CN101898141B - Preparation of molybdenum phosphide catalyst and application in methane carbon dioxide reforming - Google Patents
Preparation of molybdenum phosphide catalyst and application in methane carbon dioxide reforming Download PDFInfo
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- CN101898141B CN101898141B CN2010102402769A CN201010240276A CN101898141B CN 101898141 B CN101898141 B CN 101898141B CN 2010102402769 A CN2010102402769 A CN 2010102402769A CN 201010240276 A CN201010240276 A CN 201010240276A CN 101898141 B CN101898141 B CN 101898141B
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention discloses preparation of a molybdenum phosphide catalyst, which comprises the following steps of: (1) weighing ammonium molybdate, diammonium hydrogen phosphate, citric acid and water in a mass ratio of 1.0: 0.87: 0-3.6: 50-70, stirring the mixture, adding the mixture into an autoclave, and reacting the mixture for 10 to 15 hours at the temperature of between 363 and 383K; (2) cooling and drying the reaction product; (3) calcining the reaction product for 3 to 8 hours at the temperature of between 623 and 923K; and (4) cooling the calcined product and filling the calcined product into a tube, reducing the product at a flow rate of 20 to 100ml/minH2, heating the product to between 923 and 1,073K from 473K at a heating rate of 1K/minu, preserving the heat for 2 hours, quickly cooling the product to room temperature under H2 condition, and passivating the product for 8 to 12 hours by using 1.0 percent O2 argon. Application of molybdenum phosphide in methane carbon dioxide reforming comprises the following steps of: performing methane carbon dioxide reforming reaction on a fixed reaction bed, weighing the molybdenum phosphide and filling the molybdenum phosphide into a reaction tube, pre-treating the molybdenum phosphide at 773 to 1,173K under the condition of argon, then controlling the temperature to between 673 and 1,073K, and reducing the molybdenum phosphide for 1 to 4 hours in H2 at a flow rate of 20 to 100ml/min. The preparation has stable and efficient reaction, easily obtained catalyst synthesizing raw materials, simple and feasible process and low cost; and the conversion rate of methane reaches over 40 percent, and the conversion rate of carbon dioxide reaches over 50 percent.
Description
Technical field:
The invention belongs to catalyst and application, particularly catalyst and the application in catalytic reforming
Background technology:
Now greenhouse effects are increasing to climatic influences. serious threaten the mankind. and methane and carbon dioxide all are greenhouse gases, prepare required synthesis gas (H in the industry with methane carbon dioxide reformation at present
2And CO), play the effect of double gain. present stage catalyst be main with metallic catalyst, the noble metal performance is good, but expensive, base metal low price, but carbon deposit easily, catalyst descends because of carbon deposit is active.The active back power of regeneration that descends is very poor.
Summary of the invention
The objective of the invention is deficiency, prepare a kind of novel methane carbon dioxide reformation catalyst to prior art, and the application in methane carbon dioxide reformation.
The preparation process of molybdenum phosphide catalyst of the present invention is following:
(1) with ammonium molybdate, diammonium hydrogen phosphate, citric acid, water by ammonium molybdate: diammonium hydrogen phosphate: citric acid: the mass ratio of water=1.0: 0.87: 0-3.6: 50-70 takes by weighing, and stirs, and adds in the autoclave, and temperature 363-383K reacted 10-15 hour.
(2) after the cooling, oven dry.
(3) place under the resistance furnace 623-923K condition calcining 3-8 hour.
(4) cooling after, choose this solid pack into the pipe in, use flow velocity 20-100mlmin
-1H
2Reduction is warming up to 923-1073K from 473K, and heating rate is 1Kmin
-1, be incubated 2 hours.At H
2Be cooled to room temperature under the condition rapidly, again with containing volumetric concentration 1.0%O
2Argon gas passivation 8-12 hour.
Application in methane carbon dioxide reformation of the present invention is following:
Methane carbon dioxide reformation is reflected on the fixation reaction bed and carries out, take by weighing the phosphatization molybdenum and pack in the reaction tube, earlier under the condition of 773-1173K at argon gas preliminary treatment then temperature control 673-1073K flow velocity be 20-100mlmin
-1, H
2Reduced 1-4 hour.
Methane carbon dioxide reformation methane conversion according to the invention is more than 40%, carbon dioxide conversion is more than 50%.
Invent described molybdenum phosphide catalyst and realized the high-efficiency methane CO 2 reformation.Solved the problem that is difficult to regeneration behind the catalysqt deactivation,, made them possibly become the new catalyst of carbon dioxide methane reforming reaction because they have unique physics and chemical property.For example semiconductor property can transmit electronics, makes CO
2In electron density increase, activation energy reduces, thus reforming reaction can under lower temperature, carry out, saved lot of energy; The heat endurance electricity is another prerequisite that they become the reforming reaction catalyst.Stable reaction of the present invention, efficient has very high actual application value and environment-friendly advantage.Molybdenum phosphide catalyst synthesis material of the present invention is easy to obtain, and the prepared process simply is prone to row, is fit to large-scale low-cost and manufactures.
