Methods of making porous crystalline materials and their use in hydrocarbon sorption

Patent metadata

Field	Value
Publication number	US-2016102590-A1
Application number	US-201514865006-A
Country	US
Kind code	A1
Filing date	Sep 25, 2015
Priority date	Oct 14, 2014
Publication date	Apr 14, 2016
Grant date	—

Abstract

The present invention relates to a hydrothermally stable form of a porous crystalline material useful in applications where sorbing hydrocarbons is desired. Among such applications is sorption of hydrocarbons from an exhaust stream from an engine in a cold-start condition. A hydrocarbon sorption apparatus including the hydrothermally stable porous crystalline material is provided. In either case, the hydrothermally stable porous crystalline material can contain both 10- and 12-membered ring pore channels, or alternately an 11-membered ring pore channel, as well as have one or more other properties.

First claim

What is claimed is:

1 . A method of treating a cold-start engine exhaust gas stream comprising hydrocarbons and/or other pollutants, the method comprising:
a) flowing the exhaust gas stream over a bed of a porous crystalline material, the porous crystalline material containing both 10- and 12-membered ring pore channels to provide a first treated exhaust stream having lower total hydrocarbon content than that of the exhaust gas stream, wherein the porous crystalline material exhibits one or more of the following properties:
(i) a decrease in micropore volume no more than about 15% after exposure to 100% steam at 800° C. and atmospheric pressure for 5 hours;
(ii) a surface hydroxyl group content after exposure to 100% steam at 800° C. and atmospheric pressure for 5 hours that is less than one or more of (a) a surface hydroxyl group content of an otherwise identical but unsteamed porous crystalline material, (b) a surface hydroxyl group content of an otherwise identical porous crystalline material after exposure to 100% steam at a temperature of 550° C. and atmospheric pressure for 5 hours, and (c) a surface hydroxyl group content of an unsteamed porous crystalline material having a monovalent metal cation content of at least 1.3 wt %;
(iii) a monovalent metal cation content of 1.0 wt % or less of the porous crystalline material;
(iv) a content of ammonium ions (NH 4 + ) of at least 0.5 wt %; and
(v) a content of multivalent metal ions of at least 0.5 wt %.

2 . The method of claim 1 , wherein the first treated exhaust gas stream comprises substantially no hydrocarbons up to a hydrocarbons content of 1 wt % of the exhaust gas stream.

3 . The method of claim 1 , further comprising:
b) flowing the first treated exhaust gas stream over a catalyst to convert any residual hydrocarbons and other pollutants contained in the first treated exhaust gas stream to conversion products to provide a second treated exhaust stream; and c) discharging the second treated exhaust stream.

4 . The method of claim 1 , wherein the porous crystalline material comprises 0.2 wt % or less of monovalent metal cations.

5 . The method of claim 1 , wherein the porous crystalline material comprises substantially no potassium cations.

6 . The method of claim 1 , wherein the porous crystalline material has a silicon to aluminum ratio from 10 to 25.

7 . The method of claim 1 , wherein an IZA framework type of the porous crystalline material comprises one or more of BOG, CON, DFO, ITN, IVR, IWW, MSE, SFV, UOV, USI, and mixtures and intergrowths thereof.

8 . The method of claim 1 , wherein the porous crystalline material has an MSE framework type.

9 . The method of claim 1 , wherein the porous crystalline material contains a metal deposited thereon comprising platinum, palladium, rhodium, ruthenium, or a mixture thereof.

10 . The method of claim 9 , wherein the metal comprises a mixture of platinum and palladium.

11 . The method of claim 1 , wherein the porous crystalline material is synthesized using a structure directing agent comprising N,N,N′,N′-tetraethylbicyclo[2.2.2]oct-7-ene-2,3:5,6-dipyrrolidinium dications; N,N,N′,N′-tetraalkylbicyclo[2.2.2]octane-2,3:5,6-dipyrrolidinium dications; 1,1-dialkyl-4-cyclohexyl-piperazin-1-ium cations; 1,1-dialkyl-4-alkylcyclohexylpiperazin-1-ium cations; 3-hydroxy-1-(4-(1-methylpiperidin-1-ium-1-yl)butyl)quinuclidin-1-ium cations, 3-hydroxy-1-(5-(1-methylpiperidin-1-ium-1-yl)pentyl)quinuclidin-1-ium cations, 1,1′-(butane-1,4-diyl)bis(1-methylpiperidin-1-ium) cations, 1,1′-(pentane-1,5-diyl)bis(1-methyl-piperidin-1-ium) cations, 1,1′-(hexane-1,6-diyl)bis(1-methylpiperidin-1-ium) cations, 1,1′-((3as,6as)-octahydropentalene-2,5-diyl)bis(1-methylpiperidin-1-ium)tetraethyl-ammonium cations, a cation satisfying one or more of the following formulae, or a combination thereof:

