Production of Aromatics from Methanol Using Selective Hydrogen Combustion

Patent metadata

Field	Value
Publication number	US-2016145170-A1
Application number	US-201514876952-A
Country	US
Kind code	A1
Filing date	Oct 7, 2015
Priority date	Nov 21, 2014
Publication date	May 26, 2016
Grant date	—

Abstract

A catalyst system and processes for combined aromatization and selective hydrogen combustion of oxygenated hydrocarbons are disclosed. The catalyst system contains at least one aromatization component and at least one selective hydrogen combustion component. The process is such that the yield of hydrogen is less than the yield of hydrogen when contacting the hydrocarbons with the aromatization component alone.

First claim

What is claimed is:

1 . A catalyst system comprising: (1) at least one aromatization component for converting oxygenated hydrocarbons to aromatic compounds and (2) at least one selective hydrogen combustion component for reacting hydrogen with oxygen, said selective hydrogen combustion component consisting essentially of (a) a metal combination selected from the group consisting of:
i) at least one metal from group 3 and at least one metal from groups 4-15 of the Periodic Table of the Elements; ii) at least one metal from groups 5-15 of the Periodic Table of the Elements, and at least one metal from at least one of groups 1, 2, and 4 of the Periodic Table of the Elements; iii) at least one metal from groups 1-2, at least one metal from group 3, and at least one metal from groups 4-15 of the Periodic Table of the Elements; and iv) two or more metals from groups 4-15 of the Periodic Table of the Elements and (b) at least one of oxygen and sulfur, wherein the at least one of oxygen and sulfur is chemically bound both within and between the metals.

2 . The catalyst system of claim 1 , wherein the selective hydrogen combustion component is a combination of metal combination (a) (i) and (b) at least one of oxygen and sulfur.

3 . The catalyst system of claim 2 , wherein the at least one selective hydrogen combustion component comprises one or more of Y a In b Zn c Mn d O x±δ , La a Mn b Ni c Al d O x±δ , La a Mn b Al c O x±δ , Sc a Cu b1 Mn c O x±δ , Sc a Zn b Mn c O x±δ , La a Zr b O x±δ , Mn a Sc b O x±δ , and Pr a In b Zn c O x±δ6 , where a, b, c, and d are each between 0 and 1, the sum of a through d equals 1 to 3, x is the sum of a through d plus 1, and 6 is the vacancy concentration or excess oxygen concentration.

4 . The catalyst system of claim 1 , wherein the selective hydrogen combustion component is a combination of metal combination (a)(ii) and at least one of oxygen and sulfur.

5 . The catalyst system of claim 4 , wherein the at least one selective hydrogen combustion component comprises one or more of K a Ba b Mn c O x±δ , K a Mg b Mn c O x±δ , Na a Mg b Mn c O x±δ , Mn a Mg b O x±δ , K a Sr b Mn c O x±δ , In a Ca b Mn c O x±δ , Bi a Ca b Mn c Co d O x±δ , Bi a Ca b Mn c Ni d O x±δ , Ca a Mn b Sn c Co d O x±δ , In a Mg b Mn c Al d O x±δ , In a Zn b Mn c Al d O x±δ , Na a Ba b Mn c O x±δ , Na a Co b Mn c O x±δ , Ca a Mn b Sb c O x±δ , Ca a Mn b Co c Al d O x±δ , Sr a Sb b Sn c Mg d O x±δ , K a Co b Mn c O x±δ , Mn a Mg b O x±δ , Ni a Mg b Mn c O x±δ , Mn a Mg b Al c O x±δ , Mn a Mg b Ti c O x±δ , Sr a Sb b Ca c O x±δ , Sr a Ti b Sn c Al d O x±δ , Sr a Mn b Ti c Al d O x±δ , Ca a Mn b O x±δ , Ca a Mn b O x±δ , Ca a Zr b Al c O x±δ , Bi a Ca b Mn c O x±δ , Bi a Sr b Co c Fe d O x±δ , Ba a Mn b O x±δ , Ca a Mn b Al c O x±δ , Ca a Na b Sn c O x±δ , and Ba a Zr b O x±δ , where a, b, c, and d are each between 0 and 1, the sum of a through d equals 1 to 3, x is the sum of a through d plus 1, and 6 is the vacancy concentration or excess oxygen concentration.

6 . The catalyst system of claim 1 , wherein the selective hydrogen combustion component is a combination of metal combination (a) (iii) and at least one of oxygen and sulfur.

