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

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 m. 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.

Claims

1. A method for preparing 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 m, the method 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.

2. The method of claim 1, 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.

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

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

5. The method of claim 1, wherein a method for preparing the molecular sieve solution of mesoporous silica SBA-16 in 3) comprises: dissolving P123 (EO.sub.20PO.sub.70EO.sub.20) and F127 (EO.sub.106PO.sub.70EO.sub.106) in deionized water and stirring to yield a mixed solution; adding hydrochloric acid to the mixed solution and stirring at 355 C.; then adding TEOS (Si(OC.sub.2H.sub.5).sub.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.sub.2O=1:(1-5):(200-800):(1200-3500):(30000-120000).

6. The method of claim 2, wherein a method for preparing the molecular sieve solution of mesoporous silica SBA-16 in 3) comprises: dissolving P123 (EO.sub.20PO.sub.70EO.sub.20) and F127 (EO.sub.106PO.sub.70EO.sub.106) in deionized water and stirring to yield a mixed solution; adding hydrochloric acid to the mixed solution and stirring at 355 C.; then adding TEOS (Si(OC.sub.2H.sub.5).sub.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.sub.2O=1:(1-5):(200-800):(1200-3500):(30000-120000).

7. The method of claim 1, 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 m.

8. The method of claim 2, 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 m.

9. The method of claim 1, 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 355 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.sub.2O=1:(1-3):(350-650):(1700-3000):(50000-100000).

10. The method of claim 2, 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 355 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.sub.2O=1:(1-3):(350-650):(1700-3000):(50000-100000).

11. The method of claim 1, 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 m.

12. The method of claim 2, 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 m.

13. The method of claim 5, 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 m.

14. The method of claim 6, 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 m.

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

(1) For further illustrating the invention, experiments detailing a monolithic catalyst comprising a molecular sieve membrane on the surface of metal matrix for Fischer-Tropsch synthesis and a method for preparing the same are described below. It should be noted that the following examples are intended to describe and not to limit the invention.

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

(3) The thickness of the carrier is between 30 and 60 m.

(4) A method for preparing the monolithic catalyst comprises:

(5) 1) Pretreatment of Metal Matrixes:

(6) washing a plurality of honeycomb metal matrixes having uniform sizes using deionized water; and drying the metal matrixes in an oven at 100 C.

(7) 2) Implantation of Seed Crystal:

(8) dissolving molecular sieve powders of 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 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;

(9) where, a ratio of the mesoporous silica SBA-16 to absolute ethanol is: every 1-10 g of mesoporous silica SBA-16 powder is dissolved in 100 mL of absolute ethanol;

(10) the ratio is not strictly controlled, because when the concentration of the soak solution becomes relatively low, the soaking period can be prolonged, and when the concentration becomes relatively high, the soaking period can be shortened correspondingly; in addition, ethanol can be replaced by water, acetonitrile, etc. as a solvent.

(11) 3) In-Situ Growth of Molecular Sieve Membrane:

(12) placing the metal matrixes 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 the metal matrixes comprising the molecular sieve membrane out, washing the metal matrixes comprising the molecular sieve membrane using deionized water, and drying; finally, roasting the metal matrixes comprising the molecular sieve membrane for 4 to 8 hrs at a temperature of between 400 and 600 C.;

(13) 4) Impregnation, Aging and Roasting of Active Component and Additive:

(14) soaking the metal matrixes comprising the molecular sieve membrane in a salt solution of the active component of cobalt 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., then cooling the metal matrixes comprising the molecular sieve membrane to room temperature.

(15) In the examples, the active component is Co, and the additive is Pt and Ce; a mass ratio Co:Pt:Ce=15%:0.5%:3% in the salt solution.

(16) 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. After the 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. Finally, the metal matrixes are washed by deionized water, and dried.

(17) The soaking process in 2) is repeated for between 1 and 20 time(s). Preferably, the soaking process is repeated for between 2 and 20 times.

(18) The 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 355 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.sub.2O=1:(1-5):(200-800):(1200-3500):(30000-120000).

(19) Components of the molecular sieve solution are adjustable, and the in-situ growth is repeated in 3) to control the thickness of the carrier that is the molecular sieve membrane on the surface of the metal matrixes to be between 26 and 67 m.

(20) Preferably, 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 355 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.sub.2O=1:(1-3):(350-650):(1700-3000):(50000-100000).

Example 1

(21) 1. Pretreatment of Metal Matrixes

(22) A plurality of stainless steel honeycomb matrixes which were cylinders of 18*30 mm were washed by deionized water and dried in an oven at 100 C. The metal matrixes were treated with 0.1 mol/L of hydrochloric acid for 10 s, washed by deionized water, and dried. Then the matrixes were treated with 1 mol/L of NaOH, washed by deionized water, and dried. After the acid-alkali treatment, the metal matrixes were impregnated in acetone for 1 h, washed by deionized water, and dried. Then the metal matrixes were impregnated in hydrogen peroxide for 1 h so as to introduce hydroxyl on the surface of metal matrixes and enhance a durability of the molecular sieve membrane. Finally, the metal matrixes were washed by deionized water, and dried.

(23) 2. Implantation of Seed Crystal

(24) 2 g of SBA-16 mesoporous molecular sieve was dissolved in 200 mL of absolute ethanol to yield a mixture. The mixture was oscillated for 20 to 30 min using an ultrasonic oscillation method to form a uniformly distributed soak solution of molecular sieve powder. The metal matrixes were impregnated in the soak solution for 1 to 10 s and then taken out. When the soak solution on the metal matrixes stopped flowing and dripping down, the metal matrixes were impregnated again in the soak solution. The soaking process was repeated for a total of 20 times. Then, the metal matrixes were dried in air.

(25) 3. Primary In-Situ Growth of Molecular Sieve Membrane

(26) 5 g of P123 (EO.sub.20PO.sub.70EO.sub.20, M=5800) and 11.8 g of F127 (EO.sub.106PO.sub.70EO.sub.106, M=12600) were dissolved in 1400 mL of deionized water and stirred at a constant temperature of 35 C. to yield a mixed solution. 200 mL of 37 wt. % of hydrochloric acid was added into the mixed solution and stirred at 35 C.; then 65 mL of TEOS (Si(OC.sub.2H.sub.5).sub.4, M=208.33) was added to the mixed solution and stirred for 1 h to prepare the molecular sieve solution of mesoporous silica SBA-16. The preprocessed metal matrixes were fixed by a Teflon standoff and placed into a Teflon bottle. The molecular sieve solution of mesoporous silica SBA-16 was transferred to the Teflon bottle. The reaction still was sealed and rested for 24 hrs at 35 C. Then the mesoporous silica SBA-16 was crystalized for 24 hrs at 80 C. The reaction still was cooled and the metal matrixes comprising molecular sieve membrane were taken out.

