CN108067265A - A kind of preparation method of methane reforming catalyst - Google Patents
A kind of preparation method of methane reforming catalyst Download PDFInfo
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- CN108067265A CN108067265A CN201610991016.2A CN201610991016A CN108067265A CN 108067265 A CN108067265 A CN 108067265A CN 201610991016 A CN201610991016 A CN 201610991016A CN 108067265 A CN108067265 A CN 108067265A
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- aluminium oxide
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
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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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/15—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination
- C07C17/152—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons
- C07C17/154—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons of saturated hydrocarbons
Abstract
The present invention discloses a kind of preparation method of methane reforming catalyst, including following content：Zirconium sulfate solid acid, 2 methylimidazoles and aluminum hydroxide slurry are mixed, obtain the aluminum hydroxide slurry of sulfur acid zirconium solid acid and 2 methylimidazoles, then the aluminium oxide of zinc supported is sprayed with the aluminum hydroxide slurry of sulfur acid zirconium solid acid and 2 methylimidazoles, methane zirconyl oxyhalides reforming catalyst is made after drying, roasting.Catalyst prepared by this method can improve the conversion ratio of methane and the selectivity of target product halide simultaneously, it is suppressed that the deep oxidation of halide, and then significantly improve the yield of halide.
Description
Technical field
The present invention relates to a kind of preparation method of methane reforming catalyst, relate in particular to a kind of with core-shell structure
The preparation method of low temperature high activity, selective methane zirconyl oxyhalides reforming catalyst.
Background technology
Methane is not direct with halogen reaction but by the use of HCl, HBr or metal halide as halogen source, in the presence of oxygen
The process for carrying out reaction generation halide is known as zirconyl oxyhalides reaction.This method is earliest applied to HCl catalysis oxidation preparing chlorine gas
Industrial production is known as Deacon processes.
The methane zirconyl oxyhalides of early stage are reacted mainly using HCl as halogen source, and catalyst is mainly with CuCl2For active component,
Bromhead etc.（Bromhead J, Font-Freide J J, Westlake D J. Process for the
production of methyl or ethyl mono-chloride or bromide. EP. Patent, 0117731.
1984-09-05）CuCl on alumina2Oxychlorination catalyst is made.Conner etc.（Conner W C Jr,
Pieters W J M, Gates W, et al. The oxyhydrochlorination of methane on fumed
silica-based Cu, K, La catalysts: II. Gas phase stoichiometry. Appl Catal,
1984, 11(1): 49-58；Conner W C Jr, Pieters W J M, Signorelli A J. The
oxyhydrochlorination of methane on fumed silica-based Cu, K, La catalysts:
III. Bulk&surface analysis. Appl. Catal., 1984, 11(1): 59-71）In CuCl2Catalyst base
Dystectic alkali metal chloride KCl or rare-earth metal chloride LaCl is with the addition of on plinth3Auxiliary agent is made, uses it to rugged catalyst
Activity, so as to reduce because of CuCl2Catalyst loss caused by low boiling point obtains higher methane conversion, catalytic effect
Also stablize relatively, but also result in the rise of more chloromethane selectivity.
US 6452058 is disclosed as CuCl2The rare-earth metal chloride LaCl of main auxiliary agent3Have for oxi-chlorination
Good catalytic activity, has synthesized porous LaOCl, catalyst has good catalytic performance, is 400 in reaction temperature
DEG C, methane conversion has reached 12%, and the selectivity of monochloro methane is then 55%.
For La base catalyst, Lercher etc.（ Podkolzin S G, Stangland E E, Lercher J A,
et al. Methyl Chloride Production from Methane over Lanthanum-Based
Catalysts. J. Am. Chem. Soc., 2007, 129(9): 2569-2576）Further research has been done, has been synthesized
Catalyst LaOCl/LaCl3In 540 DEG C, gas composition V（CH4）:V（HCl）:V（O2）:V（N2）=2:1:1:Under conditions of 0.5, methane
Conversion ratio 13.3%, monochloro methane selectivity 62.6%, and catalyst has good stability.Lercher is also further ground
Reaction mechanism is studied carefully, La is to make the metal that oxi-chlorination occurs for methane and itself valence state is constant, he thinks that reaction is being catalyzed
Redox reaction, O occur for agent surface2The Cl on activated catalyst surface forms OCl, and OCl becomes after playing activation to methane
The mutual inversion of phases of Cl, Cl and OCl, enables oxi-chlorination to carry out.
Wang Ye etc.（Transformation of methane to propylene:a two step reaction
route catalyzed by modified CeO2 nanocrystals and zeolites [J]. Angewendte
Chemie Internation Edition, 2012, 51: 2438-2442；Ceric oxide nanorod loads palladium oxide and oxygen
Methane oxychloride reaction [D] Xiamen University on change Mn catalyst, 2013.）Use urging using rare earth element ce as key component
Agent has oxi-chlorination prominent activity.Catalyst activity component is CeO2And it can modify and be made through the second component
Cerium based bi-component composite oxides, be carried on (SiO on different carriers2、Al2O3、MgO、ZrO2、TiO2Deng).It is in temperature
480℃、CH4：HCl：O2：N2：He = 4:2:1:1.5:1.5th, under conditions of 40 mL/min of air speed, CH3Cl selectivity and yield
Up to 66% and 8%, 55% selectivity of the LaOCl better than Lercher, 6.6% yield.In dual-component catalyst with iron mixed effect
Preferably, 15%wtFeOx-CeO2Nanometer rods react 100 h CH4Conversion ratio 23%, CH3Cl selectivity 74%.Ce in cerium base catalyst3 +And Ce4+Between valence state conversion and cycle in oxi-chlorination activate HCl play an important role, HCl is through O2Activate the work of generation
Property Cl, active Cl and methane reaction generate monochloro methane, the Ce being reduced3+Again by O2It is oxidized to Ce4+Complete catalytic cycle.Research
It has also been found that the crystal face that the form of catalyst is exposure significantly affects the activity of catalyst, highest activity is { 100 }
Face, it is secondary it is high be { 110 } face, and the activity in { 111 } face is minimum（Using oxygen as the epoxidation of propylene of oxidant on copper-based catalysts
With methane oxychloride reaction [D] Xiamen University on cerium base catalyst, 2012.）.
