CN110292931A - One kind being used for CH4-CO2The preparation method of dry gas reformation solid solution catalyst - Google Patents

One kind being used for CH4-CO2The preparation method of dry gas reformation solid solution catalyst Download PDF

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CN110292931A
CN110292931A CN201810247594.4A CN201810247594A CN110292931A CN 110292931 A CN110292931 A CN 110292931A CN 201810247594 A CN201810247594 A CN 201810247594A CN 110292931 A CN110292931 A CN 110292931A
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preparation
ethyl alcohol
solution
dry gas
solid solution
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朱卡克
周海斌
周兴贵
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East China University of Science and Technology
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East China University of Science and Technology
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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
    • B01J23/002—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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/835—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
    • 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
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
    • 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

Abstract

The invention discloses one kind to be used for CH4‑CO2Dry gas reforms solid solution catalyst MxNiyMg100‑x‑yThe preparation method of O, the method includes the steps: (1) each metal salt is mixed with solvent system, obtains solution 1；(2) solution 1 is subjected to Crystallizing treatment, obtains solution 2；(3) processing solution 2 obtains powdered intermediate；(4) powders calcined shape intermediate is obtained for CH4‑CO2Dry gas reforms solid solution catalyst MxNiyMg100‑x‑yO；Wherein M is metallic element, is selected from Ru, Ce, Co, Sn, Mn, Pt or Ge.

