CN101912787A - Preparation of tungsten phosphide catalyst and application of tungsten phosphide in reforming methane and carbon dioxide - Google Patents

Preparation of tungsten phosphide catalyst and application of tungsten phosphide in reforming methane and carbon dioxide Download PDF

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Publication number
CN101912787A
CN101912787A CN2010102402881A CN201010240288A CN101912787A CN 101912787 A CN101912787 A CN 101912787A CN 2010102402881 A CN2010102402881 A CN 2010102402881A CN 201010240288 A CN201010240288 A CN 201010240288A CN 101912787 A CN101912787 A CN 101912787A
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carbon dioxide
tungsten phosphide
temperature
reactant
hours
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CN101912787B (en
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黎先财
杨爱军
杨沂凤
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Nanchang University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention discloses preparation of tungsten phosphide catalyst, comprising the steps of: (1) based on the mass ratio of 1.0:0.5:0-2.4:50-70, weighing and stirring ammonium tungstate, diammonium hydrogen phosphate, citric acid and water, adding the mixture into an autoclave for reaction for 10 to 15 hours at the temperature from 363 to 383K; (2) cooling and then drying the reactant; (3) roasting the reactant for 3 to 8 hours at the temperature from 623 to 923K; (4) cooling and putting the reactant in a tube for being reduced by H2 having the flow rate of 20 to 100ml.min-1, heating up the reduced reactant from 473K to 923 to 1073K at the rate of 1k.min-1, preserving heat and rapidly cooling the reactant to room temperature on condition of H2, and passivating the cooled reactant for 8 to 12 hours with argon containing O2 with 1.0% of volume concentration; the invention further discloses an application of tungsten phosphide in reforming methane and carbon dioxide: reforming reaction of methane and carbon dioxide are conducted on a fixed reaction bed, tungsten phosphide is weighed and put in a reaction tube for being pretreated at 773 to 1173K on condition of argon and then for being temperature-controlled to the condition that the temperature is 673 to 1073K and the flow rate is 20 to 100ml.min-1, and reducing for 1 to 4 hours by H2. The invention has the advantages of: stable and efficient reaction, large availability of synthetic raw material for catalyst, simple and easy technology, low cost, over 40% of conversion rate of methane and over 50% of conversion rate of carbon dioxide.

Description

The preparation of tungsten phosphide catalyst and the application in methane carbon dioxide reformation
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, now prepare industrial required synthesis gas (H with methane carbon dioxide reformation 2And CO), play the effect of double gain. present stage catalyst based on metallic catalyst, the noble metal performance is good, but price is 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 at the deficiencies in the prior art, prepare a kind of novel methane carbon dioxide reformation catalyst, and the application in methane carbon dioxide reformation.
The preparation process of tungsten phosphide catalyst of the present invention is as follows:
(1) with ammonium tungstate, diammonium hydrogen phosphate, citric acid, water by ammonium tungstate: diammonium hydrogen phosphate: citric acid: the mass ratio of water=1.0: 0.5: 0-2.4: 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) the 623-923K temperature conditions was calcined 3-8 hour down;
(4) after the cooling, choose this solid and pack in the pipe, 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 as follows:
Methane carbon dioxide reformation is reflected on the fixation reaction bed and carries out, take by weighing tungsten phosphide 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, H2 reduction 1-4 hour.
Methane carbon dioxide reformation methane conversion of the present invention is more than 40%, carbon dioxide conversion is more than 50%.
Invent described tungsten 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 may 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; Heat endurance also 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.Tungsten phosphide catalyst synthesis material of the present invention is easy to obtain, and the technology preparation process is row simply and easily, is fit to large-scale low-cost and manufactures.
The specific embodiment
The present invention will further specify by following examples.
Embodiment 1.
(1) take by weighing ammonium tungstate and the 0.50g diammonium hydrogen phosphate of 1.0g, the 1.20g citric acid, 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) pack into after the cooling in the pipe, use flow velocity 20mlmin -1H 2Reduction is warming up to 923K 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 hours.
(5) methane carbon dioxide reformation is reflected on the fixation reaction bed and carries out, and take by weighing 60-80 purpose tungsten phosphide 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 sees Table:
Figure BSA00000209920700021
Embodiment 2.
(1) take by weighing ammonium tungstate and the 0.50g diammonium hydrogen phosphate of 1.0g, add the citric acid of 1.60g, the water of 70g 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) pack into after the cooling in the pipe, use flow velocity 60mlmin -1H 2Reduction is warming up to 923K 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 hours.
(5) methane carbon dioxide reformation is reflected on the fixation reaction bed and carries out, and takes by weighing 60-80 purpose tungsten phosphide 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 sees Table:
Figure BSA00000209920700031
Embodiment 3.
(1) take by weighing ammonium tungstate and the 0.50kg diammonium hydrogen phosphate of 1.0kg, add the citric acid of 2.40kg, 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 8 hours.
(4) pack into after the cooling in the pipe, use flow velocity 60mlmin -1H 2Reduction is warming up to 923K 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 10 hours.
(5) methane carbon dioxide reformation is reflected on the fixation reaction bed and carries out, and takes by weighing 60-80 purpose tungsten phosphide 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, TCD detects with the 102M gas-chromatography, 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 sees Table:
Figure BSA00000209920700032

Claims (2)

1. the preparation of a tungsten phosphide catalyst is characterized in that:
(1) with ammonium tungstate, diammonium hydrogen phosphate, citric acid, water by ammonium tungstate: diammonium hydrogen phosphate: citric acid: the mass ratio of water=1.0: 0.5: 0-2.4: 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) the 623-923K temperature conditions was calcined 3-8 hour down;
(4) after the cooling, choose this solid and pack in the pipe, 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.
2. the application of the described tungsten phosphide catalyst of claim 1 in methane carbon dioxide reformation, it is characterized in that methane carbon dioxide reformation is reflected on the fixation reaction bed carries out, take by weighing tungsten phosphide 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.
CN2010102402881A 2010-07-29 2010-07-29 Preparation of tungsten phosphide catalyst and application of tungsten phosphide in reforming methane and carbon dioxide Expired - Fee Related CN101912787B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110499529A (en) * 2019-08-28 2019-11-26 四川大学 A kind of high temperature and pressure preparation of routine superconductor material tungsten phosphide (WP)

Citations (2)

* Cited by examiner, † Cited by third party
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
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 (2)

* Cited by examiner, † Cited by third party
Title
《催化学报》 20050731 CHENG Ruihua,et al Preparation of Molybdenum Phosphide with High Surface Area 第26卷, 第7期 2 *
《石油与天然气化工》 20080831 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 第37卷, 第4期 2 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110499529A (en) * 2019-08-28 2019-11-26 四川大学 A kind of high temperature and pressure preparation of routine superconductor material tungsten phosphide (WP)
CN110499529B (en) * 2019-08-28 2022-01-04 四川大学 High-temperature high-pressure preparation of conventional superconductor material tungsten phosphide (WP)

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