CN109364907A - A kind of Ca for methane oxidation coupling2+The preparation method and application of ion improved catalysts - Google Patents

A kind of Ca for methane oxidation coupling2+The preparation method and application of ion improved catalysts Download PDF

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CN109364907A
CN109364907A CN201811441673.5A CN201811441673A CN109364907A CN 109364907 A CN109364907 A CN 109364907A CN 201811441673 A CN201811441673 A CN 201811441673A CN 109364907 A CN109364907 A CN 109364907A
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ion
nitrate
preparation
presoma
methane
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王翔
徐骏伟
张艳
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Nanchang University
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Nanchang University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
    • C07C2/82—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
    • C07C2/84—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling catalytic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A kind of Ca for methane oxidation coupling2+The preparation method and application of ion improved catalysts.Stoichiometrically La3+:Ce4+:Ca2+=1:0.75:0.25 weighs La3+、Ce4+And Ca2+Presoma, La is made3+、Ce4+、Ca2+The mixed solution of ion nitrate；2 times of ion moles total number of citric acid is added, ammonium hydroxide tune pH value to 2 is placed on water-bath and is evaporated to obtain gel, and aging 12 hours, then roast obtained Ca2+Ion modification catalyst.The advantages that present invention is using cheap metal salt as raw material, and the catalyst prepared using Citrate Sol-gel Process is low with production cost, and synthesis technology is simple, and preparation process is easy to control.Catalyst shows excellent reactivity worth and stability in the reaction of simulation Catalyst for Oxidative Coupling of Methane and ethane.