CN201310216352.6 disclose it is a kind of prepare bromomethane and the catalyst of CO for bromine oxidation of methane, it is described to urge
Agent includes main active component and carrier, wherein the main active component is selected from FePO4、Fe2P2O7And Fe3(P2O7)2In one
Kind is several, and the carrier is selected from TiC-SiC and TiO2One or more of-SiC, and the weight of the main active component
1.0~50.0% that content is the catalyst weight are measured, the catalyst, will be containing main active component by using infusion process
Maceration extract is supported on carrier, through drying, roasting after be made, the catalyst under normal pressure and 400-800 DEG C of reaction condition,
It is capable of the mixture high activity of catalytic methane, oxygen and HBr aqueous solutions, is converted into bromomethane and CO with high selectivity.It is described to urge
Agent has good performance, without not sent out on substantially inactivation and catalyst in the tandem reaction sequence when small more than 1400
Raw carbon distribution.
CN201110198638.7 discloses a kind of methane oxychloride chloromethanes and bromine oxidation of methane bromomethane.It is described
Cerium base catalyst is reacted suitable for methane zirconyl oxyhalides, and the cerium base catalyst can be CeO2, cerium based bi-component composite oxides
Or support type cerium base oxide catalyst etc..The cerium base catalyst can efficiently, steadily catalytic methane zirconyl oxyhalides be reacted, including
Oxychloride reacts and bromine oxidation reaction, generates chloromethanes and bromomethane.The cerium base catalyst can efficient catalytic reactant for reforming
CH4, HCl, O2Carry out oxychloride reaction generation product CH3Cl and CH2Cl2；The cerium base catalyst can also Efficient Conversion CH4, HBr
(H2O), O2Carry out bromine oxidation reaction generation CH3Br, CH2Br2。
Methane zirconyl oxyhalides reaction in the prior art has the following technical problems that high temperature is conducive to improve the conversion ratio of methane,
But the halide of generation can be made to be particularly halide deep oxidation generation CO or CO2, significantly reduce halide
Selectivity, the yield for causing halide is relatively low, therefore develop at the same there is higher methane conversion and halide select
The methane zirconyl oxyhalides catalysts of selecting property are of great significance.
The content of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of methane zirconyl oxyhalides reforming catalyst with core-shell structure
Preparation method.Catalyst prepared by this method can improve the selection of the conversion ratio and target product halide of methane simultaneously
Property, it is suppressed that the deep oxidation of halide, and then significantly improve the yield of halide.
A kind of preparation method of methane reforming catalyst, including following content：By zirconium sulfate solid acid, 2-methylimidazole and
Aluminum hydroxide slurry mixes, and the aluminum hydroxide slurry of sulfur acid zirconium solid acid and 2-methylimidazole is obtained, then with sulfur acid zirconium
The aluminum hydroxide slurry of solid acid and 2-methylimidazole sprays the aluminium oxide of zinc supported, and methane oxyhalogen is made after drying, roasting
Change reforming catalyst.
In the above method, the zirconium sulfate solid acid is prepared using commercial goods or according to the prior art.
The aluminum hydroxide slurry generally uses boehmite slurries.Boehmite also known as monohydrate alumina or the soft aluminium of a false water
Stone, molecular formula AlOOHnH2O（n=0.08-0.62）.For the preparation method of aluminum hydroxide slurry, there is no particular limitation,
Can be various methods commonly used in the art, such as can be aluminium alcoholates Hydrolyze method, the acid system of aluminium salt or aluminate or alkaline process,
NaA1O2Solution is passed through CO2Carbonizatin method etc..Specific operating method is known to those skilled in the art, and details are not described herein.
In the above method, routine techniques can be used in the preparation of the aluminium oxide of zinc supported, including zinc is loaded on alumina
Either method.It is specific to can be used zinc compound dip loading in formed alumina or by the same aluminium oxide of zinc compound
Then the aluminium oxide of zinc supported is made in powder kneading and compacting through drying and roasting.The aluminium oxide may be employed commercial goods or by
Prepared according to the prior art, the zinc compound can be zinc nitrate, zinc sulfate, zinc bromide, one kind in zinc chloride or
It is several.The drying time is 1-5h, and preferably 2-4h, drying temperature is 90-150 DEG C, preferably 100-130 DEG C；During the roasting
Between for 3-8h, preferably 4-6h, temperature is 300-700 DEG C, preferably 400-500 DEG C.
In the above method, the weight of 2-methylimidazole in the aluminum hydroxide slurry of sulfur acid zirconium solid acid and 2-methylimidazole
Content is 1-10%, preferably 3-7%.With 2-methylimidazole in the aluminum hydroxide slurry of sulfur acid zirconium solid acid and 2-methylimidazole
Weight content is sprayed before the aluminium oxide of zinc supported, it is preferred to use vapor volume content is 1%-15%, and the water of preferably 1%-5% steams
Gas nitrogen mixture handles the aluminium oxide of zinc supported, and treatment temperature is 150-300 DEG C, preferably 180-200 DEG C, during processing
Between be 5-30min, preferably 5-15 min, further preferred 5-10 min.Result of study shows using above-mentioned processing mode to oxygen
Change aluminium can improve the hydroxy radical content of the oxidation aluminium surface of zinc supported while without the hydroxy radical content inside improving, and make sulfur acid zirconium
The aluminum hydroxide slurry of solid acid can be uniformly sprayed around the aluminium oxide of zinc supported, while the hydrogen-oxygen bond energy of aluminium hydroxide
The hydroxyl bonding that enough oxidation aluminium surfaces with zinc supported are rich in, is that duct is mutually got around regulations, improves the activity and target product of catalyst
Selectivity.
