wt. % of C 5+ hydrocarbon and ≤1 wt. % of diluent.

10. The process of claim 9 , wherein
(i) the catalytic dehydrogenation conditions include a temperature in the range of from 500° C. to 650° C., a pressure ≥15 psia (103 kPa), and a space velocity (WHSV) ≥0.1 hr −1 , and
(ii) the catalytic dehydrocyclization conditions include a temperature in the range of from 500° C. to 625° C., a pressure in the range of from 30 psia (207 kPa) to 80 psia (522 kPa), and a C 2+ space velocity (WHSV) in the range of from 0.1 hr −1 to 20 hr −1 .

11. A process for producing aromatic hydrocarbon, comprising:
(a) providing a synthesis hydrocarbon for catalyst synthesis, the synthesis hydrocarbon comprising ≥50 wt. % of at least one C 2+ paraffinic hydrocarbon compound;
(b) providing a catalyst precursor comprising at least one element selected from Groups 5-11 of the Periodic Table and at least one inorganic oxide having a surface area ≥10 m 2 /g and a pore volume ≥0.1 ml/g;
(c) exposing the catalyst precursor to a flow of the synthesis hydrocarbon at a temperature in the range of from 500° C. to 750° C., a pressure ≥15 psia (103 kPa), and a space velocity (WHSV) ≥0.1 hr −1 , to produce a first multi-component catalyst having dehydrogenation functionality, the first catalyst comprising (i) ≥10 wt. % of at least one inorganic oxide component having a surface area ≥10 m 2 /g and a pore volume ≥0.1 ml/g, (ii) ≥0.01 wt. % of at least one catalytically active carbonaceous component, and (iii) ≥0.05 wt. % of at least one element selected from Groups 5-11 of the Periodic Table;
(d) providing a feed which comprises ≥1 wt. % of a first hydrocarbon and further comprises a second hydrocarbon, wherein the (i) the first hydrocarbon comprises C n+ paraffinic hydrocarbon, (ii) the second hydrocarbon comprises C m− hydrocarbon, (iii) n is a positive integer ≥2 and m is a positive integer ≤n−1, and (iv) the feed has a first hydrocarbon:second hydrocarbon molar ratio in the range of from 0.001 to 100;
(e) reacting the feed in the presence of the first catalyst under catalytic dehydrogenation conditions effective for dehydrogenating ≥10 wt. % of the of the C n+ paraffinic hydrocarbon of the feed's first hydrocarbon to produce a first product comprising corresponding olefinic hydrocarbon, C m− hydrocarbon, and molecular hydrogen;
(f) providing a second multi-component catalyst, the second catalyst having dehydrocyclization functionality and comprising ≥10 wt. % of a molecular sieve component and ≥0.1 wt. % of a dehydrogenation component comprising at least one element selected from Groups 3 to 13 of the Periodic Table; and
(g) reacting ≥10 wt. % of the first product's corresponding olefinic hydrocarbon in the presence of the second catalyst under catalytic dehydrocyclization conditions to produce a second product comprising aromatics and additional molecular hydrogen.

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Chen Tan-Jen
• Keusenkothen Paul F

Classifications

• B01J27/04

  Sulfides · CPC title

• C07C2/12

  with crystalline alumino-silicates {or with catalysts comprising} molecular sieves · CPC title

• B01J21/12

  Silica and alumina · CPC title

• B01J27/045

  Platinum group metals · CPC title

• B01J27/232

  Carbonates · CPC title