CN1131100C - Zirconium-molybdenum oxide catalyst for methane oxidation to synthesize formaldehyde and its preparation method - Google Patents
Zirconium-molybdenum oxide catalyst for methane oxidation to synthesize formaldehyde and its preparation method Download PDFInfo
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- CN1131100C CN1131100C CN 02125912 CN02125912A CN1131100C CN 1131100 C CN1131100 C CN 1131100C CN 02125912 CN02125912 CN 02125912 CN 02125912 A CN02125912 A CN 02125912A CN 1131100 C CN1131100 C CN 1131100C
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- catalyst
- ammonium molybdate
- formaldehyde
- methane
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Abstract
The present invention relates to a zirconium-molybdenum oxide catalyst for methane oxidation to synthesize formaldehyde, which belongs to the technical field of chemical catalysts. The molecular formula of the catalyst is (ZrO2)x(Zr(MoO4)2)y(MoO3)z. A preparation method of the catalyst comprises: using zirconium dioxide powder and ammonium molybdate powder as raw materials, weighing the ammonium molybdate powder according to the proportion represented by the molecular formula of the catalyst and using ionized water to prepare an ammonium molybdate water solution with a certain concentration, and adding the ammonium molybdate water solution into the zirconium dioxide powder; drying the mixture, and roasting the mixture at high temperature; finally, mechanically polishing, forming by pressing, and sieving granules as the catalyst. The catalyst of the present invention has simple preparation process and good mechanical strength, and reactive active oxides are relatively active at low temperature; thus, the catalyst can be used for the selective oxidation of methane to synthesize formaldehyde under the conditions of low reaction temperature and high proportion of CH4 to O2 in reaction gas.
Description
Technical field
The present invention relates to a kind of Zirconium-molybdenum oxide catalyst that is used for methane oxidation to synthesize formaldehyde and preparation method thereof, belong to chemical industry
Technical field.
Background technology
Contain a large amount of methane (about 90～100%) in the natural gas.In the world, the explored reserves of natural gas are greater than reserves; With the coal facies ratio, the pollution of natural gas is little.Therefore, natural gas is a kind of fuel and industrial chemicals of cleaning.With the natural gas is that raw material is produced basic chemical industry products such as formaldehyde, then can bring huge economic benefit.This is natural gas (methane) one of the most attractive potential application.
In decades, worldwide carried out the research work of methane selective oxidation making formaldehyde catalyst widely.It is catalyst that people such as A.de.Lucas report with W/HZSM-5 on Applied Catalysis A General.172 (1998) 165, at 650 ℃, and air speed 7.41g h mol
-1, reaction gas proportioning CFH
4/ O
2Under=5.3 the condition, obtaining methane conversion is 4～11%, and the selectivity of formaldehyde is 2.9～4.9%.People such as A.de.Lucas report with W/SiO on Applied Catalysis AGenera1.184 (1999) 143
2Be catalyst, at 650 ℃, air speed 7.41h mol
-1, reaction gas proportioning CH
4/ O
2Under=5.3 the condition, obtain methane conversion 5～6%, the selectivity of formaldehyde is 11～18%.People such as A.Parmaliana report on Applied Catalysis A General.226 (2002) 163, at 1%wtFe
2O
3/ SiO
2Carry out the methane selective oxidation reaction on the catalyst 650 ℃ the time, obtain 78% formaldehyde selectivity, but methane conversion very low (＜1%).
The catalyst of above bibliographical information respectively has characteristics, but the selectivity of formaldehyde is generally lower, and reaction temperature is higher.This may be that promptly Lattice Oxygen is active inadequately owing to activity of such catalysts oxygen species, and catalyst needs higher reaction temperature could activate methane, and the easy like this product formaldehyde generation deep oxidation that causes generates carbon dioxide and carbon monoxide.