The specific embodiment
The present invention will further specify through following examples.
Embodiment 1
(1) take by weighing ammonium molybdate and the 0.87g diammonium hydrogen phosphate of 1.0g, the water of 50g stirs, and pours in the autoclave, puts into baking oven, and temperature control 363K reacted 12 hours.
(2) pour in the beaker after the cooling, put into baking oven, temperature 393K is up to the solution evaporate to dryness.
(3) during solid is packed quartz ampoule into, place under the resistance furnace 773K condition and calcined 3 hours.
(4) cooling after pack into the pipe in, use flow velocity 20mlmin
-1H
2Reduction is warming up to 923K from 473K, and heating rate is 1Kmin
-1, be incubated 2 hours.Under the H2 condition, be cooled to room temperature rapidly, again with containing volumetric concentration 1.0%O
2Argon gas passivation 8 hours.
(5) methane carbon dioxide reformation is reflected on the fixation reaction bed and carries out, and take by weighing 60-80 purpose phosphatization molybdenum particle 0.15g and pack in the stainless steel tube of 300mm * 10mm, earlier at 773K, preliminary treatment under the condition of argon gas, insulation 773K, flow velocity is 60mlmin
-1, H
2Reductase 12 hour. reaction products therefrom (H
2, CO, CO
2, CH
4) behind six-way valve, use the 102M gas chromatographic detection, detector is TCD, and the chromatographic column adopting carbon molecular sieve adopts the N2000 of intelligence engineering research institute of Zhejiang University type chromatographic work station. and reactant is CH
4: CO
2=1.2 mist, flow velocity are 30ml.min
-1, pressure is 0.1Mpa, and reaction temperature is the check and analysis that 973-1023K. carries out product, and activity is seen table:
Embodiment 2.
(1) take by weighing ammonium molybdate and the 0.87g diammonium hydrogen phosphate of 1.0g, add the citric acid of 1.19g, the water of 50g stirs, and pours in the autoclave, puts into baking oven, and temperature control 373K reacted 10 hours.
(2) pour in the beaker after the cooling, put into baking oven, temperature 393K is up to the solution evaporate to dryness.
(3) during solid is packed quartz ampoule into, place under the resistance furnace 773K condition and calcined 5 hours.
(4) cooling after pack into the pipe in, use flow velocity 60mlmin
-1H
2Reduction is warming up to 923K from 473K, and heating rate is 1Kmin
-1Be incubated 2 hours.Under the H2 condition, be cooled to room temperature rapidly again with containing volumetric concentration 1.0%O
2Argon gas passivation 8 hours.
(5) methane carbon dioxide reformation is reflected on the fixation reaction bed and carries out, and takes by weighing 60-80 purpose phosphatization molybdenum particle 0.15g and packs in the stainless steel tube of 300mm * 10mm, and earlier at 973K, preliminary treatment under the condition of argon gas is warming up to 923K, and flow velocity is 60mlmin
-1, H
2Reductase 12 hour. reaction products therefrom (H
2, CO, CO
2, CH
4) behind six-way valve, use the 102M gas chromatographic detection, detector is TCD, and the chromatographic column adopting carbon molecular sieve adopts the N2000 of intelligence engineering research institute of Zhejiang University type chromatographic work station. and reactant is CH
4: CO
2=1.2 mist, flow velocity are 30ml.min
-1Pressure is 0.1Mpa, and reaction temperature is the check and analysis that 973-1023K. carries out product, and activity is seen table:
Embodiment 3.
(1) take by weighing ammonium molybdate and the 0.87kg diammonium hydrogen phosphate of 1.0kg, add the citric acid of 2.38kg, add the water of 70kg, stir, pour in the autoclave, temperature control 383K reacted 12 hours.
(2) put into baking oven after the cooling, temperature 393K is up to the solution evaporate to dryness.
(3) during solid is packed pipe into, place under the resistance furnace 773K condition and calcined 6 hours.
(4) cooling after pack into the pipe in, use flow velocity 60mlmin
-1H
2Reduction is warming up to 923K from 473K, and heating rate is 1Kmin
-1Be incubated 2 hours.At H
2Be cooled to room temperature under the condition rapidly, again with containing volumetric concentration 1.0%O
2Argon gas passivation 10 hours.
(5) methane carbon dioxide reformation is reflected on the fixation reaction bed and carries out, and takes by weighing 60-80 purpose phosphatization molybdenum particle 0.15g earlier and packs in the stainless steel tube of 300mm * 10mm, and earlier at 873K, preliminary treatment under the condition of argon gas is warming up to 1073K, and flow velocity is 60mlmin
-1, H
2Reductase 12 hour. reaction products therefrom (H
2, CO, CO
2, CH
4) behind six-way valve, detect with 102M gas-chromatography TCD, the chromatographic column adopting carbon molecular sieve adopts the N2000 of intelligence engineering research institute of Zhejiang University type chromatographic work station, and reactant is CH
4: CO
2=1.2 mist, flow velocity are 30ml.min
-1, pressure is 0.1Mpa, and to be 973-1073K. draw the check and analysis of product reaction temperature, and activity is seen table:
Embodiment 4.