Description

A kind of Ca for methane oxidation coupling2+The preparation method of ion improved catalysts and Using
Technical field
The invention belongs to energy catalysis technical fields, are related to one kind and are used for oxidative coupling of methane, directly will be cheap Methane is converted to the Ca of the ethylene with high economy and industrial value and ethane product2+Ion improves La2Ce2O7Composite oxides The preparation method of catalyst.
Background technique
Methane is the main component of natural gas, is more cleaned compared to other fossil resources such as coal and petroleum and abundance； Methane is also common greenhouse gases, utilizes methane as raw material, synthesizes high level chemicals, such as methanol, ethylene, always It is the research hotspot of countries in the world scientist.And efficiently utilize methane to synthesize high level chemicals using direct method, it is dropped from source Low CH4Discharge, can not only improve atmospheric environment, but also can optimize using energy source structure, and improving to the adjustment of chemicals industrial chain has weight Big meaning.Therefore, people explore the effective ways and process that natural gas straight connects trans-utilization in effort always.Ethylene yield is Measure the mark of a national oil development of chemical industry level.Oxidative coupling of methane can directly prepare second by single step reaction Alkene either still economically considers there is its significance from thermodynamics of reactions.
There are still following problems for current methane oxidative coupling catalyst: reaction temperature is high, generally must be at 700 DEG C -900 DEG C It is reacted.Methane oxidation coupling is strong exothermal reaction and the synergistic effect that needs active oxygen species and basic center etc., is had Reaction mechanism does not have epitaxy and universality.In recent decades, researcher has been devoted to oxidative coupling of methane and urges The research of agent and its basic theory, but due to C2One-way yield is not achieved 30% minimum requirements and not yet realizes industrialization.It opens Sending out a kind of in cryogenic conditions oxidative coupling of methane superior performance, the catalyst that stability is good, cheap and easy to get is the current country Outer researcher's focus of attention.
La2Ce2O7Belong to the pyrochlore-type compound of unordered defect fluorite crystal phase structure, the oxonium ion degree of disorder in structure Greatly, transfer ability is strong, and high high-temp stability is good.For the reaction of many aerobic participations, the oxygen mobility enhancing of catalyst is obvious It can promote its reactivity worth.Therefore, La2Ce2O7Composite oxides are the catalysis materials with potential using value.Exist at present The best methane oxidative coupling catalyst of the performance generally acknowledged in world wide is Mn/Na2WO4/SiO2Class catalyst.The type Catalyst methane oxidative coupling activity is high and stability is good, but required reaction temperature is very high (725-950 DEG C), and 700 DEG C with It is lower basic without activity.The type catalyst reported at present is in 800 DEG C or more attainable maximum C2One-way yield is 20%- 27%, still not up to 30% minimum industrial requirement, therefore the catalysis material for having performance yet-to-be developed more excellent.
Summary of the invention
The invention proposes a kind of Ca for methane oxidation coupling2+Ion improves La2Ce2O7Pyrochlore-type catalyst The application performance of preparation method and the catalyst in oxidative coupling of methane.The catalyst can pass through methane oxidation idol Cheap one step of methane is directly converted in the important chemical industry such as ethane and ethylene with high economy and industrial value by connection reaction Mesosome.
The catalyst is prepared using Citrate Sol-gel Process.Under normal pressure, reaction gas group becomes 10%O2+40%CH4, 50%Ar Balance Air, under the conditions of gas flow rate is 30mL/min~60mL/min, which has high activity and stability.
A kind of Ca for methane oxidation coupling of the present invention2+The preparation method of ion improved catalysts, feature It is to include the following steps.
(1) according to stoichiometric ratio La3+:Ce4+:Ca2+=1:0.75:0.25 weighs La3+Ion presoma, Ce4+Before ion Drive body, Ca2+Ion presoma, and La is made3+Ion nitrate, Ce4+Ion nitrate, Ca2+ The mixing of ion nitrate is molten Liquid.
The La3+Ion presoma can be La3+The nitrate of ion, carbonate, oxide or hydroxide one Kind.For example La3+The nitrate of ion can be directly dissolved in distilled water；For example La3+Carbonate, oxide or the hydroxide of ion Object can first be dissolved with dilute nitric acid solution.
The Ce4+Ion presoma can be Ce4+One kind of the nitrate of ion, oxide.For example Ce4+Ion Nitrate can be directly dissolved in distilled water；For example Ce4+The oxide of ion first can add hydrogen peroxide to dissolve with dilute nitric acid solution, system At nitrate solution.
The Ca2+Ion presoma can be Ca2+One kind of the nitrate of ion, carbonate or oxide.For example Ca2 +The nitrate of ion can be directly dissolved in distilled water；For example Ca2+Carbonate, the oxide of ion can be first molten with dilute nitric acid solution Solution, is made nitrate solution.
(2) it will be equivalent to La3+Ion, Ce4+Ion and Ca2+The citric acid that 2 times of total ion concentration is added in mixed solution, PH to 2 is adjusted with ammonium hydroxide, is stirred 2-3 hours at room temperature.
(3) be evaporated in water-bath at 80-90 DEG C, gained gel 110-140 DEG C aging 12 hours.
(4) xerogel obtained by aging is ground, then with 5 DEG C/min heating rate in Muffle furnace, at 800 DEG C Under the conditions of roast 4 hours, be made Ca2+The La of ion improvement2Ce2O7Composite oxide catalysts La2Ce1.5Ca0.5O7。
A kind of Ca for methane oxidation coupling of the present invention2+The application of ion improved catalysts, it is characterized in that Under normal pressure, reaction gas group becomes 10%O2+40%CH4, 50%Ar Balance Air, gas flow rate is the item of 30mL/min~60mL/min Under part, Ca2+Ion improves La2Ce2O7Composite oxide catalysts La2Ce1.5Ca0.5O7It is directly used in methane-oxidizing and-coupling Reaction.