Description

One kind being used for CH4-CO2The preparation method of dry gas reformation solid solution catalyst
Technical field
The present invention relates to catalyst fields.Relate more specifically to a kind of for CH4-CO2Dry gas reforms solid solution catalyst MxNiyMg100-x-yThe preparation method of O.
Background technique
Since nineteen twenty-eight Fisher and Tropsch have found that methane-carbon dioxide dry gas is reformed, since the reaction can be same When convert industrial important unstripped gas for two kinds of greenhouse gases and obtained the extensive research of lot of domestic and foreign scholar.At present Being widely used in industrial nickel-base catalyst, cost is relatively low, and has good activity to dry gas reforming reaction, but carbon distribution is tight Weight, catalyst inactivation are the main problem of nickel-base catalyst.Therefore, a kind of good nickel catalyst of coking resistivity how is prepared Agent is particularly important.
In existing research, traditional method for preparing solid solution catalyst is but these sides based on coprecipitation method Method is easy to generate the continuous solid solution of composition variation, the homogeneous distribution without can control element.Nor it is able to achieve to crystal Effective control of orientation and surface texture, catalysis and surface property are often the comprehensive contribution of microcosmic mixture, for association Surface of solids structure and catalyst performance form challenge.It can be obtained at present with coking resistivity and microcosmic homogeneity Be not suitable for industrialized production with the preparation method of the good catalyst of overall stability.
Therefore, there is an urgent need in the art to provide a kind of good nickel-base catalyst of the coking resistivity suitable for industrialized production Preparation method.
Summary of the invention
The present invention is intended to provide a kind of coking resistivity suitable for industrialized production is good to be used for CH4-CO2Dry gas is reformed The preparation method of solid solution nickel-base catalyst.
The present invention provides one kind to be used for CH4-CO2Dry gas reforms solid solution catalyst MxNiyMg100-x-yThe preparation method of O, The method includes the steps:
(1) each metal salt is mixed with solvent system, obtains solution 1；
(2) solution 1 is subjected to Crystallizing treatment, obtains solution 2；
(3) processing solution 2 obtains powdered intermediate；With
(4) powders calcined shape intermediate is obtained for CH4-CO2Dry gas reforms solid solution catalyst MxNiyMg100-x-yO；
Wherein M is metallic element, is selected from Ru, Ce, Co, Sn, Mn, Pt or Ge.
In another preferred example, water and ethyl alcohol are contained in step (1) described solvent system；It is highly preferred that the solvent system System is made of water and ethyl alcohol.
In another preferred example, the molar fraction of water is no more than 50% in the solvent system；The molar fraction of ethyl alcohol is small In 100%.
In another preferred example, the volume ratio of second alcohol and water is 1-20:1 in the solvent system；More preferably 1-9:1； Most preferably 2-9:1.
In another preferred example, step (2) the Crystallizing treatment time is 24-72 hours；More preferably 24-48 hours.
In another preferred example, step (2) the Crystallizing treatment temperature is 100-200 DEG C；More preferably 120-180 DEG C； Most preferably 150-180 DEG C.
In another preferred example, step (3) processing includes filtering, being dry.
In another preferred example, step (4) maturing temperature is 500-800 DEG C；Calcining time is 4-6 hours.
In another preferred example, the concentration of step (1) described magnesium salts is 0.1-1.0mol/L；The magnesium salts and nickel salt rub You are than being 49-9:1.
Accordingly, the present invention provides a kind of preparations of good nickel-base catalyst of the coking resistivity suitable for industrialized production Method.
Detailed description of the invention
Fig. 1 is the Ni obtained under the conditions of embodiment 17Mg93O intermediate SEM figure and Mapping scanning figure；Wherein
A-c is SEM figure, and d is the region for being Mapping, and f, g, h, i are respectively Mg, Ni, C, the Mapping figure of O element, e For the superposition of each element, bright colored portion is the region Mapping in d.
Fig. 2 is the catalyst M obtained after embodiment 1-5 is calcinedxNiyMg100-x-yThe XRD diagram of O；Wherein
(a)Ni7Mg93O, 75ml ethyl alcohol, 25ml H2O (corresponds to example 1) for 24 hours
(b)Ru0.5Ni7.5Mg92O, 80ml ethyl alcohol, 20ml H2O, 36h (correspond to example 2)
(c)Ce1.5Ni8.5Mg90O, 60ml ethyl alcohol, 40ml H2O (corresponds to example 3) for 24 hours
(d)Co1Ni9Mg90O, 75ml ethyl alcohol, 25ml H2O, 48h (correspond to example 4)
(e)Sn2Ni6Mg92O, 90ml ethyl alcohol, 10ml H2O, 36h (correspond to example 5).
Fig. 3 is Co after the calcining that embodiment 4 obtains1Ni9Mg90O SEM figure and Mapping scanning figure (75ml ethyl alcohol, 25ml H2O,48h)。
Fig. 4 is Sn after the calcining that embodiment 5 obtains2Ni6Mg92O SEM figure and Mapping scanning figure (90ml ethyl alcohol, 10ml H2O, 36h).
Fig. 5 be it is each under the conditions of the Ni that obtains7Mg93The XRD diagram of O intermediate；Wherein
(a) 100ml methanol, 180 DEG C, for 24 hours
(b) 100ml ethyl alcohol, 180 DEG C, for 24 hours
(c) 75ml ethyl alcohol, 25ml deionized water, 180 DEG C, for 24 hours
(d) 50ml ethyl alcohol, 50ml deionized water, 180 DEG C, for 24 hours
(e) 98ml ethyl alcohol, 2ml deionized water, 180 DEG C, for 24 hours
(f) 75ml ethyl alcohol, 25ml deionized water, 180 DEG C, 72h
(g) 50ml normal propyl alcohol, 50ml methanol, 180 DEG C, for 24 hours.
Specific embodiment