Summary of the invention
The objective of the invention is to propose a kind of Zirconium-molybdenum oxide catalyst that is used for methane oxidation to synthesize formaldehyde and preparation method thereof, so that this catalyst is being used for the reaction of methane selective oxidation synthesizing formaldehyde, reaction temperature is lower, and obtains higher formaldehyde selectivity and methane conversion.
The Zirconium-molybdenum oxide catalyst that is used for methane oxidation to synthesize formaldehyde that the present invention proposes, its molecular formula is (ZrO
2)
x(Zr (MoO
4)
2)
y(MoO
3)
z, wherein, x, y, z represent the percentage by weight of each component described in the catalyst molecule formula respectively, x=0.2～0.9, y=0.1～0.4, z=0～0.6, x+y+z=1.0.
Above-mentioned Preparation of catalysts method comprises following each step:
1, particle size is the zirconium dioxide (ZrO of 16～18nm
2) powder and ammonium molybdate ((NH
4)
6Mo
7O
244H
2O, chemical reagent factory in Tianjin analyzes pure) be the feedstock production catalyst;
2, metering weighing the ammonium molybdate ((NH that represents by above-mentioned catalyst molecule formula
4)
6Mo
7O
244H
2O, chemical reagent factory in Tianjin analyzes pure) powder, be made into certain density ammonium molybdate aqueous solution with deionized water.This ammonium molybdate aqueous solution joined in the Zirconium dioxide powder that particle size is 16～18nm go;
3, with said mixture 90～120 ℃ of dryings 6～10 hours, then high-temperature roasting 8～12 hours, sintering temperature is 500～700 ℃;
4, pass through mechanical lapping again 4～6 hours, the compression moulding of 1.5～2.0MPa pressure of the catalyst precarsor after the roasting, screening 20～40 purpose particles are as catalyst.Zr (MoO in the catalyst
4)
2Particle size is 25～45nm.
Method for preparing catalyst of the present invention is simple, mechanical strength is good, because catalyst has ultra-fine particle, so its Lattice Oxygen, be that reactive activity oxygen species are just relatively active under lower temperature, this make this catalyst can be in lower reaction temperature (300～400 ℃), reaction gas CH
4/ O
2Be used for the methane selective oxidation synthesizing formaldehyde under the ratio condition with higher.This life of catalyst was not less than 100 hours.Performance to the catalyst that utilizes method of the present invention preparation is estimated on high pressure, continuous flow fixed bed reactor.Reaction condition is: the reaction gas proportioning is CH
4/ O
2/ N
2=10: 1: 3, air speed 12000ml/ (g.cat) .h
-1, pressure 5.0MPa, reaction temperature is generally between 350～400 ℃.Carry out methane selective oxidation making formaldehyde reaction on such catalyst, the methane maximum conversion is 8%, and the high selectivity of formaldehyde is 90.0%, and the highest yield of formaldehyde is 4%.Compare with the catalyst performance result who has reported, formaldehyde selectivity and yield are higher in the reaction.
The specific embodiment
Calculate preparation catalyst (ZrO in this method
2)
x(Zr (MoO
4)
2)
y(MoO
3)
zThe method of the weight of needed raw material zirconium dioxide and ammonium molybdate is as follows:
The catalyst weight of the weight of raw material zirconium dioxide=(0.43y+x) * will prepare;
The catalyst weight of the weight of raw material ammonium molybdate=(y+1.5z) * will prepare;
Embodiment 1
Calculate required raw material ammonium molybdate ((NH by above-mentioned formula
4)
6Mo
7O
244H
2O, chemical reagent factory in Tianjin analyzes pure) amount, be made into the ammonium molybdate aqueous solution that concentration is 0.13g/mL.Is 10.0mL concentration that the ammonium molybdate aqueous solution of 0.13g/mL joins in the Zirconium dioxide powder that the 2.7g particle size is 18nm and goes, and 110 ℃ of dryings 8 hours, and makes catalyst (ZrO in 10 hours 600 ℃ of high-temperature roastings
2)
0.63(Zr (MoO
4)
2)
0.36(MoO
3)
0Zr (MoO in the catalyst
4)
2Particle size be 35nm.Then, catalyst is standby through grinding in 4 hours, the compression moulding of 1.5MPa pressure, screening 40 purpose particles.Prepared catalyst is used for the reaction of methane selective oxidation synthesizing formaldehyde.Being reflected at the reaction gas proportioning is CH
4/ O
2/ N
2=10/1/3, air speed 12000ml/ (g.cat) .h
-1, pressure 5.0MPa, reaction temperature is to carry out under 400 ℃ the condition.Catalyst amount 0.5g.Analytical reactions tail gas, obtaining methane conversion is 8.0%, and the formaldehyde selectivity is 47.8%, and the formaldehyde yield is 4.0%.