(27) The metal matrixes comprising molecular sieve membrane were washed by deionized water to PH=7, dried for 12 hrs in the oven at 100 C., and cooled in air.

(28) Finally, the metal matrixes comprising molecular sieve membrane were roasted in a muffle furnace. In the furnace, the temperature was heated to 400 C. at a speed of 1 C./min and kept for 1 h; Then the temperature was heated to 550 C. at a speed of 1 C./min and kept for 4 hrs; after that, the temperature was decreased to the room temperature at a speed of 0.5 C./min.

(29) The thickness of the molecular sieve membrane on the surface of the metal matrixes is 26 m under scanning electron microscopy.

(30) 4. Impregnation, Aging and Roasting of Active Component and Additive

(31) 14.81 g of Co(NO.sub.3).sub.2.6H.sub.2O, 0.16 g of dinitroso diammineplatinum, and 1.86 g of Ce(NO.sub.3).sub.3.6H.sub.2O were dissolved in deionized water to prepare 15 mL of solvent. The metal matrixes comprising molecular sieve membrane were impregnated in the solvent for 5 min, dried at room temperature for 3 hrs, and dried in the oven for 10 hrs at 100 C. Then the metal matrixes comprising molecular sieve membrane were roasted in the muffle furnace for 6 hrs. In the furnace, the temperature was heated to 400 C. at a speed of 1 C./min for the 6 hours of roasting, and decreased to the room temperature at a speed of 0.5 C./min to yield a catalyst A comprising SBA-16 membrane on the stainless steel matrixes. Components of the catalyst A by the result of XRF are: 15.09% of Co, 0.46% of Pt, and 3.02% of Ce.

Example 2

(32) 1. Pretreatment of Metal Matrixes

(33) A plurality of stainless steel honeycomb matrixes which were cylinders of 18*30 mm were washed by deionized water and dried in an oven at 100 C. The metal matrixes were treated with 0.2 mol/L of hydrochloric acid for 10 s, washed by deionized water, and dried. Then the matrixes were treated with 1 mol/L of NaOH, washed by deionized water, and dried. After the acid-alkali treatment, the metal matrixes were impregnated in acetone for 0.5 h, washed by deionized water, and dried. Then the metal matrixes were impregnated in hydrogen peroxide for 1 h so as to introduce hydroxyl on the surface of metal matrixes and enhance a durability of the molecular sieve membrane. Finally, the metal matrixes were washed by deionized water, and dried.

(34) 2. Implantation of Seed Crystal

(35) 6 g of SBA-16 mesoporous molecular sieve was dissolved in 200 mL of absolute ethanol to yield a mixture. The mixture was oscillated for 20 to 30 min using an ultrasonic oscillation method to form a uniformly distributed soak solution of molecular sieve powder. The metal matrixes were impregnated in the soak solution for 1 to 10 s and then taken out. When the soak solution on the metal matrixes stopped flowing and dripping down, the metal matrixes were impregnated again in the soak solution. The soaking process was repeated for a total of 5 times. Then, the metal matrixes were dried in air.

(36) 3. Primary In-Situ Growth of Molecular Sieve Membrane

(37) 5 g of P123 (EO.sub.20PO.sub.70EO.sub.20, M=5800) and 14.99 g of F127 (EO.sub.106PO.sub.70EO.sub.106, M=12600) were dissolved in 830 mL of deionized water and stirred at a constant temperature of 35 C. to yield a mixed solution. 142 mL of 37 wt. % of hydrochloric acid was added into the mixed solution and stirred at 35 C.; then 76 mL of TEOS (Si(OC.sub.2H.sub.5).sub.4, M=208.33) was added to the mixed solution and stirred for 1 h to prepare the molecular sieve solution of mesoporous silica SBA-16. The preprocessed metal matrixes were fixed by a Teflon standoff and placed into a Teflon bottle. The molecular sieve solution of mesoporous silica SBA-16 was transferred to the Teflon bottle. The reaction still was sealed and rested for 24 hrs at 35 C. Then the mesoporous silica SBA-16 was crystalized for 24 hrs at 90 C. The reaction still was cooled and the metal matrixes comprising molecular sieve membrane were taken out.

(38) The metal matrixes comprising molecular sieve membrane were washed by deionized water to PH=7, dried for 12 hrs in the oven at 100 C., and cooled in air.

(39) Finally, the metal matrixes comprising molecular sieve membrane were roasted in a muffle furnace. In the furnace, the temperature was heated to 400 C. at a speed of 1 C./min and kept for 1 h; Then the temperature was heated to 550 C. at a speed of 1 C./min and kept for 4 hrs; after that, the temperature was decreased to the room temperature at a speed of 0.5 C./min.

(40) The thickness of the molecular sieve membrane on the surface of the metal matrixes is 31 m under scanning electron microscopy.

(41) 4. Impregnation, Aging and Roasting of Active Component and Additive

(42) 14.81 g of Co(NO.sub.3).sub.2.6H.sub.2O, 0.16 g of dinitroso diammineplatinum, and 1.86 g of Ce(NO.sub.3).sub.3.6H.sub.2O were dissolved in deionized water to prepare 15 mL of solvent. The metal matrixes comprising molecular sieve membrane were impregnated in the solvent for 5 min, dried at room temperature for 3 hrs, and dried in the oven for 10 hrs at 100 C. Then the metal matrixes comprising molecular sieve membrane were roasted in the muffle furnace for 6 hrs. In the furnace, the temperature was heated to 400 C. at a speed of 1 C./min for the 6 hours of roasting, and decreased to the room temperature at a speed of 0.5 C./min to yield a catalyst B comprising SBA-16 membrane on the stainless steel matrixes. Components of the catalyst B by the result of XRF are: 15.43% of Co, 0.56% of Pt, and 3.10% of Ce.

Example 3

(43) 1. Pretreatment of Metal Matrixes

(44) A plurality of stainless steel honeycomb matrixes which were cylinders of 18*30 mm were washed by deionized water and dried in an oven at 100 C. The metal matrixes were treated with 0.3 mol/L of hydrochloric acid for 10 s, washed by deionized water, and dried. Then the matrixes were treated with 0.5 mol/L of NaOH, washed by deionized water, and dried. After the acid-alkali treatment, the metal matrixes were impregnated in acetone for 1 h, washed by deionized water, and dried. Then the metal matrixes were impregnated in hydrogen peroxide for 2 hrs so as to introduce hydroxyl on the surface of metal matrixes and enhance a durability of the molecular sieve membrane. Finally, the metal matrixes were washed by deionized water, and dried.