A kind of methane reforming catalyst prepared using the above method, the catalyst have core-shell structure, the catalysis
The core of agent is the aluminium oxide of zinc supported, and shell is the aluminium oxide of sulfur acid zirconium solid acid, wherein, the aluminium oxide and sulfur acid of zinc supported
The weight ratio of the aluminium oxide of zirconium solid acid is 10:1-2:1, it is preferably 8:1-5:1；With the weight of the aluminium oxide of sulfur acid zirconium solid acid
On the basis of amount, zirconium sulfate solid acid weight content is 5wt%-10wt%, is preferably 8wt%-15wt%, with the aluminium oxide weight of zinc supported
On the basis of amount, zinc is using the content that oxide is counted as 5wt%-30wt%, preferably 10 wt%-25wt%.
In above-mentioned catalyst, the thickness of the shell is 5 μm -200 μm, is preferably 10 μm -150 μm, still more preferably for
15μm-100μm。
In above-mentioned catalyst, the aluminium oxide of the zinc supported can be spherical or bar shaped, preferably spherical；The oxidation of zinc supported
The equivalent thickness of aluminium a diameter of 1mm-5mm, preferably 2mm-5mm, preferably 2mm-3mm.
Application of the above-mentioned catalyst in the conversion of methane zirconyl oxyhalides, using fixed-bed process, with methane, oxygen, halogen acids
Methane zirconyl oxyhalides are carried out under the effect of the catalyst for reactant or using methane, oxygen, aqueous solution of halogen acid as reactant to turn
Change, reaction temperature is 250-600 DEG C, and preferably 300-450 DEG C, methane, halogen acids, the input material volume ratio of oxygen are (3-5):(1-
3):1, the flow of methane is 10-50ml/min, preferably 20-40ml/min.The haloid acid for hydrogen chloride or hydrogen bromide or its
Aqueous solution, preferably aqueous solution of hydrogen bromide.
Result of study show methane zirconyl oxyhalides conversion reaction be related to methane-steam reforming, methane oxidation,
The many reactions of halide deep oxidation, cause the selectivity of halide can not effectively to improve.Prepared by the present invention has
The catalyst of nucleocapsid can be realized to above-mentioned the difference of the sensitivity of differential responses with the different component of core-shell structure
The relation control of reaction.The aluminium oxide of the specifically kernel zinc supported of catalyst is more advantageous to progress halogen acids and is converted into halogen
The reaction of free radical and a small amount of methane halogenation reaction occurs, particularly reduce the acid content of aluminium oxide, be conducive to improve on core
Halogen acids content, shell is substantially carried out the halogenation of methane, the halogen of interior karyogenesis for the aluminium oxide of sulfur acid zirconium solid acid
Plain free radical can be diffused rapidly to progress methane halogenating reaction in shell, and the outer of catalyst is rapidly diffused into after generating halogenated hydrocarbons
Portion, it is therefore prevented that it is further aoxidized, and significantly improves the selectivity of halogenated hydrocarbons and the conversion ratio of methane.
Methane reforming catalyst prepared by the method for the present invention, adds 2-methylimidazole template during preparation,
Specific duct is formed in the shell of catalyst, is conducive to the reaction of methane and bromine free radical in shell.
Specific embodiment
A kind of methane zirconyl oxyhalides reforming catalyst and preparation method thereof is further illustrated the present invention with reference to embodiment
With using functions and effects, but following embodiment is not construed as limiting the invention.Transmission may be employed in the catalyst of the present invention
The means such as electron microscopic observation, electron diffraction analysis and Elemental Composition analysis confirm its nucleocapsid structure, and measure its center and shell
Composition.Catalyst core shell structure it is definite it is specific with the following method：Use Japanese 2100 LaB6 high scores of JEOL companies JEM
Distinguish transmission electron microscope, 0.23 nm of resolution ratio, the X ray energy dispersion spectroscopy instrument equipped with EDAX companies（EDX）, sample is placed in agate
It is fully ground in Nao mortars, then ultrasonic wave disperses 20 min in absolute ethyl alcohol.2-3 drop suspensions is taken to drop in copper mesh support
On micro-grid carbon film, TEM observations, electron diffraction analysis and Elemental Composition analysis are carried out to sample after sample drying.
Embodiment 1
Aluminum hydroxide slurry is prepared using aluminium isopropoxide Hydrolyze method：By water and aluminium isopropoxide in molar ratio 120:1 mixing, hydrolysis temperature
Degree control is at 80 DEG C -85 DEG C, after making aluminium isopropoxide hydrolysis 1.5h, carries out aging, aging temperature control is at 90 DEG C -95 DEG C, aging
Time is 18h, obtains the aluminum hydroxide slurry that solid content is 21.3wt%.
Prepare the aluminium oxide of zinc supported：Using equi-volume impregnating in aluminium oxide（Commercial goods, property are as follows：L acid contains
It measures as 0.2mmol g-1；BET specific surfaces are 200；Pore volume is 0.3ml/g）Zinc nitrate solution is impregnated, is dried, roasts after dipping
It burns, the drying time is 2h, and drying temperature is 130 DEG C；The roasting time 4h, temperature are 400 DEG C, the oxygen of the zinc supported
Change aluminium as spherical shape, the aluminium oxide equivalent diameter of zinc supported is 2mm；
Spray process：Suitable zirconium sulfate solid acid, 2-methylimidazole and aluminum hydroxide slurry are mixed, sulfur acid zirconium is obtained and consolidates
The aluminum hydroxide slurry of body acid, the mass content of 2-methylimidazole is 3% in slurries, and the oxidation of zinc supported is then sprayed with slurries
Methane zirconyl oxyhalides reforming catalyst is made in aluminium after drying, roasting, and the drying time is 4h, and drying temperature is 100 DEG C；Institute
Roasting time 6h is stated, temperature is 400 DEG C.