Embodiment 2
Is 10.0mL concentration the ammonium molybdate ((NH of 0.087g/mL
4)
6Mo
7O
244H
2O, chemical reagent factory in Tianjin analyzes pure) aqueous solution joins in the Zirconium dioxide powder that the 3.0g particle size is 16nm and goes, and 120 ℃ of dryings 6 hours, and makes catalyst (ZrO in 11 hours 550 ℃ of high-temperature roastings
2)
0.74(Zr (MoO
4)
2)
0.25(MoO
3)
0.01Zr (MoO in the catalyst
4)
2Particle size be 30nm.Then, catalyst is through grinding in 4 hours, 180Kg/cm
2Pressure compression moulding, the screening 30 purpose particles standby.Prepared catalyst is used for the reaction of methane selective oxidation synthesizing formaldehyde.Being reflected at the reaction gas proportioning is CH
4/ O
2/ N
2=10/1/3, air speed 12000ml/ (g.cat) .h
-1, pressure 5.0MPa, reaction temperature is to carry out under 380 ℃ the condition.Catalyst amount 0.5g.Analytical reactions tail gas, obtaining methane conversion is 3.3%, and the formaldehyde selectivity is 53.8%, and the formaldehyde yield is 1.8%.
Embodiment 3
Is 10.0mL concentration the ammonium molybdate ((NH of 0.24g/mL
4)
6Mo
7O
244H
2O, chemical reagent factory in Tianjin analyzes pure) aqueous solution joins the ultra-fine zirconium dioxide (ZrO of 1.3g
2) go in the powder, 100 ℃ of dryings 9 hours, and made catalyst (ZrO in 9 hours 650 ℃ of high-temperature roastings
2)
0.38(Zr (MoO
4)
2)
0.20(MoO
3)
0.42Zr (MoO in the catalyst
4)
2Particle size be 44nm.Then, catalyst is through grinding in 5 hours, 190Kg/cm
2Pressure compression moulding, the screening 20 purpose particles standby.Prepared catalyst is used for the reaction of methane selective oxidation synthesizing formaldehyde.Being reflected at the reaction gas proportioning is CH
4/ O
2/ N
2=10/1/3, air speed 12000ml/ (g.cat) .h
-1, pressure 5.0MPa, reaction temperature is to carry out under 400 ℃ the condition.Catalyst amount 0.5g.Analytical reactions tail gas, obtaining methane conversion is 7.0%, and the formaldehyde selectivity is 36.0%, and the formaldehyde yield is 2.5%.
Embodiment 4
Is 10.0mL concentration the ammonium molybdate ((NH of 0.41g/mL
4)
6Mo
7O
244H
2O, chemical reagent factory in Tianjin analyzes pure) aqueous solution joins in the Zirconium dioxide powder that the 1.3g particle size is 18nm and goes, and 90 ℃ of dryings 10 hours, and makes catalyst (ZrO in 8 hours 700 ℃ of high-temperature roastings
2)
0.26(Zr (MoO
4)
2)
0.13(MoO
3)
0.61Zr (MoO
4)
2Particle size be 45nm.Then, catalyst is through grinding in 6 hours, 200Kg/cm
2Pressure compression moulding, the screening 30 purpose particles standby.Prepared catalyst is used for the reaction of methane selective oxidation synthesizing formaldehyde.Being reflected at the reaction gas proportioning is CH
4/ O
2/ N
2=10/1/3, air speed 12000ml/ (g.cat) .h
-1, pressure 5.0MPa, reaction temperature is to carry out under 350 ℃ the condition.Catalyst amount 0.5g.Analytical reactions tail gas, obtaining methane conversion is 3.2%, and the formaldehyde selectivity is 52.6%, and the formaldehyde yield is 1.7%.