(45) 2. Implantation of Seed Crystal

(46) 5 g of SBA-16 mesoporous molecular sieve was dissolved in 200 mL of absolute ethanol to yield a mixture. The mixture was oscillated for 20 to 30 min using an ultrasonic oscillation method to form a uniformly distributed soak solution of molecular sieve powder. The metal matrixes were impregnated in the soak solution for 1 to 10 s and then taken out. When the soak solution on the metal matrixes stopped flowing and dripping down, the metal matrixes were impregnated again in the soak solution. The soaking process was repeated for a total of 5 times. Then, the metal matrixes were dried in air.

(47) 3. Secondary In-Situ Growth of Molecular Sieve Membrane

(48) To increase the thickness of the molecular sieve membrane, in the example, the molecular sieve membrane grew in-situ twice on the surface of the metal matrixes, which means to repeat the in-situ growth of the molecular sieve membrane after the molecular sieve membrane has grown in-situ, been washed by deionized water, dried, and roasted.

(49) 5 g of P123 (EO.sub.20PO.sub.70EO.sub.20, M=5800) and 10.9 g of F127 (EO.sub.106PO.sub.70EO.sub.106, M=12600) were dissolved in 1550 mL of deionized water and stirred at a constant temperature of 35 C. to yield a first mixed solution. 221.5 mL of 37 wt. % of hydrochloric acid was added into the first mixed solution and stirred at 35 C.; then 117 mL of TEOS (Si(OC.sub.2H.sub.5).sub.4, M=208.33) was added to the mixed solution and stirred for 1 h to prepare the molecular sieve solution of mesoporous silica SBA-16. The preprocessed metal matrixes were fixed by a Teflon standoff and placed into a Teflon bottle. The molecular sieve solution of mesoporous silica SBA-16 was transferred to the Teflon bottle. The reaction still was sealed and rested for 24 hrs at 35 C. Then the mesoporous silica SBA-16 was crystalized for 24 hrs at 100 C. The reaction still was cooled and the metal matrixes comprising molecular sieve membrane were taken out.

(50) The metal matrixes comprising molecular sieve membrane were washed by deionized water to PH=7, dried for 12 hrs in the oven at 100 C., and cooled in air.

(51) Finally, the metal matrixes comprising molecular sieve membrane were roasted in a muffle furnace. In the furnace, the temperature was heated to 400 C. at a speed of 1 C./min and kept for 1 h; Then the temperature was heated to 550 C. at a speed of 1 C./min and kept for 4 hrs; after that, the temperature was decreased to the room temperature at a speed of 0.5 C./min.

(52) Again 5 g of P123 (EO.sub.20PO.sub.70EO.sub.20, M=5800) and 10.9 g of F127 (EO.sub.106PO.sub.70EO.sub.106, M=12600) were dissolved in 1550 mL of deionized water and stirred at a constant temperature of 35 C. to yield a second mixed solution. 223 mL of 37 wt. % of hydrochloric acid was added into the second mixed solution and stirred at 35 C.; then 117 mL of TEOS (Si(OC.sub.2H.sub.5).sub.4, M=208.33) was added to the second mixed solution and stirred for 1 h to prepare the molecular sieve solution of mesoporous silica SBA-16. The metal matrixes comprising molecular sieve membrane were fixed by a Teflon standoff and placed into a Teflon bottle. The molecular sieve solution of mesoporous silica SBA-16 was transferred to the Teflon bottle. The reaction still was sealed and rested for 24 hrs at 35 C. Then the mesoporous silica SBA-16 was crystalized for 24 hrs at 90 C. The reaction still was cooled and the metal matrixes comprising molecular sieve membrane were taken out.

(53) The metal matrixes comprising molecular sieve membrane were washed by deionized water to PH=7, dried for 12 hrs in the oven at 100 C., and cooled in air.

(54) Finally, the metal matrixes comprising molecular sieve membrane were roasted in a muffle furnace. In the furnace, the temperature was heated to 400 C. at a speed of 1 C./min and kept for 1 h; Then the temperature was heated to 550 C. at a speed of 1 C./min and kept for 4 hrs; after that, the temperature was decreased to the room temperature at a speed of 0.5 C./min.

(55) The thickness of the molecular sieve membrane on the surface of the metal matrixes is 43 m under scanning electron microscopy.

(56) 4. Impregnation, Aging and Roasting of Active Component and Additive

(57) 14.81 g of Co(NO.sub.3).sub.2.6H.sub.2O, 0.16 g of dinitroso diammineplatinum, and 1.86 g of Ce(NO.sub.3).sub.3.6H.sub.2O were dissolved in deionized water to prepare 15 mL of solvent. The metal matrixes comprising molecular sieve membrane were impregnated in the solvent for 5 min, dried at room temperature for 3 hrs, and dried in the oven for 10 hrs at 100 C. Then the metal matrixes comprising molecular sieve membrane were roasted in the muffle furnace for 6 hrs. In the furnace, the temperature was heated to 400 C. at a speed of 1 C./min for the 6 hours of roasting, and decreased to the room temperature at a speed of 0.5 C./min to yield a catalyst C comprising SBA-16 membrane on the stainless steel matrixes. Components of the catalyst C by the result of XRF are: 14.97% of Co, 0.49% of Pt, and 3.06% of Ce.

Example 4

(58) 1. Pretreatment of Metal Matrixes

(59) A plurality of stainless steel honeycomb matrixes which were cylinders of 18*30 mm were washed by deionized water and dried in an oven at 100 C. The metal matrixes were treated with 0.1 mol/L of hydrochloric acid for 30 s, washed by deionized water, and dried. Then the matrixes were treated with 1 mol/L of NaOH, washed by deionized water, and dried. After the acid-alkali treatment, the metal matrixes were impregnated in acetone for 0.5 h, washed by deionized water, and dried. Then the metal matrixes were impregnated in hydrogen peroxide for 1 h so as to introduce hydroxyl on the surface of metal matrixes and enhance a durability of the molecular sieve membrane. Finally, the metal matrixes were washed by deionized water, and dried.

(60) 2. Implantation of Seed Crystal

(61) 4 g of SBA-16 mesoporous molecular sieve was dissolved in 200 mL of absolute ethanol to yield a mixture. The mixture was oscillated for 20 to 30 min using an ultrasonic oscillation method to form a uniformly distributed soak solution of molecular sieve powder. The metal matrixes were impregnated in the soak solution for 1 to 10 s and then taken out. When the soak solution on the metal matrixes stopped flowing and dripping down, the metal matrixes were impregnated again in the soak solution. The soaking process was repeated for a total of 10 times. Then, the metal matrixes were dried in air.