Compared with prior art, catalyst prepared by the present invention has the following advantages that.
(1) the invention has the advantages of low raw material cost, preparation process is simple and easy, equipment requirement is low, nontoxic solvent is harmless, to environment It is without secondary pollution.
(2) present invention prepares series Ca using traditional citric acid sol-gel method the preparation method2+The La of ion improvement2Ce2O7 Composite oxide catalysts, preparation process is simple, and preparation process is easy to control.
(3) Ca prepared by the present invention2+Ion improves La2Ce2O7Composite oxide catalysts La2Ce1.5Ca0.5O7In methane Excellent reactivity and stability are shown in oxidative coupling reaction.
Detailed description of the invention
Fig. 1 is the Ca of the method for the present invention preparation2+Ion improves La2Ce2O7Composite oxide catalysts La2Ce1.5Ca0.5O7- A and La2Ce1.5Ca0.5O7The XRD spectra of-C.Synthesized catalyst is illustrated as defect fluorite type pyrochlore constitution.
Fig. 2 is the La of the method for the present invention preparation2Ce1.5Ca0.5O7- A and La2Ce1.5Ca0.5O7- C pyrochlore catalyst With the current Mn/Na for generally acknowledging that performance is best2WO4/SiO 2Class catalyst methane oxidative coupling reaction performance comparison result.
Fig. 3 is the La of the method for the present invention preparation2Ce1.5Ca0.5O7- A pyrochlore catalyst stability test result.
Specific embodiment
Illustrate the present invention in order to clearer, enumerates following embodiment, but it is without any restrictions to the scope of the present invention.
Embodiment 1.
Each presoma is the preparation process of nitrate: weighing 4.33g lanthanum nitrate (pentahydrate), 3.23g cerous nitrate (six Hydrate) and 0.59g calcium nitrate (tetrahydrate) in 200ml beaker, add 50ml deionized water dissolving, add 4.2g lemon Acid stirring half an hour；Ammonium hydroxide is added dropwise dropwise and adjusts pH=2, continues stirring 1-2 hours.Beaker is placed on 80-90 DEG C of water in water-bath Bath is evaporated residual moisture, is placed on aging 12 hours in 110-140 DEG C of baking oven.Later with the heating of 5 DEG C/min in Muffle furnace Catalyst La is made in rate, the constant temperature calcining 4 hours under the conditions of 800 DEG C2Ce1.5Ca0.5O7-A。
Embodiment 2.
La3+Ion presoma is the preparation process of its hydroxide, oxide or carbonate: weighing 1.92g lanthanum hydroxide Or it 1.63g lanthana or 2.29g lanthanum carbonate and 50ml dust technology is added is dissolved in 200ml beaker.It is added after solution clarification 3.23g cerous nitrate (hexahydrate), 0.59g calcium nitrate (tetrahydrate) and 4.2g citric acid stir half an hour, and ammonia is added dropwise dropwise Water adjusts pH=2, continues stirring 1-2 hours.Beaker is placed on 80-90 DEG C of water bath method residual moisture in water-bath, is placed on Aging 12 hours in 110-140 DEG C of baking oven.Later with the heating rate of 5 DEG C/min in Muffle furnace, constant temperature under the conditions of 800 DEG C Catalyst La is made in roasting 4 hours2Ce1.5Ca0.5O7-B。
Embodiment 3.
Ce4+Ion presoma is the preparation process of its oxide: weighing 1.29g cerium oxide, it is molten that suitable dust technology is added Liquid and 30% hydrogen peroxide solution are placed in 80 DEG C of water-baths in 200ml beaker and dissolve by heating.After solution clarification, prepared Ce4+Ion nitrate solution adds 4.33g lanthanum nitrate (pentahydrate), or the 1.92g hydrogen-oxygen dissolved with dilute nitric acid solution Change lanthanum nitrate hexahydrate and 0.59g calcium nitrate (tetrahydrate) and 4.2g made from lanthanum or 1.63g lanthana or 2.29g lanthanum carbonate Citric acid and stir half an hour.Ammonium hydroxide is added dropwise dropwise and adjusts pH=2, continues stirring 1-2 hours.Beaker is placed in water-bath 80-90 DEG C of water bath method residual moisture is placed on aging 12 hours in 110-140 DEG C of baking oven.Later in Muffle furnace with 5 DEG C/ The heating rate of min roasts 4 hours under the conditions of 800 DEG C, and catalyst La is made2Ce1.5Ca0.5O7-C。
Embodiment 4.
Ca2+Ion presoma is the preparation process of its carbonate or oxide: weighing 0.25g calcium carbonate or 0.14g oxidation Its nitrate solution is made with dilute nitric acid dissolution in calcium.In the Ca of formation2+(five hydrations of 4.33g lanthanum nitrate are added in ion nitrate Object), or with dilute nitric acid solution to dissolve lanthanum nitrate made from 1.92g lanthanum hydroxide or 1.63g lanthana or 2.29g lanthanum carbonate molten Liquid and 3.23g cerous nitrate (hexahydrate) or dust technology and hydrogen peroxide dissolution 1.29g cerium oxide made from cerous nitrate solution with And 4.2g citric acid stirs half an hour in 200ml beaker.Ammonium hydroxide is added dropwise dropwise and adjusts pH=2, continues stirring 1-2 hours.It will burn Cup is placed on 80-90 DEG C of water bath method residual moisture in water-bath, aging 12 hours in 110-120 DEG C of baking oven is placed on, in Muffle With the heating rate of 5 DEG C/min in furnace, catalyst La is made in the constant temperature calcining 4 hours under the conditions of 800 DEG C2Ce1.5Ca0.5O7-D。
The experimental results showed that the La that above four examples are prepared2Ce1.5Ca0.5O7Catalyst is anti-for methane oxidation coupling Excellent reactivity worth should be shown, and its reactivity worth is without too big difference.Fig. 2 is indicated in case study on implementation La2Ce1.5Ca0.5O7- A and La2Ce1.5Ca0.5O7- C pyrochlore catalyst and the at present best Mn/Na of generally acknowledged performance2WO4/SiO 2 Class catalyst methane oxidative coupling reaction low temperature active comparing result.The result shows that catalyst is at 550 DEG C -750 DEG C in the present invention More superior activity is shown in range；Fig. 3 indicates La in case study on implementation2Ce1.5Ca0.5O7- A pyrochlore catalyst stability is surveyed Test result.Well stable activity, C are remained in 100 hours stability tests2Yield maintains 23.0%, no mistake Life birth is raw.