Embodiment 5
Is 10.0mL concentration the ammonium molybdate ((NH of 0.0225g/mL
4)
6Mo
7O
244H
2O, chemical reagent factory in Tianjin analyzes pure) aqueous solution joins in the Zirconium dioxide powder that the 1.8g particle size is 16nm and goes, and 110 ℃ of dryings 9 hours, and makes catalyst (ZrO in 10 hours 550 ℃ of high-temperature roastings
2)
0.87(Zr (MoO
4)
2)
0.12(MoO
3)
0.01Zr (MoO
4)
2Particle size be 25nm.Then, catalyst is through grinding in 6 hours, 170Kg/cm
2Pressure compression moulding, the screening 40 purpose particles standby.Prepared catalyst is used for the reaction of methane selective oxidation synthesizing formaldehyde.Being reflected at the reaction gas proportioning is CH
4/ O
2/ N
2=10/1/3, air speed 12000ml/ (g.cat) .h
-1, pressure 5.0MPa, reaction temperature is to carry out under 400 ℃ the condition.Catalyst amount 0.5g.Analytical reactions tail gas, obtaining methane conversion is 2.2%, and the formaldehyde selectivity is 49.6%, and the formaldehyde yield is 1.1%.
Claims (2)
1, a kind of cobalt-lanthanum-molybdenum oxide catalyst that is used for synthesizing formaldehyde by means of methane is characterized in that the molecular formula of this catalyst is: Mo
x(LaCoO
3)
y, x wherein, y is respectively Mo and LaCoO
3Weight percent content, x=0.01～0.2, y=0.80～0.99.
2, a kind of preparation method who is used for the cobalt-lanthanum-molybdenum oxide catalyst of synthesizing formaldehyde by means of methane as claimed in claim 1 is characterized in that comprising following each step:
(1) be the feedstock production catalyst with lanthanum cobalt powder and ammonium molybdate powder;
(2) metering of representing by above-mentioned catalyst molecule formula, the weighing ammonium molybdate powder is made into certain density ammonium molybdate aqueous solution with deionized water, and the ammonium molybdate aqueous solution that measures is joined LaCoO
3In the powder;
(3) said mixture was descended dry 8～10 hours at 90～120 ℃, then high-temperature roasting 5～8 hours, sintering temperature is 400～600 ℃;
(4) compound after the above-mentioned roasting was passed through mechanical lapping after 4～6 hours, compression moulding under 1.5～2.0MPa pressure, screening 20～40 purpose particles are as catalyst.
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|---|---|---|---|
| CN 02125912 CN1131100C (en) | 2002-08-02 | 2002-08-02 | Zirconium-molybdenum oxide catalyst for methane oxidation to synthesize formaldehyde and its preparation method |
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|---|---|---|---|
| CN 02125912 CN1131100C (en) | 2002-08-02 | 2002-08-02 | Zirconium-molybdenum oxide catalyst for methane oxidation to synthesize formaldehyde and its preparation method |
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| Publication Number | Publication Date |
|---|---|
| CN1394681A CN1394681A (en) | 2003-02-05 |
| CN1131100C true CN1131100C (en) | 2003-12-17 |
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| CN111138167B (en) * | 2019-12-31 | 2022-04-29 | 南京环福新材料科技有限公司 | Ceramic catalyst taking red mud waste residue as carrier and preparation method and application thereof |
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