After extensive and in-depth study, discovery is being used for CH using solvent hot preparation to inventor4-CO2Dry gas reforms solid solution Body catalyst MxNiyMg100-x-yIn the method for O, it is highly detrimental to industrialized production using the strong methanol of reproducibility, however is only used The replacement of the lower alcohols such as ethyl alcohol or normal propyl alcohol can not but obtain desired product.Inventor is it was unexpectedly observed that use ethyl alcohol and water shape At solvent system, can obtain with coking resistivity and microcosmic homogeneity and the good nickel catalyst of overall stability Agent.Further, inventor has found the content of water in the solvent system no more than 50%.On this basis, this hair is completed It is bright.
Specifically, one kind provided by the invention is used to prepare CH4-CO2Dry gas reforms solid solution catalyst MxNiyMg100-x-yO Solvent thermal process comprising steps of
Magnesium salts, nickel salt and promoter metal (M) salt are mixed with solvent system, obtain solution 1 by the first step；
Solution 1 is carried out Crystallizing treatment, obtains solution 2 by second step；
Third step, processing solution 2 obtain powdered intermediate；
4th step, powders calcined shape intermediate are obtained for CH4-CO2Dry gas reforms solid solution catalyst MxNiyMg100-x-yO Powder.
In the above-mentioned first step, the M is selected from Ru, Ce, Co, Sn, Mn, Pt or Ge.
In the above-mentioned first step, the dosage of the magnesium salts, nickel salt and promoter metal (M) salt can be according to metal each in target product Depending on the content of element.An advantage of the invention is exactly that can be adjusted according to the content of metallic element each in required target product The dosage of each metal salt of investment.
The acid ion of metal salt involved in the above-mentioned first step may optionally be organic acid anions or inorganic acid radical from Son, preferably acetate；It is preferred that the acid ion of each metal salt is identical.
The concentration range general control of magnesium salts is in 0.1mol/L -1.0mol/L in the above-mentioned first step；And magnesium salts and nickel salt Molar ratio is controlled in 49-9:1.
Water and ethyl alcohol must be contained in solvent system involved in the above-mentioned first step；It is described in a preferred embodiment of the invention Solvent system is made of water and ethyl alcohol.
In one embodiment of the invention, the molar fraction of water is no more than in the solvent system that the above-mentioned first step is related to 50%；In an of the invention preferred embodiment, the volume ratio of the second alcohol and water in solvent system is 1-20:1, more preferably 1-9:1, Most preferably 2-9:1.
In one embodiment of the invention, the above-mentioned first step be magnesium salts, nickel salt and promoter metal (M) salt are added to it is molten It is evenly dispersed in agent system to obtain solution 1.
In above-mentioned second step, the Crystallizing treatment carries out in a high pressure reaction kettle.In a kind of example of the invention, on Stating second step is that the solution 1 for obtaining the first step is transferred in autoclave, is placed at a temperature of Crystallizing treatment by a timing Between crystallization.
In one embodiment of the invention, the Crystallizing treatment time is 24-72 hours, preferably 24-48 hours.
In one embodiment of the invention, the Crystallizing treatment temperature in above-mentioned second step is 100-200 DEG C, preferably 120-180 DEG C, more preferably 150-180 DEG C.
In one embodiment of the invention, the solution 2 for taking out reaction kettle is handled in above-mentioned third step, it is described Processing carries out after solution 2 is cooling；The processing includes but is not limited to filter, dry.
In one embodiment of the invention, above-mentioned 4th step is to carry out powdered midbody product in Muffle furnace Roasting, maturing temperature are 500-800 DEG C；Calcining time is 4-6 hours.
Solid solution catalyst MxNiyMg100-x-yO powder
Provided by the present invention for CH4-CO2Dry gas reforms solid solution catalyst MxNiyMg100-x-yO intermediate has sheet Structure (referring to the a-c of attached drawing 1), Metal Distribution therein is uniform (referring to the f-i of attached drawing 1), and in side provided by the invention The M obtained (after calcining) under the conditions of methodxNiyMg100-x-yThe Elemental redistribution of O powder is uniformly (referring to attached drawing 3 and 4).
It can not find very flat surface when general Mapping, theoretically select very flat surface color just can be completely the same, it is attached Fig. 4 is just more conform with.
The region for comparing each color and Mapping can analyze out that method provided by the invention obtains for CH4-CO2 Dry gas reforms solid solution catalyst MxNiyMg100-x-yThe M of O, Mg, Ni, O Elemental redistribution are uniform.
The feature that the features described above or embodiment that the present invention mentions are mentioned can be in any combination.Disclosed in this case specification All features can be used in combination with any composition form, each feature disclosed in specification, any can provide it is identical, The alternative characteristics of impartial or similar purpose replace.Therefore except there is special instruction, revealed feature is only impartial or similar spy The general example of sign.
Main advantages of the present invention are: method provided by the invention can not only prepare the very strong solid solution catalyst of activity MxNiyMg100-x-yO, but also simpler convenience and guarantee that metal is uniformly distributed.