Claims (5)

1. a kind of Ca for methane oxidation coupling2+The preparation method of ion improved catalysts, it is characterized in that the following steps are included:
(1) according to stoichiometric ratio La3+:Ce4+:Ca2+=1:0.75:0.25 weighs La3+Ion presoma, Ce4+Ion presoma, Ca2+Ion presoma, and La is made3+Ion nitrate, Ce4+Ion nitrate, Ca2+ The mixed solution of ion nitrate；
(2) it will be equivalent to La3+Ion, Ce4+Ion and Ca2+The citric acid that 2 times of total ion concentration is added in mixed solution, uses ammonia Water adjusts pH to 2, stirs 2-3 hours at room temperature；
(3) be evaporated in water-bath at 80-90 DEG C, gained gel 110-140 DEG C aging 12 hours；
(4) xerogel obtained by aging is ground, then with 5 DEG C/min heating rate in Muffle furnace, in 800 DEG C of condition Lower roasting 4 hours, is made Ca2+The La of ion improvement2Ce2O7Composite oxide catalysts La2Ce1.5Ca0.5O7。
2. a kind of Ca for methane oxidation coupling according to claim 12+The preparation method of ion improved catalysts, It is characterized in La described in step (1)3+Ion presoma is La3+The nitrate of ion, carbonate, oxide or hydroxide It is a kind of.
3. a kind of Ca for methane oxidation coupling according to claim 12+The preparation method of ion improved catalysts, It is characterized in Ce described in step (1)4+Ion presoma is Ce4+One kind of the nitrate of ion, oxide.
4. a kind of Ca for methane oxidation coupling according to claim 12+The preparation method of ion improved catalysts, It is characterized in Ca described in step (1)2+Ion presoma is Ca2+One kind of the nitrate of ion, carbonate or oxide.
5. a kind of Ca for methane oxidation coupling described in claim 12+The application of ion improved catalysts, it is characterized in that Under normal pressure, reaction gas group becomes 10%O2+40%CH4, 50%Ar Balance Air, gas flow rate is the item of 30mL/min~60mL/min Under part, reacted for methane-oxidizing and-coupling.
CN201811441673.5A 2018-11-29 2018-11-29 A kind of Ca for methane oxidation coupling2+The preparation method and application of ion improved catalysts Pending CN109364907A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101954289A (en) * 2010-08-13 2011-01-26 华南理工大学 Halogen doped perovskite composite oxide catalyst as well as preparation method and application thereof
CN107649114A (en) * 2017-09-18 2018-02-02 南昌大学 A kind of B positions for methane oxidation coupling are the preparation method and application of the pyrochlore catalyst of cerium
WO2018175533A1 (en) * 2017-03-22 2018-09-27 Sabic Global Technologies, B.V. Mixed oxides catalysts for oxidative coupling of methane

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101954289A (en) * 2010-08-13 2011-01-26 华南理工大学 Halogen doped perovskite composite oxide catalyst as well as preparation method and application thereof
WO2018175533A1 (en) * 2017-03-22 2018-09-27 Sabic Global Technologies, B.V. Mixed oxides catalysts for oxidative coupling of methane
CN107649114A (en) * 2017-09-18 2018-02-02 南昌大学 A kind of B positions for methane oxidation coupling are the preparation method and application of the pyrochlore catalyst of cerium

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
VÍCTOR J. FERREIRA ET AL.: "Effect of Mg, Ca, and Sr on CeO2 Based Catalysts for the Oxidative Coupling of Methane: Investigation on the Oxygen Species Responsible for Catalytic Performance", 《INDUSTRISL & ENGINEERING CHEMISTRY RESEARCH》 *
徐法强等: "添加碱土金属化合物对CeO2甲烷氧化偶联催化性能的影响", 《分子催化》 *
杨艳玲等: "Ca，Sr 共掺杂铈氧化物及其在甲烷氧化偶联反应中的应用", 《高等学校化学学报》 *

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