(62) 3. Secondary In-Situ Growth of Molecular Sieve Membrane

(63) To increase the thickness of the molecular sieve membrane, in the example, the molecular sieve membrane grew in-situ twice on the surface of the metal matrixes, which means to repeat the in-situ growth of the molecular sieve membrane after the molecular sieve membrane has grown in-situ, been washed by deionized water, dried, and roasted.

(64) 5 g of P123 (EO.sub.20PO.sub.70EO.sub.20, M=5800) and 25.10 g of F127 (EO.sub.106PO.sub.70EO.sub.106, M=12600) were dissolved in 1400 mL of deionized water and stirred at a constant temperature of 35 C. to yield a first mixed solution. 202.9 mL of 37 wt. % of hydrochloric acid was added into the first mixed solution and stirred at 35 C.; then 113 mL of TEOS (Si(OC.sub.2H.sub.5).sub.4, M=208.33) was added to the mixed solution and stirred for 1 h to prepare the molecular sieve solution of mesoporous silica SBA-16. The preprocessed metal matrixes were fixed by a Teflon standoff and placed into a Teflon bottle. The molecular sieve solution of mesoporous silica SBA-16 was transferred to the Teflon bottle. The reaction still was sealed and rested for 24 hrs at 35 C. Then the mesoporous silica SBA-16 was crystalized for 24 hrs at 75 C. The reaction still was cooled and the metal matrixes comprising molecular sieve membrane were taken out.

(65) The metal matrixes comprising molecular sieve membrane were washed by deionized water to PH=7, dried for 12 hrs in the oven at 100 C., and cooled in air.

(66) Finally, the metal matrixes comprising molecular sieve membrane were roasted in a muffle furnace. In the furnace, the temperature was heated to 400 C. at a speed of 1 C./min and kept for 1 h; Then the temperature was heated to 550 C. at a speed of 1 C./min and kept for 4 hrs; after that, the temperature was decreased to the room temperature at a speed of 0.5 C./min.

(67) Again 5 g of P123 (EO.sub.20PO.sub.70EO.sub.20, M=5800) and 25.10 g of F127 (EO.sub.106PO.sub.70EO.sub.106, M=12600) were dissolved in 1400 mL of deionized water and stirred at a constant temperature of 35 C. to yield a second mixed solution. 202.9 mL of 37 wt. % of hydrochloric acid was added into the second mixed solution and stirred at 35 C.; then 113 mL of TEOS (Si(OC.sub.2H.sub.5).sub.4, M=208.33) was added to the second mixed solution and stirred for 1 h to prepare the molecular sieve solution of mesoporous silica SBA-16. The metal matrixes comprising molecular sieve membrane were fixed by a Teflon standoff and placed into a Teflon bottle. The molecular sieve solution of mesoporous silica SBA-16 was transferred to the Teflon bottle. The reaction still was sealed and rested for 24 hrs at 35 C. Then the mesoporous silica SBA-16 was crystalized for 24 hrs at 75 C. The reaction still was cooled and the metal matrixes comprising molecular sieve membrane were taken out.

(68) The metal matrixes comprising molecular sieve membrane were washed by deionized water to PH=7, dried for 12 hrs in the oven at 100 C., and cooled in air.

(69) Finally, the metal matrixes comprising molecular sieve membrane were roasted in a muffle furnace. In the furnace, the temperature was heated to 400 C. at a speed of 1 C./min and kept for 1 h; Then the temperature was heated to 550 C. at a speed of 1 C./min and kept for 4 hrs; after that, the temperature was decreased to the room temperature at a speed of 0.5 C./min.

(70) The thickness of the molecular sieve membrane on the surface of the metal matrixes is 46 m under scanning electron microscopy.

(71) 4. Impregnation, Aging and Roasting of Active Component and Additive

(72) 14.81 g of Co(NO.sub.3).sub.2.6H.sub.2O, 0.16 g of dinitroso diammineplatinum, and 1.86 g of Ce(NO.sub.3).sub.3.6H.sub.2O were dissolved in deionized water to prepare 15 mL of solvent. The metal matrixes comprising molecular sieve membrane were impregnated in the solvent for 5 min, dried at room temperature for 3 hrs, and dried in the oven for 10 hrs at 100 C. Then the metal matrixes comprising molecular sieve membrane were roasted in the muffle furnace for 6 hrs. In the furnace, the temperature was heated to 400 C. at a speed of 1 C./min for the 6 hours of roasting, and decreased to the room temperature at a speed of 0.5 C./min to yield a catalyst D comprising SBA-16 membrane on the stainless steel matrixes. Components of the catalyst D by the result of XRF are: 15.22% of Co, 0.59% of Pt, and 2.95% of Ce.

Example 5

(73) 1. Pretreatment of Metal Matrixes

(74) A plurality of stainless steel honeycomb matrixes which were cylinders of 18*30 mm were washed by deionized water and dried in an oven at 100 C. The metal matrixes were treated with 0.1 mol/L of hydrochloric acid for 15 s, washed by deionized water, and dried. Then the matrixes were treated with 1 mol/L of NaOH, washed by deionized water, and dried. After the acid-alkali treatment, the metal matrixes were impregnated in acetone for 0.5 h, washed by deionized water, and dried. Then the metal matrixes were impregnated in hydrogen peroxide for 0.5 h so as to introduce hydroxyl on the surface of metal matrixes and enhance a durability of the molecular sieve membrane. Finally, the metal matrixes were washed by deionized water, and dried.

(75) 2. Implantation of Seed Crystal

(76) 3 g of SBA-16 mesoporous molecular sieve was dissolved in 200 mL of absolute ethanol to yield a mixture. The mixture was oscillated for 20 to 30 min using an ultrasonic oscillation method to form a uniformly distributed soak solution of molecular sieve powder. The metal matrixes were impregnated in the soak solution for 1 to 10 s and then taken out. When the soak solution on the metal matrixes stopped flowing and dripping down, the metal matrixes were impregnated again in the soak solution. The soaking process was repeated for a total of 15 times. Then, the metal matrixes were dried in air.

(77) 3. Secondary In-Situ Growth of Molecular Sieve Membrane

(78) To increase the thickness of the molecular sieve membrane, in the example, the molecular sieve membrane grew in-situ three times on the surface of the metal matrixes, which means to repeat twice the in-situ growth of the molecular sieve membrane after the molecular sieve membrane has grown in-situ, been washed by deionized water, dried, and roasted.

