Monolithic catalyst comprising molecular sieve membrane and method for perparing the monolithic catalyst

Patent metadata

Field	Value
Publication number	US-2016288104-A1
Application number	US-201615186583-A
Country	US
Kind code	A1
Filing date	Jun 20, 2016
Priority date	Dec 18, 2013
Publication date	Oct 6, 2016
Grant date	—

Abstract

A monolithic catalyst, including cobalt, a metal matrix, a molecular sieve membrane, and an additive. The metal matrix is silver, gold, copper, platinum, titanium, molybdenum, iron, tin, or an alloy thereof. The molecular sieve membrane is mesoporous silica SBA-16 which is disposed on the surface of the metal matrix and is a carrier of the active component and the additive. The thickness of the carrier is between 26 and 67 μm. The additive is lanthanum, zirconium, cerium, rhodium, platinum, rhenium, ruthenium, titanium, magnesium, calcium, strontium, or a mixture thereof. A method for preparing the monolithic catalyst is also provided.

First claim

The invention claimed is:

1 . A monolithic catalyst, comprising:
cobalt; a matrix, the matrix comprising at least one metal selected from the group consisting of silver, gold, copper, platinum, titanium, molybdenum, iron, and tin; an additive, the additive being lanthanum, zirconium, cerium, rhodium, platinum, rhenium, ruthenium, titanium, magnesium, calcium, strontium, or a mixture thereof; and a molecular sieve membrane, the molecular sieve membrane being mesoporous silica SBA-16 which is disposed on a surface of the metal matrix and is a carrier of the cobalt and the additive;
wherein
a thickness of the carrier of the molecular sieve membrane is between 26 and 67 μm.

2 . The catalyst of claim 1 , wherein the thickness of the carrier is between 30 and 60 μm.

3 . A method for preparing a monolithic catalyst of claim 1 , comprising:
1) washing a plurality of metal matrixes having a honeycomb-shape and uniform sizes using deionized water; and drying the metal matrixes in an oven at 100° C.; 2) dissolving molecular sieve powders of the mesoporous silica SBA-16 in absolute ethanol to yield a mixture; oscillating the mixture for 20 to 30 min using an ultrasonic oscillation method to form a uniformly distributed soak solution of the molecular sieve powders; soaking the metal matrixes pretreated in 1) in the soak solution for 1 to 10 s; taking the metal matrixes out, and when the soak solution on the metal matrixes stops flowing and dripping down, soaking the metal matrixes in the soak solution again; repeating the impregnation of the metal matrixes, and then drying the metal matrixes in air; 3) placing the metal matrixes obtained in 2) in a molecular sieve solution of mesoporous silica SBA-16 and crystallizing the mesoporous silica SBA-16 for 5 to 120 hrs at a temperature of between 70 and 150° C. in a reaction still; allowing the mesoporous silica SBA-16 to grow in-situ on a surface of the metal matrixes to yield metal matrixes comprising a molecular sieve membrane; taking out the metal matrixes comprising the molecular sieve membrane, washing the metal matrixes comprising the molecular sieve membrane using deionized water, and drying; and roasting the metal matrixes comprising the molecular sieve membrane for 4 to 8 hrs at a temperature of between 400 and 600° C.; and 4) soaking the metal matrixes comprising the molecular sieve membrane obtained in 3) in a solution of a cobalt salt and the additive for 1 to 20 min; drying the metal matrixes comprising the molecular sieve membrane and aging at room temperature for 3 to 36 hrs; roasting the metal matrixes comprising the molecular sieve membrane for 6 to 12 hrs at a programmed temperature of between 300 and 550° C., and then gradually cooling the metal matrixes comprising the molecular sieve membrane to room temperature.

4 . The method of claim 3 , wherein after the metal matrixes are dried in the oven at 100° C. in 1), the metal matrixes are treated with 0.1 mol/L of hydrochloric acid for 5 to 60 s, washed by deionized water, and dried; then the metal matrixes are treated with 1 mol/L of NaOH, washed by deionized water, and dried; following acid-alkali treatment, the metal matrixes are impregnated in acetone for 0.5 to 1 h, washed by deionized water, and dried; then the metal matrixes are impregnated in hydrogen peroxide for 0.5 to 1 h so as to introduce hydroxyl on the surface of metal matrixes and enhance a durability of the molecular sieve membrane; and then the metal matrixes are washed by deionized water, and dried.

5 . The method of claim 3 , wherein an soaking process in 2) is repeated for between 1 and 20 time(s).

6 . The method of claim 4 , wherein an soaking process in 2) is repeated for between 1 and 20 time(s).