Catalyst property is as follows：The catalyst has nucleocapsid, and core is the aluminium oxide of zinc supported, and shell is consolidated for sulfur acid zirconium
The aluminium oxide of body acid, wherein, the weight ratio of the aluminium oxide of zinc supported and the aluminium oxide of sulfur acid zirconium solid acid is 8：1；With sulfur-bearing
On the basis of the weight of the aluminium oxide of sour zirconium solid acid, zirconium sulfate solid acid weight content is 8wt%, with the aluminium oxide weight of zinc supported
On the basis of amount, zinc is using the content that oxide is counted as 25wt%；The thickness of the shell is 15 μm.
Methane zirconyl oxyhalides evaluation is carried out to above-mentioned catalyst, evaluation condition is as follows：Methane oxygen bromination reaction is fixed in normal pressure
It is carried out in bed microreactor.10ml 20-40 mesh catalyst is taken to be fitted into crystal reaction tube, catalyst bed is made to be located at heating
In the middle part of stove, bed fills quartz sand up and down.Reaction gas adjusts flow, the flow peristaltic pump control of hydrobromic acid with mass flowmenter
System.Temperature programming is to 350 DEG C under nitrogen protection, after constant temperature, by methane, halogen acids, oxygen, nitrogen by volume 4：
2：1：1 is passed through in reactor, and the flow of methane is 30ml/min.Tail gas divides SP- after washing, drying with north after reaction 2h
3420A type gas-chromatography on-line analyses.Evaluation result is shown in Table 1
Embodiment 2
Aluminum hydroxide slurry is prepared using aluminium isopropoxide Hydrolyze method：By water and aluminium isopropoxide in molar ratio 120:1 mixing, hydrolysis temperature
Degree control is at 80 DEG C -85 DEG C, after making aluminium isopropoxide hydrolysis 1.5h, carries out aging, aging temperature control is at 90 DEG C -95 DEG C, aging
Time is 18h, obtains the aluminum hydroxide slurry that solid content is 21.3wt%.
Prepare the aluminium oxide of zinc supported：Using equi-volume impregnating in aluminium oxide（Commercial goods, L acid contents are
0.1mmol•g-1；BET specific surfaces are 300m2/g；Pore volume is 0.5ml/g）Solution of zinc sulfate is impregnated, is dried, roasts after dipping
It burns, the drying time is 3h, and drying temperature is 120 DEG C；The roasting time 5h, temperature are 450 DEG C, the oxygen of the zinc supported
Change aluminium as spherical shape, the aluminium oxide equivalent diameter of zinc supported is 2mm；
Spray process：Suitable zirconium sulfate solid acid, 2-methylimidazole and aluminum hydroxide slurry are mixed, sulfur acid zirconium is obtained and consolidates
The aluminum hydroxide slurry of body acid, the mass content of 2-methylimidazole is 7% in slurries, and the oxidation of zinc supported is then sprayed with slurries
Methane zirconyl oxyhalides reforming catalyst is made in aluminium after drying, roasting, and the drying time is 3h, and drying temperature is 100 DEG C；Institute
Roasting time 4h is stated, temperature is 450 DEG C.
Catalyst property is as follows：The catalyst has nucleocapsid, and core is the aluminium oxide of zinc supported, and shell is consolidated for sulfur acid zirconium
The aluminium oxide of body acid, wherein, the weight ratio of the aluminium oxide of zinc supported and the aluminium oxide of sulfur acid zirconium solid acid is 7：1；With sulfur-bearing
On the basis of the weight of the aluminium oxide of sour zirconium solid acid, zirconium sulfate solid acid weight content is 11wt%, with the aluminium oxide weight of zinc supported
On the basis of amount, zinc is using the content that oxide is counted as 15wt%；The thickness of the shell is 30 μm.
Methane zirconyl oxyhalides evaluation is carried out to above-mentioned catalyst, for evaluation condition with embodiment 1, evaluation result is shown in Table 1.
Embodiment 3
Aluminum hydroxide slurry is prepared using aluminium isopropoxide Hydrolyze method：By water and aluminium isopropoxide in molar ratio 120:1 mixing, hydrolysis temperature
Degree control is at 80 DEG C -85 DEG C, after making aluminium isopropoxide hydrolysis 1.5h, carries out aging, aging temperature control is at 90 DEG C -95 DEG C, aging
Time is 18h, obtains the aluminum hydroxide slurry that solid content is 21.3wt%.
Prepare the aluminium oxide of zinc supported：Using equi-volume impregnating in aluminium oxide（Commercial goods, property are as follows：L acid contains
It measures as 0.05 mmol g-1；BET specific surfaces are 250m2/g；Pore volume is 0.3~0.6ml/g, and preferably pore volume is 0.4ml/g,）Leaching
Stain bromide solutions are dried after dipping, roast, and the drying time is 4h, and drying temperature is 100 DEG C；During the roasting
Between 4h, temperature is 500 DEG C, and the aluminium oxide of the zinc supported is spherical shape, and the aluminium oxide equivalent diameter of zinc supported is 3mm；
Spray process：Suitable zirconium sulfate solid acid, 2-methylimidazole and aluminum hydroxide slurry are mixed, sulfur acid zirconium is obtained and consolidates
The aluminum hydroxide slurry of body acid, the mass content of 2-methylimidazole is 5% in slurries, and the oxidation of zinc supported is then sprayed with slurries
Methane zirconyl oxyhalides reforming catalyst is made in aluminium after drying, roasting, and the drying time is 3h, and drying temperature is 100 DEG C；Institute
Roasting time 4h is stated, temperature is 450 DEG C.