(79) 5 g of P123 (EO.sub.20PO.sub.70EO.sub.20, M=5800) and 32.6 g of F127 (EO.sub.106PO.sub.70EO.sub.106, M=12600) were dissolved in 790 mL of deionized water and stirred at a constant temperature of 35 C. to yield a first mixed solution. 125.3 mL of 37 wt. % of hydrochloric acid was added into the first mixed solution and stirred at 35 C.; then 90 mL of TEOS (Si(OC.sub.2H.sub.5).sub.4, M=208.33) was added to the mixed solution and stirred for 1 h to prepare the molecular sieve solution of mesoporous silica SBA-16. The preprocessed metal matrixes were fixed by a Teflon standoff and placed into a Teflon bottle. The molecular sieve solution of mesoporous silica SBA-16 was transferred to the Teflon bottle. The reaction still was sealed and rested for 24 hrs at 35 C. Then the mesoporous silica SBA-16 was crystalized for 24 hrs at 85 C. The reaction still was cooled and the metal matrixes comprising molecular sieve membrane were taken out.

(80) The metal matrixes comprising molecular sieve membrane were washed by deionized water to PH=7, dried for 12 hrs in the oven at 100 C., and cooled in air.

(81) Finally, the metal matrixes comprising molecular sieve membrane were roasted in a muffle furnace. In the furnace, the temperature was heated to 400 C. at a speed of 1 C./min and kept for 1 h; Then the temperature was heated to 550 C. at a speed of 1 C./min and kept for 4 hrs; after that, the temperature was decreased to the room temperature at a speed of 0.5 C./min.

(82) Again 5 g of P123 (EO.sub.20PO.sub.70EO.sub.20, M=5800) and 32.6 g of F127 (EO.sub.106PO.sub.70EO.sub.106, M=12600) were dissolved in 790 mL of deionized water and stirred at a constant temperature of 35 C. to yield a second mixed solution. 125.3 mL of 37 wt. % of hydrochloric acid was added into the second mixed solution and stirred at 35 C.; then 90 mL of TEOS (Si(OC.sub.2H.sub.5).sub.4, M=208.33) was added to the second mixed solution and stirred for 1 h to prepare the molecular sieve solution of mesoporous silica SBA-16. The metal matrixes comprising molecular sieve membrane were fixed by a Teflon standoff and placed into a Teflon bottle. The molecular sieve solution of mesoporous silica SBA-16 was transferred to the Teflon bottle. The reaction still was sealed and rested for 24 hrs at 35 C. Then the mesoporous silica SBA-16 was crystalized for 24 hrs at 85 C. The reaction still was cooled and the metal matrixes comprising molecular sieve membrane were taken out.

(83) The metal matrixes comprising molecular sieve membrane were washed by deionized water to PH=7, dried for 12 hrs in the oven at 100 C., and cooled in air.

(84) Finally, the metal matrixes comprising molecular sieve membrane were roasted in a muffle furnace. In the furnace, the temperature was heated to 400 C. at a speed of 1 C./min and kept for 1 h; Then the temperature was heated to 550 C. at a speed of 1 C./min and kept for 4 hrs; after that, the temperature was decreased to the room temperature at a speed of 0.5 C./min.

(85) Once again, 5 g of P123 (EO.sub.20PO.sub.70EO.sub.20, M=5800) and 32.6 g of F127 (EO.sub.106PO.sub.70EO.sub.106, M=12600) were dissolved in 790 mL of deionized water and stirred at a constant temperature of 35 C. to yield a third mixed solution. 125.3 mL of 37 wt. % of hydrochloric acid was added into the third mixed solution and stirred at 35 C.; then 90 mL of TEOS (Si(OC.sub.2H.sub.5).sub.4, M=208.33) was added to the second mixed solution and stirred for 1 h to prepare the molecular sieve solution of mesoporous silica SBA-16. The metal matrixes comprising molecular sieve membrane were fixed by a Teflon standoff and placed into a Teflon bottle. The molecular sieve solution of mesoporous silica SBA-16 was transferred to the Teflon bottle. The reaction still was sealed and rested for 24 hrs at 35 C. Then the mesoporous silica SBA-16 was crystalized for 24 hrs at 85 C. The reaction still was cooled and the metal matrixes comprising molecular sieve membrane were taken out.

(86) The metal matrixes comprising molecular sieve membrane were washed by deionized water to PH=7, dried for 12 h in the oven at 100 C., and cooled in air.

(87) Finally, the metal matrixes comprising molecular sieve membrane were roasted in a muffle furnace. In the furnace, the temperature was heated to 400 C. at a speed of 1 C./min and kept for 1 h; Then the temperature was heated to 550 C. at a speed of 1 C./min and kept for 4 hrs; after that, the temperature was decreased to the room temperature at a speed of 0.5 C./min.

(88) The thickness of the molecular sieve membrane on the surface of the metal matrixes is 73 m under scanning electron microscopy.

(89) 4. Impregnation, Aging and Roasting of Active Component and Additive

(90) 14.81 g of Co(NO.sub.3).sub.2.6H.sub.2O, 0.16 g of dinitroso diammineplatinum, and 1.86 g of Ce(NO.sub.3).sub.3.6H.sub.2O were dissolved in deionized water to prepare 15 mL of solvent. The metal matrixes comprising molecular sieve membrane were impregnated in the solvent for 5 min, dried at room temperature for 3 hrs, and dried in the oven for 10 hrs at 100 C. Then the metal matrixes comprising molecular sieve membrane were roasted in the muffle furnace for 6 hrs. In the furnace, the temperature was heated to 400 C. at a speed of 1 C./min for the 6 hours of roasting, and decreased to the room temperature at a speed of 0.5 C./min to yield a catalyst E comprising SBA-16 membrane on the stainless steel matrixes. Components of the catalyst E by the result of XRF are: 15.22% of Co, 0.59% of Pt, and 2.95% of Ce.

Example 6

(91) 1. Pretreatment of Metal Matrixes

(92) A plurality of stainless steel honeycomb matrixes which were cylinders of 18*30 mm were washed by deionized water and dried in an oven at 100 C. The metal matrixes were treated with 0.1 mol/L of hydrochloric acid for 10 s, washed by deionized water, and dried. Then the matrixes were treated with 1 mol/L of NaOH, washed by deionized water, and dried. After the acid-alkali treatment, the metal matrixes were impregnated in acetone for 1 h, washed by deionized water, and dried. Then the metal matrixes were impregnated in hydrogen peroxide for 1.5 hrs so as to introduce hydroxyl on the surface of metal matrixes and enhance a durability of the molecular sieve membrane. Finally, the metal matrixes were washed by deionized water, and dried.