where A is a >CR 13 R 14 group, a >C═O group, or an >O group, where R 1 , R 2 , R 3 , R 4 , R 7 , R 8 , R 9 , and R 10 are each independently hydrogen, a hydroxyl group, or a C 1 -C 5 hydrocarbon chain, where R 13 and R 14 are each independently hydrogen, a C 1 -C 5 hydrocarbon chain, a piperidinyl group or a pyrrolidinyl group, where R 5 , R 6 , R 11 , and R 12 are each independently a C 1 -C 5 hydrocarbon chain.

12 . The method of claim 1 , wherein the porous crystalline material bed contains at least one further porous crystalline material having 10-membered ring pore channels or 12-membered ring pore channels, but not both 10-membered ring and 12-membered ring pore channels.

13 . The method of claim 12 , wherein the at least one further porous crystalline material has a framework type comprising BEA, FAU, MFI, FER, or a combination or intergrowth thereof.

14 . The method of claim 1 , wherein the porous crystalline material comprises MCM-68 having a Si/Al 2 mole ratio greater than 8.

15 . A method of treating a cold-start engine exhaust gas stream comprising hydrocarbons and/or other pollutants, the method comprising:
a) flowing the exhaust gas stream over a bed of a porous crystalline material, the porous crystalline material containing an 11-membered ring pore channel to provide a first treated exhaust stream having lower total hydrocarbon content than that of the exhaust gas stream, wherein the porous crystalline material exhibits one or more of the following properties:
(i) a decrease in micropore volume no more than about 15% after exposure to 100% steam at 800° C. and atmospheric pressure for 5 hours;
(ii) a surface hydroxyl group content after exposure to 100% steam at 800° C. and atmospheric pressure for 5 hours that is less than one or more of (a) a surface hydroxyl group content of an otherwise identical but unsteamed porous crystalline material, (b) a surface hydroxyl group content of an otherwise identical porous crystalline material after exposure to 100% steam at a temperature of 550° C. and atmospheric pressure for 5 hours, and (c) a surface hydroxyl group content of an unsteamed porous crystalline material having a monovalent metal cation content of at least 1.3 wt %;
(iii) a monovalent metal cation content of 1.0 wt % or less of the porous crystalline material;
(iv) a content of ammonium ions (NH 4 + ) of at least 0.5 wt %; and
(v) a content of multivalent metal ions of at least 0.5 wt %.

16 . The method of claim 15 , wherein the porous crystalline material comprises EMM-17, NU-86, or a mixture or intergrowth thereof.

17 . A hydrocarbon sorption apparatus comprising a porous crystalline material bed, the porous crystalline material bed comprising a porous crystalline material (1) containing both 10- and 12-membered ring pore channels or (2) containing an 11-membered ring pore channel, wherein the porous crystalline material exhibits one or more of the following properties:
(i) a decrease in micropore volume no more than about 15% after exposure to 100% steam at 800° C. and atmospheric pressure for 5 hours; (ii) a surface hydroxyl group content after exposure to 100% steam at 800° C. and atmospheric pressure for 5 hours that is less than one or more of (a) a surface hydroxyl group content of an otherwise identical but unsteamed porous crystalline material, (b) a surface hydroxyl group content of an otherwise identical porous crystalline material after exposure to 100% steam at a temperature of 550° C. and atmospheric pressure for 5 hours, and (c) a surface hydroxyl group content of an unsteamed porous crystalline material having a mo

Assignees

• Weiss Brian M
• Weigel Scott J
• Strohmaier Karl G
• Lonergan William W
• Exxonmobil Res & Eng Co

Inventors

• Weiss Brian M
• Weigel Scott J
• Strohmaier Karl G
• Lonergan William W

Classifications

• C01B39/026 Primary

  After-treatment · CPC title

• B01D2253/10

  Inorganic adsorbents · CPC title

• B01D2253/1085

  characterized by a silicon-aluminium ratio · CPC title

• F01N3/0807 Primary

  by using absorbents or adsorbents · CPC title

• B01D53/864

  Removing carbon monoxide or hydrocarbons · CPC title