Catalyst property is as follows：The catalyst has nucleocapsid, and core is the aluminium oxide of zinc supported, and shell is consolidated for sulfur acid zirconium
The aluminium oxide of body acid, wherein, the weight ratio of the aluminium oxide of zinc supported and the aluminium oxide of sulfur acid zirconium solid acid is 5：1；With sulfur-bearing
On the basis of the weight of the aluminium oxide of sour zirconium solid acid, zirconium sulfate solid acid weight content is 15wt%, with the aluminium oxide weight of zinc supported
On the basis of amount, zinc is using the content that oxide is counted as 10wt%；The thickness of the shell is 60 μm.
Methane zirconyl oxyhalides evaluation is carried out to above-mentioned catalyst, for evaluation condition with embodiment 1, evaluation result is shown in Table 1.
Embodiment 4
Aluminum hydroxide slurry is prepared using aluminium isopropoxide Hydrolyze method：By water and aluminium isopropoxide in molar ratio 120:1 mixing, hydrolysis temperature
Degree control is at 80 DEG C -85 DEG C, after making aluminium isopropoxide hydrolysis 1.5h, carries out aging, aging temperature control is at 90 DEG C -95 DEG C, aging
Time is 18h, obtains the aluminum hydroxide slurry that solid content is 21.3wt%.
Prepare the aluminium oxide of zinc supported：Using equi-volume impregnating in aluminium oxide（Commercial goods, property are as follows：L acid contains
It measures as 0.1 mmol g-1；BET specific surfaces are 280300m2/g；Pore volume is 0.5ml/g,）Solution of zinc sulfate is impregnated, dipping is laggard
Row is dry, roasting, and the drying time is 3h, and drying temperature is 120 DEG C；The roasting time 5h, temperature is 450 DEG C, described
The aluminium oxide of zinc supported is spherical shape, and the aluminium oxide equivalent diameter of zinc supported is 2mm；Use volume content for 1% vapor nitrogen
Gaseous mixture carries out the aluminium oxide of zinc supported hydro-thermal process, and treatment temperature is 200 DEG C, processing time 10min.
Spray process：Suitable zirconium sulfate solid acid, 2-methylimidazole and aluminum hydroxide slurry are mixed, obtain sulfur acid
The aluminum hydroxide slurry of zirconium solid acid, the mass content of 2-methylimidazole is 2% in slurries, then sprays zinc supported with slurries
Aluminium oxide, is made methane zirconyl oxyhalides reforming catalyst after drying, roasting, and the drying time is 3h, drying temperature 100
℃；The roasting time 4h, temperature are 450 DEG C.
Catalyst property is as follows：The catalyst has nucleocapsid, and core is the aluminium oxide of zinc supported, and shell is consolidated for sulfur acid zirconium
The aluminium oxide of body acid, wherein, the weight ratio of the aluminium oxide of zinc supported and the aluminium oxide of sulfur acid zirconium solid acid is 7：1；With sulfur-bearing
On the basis of the weight of the aluminium oxide of sour zirconium solid acid, zirconium sulfate solid acid weight content is 11wt%, with the aluminium oxide weight of zinc supported
On the basis of amount, zinc is using the content that oxide is counted as 15wt%；The thickness of the shell is 30 μm.
Methane zirconyl oxyhalides evaluation is carried out to above-mentioned catalyst, for evaluation condition with embodiment 1, evaluation result is shown in Table 1.
Embodiment 5
Using the preparing aluminum hydroxide through carbonization slurries that carbon dioxide is passed through into sodium aluminate solution：30wt%CO will be contained2
CO2/N2Gaseous mixture is passed through in sodium aluminate solution, and plastic reaction is carried out at 30 DEG C, and it is 10.5- to control reaction end pH
11.0, after the completion of reaction, aging, it is 6.5 to be washed at 60 DEG C through deionized water to filtrate pH, obtains solid content as 31.2wt%
Aluminum hydroxide slurry；
Prepare the aluminium oxide of zinc supported：Using equi-volume impregnating in aluminium oxide（Commercial goods, property are as follows：L acid contents are
0.1mmol•g-1；BET specific surfaces are 300m2/g；Pore volume is 0.5ml/g）Zinc nitrate solution is impregnated, is dried, roasts after dipping
It burns, the drying time is 2h, and drying temperature is 130 DEG C；The roasting time 4h, temperature are 400 DEG C, the oxygen of the zinc supported
Change aluminium as spherical shape, the aluminium oxide equivalent diameter of zinc supported is 2mm；
Spray process：Suitable zirconium sulfate solid acid, 2-methylimidazole and aluminum hydroxide slurry are mixed, sulfur acid zirconium is obtained and consolidates
The aluminum hydroxide slurry of body acid, the mass content of 2-methylimidazole is 8% in slurries, and the oxidation of zinc supported is then sprayed with slurries
Methane zirconyl oxyhalides reforming catalyst is made in aluminium after drying, roasting, and the drying time is 4h, and drying temperature is 100 DEG C；Institute
Roasting time 6h is stated, temperature is 400 DEG C.
Catalyst property is as follows：The catalyst has nucleocapsid, and core is the aluminium oxide of zinc supported, and shell is consolidated for sulfur acid zirconium
The aluminium oxide of body acid, wherein, the weight ratio of the aluminium oxide of zinc supported and the aluminium oxide of sulfur acid zirconium solid acid is 8：1；With sulfur-bearing
On the basis of the weight of the aluminium oxide of sour zirconium solid acid, zirconium sulfate solid acid weight content is 8wt%, with the aluminium oxide weight of zinc supported
On the basis of amount, zinc is using the content that oxide is counted as 25wt%；The thickness of the shell is 15 μm.