(93) 2. Implantation of Seed Crystal

(94) 8 g of SBA-16 mesoporous molecular sieve was dissolved in 200 mL of absolute ethanol to yield a mixture. The mixture was oscillated for 20 to 30 min using an ultrasonic oscillation method to form a uniformly distributed soak solution of molecular sieve powder. The metal matrixes were impregnated in the soak solution for 1 to 10 s and then taken out. When the soak solution on the metal matrixes stopped flowing and dripping down, the metal matrixes were impregnated again in the soak solution. The soaking process was repeated for a total of 3 times. Then, the metal matrixes were dried in air.

(95) 3. Secondary In-Situ Growth of Molecular Sieve Membrane

(96) To increase the thickness of the molecular sieve membrane, in the example, the molecular sieve membrane grew in-situ three times on the surface of the metal matrixes, which means to repeat twice the in-situ growth of the molecular sieve membrane after the molecular sieve membrane has grown in-situ, been washed by deionized water, dried, and roasted.

(97) 5 g of P123 (EO.sub.20PO.sub.70EO.sub.20, M=5800) and 16.3 g of F127 (EO.sub.106PO.sub.70EO.sub.106, M=12600) were dissolved in 1089 mL of deionized water and stirred at a constant temperature of 35 C. to yield a first mixed solution. 132 mL of 37 wt. % of hydrochloric acid was added into the first mixed solution and stirred at 35 C.; then 72 mL of TEOS (Si(OC.sub.2H.sub.5).sub.4, M=208.33) was added to the mixed solution and stirred for 1 h to prepare the molecular sieve solution of mesoporous silica SBA-16. The preprocessed metal matrixes were fixed by a Teflon standoff and placed into a Teflon bottle. The molecular sieve solution of mesoporous silica SBA-16 was transferred to the Teflon bottle. The reaction still was sealed and rested for 24 hrs at 35 C. Then the mesoporous silica SBA-16 was crystalized for 24 hrs at 80 C. The reaction still was cooled and the metal matrixes comprising molecular sieve membrane were taken out.

(98) The metal matrixes comprising molecular sieve membrane were washed by deionized water to PH=7, dried for 12 hrs in the oven at 100 C., and cooled in air.

(99) Finally, the metal matrixes comprising molecular sieve membrane were roasted in a muffle furnace. In the furnace, the temperature was heated to 400 C. at a speed of 1 C./min and kept for 1 h; Then the temperature was heated to 550 C. at a speed of 1 C./min and kept for 4 hrs; after that, the temperature was decreased to the room temperature at a speed of 0.5 C./min.

(100) Again 5 g of P123 (EO.sub.20PO.sub.70EO.sub.20, M=5800) and 16.3 g of F127 (EO.sub.106PO.sub.70EO.sub.106, M=12600) were dissolved in 1089 mL of deionized water and stirred at a constant temperature of 35 C. to yield a second mixed solution. 132 mL of 37 wt. % of hydrochloric acid was added into the second mixed solution and stirred at 35 C.; then 72 mL of TEOS (Si(OC.sub.2H.sub.5).sub.4, M=208.33) was added to the mixed solution and stirred for 1 h to prepare the molecular sieve solution of mesoporous silica SBA-16. The metal matrixes comprising molecular sieve membrane were fixed by a Teflon standoff and placed into a Teflon bottle. The molecular sieve solution of mesoporous silica SBA-16 was transferred to the Teflon bottle. The reaction still was sealed and rested for 24 hrs at 35 C. Then the mesoporous silica SBA-16 was crystalized for 24 hrs at 80 C. The reaction still was cooled and the metal matrixes comprising molecular sieve membrane were taken out.

(101) The metal matrixes comprising molecular sieve membrane were washed by deionized water to PH=7, dried for 12 hrs in the oven at 100 C., and cooled in air.

(102) Finally, the metal matrixes comprising molecular sieve membrane were roasted in a muffle furnace. In the furnace, the temperature was heated to 400 C. at a speed of 1 C./min and kept for 1 h Then the temperature was heated to 550 C. at a speed of 1 C./min and kept for 4 hrs; after that, the temperature was decreased to the room temperature at a speed of 0.5 C./min.

(103) Once again, 5 g of P123 (EO.sub.20PO.sub.70EO.sub.20, M=5800) and 16.3 g of F127 (EO.sub.106PO.sub.70EO.sub.106, M=12600) were dissolved in 1089 mL of deionized water and stirred at a constant temperature of 35 C. to yield a third mixed solution. 132 mL of 37 wt. % of hydrochloric acid was added into the third mixed solution and stirred at 35 C.; then 72 mL of TEOS (Si(OC.sub.2H.sub.5).sub.4, M=208.33) was added to the mixed solution and stirred for 1 h to prepare the molecular sieve solution of mesoporous silica SBA-16. The metal matrixes comprising molecular sieve membrane were fixed by a Teflon standoff and placed into a Teflon bottle. The molecular sieve solution of mesoporous silica SBA-16 was transferred to the Teflon bottle. The reaction still was sealed and rested for 24 hrs at 35 C. Then the mesoporous silica SBA-16 was crystalized for 24 hrs at 80 C. The reaction still was cooled and the metal matrixes comprising molecular sieve membrane were taken out.

(104) The metal matrixes comprising molecular sieve membrane were washed by deionized water to PH=7, dried for 12 hrs in the oven at 100 C., and cooled in air.

(105) Finally, the metal matrixes comprising molecular sieve membrane were roasted in a muffle furnace. In the furnace, the temperature was heated to 400 C. at a speed of 1 C./min and kept for 1 h; Then the temperature was heated to 550 C. at a speed of 1 C./min and kept for 4 hrs; after that, the temperature was decreased to the room temperature at a speed of 0.5 C./min.

(106) The thickness of the molecular sieve membrane on the surface of the metal matrixes is 60 m under scanning electron microscopy.

(107) 4. Impregnation, Aging and Roasting of Active Component and Additive

(108) 14.81 g of Co(NO.sub.3).sub.2.6H.sub.2O, 0.16 g of dinitroso diammineplatinum, and 1.86 g of Ce(NO.sub.3).sub.3.6H.sub.2O were dissolved in deionized water to prepare 15 mL of solvent. The metal matrixes comprising molecular sieve membrane were impregnated in the solvent for 5 min, dried at room temperature for 3 hrs, and dried in the oven for 10 hrs at 100 C. Then the metal matrixes comprising molecular sieve membrane were roasted in the muffle furnace for 6 hrs. In the furnace, the temperature was heated to 400 C. at a speed of 1 C./min for the 6 hours of roasting, and decreased to the room temperature at a speed of 0.5 C./min to yield a catalyst F comprising SBA-16 membrane on the stainless steel matrixes. Components of the catalyst F by the result of XRF are: 15.31% of Co, 0.46% of Pt, and 3.03% of Ce.

