Hydrocarbon conversion

Patent metadata

Field	Value
Publication number	US-9988325-B2
Application number	US-201615240562-A
Country	US
Kind code	B2
Filing date	Aug 18, 2016
Priority date	Sep 25, 2015
Publication date	Jun 5, 2018
Grant date	Jun 5, 2018

Abstract

The invention relates to the hydrocarbon upgrading to produce aromatic hydrocarbon, to equipment and materials useful in such upgrading, and to the use of such upgrading for, e.g., producing aromatic hydrocarbon natural gas. The upgrading can be carried out in the presence of a dehydrocyclization catalyst comprising at least one dehydrogenation component and at least one molecular sieve.

First claim

The invention claimed is:

1. A hydrocarbon conversion process, comprising:
(a) providing a feed comprising A 1 wt. % ethane, A 1 being at least 1, and at least 1 wt. % of C 3+ paraffinic hydrocarbon;
(b) providing first and second catalysts, wherein (i) the first catalyst comprises at least 10 wt. % of a first molecular sieve component and at least 0.005 wt. % of a first dehydrogenation component and (ii) the second catalyst comprises at least 10 wt. % of a second molecular sieve component and at least 0.005 wt. % of a second dehydrogenation component;
(c) contacting the feed with the first catalyst under catalytic dehydrocyclization conditions, including a temperature T 1 in the range of from 400° C. to 630° C. and a pressure P 1 greater than 35 psia (241.3 kPa), to produce a first product comprising (i) at least 1 wt. % of aromatic hydrocarbon, (ii) molecular hydrogen, (iii) A 2 wt. % ethane, A 2 being at least 0.75·A 1 ;
(d) producing a raffinate by removing from the first product an extract comprising at least 50 wt. % of the first product's aromatic hydrocarbon, wherein the raffinate comprises ethane in an amount A 3 wt. %, A 3 being greater than A 2 ; and
(e) contacting at least a portion of the raffinate with the second catalyst under catalytic dehydrocyclization conditions, including a temperature T 2 in the range of from 450° C. to 700° C., and a pressure P 2 ≤35 psia (241.3 kPa), to produce a second product comprising at least 0.5 wt. % of additional aromatic hydrocarbon and ethane in an amount A 4 wt. %, wherein T 1 does not exceed 0.90·T 2 , P 2 is less than P 1 , A 4 is less than A 3 , and (A 4 /A 3 ) is less than (A 2 /A 1 ).

2. The process of claim 1 , wherein (i) the first and second molecular sieve components each comprise (i) one or more of MCM-22, ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, and ZSM-48 and/or (ii) the first and second dehydrogenation components each comprise one or more of Ga, Zn, Cu, Re, Mo, W, La, Fe, Ag, Pt, and Pd.

3. The process of claim 1 , wherein the first and second catalysts have substantially the same composition.

4. The process of claim 1 , wherein
(i) the catalytic dehydrocyclization conditions of step (c) include one or more of T 1 in the range of from 450° C. to 605° C., P 1 in the range of from 37 psia (255.1 kPa) to 80 psia (522 kPa), and a space velocity (WHSV) in the range of from 0.1 hr −1 to 20 hr −1 , and the catalytic dehydrocyclization conditions of step (e) include one or more of T 2 in the range of from 500° C. to 675° C., P 2 ≤30 psia (207 kPa), and a space velocity (WHSV) in the range of from 0.1 hr −1 to 20 hr −1 .

5. The process of claim 1 , wherein
(i) A 1 is in the range of from 10 to 40, and the feed further comprises methane, propane, and butanes;
(ii) A 2 is greater than or equal to A 1 ;
(iii) A 4 is less than 0.90·A 3 ; and
(iv) (A 4 /A 3 ) does not exceed 0.90·(A 2 /A 1 ).

6. The process of claim 1 , wherein
(i) the feed comprises 1 wt. % to 40 wt. % methane; A 1 wt. % ethane, A 1 being in the range of from 10 wt. % to 40 wt. %; 20 wt. % to 50 wt. % propane; and 20 wt. % to 50 wt. % butanes; and substantially saturated C 5+ hydrocarbon;
(ii) A 2 is a least 10, the first product comprises at least 5 wt. % aromatic hydrocarbon and at least 1 wt. % molecular hydrogen, and the first product further comprises at least 10 wt. % methane, no more than 2 wt. % propane, and no more than 1 wt. % butanes;
(iii) the raffinate comprises at least 10 wt. % of the first product's molecular hydrogen, at least 10 wt. % of the first product's methane, and at least 95 wt. % of the first product's ethane; but no more than 5 wt. % of the first product's aromatic hydrocarbon;
(iv) A 4 does not exceed 0.75·A 3 , and the second product comprises at least 2 wt. % of the additional aromatic hydrocarbon;
(v) (A 4 /A 3 ) does not exceed 0.75·(A 2 /A 1 ); and
(vi) P 2 does not exceed 0.80·P 1 .