7 . The catalyst system of claim 6 , wherein the at least one selective hydrogen combustion component comprises one or more of La a Ca b Mn c Co d Ti c O x±δ , La a Ca b Mn c Co d Sn c O x±δ , La a Ca b Co c O x±δ , La a Ca b Mn c Ni d O x±δ , La a Ca b Mn c Co d Sn c O x±δ , La a Ca b Mn c Co d Al c O x±δ , La a Ca b Mn c Co d O x±δ , Ba a K b Bi c La d O x±δ , La a Ca b Mn c Ti d Al c O x±δ , La a Ca b Co c Ni d Al c O x±δ , La a Ca b Co c Ti d O x±δ , La a Ca b Mn c O x±δ , Ba a Bi b La c O x±δ , La a Ca b Mn c Mg d O x±δ , La a Ca b Mn c Fe d O x±δ , La a Sr b Co c Al d O x±δ , Ba a Bi b Yb c O x±δ , La a Ca b Mn c Ga d O x±δ , La a Ca b Mn c Sn d Al c O x±δ , La a Ca b Mn c Cu d O x±δ , La a Ca b Mn c Co d Ga c O x±δ , La a Ca b Mn c Al d O x±δ , La a Ca b Co c Al d O x±δ , Ba a Bi b Sn c La d O x±δ , La a Ca b Mn c Co d Ni c Al f O x±δ , Y a Ca b Mn c O x±δ , La a Ca b Fe c Co d O x±δ , and Sr a Na b Sn e Y d 0 x + 6 , where a, b, c, d, e and f are each between 0 and 1, the sum of a through f equals 1 to 3, x is the sum of a through f plus 1, and 6 is the vacancy concentration or excess oxygen concentration.

8 . The catalyst system of claim 1 , wherein the selective hydrogen combustion component is a combination of metal combination (a) (iv) and at least one of oxygen and sulfur.

9 . The catalyst system of claim 8 , wherein the at least one selective hydrogen combustion component comprises one or more of In a Cu b Mn e O x±δ , Mn a Co b O x±δ , In a Zn b Mn c Al d O x±δ , In a Zn b Mn c O x±δ , Mn a Zn b O x±δ , Mn a Zn b Al c O x±δ , In a Mn b O x±δ , In a Mn b Al c O x±δ , and Mn a Zn b Ti c O x±δ , where a, b, c, and d are each between 0 and 1, the sum of a through d equals 1 to 3, x is the sum of a through d plus 1, and 6 is the vacancy concentration or excess oxygen concentration.

10 . The catalyst system of claim 1 , wherein the selective hydrogen combustion component comprises at least one crystal structure selected from perovskite crystal structure, spinel crystal structure, or birnessite crystal structure.

11 . The catalyst system of claim 1 , wherein the aromatization component and/or the selective hydrogen combustion component further comprises at least one of at least one support, at least one filler and at least one binder.

12 . The catalyst system of claim 1 , wherein the aromatization component comprises (i) at least one zeolite molecular sieve and, optionally, (ii) a group 8-14 element or a combination of metals from the same group of the Periodic Table.

13 . The catalyst system of claim 1 , wherein the aromatization component is in physical admixture with the selective hydrogen combustion component.

14 . The catalyst system of claim 1 , wherein the aromatization component and the selective hydrogen combustion component are chemically bound.

15 . A hydrocarbon conversion process, comprising:
(a) providing a flow-through reactor system containing a catalyst system comprising (i) at least one aromatization component and (ii) at least one selective hydrogen combustion component; (b) during a first time interval,
i. passing oxidant through the flow-through reactor system,
ii. transferring at least a portion of the oxidant's oxygen to the selective hydrogen combustion component for storage,
iii. removing at least a portion of any coke from the catalyst system by oxidation or combustion with the oxidant's oxygen, and
v. lessening or discontinuing the passing of the oxidant through the flow-through reactor;
(c) during a second time interval,
i. passing an oxygenated hydrocarbon feed through the flow-through reactor system,
ii. converting at least a portion of the oxygenated hydrocarbon feed to aromatics and hydrogen in the presence of at least the aromatization component of the catalyst system,
iii. selectively combusting at least a portion of the hydrogen with stored oxygen in the selective hydrogen combustion component of the catalyst system to form water without substantially combusting any of the aromatics or any of the oxygenated hydrocarbon feed; and
(d) conducting at least a portion of a conversion products mixture comprising aromatics and water away from the flow-through reactor system.

16 . The process of claim 15 , wherein the selective hydrogen combustion component of the catalyst system consists essentially of (a) a metal combination selected from the group consisting of:
i) at least one metal from group

Assignees

• Exxonmobil Chem Patents Inc

Inventors

• Keusenkothen Paul F
• Washburn Seth M
• Sangar Neeraj
• Soultanidis Nikolaos
• Shekhar Mayank

Classifications

• B01J29/46

  Iron group metals or copper · CPC title

• C10G3/49

  containing crystalline aluminosilicates, e.g. molecular sieves · CPC title

• B01J8/1863

  followed by a downward movement outside the reactor and subsequently re-entering it · CPC title

• B01J8/0278

  Feeding reactive fluids (for solid material B01J8/0015) · CPC title

• C10G3/46

  in combination with chromium, molybdenum, tungsten metals or compounds thereof · CPC title