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention Rather than it limits the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually according to conventional strip Part or according to the normal condition proposed by manufacturer.Unless otherwise stated, otherwise all percentage, ratio, ratio or number is pressed Poidometer.The unit in percent weight in volume in the present invention is well-known to those skilled in the art, such as is referred to 100 The weight of solute in the solution of milliliter.Unless otherwise defined, all professional and scientific terms as used herein and this field are ripe It is identical to practice meaning known to personnel.In addition, any method similar to or equal to what is recorded and material all can be applied to In the method for the present invention.The preferred methods and materials described herein are for illustrative purposes only.
Embodiment 1
Preparation is used for CH4-CO2Dry gas reforms solid solution catalyst Ni7Mg93O powder
The magnesium acetate and 0.0014mol nickel acetate for weighing 0.0186mol are added to 75ml ethyl alcohol and 25ml deionized water is mixed It closes in solution, after evenly dispersed, be transferred in the autoclave that volume is 200ml, be placed in air dry oven, temperature is 180 DEG C, crystallization time is 24 hours.Reaction kettle is taken out, filtered, dried after cooling, obtain midbody product, be placed in It is roasted in Muffle furnace, maturing temperature is 800 DEG C, and calcining time is 4 hours, obtains Ni7Mg93O powder.
Embodiment 2
Preparation is used for CH4-CO2Dry gas reforms solid solution catalyst M0.5Ni7.5Mg92O powder
Weigh 0.0184mol magnesium acetate, 0.0015mol nickel acetate, 0.0001mol auxiliary agent acetate M (M Ru, Ce, Co, Sn, Mn, Pt, Ge) it is added in 80ml ethyl alcohol and 20ml deionized water mixed solution, after evenly dispersed, being transferred to volume is It in the autoclave of 200ml, is placed in air dry oven, temperature is 150 DEG C, and crystallization time is 36 hours.Take out reaction Kettle is filtered after cooling, is dried, obtain midbody product, is placed in Muffle furnace and roasted, maturing temperature 800 DEG C, calcining time is 5 hours, obtains M0.5Ni7.5Mg92O powder.
Embodiment 3
Preparation is used for CH4-CO2Dry gas reforms solid solution catalyst M1.5Ni8.5Mg90O powder
Weigh 0.054mol magnesium acetate, 0.0051mol nickel acetate, 0.0009mol auxiliary agent acetate M (M Ru, Ce, Co, Sn, Mn, Pt, Ge), it is added in 60ml ethyl alcohol and 40ml deionized water mixed solution, after evenly dispersed, being transferred to volume is It in the autoclave of 200ml, is placed in air dry oven, temperature is 150 DEG C, and crystallization time is 24 hours.Take out reaction Kettle is filtered after cooling, is dried, obtain midbody product, is placed in Muffle furnace and roasted, maturing temperature 550 DEG C, calcining time is 6 hours, obtains M1.5Ni8.5Mg90O powder.
Embodiment 4
Preparation is used for CH4-CO2Dry gas reforms solid solution catalyst M1Ni9Mg90O powder
Weigh 0.036mol magnesium acetate, 0.0036mol nickel acetate, 0.0004mol auxiliary agent acetate M (M Ru, Ce, Co, Sn, Mn, Pt, Ge), it is added in 75ml ethyl alcohol and 25ml deionized water mixed solution, after evenly dispersed, being transferred to volume is It in the autoclave of 200ml, is placed in air dry oven, temperature is 180 DEG C, and crystallization time is 48 hours.Take out reaction Kettle is filtered after cooling, is dried, obtain midbody product, is placed in Muffle furnace and roasted, maturing temperature 700 DEG C, calcining time is 4 hours, obtains M1Ni9Mg90O powder.
Embodiment 5
Preparation is used for CH4-CO2Dry gas reforms solid solution catalyst M2Ni6Mg92O powder
Weigh 0.0276mol magnesium acetate, 0.0018mol nickel acetate, 0.0006mol auxiliary agent acetate M (M Ru, Ce, Co, Sn, Mn, Pt, Ge), it is added in 90ml ethyl alcohol and 10ml deionized water mixed solution, after evenly dispersed, being transferred to volume is It in the autoclave of 200ml, is placed in air dry oven, temperature is 170 DEG C, and crystallization time is 36 hours.Take out reaction Kettle is filtered after cooling, is dried, obtain midbody product, is placed in Muffle furnace and roasted, maturing temperature 600 DEG C, calcining time is 6 hours, obtains M2Ni6Mg92O powder.
Comparative example
In addition to the condition variation of following (a)-(g), intermediate is obtained essentially according to the method for embodiment 1.These intermediates XRD diagram be detailed in attached drawing 5.
The reaction condition that (a)-(g) is related in attached drawing 5 corresponds respectively to:
(a) 100ml methanol, 180 DEG C, for 24 hours；Intermediate structure is Ni7Mg93(OH)(OCH3)。
(b) 100ml ethyl alcohol, 180 DEG C, for 24 hours；It can be seen that there are many miscellaneous peaks, illustrate that solvent only has ethyl alcohol that can not succeed.
(c) 75ml ethyl alcohol, 25ml deionized water, 180 DEG C, for 24 hours；Intermediate structure is hydroxide.
(d) 50ml ethyl alcohol, 50ml deionized water, 180 DEG C, for 24 hours；Intermediate structure is hydroxide.
(e) 98ml ethyl alcohol, 2ml deionized water, 180 DEG C, for 24 hours；Intermediate there are many miscellaneous peak, as a result with ethyl alcohol is used alone It is similar.
(f) 75ml ethyl alcohol, 25ml deionized water, 180 DEG C, 72h；There are many miscellaneous peaks for intermediate structure.
(g) 50ml normal propyl alcohol, 50ml methanol, 180 DEG C, for 24 hours；As can be seen from the figure there are many miscellaneous peaks.
The foregoing is merely illustrative of the preferred embodiments of the present invention, the substantial technological content model being not intended to limit the invention It encloses, substantial technological content of the invention is broadly defined in the scope of the claims of application, any technology that other people complete Entity or method also or a kind of equivalent change, will if identical with defined in the scope of the claims of application It is considered as being covered by among the scope of the claims.