7. The process of claim 1 , further comprising (i) separating from the second product ≥90 wt. % of the additional aromatic hydrocarbon and (ii) combining at least a portion of the separated additional aromatic hydrocarbon with at least a portion of the extract's aromatic hydrocarbon.

8. The process of claim 1 , wherein raffinate includes at least 25 wt. % of the first product's molecular hydrogen.

9. The process of claim 1 , wherein at least 90 wt. % of the first catalyst is located in a first fixed catalyst bed and at least 90 wt. % of the second catalyst is located in a second fixed catalyst bed.

10. The process of claim 1 , wherein (i) the catalytic dehydrocyclization conditions of step (e) encompass a maximum ethane conversion to aromatic hydrocarbon X ME , (ii) during step (e) the raffinate's ethane is converted to aromatic hydrocarbon at a conversion X 3 , (iii) X 3 does not exceed 0.90·X ME , and (iv) step (e) is carried out for an average cycle time of at least 120 hours.

11. A hydrocarbon upgrading process, comprising:
(a) providing a feed comprising A 1 wt. % ethane, A 1 being at least 10; 1 wt. % to 40 wt. % methane; 20 wt. % to 50 wt. % propane; and 20 to 50 wt. % butanes;
(b) providing first and second catalysts, wherein (i) the first catalyst comprises ≥25 wt. % of a first molecular sieve component and ≥0.5 wt. % of a first dehydrogenation component and (ii) the second catalyst comprises ≥25 wt. % of a second molecular sieve component and ≥0.5 wt. % of a second dehydrogenation component;
(c) contacting the feed with the first catalyst under catalytic dehydrocyclization conditions, including a temperature T 1 in the range of from 400° C. to 630° C. and a pressure P 1 greater than 35 psia (241.3 kPa), to produce a first product comprising ≥10 wt. % aromatic hydrocarbon; molecular hydrogen; A 2 wt. % ethane, A 2 being greater than or equal to A 1 ; 1 wt. % to 40 wt. % methane; ≤1 wt. % propane, and ≤1 wt. % butanes;
(d) producing a raffinate by removing from the first product an extract comprising ≥90 wt. % of the first product's aromatic hydrocarbon, wherein (i) the raffinate comprises A 3 wt. % ethane and (ii) A 3 is at least 1.25·A 2 ; and
(e) contacting at least a portion of the raffinate with the second catalyst under catalytic dehydrocyclization conditions, including a temperature T 2 in the range of from 450° C. to 700° C., and a pressure P 2 that does not exceed 35 psia (241.3 kPa), to produce a second product comprising at least 0.5 wt. % of additional aromatic hydrocarbon and an amount A 4 wt. % of ethane; wherein T 1 does not exceed 0.90·T 2 , P 2 is less than P 1 , A 4 does not exceed 0.95·A 3 , and (A 4 /A 3 ) does not exceed 0.95·(A 2 /A 1 ).

12. The process of claim 11 , wherein (i) the first catalyst comprises at least 90 wt. % of the first molecular sieve component; the second catalyst comprises at least 90 wt. % of the second molecular sieve component; the first and second molecular sieve components each comprise one or more of MCM-22, ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, and ZSM-48; the first catalyst comprises at least 1 wt. % the first dehydrogenation component; the second catalyst comprises at least 1 wt. % the second dehydrogenation component; and the first and second dehydrogenation components each comprise two or more of Ga, Zn, Cu, Re, Mo, W, La, Fe, Ag, Pt, and Pd.

13. The process of claim 11 , wherein (i) the first catalyst comprises at least 50 wt. % of the first molecular sieve component and at least 1 wt. % of the first dehydrogenation component; (ii) the first molecular sieve component comprises at least 90 wt. % of (A) ZSM-5 and/or (B) ZSM-12; and (iii) the first dehydrogenation component comprises ≥90 wt. % of (

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Keusenkothen Paul F
• Buchanan John S
• Ilias Samia
• Shekhar Mayank

Classifications

• C07C2529/06

  Crystalline aluminosilicate zeolites; Isomorphous compounds thereof · CPC title

• C07C5/415 Primary

  with metals · CPC title

• C07C2/76 Primary

  by condensation of hydrocarbons with partial elimination of hydrogen · CPC title

• C10G2300/1051

  Kerosene having a boiling range of about 180 - 230 °C · CPC title

• C10G11/00

  Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils (cracking in direct contact with molten metals or salts C10G9/34) · CPC title