Methane zirconyl oxyhalides evaluation is carried out to above-mentioned catalyst, for evaluation condition with embodiment 1, evaluation result is shown in Table 1.
Embodiment 6
Using the preparing aluminum hydroxide through carbonization slurries that carbon dioxide is passed through into sodium aluminate solution：30wt%CO will be contained2
CO2/N2Gaseous mixture is passed through in sodium aluminate solution, and plastic reaction is carried out at 30 DEG C, and it is 10.5- to control reaction end pH
11.0, after the completion of reaction, aging, it is 6.5 to be washed at 60 DEG C through deionized water to filtrate pH, obtains solid content as 31.2wt%
Aluminum hydroxide slurry；
Prepare the aluminium oxide of zinc supported：Using equi-volume impregnating in aluminium oxide（Commercial goods, property are as follows：L acid contents are
0.1mmol•g-1；BET specific surfaces are 300m2/g；Pore volume is 0.5ml/g）Solution of zinc sulfate is impregnated, is dried, roasts after dipping
It burns, the drying time is 3h, and drying temperature is 120 DEG C；The roasting time 5h, temperature are 450 DEG C, the oxygen of the zinc supported
Change aluminium as spherical shape, the aluminium oxide equivalent diameter of zinc supported is 2mm；
Spray process：Suitable zirconium sulfate solid acid, 2-methylimidazole and aluminum hydroxide slurry are mixed, sulfur acid zirconium is obtained and consolidates
The aluminum hydroxide slurry of body acid, the mass content of 2-methylimidazole is 5% in slurries, and the oxidation of zinc supported is then sprayed with slurries
Methane zirconyl oxyhalides reforming catalyst is made in aluminium after drying, roasting, and the drying time is 3h, and drying temperature is 100 DEG C；Institute
Roasting time 4h is stated, temperature is 450 DEG C.
Catalyst property is as follows：The catalyst has nucleocapsid, and core is the aluminium oxide of zinc supported, and shell is consolidated for sulfur acid zirconium
The aluminium oxide of body acid, wherein, the weight ratio of the aluminium oxide of zinc supported and the aluminium oxide of sulfur acid zirconium solid acid is 7：1；With sulfur-bearing
On the basis of the weight of the aluminium oxide of sour zirconium solid acid, zirconium sulfate solid acid weight content is 11wt%, with the aluminium oxide weight of zinc supported
On the basis of amount, zinc is using the content that oxide is counted as 15wt%；The thickness of the shell is 30 μm.
Methane zirconyl oxyhalides evaluation is carried out to above-mentioned catalyst, for evaluation condition with embodiment 1, evaluation result is shown in Table 1.
Embodiment 7
Using the preparing aluminum hydroxide through carbonization slurries that carbon dioxide is passed through into sodium aluminate solution：30wt%CO will be contained2
CO2/N2Gaseous mixture is passed through in sodium aluminate solution, and plastic reaction is carried out at 30 DEG C, and it is 10.5- to control reaction end pH
11.0, after the completion of reaction, aging, it is 6.5 to be washed at 60 DEG C through deionized water to filtrate pH, obtains solid content as 31.2wt%
Aluminum hydroxide slurry；
Prepare the aluminium oxide of zinc supported：Using equi-volume impregnating in aluminium oxide（Commercial goods, property are as follows：L acid contents are
0.1mmol•g-1；BET specific surfaces are 300m2/g；Pore volume is 0.5ml/g）Bromide solutions are impregnated, is dried, roasts after dipping
It burns, the drying time is 4h, and drying temperature is 100 DEG C；The roasting time 4h, temperature are 500 DEG C, the oxygen of the zinc supported
Change aluminium as spherical shape, the aluminium oxide equivalent diameter of zinc supported is 3mm；
Spray process：Suitable zirconium sulfate solid acid, 2-methylimidazole and aluminum hydroxide slurry are mixed, sulfur acid zirconium is obtained and consolidates
The aluminum hydroxide slurry of body acid, the mass content of 2-methylimidazole is 5% in slurries, and the oxidation of zinc supported is then sprayed with slurries
Methane zirconyl oxyhalides reforming catalyst is made in aluminium after drying, roasting, and the drying time is 3h, and drying temperature is 100 DEG C；Institute
Roasting time 4h is stated, temperature is 450 DEG C.
Catalyst property is as follows：The catalyst has nucleocapsid, and core is the aluminium oxide of zinc supported, and shell is consolidated for sulfur acid zirconium
The aluminium oxide of body acid, wherein, the weight ratio of the aluminium oxide of zinc supported and the aluminium oxide of sulfur acid zirconium solid acid is 5：1；With sulfur-bearing
On the basis of the weight of the aluminium oxide of sour zirconium solid acid, zirconium sulfate solid acid weight content is 15wt%, with the aluminium oxide weight of zinc supported
On the basis of amount, zinc is using the content that oxide is counted as 10wt%；The thickness of the shell is 60 μm.
Methane zirconyl oxyhalides evaluation is carried out to above-mentioned catalyst, for evaluation condition with embodiment 1, evaluation result is shown in Table 1.
Embodiment 8
Using the preparing aluminum hydroxide through carbonization slurries that carbon dioxide is passed through into sodium aluminate solution：30wt%CO will be contained2
CO2/N2Gaseous mixture is passed through in sodium aluminate solution, and plastic reaction is carried out at 30 DEG C, and it is 10.5- to control reaction end pH
11.0, after the completion of reaction, aging, it is 6.5 to be washed at 60 DEG C through deionized water to filtrate pH, obtains solid content as 31.2wt%
Aluminum hydroxide slurry；
Prepare the aluminium oxide of zinc supported：Using equi-volume impregnating in aluminium oxide（Commercial goods, property are as follows：L acid contents are
0.1mmol•g-1；BET specific surfaces are 300m2/g；Pore volume is 0.5ml/g）Solution of zinc sulfate is impregnated, is dried, roasts after dipping
It burns, the drying time is 3h, and drying temperature is 120 DEG C；The roasting time 5h, temperature are 450 DEG C, the oxygen of the zinc supported
Change aluminium as spherical shape, the aluminium oxide equivalent diameter of zinc supported is 2mm；The vapor nitrogen mixture that volume content is 5% is used to bearing
The aluminium oxide for carrying zinc carries out hydro-thermal process, and treatment temperature is 200 DEG C, processing time 10min.