Example 7

(109) 1. Pretreatment of Metal Matrixes

(110) A plurality of stainless steel honeycomb matrixes which were cylinders of 18*30 mm were washed by deionized water and dried in an oven at 100 C. The metal matrixes were treated with 0.1 mol/L of hydrochloric acid for 10 s, washed by deionized water, and dried. Then the matrixes were treated with 1 mol/L of NaOH, washed by deionized water, and dried. After the acid-alkali treatment, the metal matrixes were impregnated in acetone for 1 h, washed by deionized water, and dried. Then the metal matrixes were impregnated in hydrogen peroxide for 2 hrs so as to introduce hydroxyl on the surface of metal matrixes and enhance a durability of the molecular sieve membrane. Finally, the metal matrixes were washed by deionized water, and dried.

(111) 2. Implantation of Seed Crystal

(112) 10 g of SBA-16 mesoporous molecular sieve was dissolved in 200 mL of absolute ethanol to yield a mixture. The mixture was oscillated for 20 to 30 min using an ultrasonic oscillation method to form a uniformly distributed soak solution of molecular sieve powder. The metal matrixes were impregnated in the soak solution for 1 to 10 s and then taken out. When the soak solution on the metal matrixes stopped flowing and dripping down, the metal matrixes were impregnated again in the soak solution. Then, the metal matrixes were dried in air.

(113) 3. Primary In-Situ Growth of Molecular Sieve Membrane

(114) 5 g of P123 (EO.sub.20PO.sub.70EO.sub.20, M=5800) and 32.6 g of F127 (EO.sub.106PO.sub.70EO.sub.106, M=12600) were dissolved in 1300 mL of deionized water and stirred at a constant temperature of 35 C. to yield a mixed solution. 161 mL of 37 wt. % of hydrochloric acid was added into the mixed solution and stirred at 35 C.; then 63 mL of TEOS (Si(OC.sub.2H.sub.5).sub.4, M=208.33) was added to the mixed solution and stirred for 1 h to prepare the molecular sieve solution of mesoporous silica SBA-16. The preprocessed metal matrixes were fixed by a Teflon standoff and placed into a Teflon bottle. The molecular sieve solution of mesoporous silica SBA-16 was transferred to the Teflon bottle. The reaction still was sealed and rested for 24 hrs at 35 C. Then the mesoporous silica SBA-16 was crystalized for 24 hrs at 105 C. The reaction still was cooled and the metal matrixes comprising molecular sieve membrane were taken out.

(115) The metal matrixes comprising molecular sieve membrane were washed by deionized water to PH=7, dried for 12 h in the oven at 100 C., and cooled in air.

(116) Finally, the metal matrixes comprising molecular sieve membrane were roasted in a muffle furnace. In the furnace, the temperature was heated to 400 C. at a speed of 1 C./min and kept for 1 h; Then the temperature was heated to 550 C. at a speed of 1 C./min and kept for 4 hrs; after that, the temperature was decreased to the room temperature at a speed of 0.5 C./min.

(117) The thickness of the molecular sieve membrane on the surface of the metal matrixes is 39 m under scanning electron microscopy.

(118) 4. Impregnation, Aging and Roasting of Active Component and Additive

(119) 14.81 g of Co(NO.sub.3).sub.2.6H.sub.2O, 0.16 g of dinitroso diammineplatinum, and 1.86 g of Ce(NO.sub.3).sub.3.6H.sub.2O were dissolved in deionized water to prepare 15 mL of solvent. The metal matrixes comprising molecular sieve membrane were impregnated in the solvent for 5 min, dried at room temperature for 3 hrs, and dried in the oven for 10 hrs at 100 C. Then the metal matrixes comprising molecular sieve membrane were roasted in the muffle furnace for 6 hrs. In the furnace, the temperature was heated to 400 C. at a speed of 1 C./min for the 6 hours of roasting, and decreased to the room temperature at a speed of 0.5 C./min to yield a catalyst G comprising SBA-16 membrane on the stainless steel matrixes. Components of the catalyst G by the result of XRF are: 14.89% of Co, 0.52% of Pt, and 3.09% of Ce.

Comparison Example 1

(120) 10 g of P123 (EO.sub.20PO.sub.70EO.sub.20, M=5800) and 23.6 g of F127 (EO.sub.106PO.sub.70EO.sub.106, M=12600) were dissolved in 2800 mL of deionized water and stirred at a constant temperature of 35 C. to yield a mixed solution. 400 mL of 37 wt. % of hydrochloric acid was added into the mixed solution and stirred at 35 C.; then 130 mL of TEOS (Si(OC.sub.2H.sub.5).sub.4, M=208.33) was added to the mixed solution and stirred for 1 h to prepare the molecular sieve solution of mesoporous silica SBA-16. The molecular sieve solution of mesoporous silica SBA-16 was transferred to a stainless steel reaction still with polytetrafluoroethylene substrate (Teflon bottle). The reaction still was sealed and rested for 24 hrs at 35 C. Then the mesoporous silica SBA-16 was crystalized for 24 hrs at 100 C. The reaction still was cooled, filtrated, and washed to PH=7. The mesoporous silica SBA-16 was dried at 120 C. for 5 hrs, and was roasted at 550 C. for 5 hrs to yield white powder of mesoporous silica SBA-16 featuring cage microstructure and having a pore diameter between 6 and 20 nm.

(121) 26.66 g of Co(NO.sub.3).sub.2.6H.sub.2O, 0.27 g of dinitroso diammineplatinum, and 3.35 g of Ce(NO.sub.3).sub.3.6H.sub.2O were dissolved in deionized water to prepare 28 mL of solvent. 29.3 g of the mesoporous silica SBA-16 was used as the carrier, impregnated in the solvent, dried at room temperature for 3 hrs, and dried in the oven for 10 hrs at 100 C. Then the molecular sieve was roasted in the muffle furnace for 6 hrs. In the furnace, the temperature was heated to 400 C. at a speed of 1 C./min for the 6 hours of roasting, and decreased to the room temperature naturally to yield an SBA-16 powder catalyst H. Components of the catalyst H by the result of XRF are: 15.24% of Co, 0.55% of Pt, and 2.98% of Ce. The powder catalyst was compressed to be tablets and sieved to select particles having particle sizes of between 30 and 60 meshes to perform subsequent experiments of catalyst activity evaluation.