(1) take by weighing ammonium molybdate and the 0.87kg diammonium hydrogen phosphate of 1.0kg, add the citric acid of 3.6kg, add the water of 50kg, stir, pour in the autoclave, temperature control 383K reacted 15 hours.
(2) put into baking oven after the cooling, temperature 393K is up to the solution evaporate to dryness.
(3) during solid is packed pipe into, place under the resistance furnace 773K condition and calcined 8 hours.
(4) cooling after pack into the pipe in, use flow velocity 100mlmin
-1H
2Reduction is warming up to 1073K from 473K, and heating rate is 1Kmin
-1, be incubated 2 hours.At H
2Be cooled to room temperature under the condition rapidly, again with containing volumetric concentration 1.0%O
2Argon gas passivation 12 hours.
(5) methane carbon dioxide reformation is reflected on the fixation reaction bed and carries out, and takes by weighing 60-80 purpose phosphatization molybdenum particle 0.15g earlier and packs in the stainless steel tube of 300mm * 10mm, and earlier at 973K, preliminary treatment under the condition of argon gas is warming up to 1023K, and flow velocity is 60mlmin
-1, H
2Reductase 12 hour. reaction products therefrom (H
2, CO, CO
2, CH
4) behind six-way valve, detect with 102M gas-chromatography TCD, the chromatographic column adopting carbon molecular sieve adopts the N2000 of intelligence engineering research institute of Zhejiang University type chromatographic work station, and reactant is C H
4: CO
2=1.2 mist, flow velocity are 30ml.min
-1, pressure is 0.1Mpa, and to be 1023-1073K. draw the check and analysis of product reaction temperature, and activity is seen table:
Claims (1)
1. the application of molybdenum phosphide catalyst in methane carbon dioxide reformation is characterized in that described molybdenum phosphide catalyst is prepared by the following step:
(1) with ammonium molybdate, diammonium hydrogen phosphate, citric acid, water by ammonium molybdate: diammonium hydrogen phosphate: citric acid: the mass ratio of water=1.0: 0.87: 0-3.6: 50-70 takes by weighing, and stirs, and adds in the autoclave, and temperature 363-383K reacted 10-15 hour;
(2) after the cooling, oven dry;
(3) place under the resistance furnace 623-923K condition calcining 3-8 hour;
(4) cooling after, choose this solid pack into the pipe in, use flow velocity 20-100mlmin
-1H
2Reduction is warming up to 923-1073K from 473K, and heating rate is 1Kmin
-1, be incubated 2 hours; At H
2Be cooled to room temperature under the condition rapidly, again with containing volumetric concentration 1.0%O
2Argon gas passivation 8-12 hour;
Its application is: methane carbon dioxide reformation is reflected on the fixation reaction bed and carries out, and take by weighing the phosphatization molybdenum and pack in the reaction tube, earlier at 773-1173K, preliminary treatment under the condition of argon gas, temperature control 673-1073K then, flow velocity is 20-100mlmin
-1, H
2Reduced 1-4 hour.
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|---|---|---|---|
| CN2010102402769A CN101898141B (en) | 2010-07-29 | 2010-07-29 | Preparation of molybdenum phosphide catalyst and application in methane carbon dioxide reforming |
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|---|---|---|---|
| CN2010102402769A CN101898141B (en) | 2010-07-29 | 2010-07-29 | Preparation of molybdenum phosphide catalyst and application in methane carbon dioxide reforming |
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| CN101898141B true CN101898141B (en) | 2012-11-21 |
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| CN108615613B (en) * | 2018-05-11 | 2020-02-18 | 武汉理工大学 | MoP @ C nanowire and preparation method and application thereof |
| CN109012711A (en) * | 2018-08-30 | 2018-12-18 | 西京学院 | A method of improving transition metal composite material catalytic performance |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1660695A (en) * | 2004-02-26 | 2005-08-31 | 中国科学院大连化学物理研究所 | Method for preparing phosphide of transition metal |
| CN1666817A (en) * | 2004-03-12 | 2005-09-14 | 中国科学院大连化学物理研究所 | Method for preparing transition metal phosphide |
-
2010
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1660695A (en) * | 2004-02-26 | 2005-08-31 | 中国科学院大连化学物理研究所 | Method for preparing phosphide of transition metal |
| CN1666817A (en) * | 2004-03-12 | 2005-09-14 | 中国科学院大连化学物理研究所 | Method for preparing transition metal phosphide |
Non-Patent Citations (3)
| Title |
|---|
| CHENG Ruihua,et al."Preparation of Molybdenum Phosphide with High Surface Area".《催化学报》.2005,第26卷(第7期),第531页第2段. |
| Diana C. Phillips et al.."Synthesis,Characterization, and Hydrodesulfurization Properties of Silica-Supported Molybdenum Phosphide Catalysts".《Journal of Catalysis》.2002,第207卷第266-273页. |
| 李穗玲等.甲烷二氧化碳催化重整制合成气的催化剂研究新进展.《石油与天然气化工》.2008,第37卷(第4期),2,285-290. * |
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