Spray process：Suitable zirconium sulfate solid acid, 2-methylimidazole and aluminum hydroxide slurry are mixed, obtain sulfur acid
The aluminum hydroxide slurry of zirconium solid acid, the mass content of 2-methylimidazole is 5% in slurries, then sprays zinc supported with slurries
Aluminium oxide, is made methane zirconyl oxyhalides reforming catalyst after drying, roasting, and the drying time is 3h, drying temperature 100
℃；The roasting time 4h, temperature are 450 DEG C.
Catalyst property is as follows：The catalyst has nucleocapsid, and core is the aluminium oxide of zinc supported, and shell is consolidated for sulfur acid zirconium
The aluminium oxide of body acid, wherein, the weight ratio of the aluminium oxide of zinc supported and the aluminium oxide of sulfur acid zirconium solid acid is 7：1；With sulfur-bearing
On the basis of the weight of the aluminium oxide of sour zirconium solid acid, zirconium sulfate solid acid weight content is 11wt%, with the aluminium oxide weight of zinc supported
On the basis of amount, zinc is using the content that oxide is counted as 15wt%；The thickness of the shell is 30 μm.
Comparative example 1
The aluminium oxide of zirconium sulfate solid acid modification is prepared using aluminium isopropoxide Hydrolyze method：By water and aluminium isopropoxide in molar ratio 120:
1 mixing, hydrolysis temperature are controlled at 80 DEG C -85 DEG C, after making aluminium isopropoxide hydrolysis 1.5h, carry out aging, aging temperature is controlled 90
DEG C -95 DEG C, ageing time 18h, the aluminum hydroxide slurry that solid content is 21.3wt% is obtained, by suitable zirconium sulfate solid acid
It is mixed with aluminum hydroxide slurry, obtains the aluminum hydroxide slurry of sulfur acid zirconium solid acid, sulphur is made after filtered, dry, roasting
The aluminium oxide that sour zirconium solid acid is modified；
Prepare the aluminium oxide of zinc supported：Using equi-volume impregnating in aluminium oxide（Commercial goods, property are as follows：L acid contents are
0.2mmol•g-1；BET specific surfaces are 200；Pore volume is 0.3ml/g）Zinc nitrate solution is impregnated, is dried, roasts, institute after dipping
Drying time is stated as 2h, drying temperature is 130 DEG C；The roasting time 4h, temperature are 400 DEG C, the aluminium oxide of the zinc supported
For powder shape；
Aluminium oxide and the alumina powder kneading and compacting of zinc supported that zirconium sulfate solid acid is modified are added in equal in embodiment
Catalyst is made through drying, roasting in the 2-methylimidazole of quality.The aluminium oxide of zinc supported and sulfur acid zirconium solid acid in catalyst
Aluminium oxide weight ratio be 8：1；On the basis of the weight of the aluminium oxide of sulfur acid zirconium solid acid, zirconium sulfate solid acid weight contains
It measures as 8wt%, on the basis of the alumina weight of zinc supported, for zinc using the content that oxide is counted as 25wt%, the composition of catalyst is same
Embodiment 1.
Methane zirconyl oxyhalides evaluation is carried out to above-mentioned catalyst, for evaluation condition with embodiment 1, evaluation result is shown in Table 1.
1 different catalysts of table are used for methane oxygen bromination reaction result
Claims (12)
1. a kind of preparation method of methane reforming catalyst, it is characterised in that：Including following content：By zirconium sulfate solid acid, 2-
Methylimidazole and aluminum hydroxide slurry mixing, obtain the aluminum hydroxide slurry of sulfur acid zirconium solid acid and 2-methylimidazole, then
The aluminium oxide of zinc supported is sprayed with the aluminum hydroxide slurry of sulfur acid zirconium solid acid and 2-methylimidazole, is made after drying, roasting
Obtain methane reforming catalyst.
2. according to the method described in claim 1, it is characterized in that：The zirconium sulfate solid acid using commercial goods or according to
It is prepared by the prior art.
3. according to the method described in claim 1, it is characterized in that：The preparation of the aluminium oxide of zinc supported is used zinc compound
Dip loading formed alumina or by zinc compound with alumina powder kneading and compacting, be then made through drying, roasting
The aluminium oxide of zinc supported.
4. according to the method described in claim 3, it is characterized in that：The zinc compound is zinc nitrate, zinc sulfate, bromination
One or more of zinc, zinc chloride.
5. according to the method described in claim 3, it is characterized in that：The drying time is 1-5h, drying temperature 90-150
℃；The roasting time is 3-8h, and temperature is 300-700 DEG C.
6. according to the method described in claim 1, it is characterized in that：The aluminium hydroxide of sulfur acid zirconium solid acid and 2-methylimidazole
The weight content of 2-methylimidazole is 1-10% in slurries.
7. according to the method described in claim 1, it is characterized in that：With sulfur acid zirconium solid acid and the hydroxide of 2-methylimidazole
Before the weight content of 2-methylimidazole sprays the aluminium oxide of zinc supported in aluminium paste liquid, it is preferred to use vapor volume content is
The vapor nitrogen mixture of 1%-15% handles the aluminium oxide of zinc supported, and treatment temperature is 150-300 DEG C, processing time
For 5-30min.