Comparison Example 2

(122) 10 g of P123 (EO.sub.20PO.sub.70EO.sub.20, M=5800) and 65 g of F127 (EO.sub.106PO.sub.70EO.sub.106, M=12600) were dissolved in 2600 mL of deionized water and stirred at a constant temperature of 35 C. to yield a mixed solution. 320 mL of 37 wt. % of hydrochloric acid was added into the mixed solution and stirred at 35 C.; then 125 mL of TEOS (Si(OC.sub.2H.sub.5).sub.4, M=208.33) was added to the mixed solution and stirred for 1 h to prepare the molecular sieve solution of mesoporous silica SBA-16. The molecular sieve solution of mesoporous silica SBA-16 was transferred to a stainless steel reaction still with polytetrafluoroethylene substrate (Teflon bottle). The reaction still was sealed and rested for 24 hrs at 35 C. Then the mesoporous silica SBA-16 was crystalized for 24 hrs at 95 C. The reaction still was cooled, filtrated, and washed to PH=7. The mesoporous silica SBA-16 was dried at 120 C. for 5 hrs, and was roasted at 550 C. for 5 hrs to yield white powder of mesoporous silica SBA-16 featuring cage microstructure and having a pore diameter between 6 and 20 nm.

(123) 26.66 g of Co(NO.sub.3).sub.2.6H.sub.2O, 0.27 g of dinitroso diammineplatinum, and 3.35 g of Ce(NO.sub.3).sub.3.6H.sub.2O were dissolved in deionized water to prepare 28 mL of solvent. 29.3 g of the mesoporous silica SBA-16 was used as the carrier, impregnated in the solvent, dried at room temperature for 3 hrs, and dried in the oven for 10 hrs at 100 C. Then the molecular sieve was roasted in the muffle furnace for 6 hrs. In the furnace, the temperature was heated to 400 C. at a speed of 1 C./min for the 6 hours of roasting, and decreased to the room temperature naturally to yield an SBA-16 powder catalyst I. Components of the catalyst I by the result of XRF are: 15.16% of Co, 0.47% of Pt, and 3.12% of Ce. The powder catalyst was compressed to be tablets and sieved to select particles having particle sizes of between 30 and 60 meshes to perform subsequent experiments of catalyst activity evaluation.

(124) Molar Ratios of components in the molecular sieve solution of mesoporous silica SBA-16s of the examples are shown in Table 1:

(125) TABLE-US-00001 TABLE 1 Molar ratios P123 F127 TEOS HCl H.sub.2O Example 1 1 1.09 335 2750 90000 Example 2 1 1.38 423 1926 53972 Example 3 1 1 650 3000 100000 Example 4 1 2.31 625 2750 90000 Example 5 1 3 500 1700 51000 Example 6 1 1.5 400 1800 70000 Example 7 1 3 350 2200 84000 Comparison Example 1 1 1.09 335 2750 90000 Comparison Example 2 1 3 350 2200 84000

(126) Evaluation and Contrast of Catalyst Activation and Catalytic Activity

(127) No more than three pieces of monolithic catalyst were taken. A difference method is employed to determine the catalyst mass: the mass of the monolithic catalyst comprising molecular sieve membrane after soaking in the salt solution and roasting minus the mass of the preprocessed metal matrixes. And more than 3 g of catalyst G was added into a 18 mm fixed bed reactor to be evaluated. Under the pressure of 0.5 MPa and under hydrogen atmosphere with GHSV=3SL/(g.Math.h), the reactor was heated from the room temperature at a speed of 1 C./min; when the temperature reached 200 C., 250 C., 300 C., 350 C., the temperature was kept for 30 min, then continued to rise. Finally, the catalyst was activated in-situ at 400 C. for 10 hrs. Then the reactor was cooled to the room temperature at a speed of 0.5 C./min.

(128) Gases used by the activity evaluation experiment were mixed gases of nitrogen and synthesis gas (V.sub.N2:Vsyn.sub.gas=1:1), and a molar composition of the synthesis gas is H.sub.2/CO=2. The reaction is performed under a pressure of 2.0 MPa at 210 C., and GHSV=6 SL/(g.Math.h). Components are measured by XRF, and the result of the catalyst activity evaluation was shown in Table 2:

(129) TABLE-US-00002 TABLE 2 Evaluation of catalysts in Fischer-Tropsch synthesis reaction Thickness CO conversion CH.sub.4 C.sub.5.sup.+ Catalyst SBA-16 catalyst components of carrier rate selectivity selectivity A 15.09% Co/0.46% Pt/3.02% Ce 26 m 41.6% 6.4% 81.3% B 15.43% Co/0.56% Pt/3.10% Ce 30 m 42.8% 6.1% 82.9% C 14.97% Co/0.49% Pt/3.06% Ce 43 m 47.5% 5.8% 85.9% D 15.22% Co/0.59% Pt/2.95% Ce 46 m 49.1% 5.7% 86.5% E 15.02% Co/0.44% Pt/3.05% Ce 73 m 44.0% 6.8% 83.8% F 15.31% Co/0.46% Pt/3.03% Ce 60 m 47.9% 5.9% 86.1% G 14.89% Co/0.52% Pt/3.09% Ce 39 m 45.7% 6.0% 85.5% H 15.24% Co/0.55% Pt/2.98% Ce / 38.3% 8.4% 80.4% I 15.16% Co/0.47% Pt/3.12% Ce / 37.7% 8.6% 80.0%

(130) The result shows that monolithic catalyst comprising molecular sieve membrane, especially when the thickness of the molecular sieve membrane is between 30 and 60 m, has a relatively high CO conversion rate, high C.sub.5.sup.+ selectivity, and low selectivity of the byproduct CH.sub.4. Compared with powder Co/SBA-16 catalyst, the monolithic catalyst comprising molecular sieve membrane displays stronger catalytic activity.

(131) During the experiment, the temperature control of the monolithic catalyst comprising molecular sieve membrane is stable and the temperature fluctuates within 1.5 C., while the temperatures of the catalyst H and I change between 206 and 217.7 during the experiment. Therefore, the monolithic catalyst features better heat transfer property.

(132) To sum up, because of the special structure that the molecular sieve membrane grows in-situ on the surface of the metal matrixes, the monolithic catalyst eliminates diffusion limitation in a pore channel of the catalyst, improves the mass transfer effect, and increases the catalyst activity and selectivity of product.

(133) Unless otherwise indicated, the numerical ranges involved in the invention include the end values. While particular embodiments of the invention have been shown and described, it will be obvious to those skilled in the art that changes and modifications may be made without departing from the invention in its broader aspects, and therefore, the aim in the appended claims is to cover all such changes and modifications as fall within the true spirit and scope of the invention.