7 . The method of claim 3 , wherein a method for preparing the molecular sieve solution of mesoporous silica SBA-16 in 3) comprises: dissolving P123 (EO 20 PO 70 EO 20 ) and F127 (EO 106 PO 70 EO 106 ) in deionized water and stirring to yield a mixed solution; adding hydrochloric acid to the mixed solution and stirring at 35±5° C.; then adding TEOS (Si(OC 2 H 5 ) 4 ) to the mixed solution and stirring for 1 to 1.2 h; a molar ratio of materials in the molecular sieve solution of mesoporous silica SBA-16 is P123:F127:TEOS:HCl:H 2 O=1:(1-5):(200-800):(1200-3500):(30000-120000).

8 . The method of claim 4 , wherein a method for preparing the molecular sieve solution of mesoporous silica SBA-16 in 3) comprises: dissolving P123 (EO 20 PO 70 EO 20 ) and F127 (EO 106 PO 70 EO 106 ) in deionized water and stirring to yield a mixed solution; adding hydrochloric acid to the mixed solution and stirring at 35±5° C.; then adding TEOS (Si(OC 2 H 5 ) 4 ) to the mixed solution and stirring for 1 to 1.2 h; a molar ratio of materials in the molecular sieve solution of mesoporous silica SBA-16 is P123:F127:TEOS:HCl:H 2 O=1:(1-5):(200-800):(1200-3500):(30000-120000).

9 . The method of claim 3 , wherein in 3), by adjusting components of the molecular sieve solution or repeating times of the in-situ growth of the mesoporous silica SBA-16, the thickness of the molecular sieve membrane is controlled to be between 26 and 67 μm.

10 . The method of claim 4 , wherein in 3), by adjusting components of the molecular sieve solution or repeating times of the in-situ growth of the mesoporous silica SBA-16, the thickness of the molecular sieve membrane is controlled to be between 26 and 67 μm.

11 . The method of claim 3 , wherein a method for preparing the molecular sieve solution of mesoporous silica SBA-16 in 3) comprises: dissolving P123 and F127 in deionized water and stirring to yield a mixed solution; adding hydrochloric acid into the mixed solution and stirring at 35±5° C.; then adding TEOS to the mixed solution and stirring for 1 to 1.2 h; a molar ratio of materials in the molecular sieve solution of mesoporous silica SBA-16 is P123:F127:TEOS:HCl:H 2 O=1:(1-3):(350-650):(1700-3000):(50000-100000).

12 . The method of claim 4 , wherein a method for preparing the molecular sieve solution of mesoporous silica SBA-16 in 3) comprises: dissolving P123 and F127 in deionized water and stirring to yield a mixed solution; adding hydrochloric acid into the mixed solution and stirring at 35±5° C.; then adding TEOS to the mixed solution and stirring for 1 to 1.2 h; a molar ratio of materials in the molecular sieve solution of mesoporous silica SBA-16 is P123:F127:TEOS:HCl:H 2 O=1:(1-3):(350-650):(1700-3000):(50000-100000).

13 . The method of claim 3 , wherein by adjusting components of the molecular sieve solution or repeating times of the in-situ growth of the mesoporous silica SBA-16 in 3), the thickness of the molecular sieve membrane is controlled to be between 30 and 60 μm.

14 . The method of claim 4 , wherein by adjusting components of the molecular sieve solution or repeating times of the in-situ growth of the mesoporous silica SBA-16 in 3), the thickness of the molecular sieve membrane is controlled to be between 30 and 60 μm.

15 . The method of claim 7 , wherein by adjusting components of the molecular sieve solution or repeating times of the in-situ growth of the mesoporous silica SBA-16 in 3), the thickness of the molecular sieve membrane is controlled to be between 30 and 60 μm.

16 . The method of claim 8 , wherein by adjusting components of the molecular sieve solution or repeating times of the in-situ growth of the mesoporous silica SBA-16 in 3), the thickness of the molecular sieve membrane is controlled to be between 30 and 60 μm.

Assignees

• Wuhan Kaidi Eng Tech Res Inst

Inventors

• Li Changyuan
• Liu Qianqian
• Song Dechen
• Yang Weiguang
• Zhan Xiaodong
• Jin Jiaqi
• Zhang Yanfeng

Classifications

• B01J35/56

  Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional [3D] monoliths · CPC title

• B01J23/894 Primary

  with rare earths or actinides · CPC title

• B01J29/70

  of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 · CPC title

• B01J37/343

  of ultrasonic wave energy · CPC title

• B01J37/0217

  Pretreatment of the substrate before coating · CPC title