8. a kind of catalyst prepared using claim 1 to 7 either method, it is characterised in that：The catalyst has shell core
Structure, the core of the catalyst are the aluminium oxide of zinc supported, and shell is the aluminium oxide of sulfur acid zirconium solid acid, wherein, zinc supported
The weight ratio of aluminium oxide and the aluminium oxide of sulfur acid zirconium solid acid is 10:1-2:1；With the weight of the aluminium oxide of sulfur acid zirconium solid acid
On the basis of amount, zirconium sulfate solid acid weight content is 5wt%-10wt%, and on the basis of the alumina weight of zinc supported, zinc is to aoxidize
The content of object meter is 5wt%-30wt%.
9. catalyst according to claim 8, it is characterised in that：The aluminium oxide of zinc supported and sulfur acid zirconium solid acid
The weight ratio of aluminium oxide is 8:1-5:1；On the basis of the weight of the aluminium oxide of sulfur acid zirconium solid acid, zirconium sulfate solid acid weight
Content is 8wt%-15wt%, and on the basis of the alumina weight of zinc supported, zinc is using the content that oxide is counted as 10 wt%-25wt%.
10. catalyst according to claim 8, it is characterised in that：The thickness of the shell is 5 μm -200 μm.
11. catalyst according to claim 8, it is characterised in that：The aluminium oxide of the zinc supported is spherical or bar shaped；It is negative
The aluminium oxide equivalent diameter for carrying zinc is 1mm-5mm.
12. application of the catalyst in methane conversion described in claim 8, it is characterised in that：Using fixed-bed process, with first
Alkane, oxygen, halogen acids be reactant or using methane, oxygen, aqueous solution of halogen acid as reactant under the effect of the catalyst into
Row methane zirconyl oxyhalides convert, and reaction temperature is 250-600 DEG C, and methane, halogen acids, the input material volume ratio of oxygen are (3-5):(1-
3):1, the flow of methane is 10-50ml/min.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109465014A (en) * | 2018-12-19 | 2019-03-15 | 中大立信（北京）技术发展有限公司 | A kind of dual purpose catalyst, the preparation method and the usage of controllable ozone and decomposing hydrogen dioxide solution speed |
| CN111889113A (en) * | 2019-05-05 | 2020-11-06 | 中国石油化工股份有限公司 | Coal gas layer treatment catalyst and preparation method thereof |
| CN114797904A (en) * | 2022-04-15 | 2022-07-29 | 新奥科技发展有限公司 | Application of supported sodium catalyst in catalytic coal gasification reaction |
| CN115069306A (en) * | 2022-07-06 | 2022-09-20 | 南京大学 | Absorbent CO for promoting decarburization 2 Process for preparing catalyst with absorption rate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0575915A1 (en) * | 1992-06-19 | 1993-12-29 | Asahi Glass Company | Method for producing methyl chloride |
| CN102197011A (en) * | 2008-10-27 | 2011-09-21 | 陶氏环球技术有限责任公司 | Oxidative mono-halogenation of methane |
| CN102344339A (en) * | 2011-07-15 | 2012-02-08 | 厦门大学 | Application of cerium-based catalyst in methane oxyhalogenation methods used for preparing halogenated methane |
| CN104624210A (en) * | 2013-11-07 | 2015-05-20 | 中国石油化工股份有限公司 | Supported catalyst as well as preparation method and application thereof and method for preparing isobutene from halogenated methane |
-
2016
- 2016-11-11 CN CN201610991016.2A patent/CN108067265B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0575915A1 (en) * | 1992-06-19 | 1993-12-29 | Asahi Glass Company | Method for producing methyl chloride |
| CN102197011A (en) * | 2008-10-27 | 2011-09-21 | 陶氏环球技术有限责任公司 | Oxidative mono-halogenation of methane |
| CN102344339A (en) * | 2011-07-15 | 2012-02-08 | 厦门大学 | Application of cerium-based catalyst in methane oxyhalogenation methods used for preparing halogenated methane |
| CN104624210A (en) * | 2013-11-07 | 2015-05-20 | 中国石油化工股份有限公司 | Supported catalyst as well as preparation method and application thereof and method for preparing isobutene from halogenated methane |
Non-Patent Citations (2)
| Title |
|---|
| ANTONIO等: "Oxyhalogenation of Activated Arenes with Nanocrystalline Ceria", 《ACS CATALYSIS》 * |
| L. SAIKIA等: "Regiospecific Oxyhalogenation of Aromatics Over SBA-15-Supported Nanoparticle Group IV–VI Metal Oxides", 《CATAL LETT》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109465014A (en) * | 2018-12-19 | 2019-03-15 | 中大立信（北京）技术发展有限公司 | A kind of dual purpose catalyst, the preparation method and the usage of controllable ozone and decomposing hydrogen dioxide solution speed |
| CN109465014B (en) * | 2018-12-19 | 2021-08-03 | 中大立信（北京）技术发展有限公司 | Double-effect catalyst capable of regulating and controlling decomposition rate of ozone and hydrogen peroxide, preparation method and application thereof |
| CN111889113A (en) * | 2019-05-05 | 2020-11-06 | 中国石油化工股份有限公司 | Coal gas layer treatment catalyst and preparation method thereof |
| CN111889113B (en) * | 2019-05-05 | 2022-08-12 | 中国石油化工股份有限公司 | Coal gas layer treatment catalyst and preparation method thereof |
| CN114797904A (en) * | 2022-04-15 | 2022-07-29 | 新奥科技发展有限公司 | Application of supported sodium catalyst in catalytic coal gasification reaction |
| CN115069306A (en) * | 2022-07-06 | 2022-09-20 | 南京大学 | Absorbent CO for promoting decarburization 2 Process for preparing catalyst with absorption rate |
| CN115069306B (en) * | 2022-07-06 | 2023-06-06 | 南京大学 | Absorbent CO for promoting decarburization 2 Process for preparing catalyst with absorption rate |
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