Claims (10)

1. one kind is used for CH4-CO2Dry gas reforms solid solution catalyst MxNiyMg100-x-yThe preparation method of O, which is characterized in that institute State method comprising steps of
(1) each metal salt is mixed with solvent system, obtains solution 1；
(2) solution 1 is subjected to Crystallizing treatment, obtains solution 2；
(3) processing solution 2 obtains powdered intermediate；
(4) powders calcined shape intermediate is obtained for CH4-CO2Dry gas reforms solid solution catalyst MxNiyMg100-x-yO；
Wherein M is metallic element, is selected from Ru, Ce, Co, Sn, Mn, Pt or Ge.
2. preparation method as described in claim 1, which is characterized in that contain water and ethyl alcohol in step (1) described solvent system.
3. preparation method as claimed in claim 2, which is characterized in that the solvent system is made of water and ethyl alcohol.
4. preparation method as claimed in claim 2 or claim 3, which is characterized in that the molar fraction of water does not surpass in the solvent system Cross 50%；The molar fraction of ethyl alcohol is less than 100%.
5. preparation method as claimed in claim 4, which is characterized in that the volume ratio of second alcohol and water is 1- in the solvent system 20:1；Preferably 1-9:1；More preferably 2-9:1.
6. preparation method as described in claim 1, which is characterized in that step (2) the Crystallizing treatment time is that 24-72 is small When；Preferably 24-48 hours.
7. preparation method as described in claim 1, which is characterized in that step (2) the Crystallizing treatment temperature is 100-200 ℃；Preferably 120-180 DEG C；More preferably 150-180 DEG C.
8. preparation method as described in claim 1, which is characterized in that step (3) processing includes filtering, being dry.
9. preparation method as described in claim 1, which is characterized in that step (4) maturing temperature is 500-800 DEG C；Roasting Burning the time is 4-6 hours.
10. preparation method as described in claim 1, which is characterized in that the concentration of step (1) described magnesium salts is 0.1- 1.0mol/L；The molar ratio of the magnesium salts and nickel salt is 49-9:1.
CN201810247594.4A 2018-03-23 2018-03-23 One kind being used for CH4-CO2The preparation method of dry gas reformation solid solution catalyst Pending CN110292931A (en)

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