CN108067263A - A kind of catalyst with core-shell structure and its preparation method and application - Google Patents
A kind of catalyst with core-shell structure and its preparation method and application Download PDFInfo
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- CN108067263A CN108067263A CN201610991009.2A CN201610991009A CN108067263A CN 108067263 A CN108067263 A CN 108067263A CN 201610991009 A CN201610991009 A CN 201610991009A CN 108067263 A CN108067263 A CN 108067263A
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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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
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Abstract
The present invention discloses a kind of catalyst with core-shell structure and its preparation method and application, and the core of the catalyst is the aluminium oxide of zinc supported, and the aluminium oxide L acid contents are less than 0.2mmol g‑1；BET specific surfaces are 200~350m2/g；Pore volume is 0.3~0.6ml/g；Shell is the aluminium oxide of sulfur acid zirconium solid acid, wherein, the weight ratio of the aluminium oxide of zinc supported and the aluminium oxide of sulfur acid zirconium solid acid is 10:1‑2:1；On the basis of the weight of the aluminium oxide of sulfur acid zirconium solid acid, zirconium sulfate solid acid weight content is 5wt% 10wt%, and on the basis of the alumina weight of zinc supported, zinc is using the content that oxide is counted as 5wt% 30wt%.The catalyst 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 catalyst with core-shell structure and its preparation method and application, relate in particular to one kind
Low temperature high activity with core-shell structure, selective methane zirconyl oxyhalides reforming catalyst and its preparation method and application.
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 provide a kind of methane zirconyl oxyhalides reforming catalyst with core-shell structure and
Its preparation method and application.The catalyst can improve the conversion ratio of methane and the selectivity of target product halide simultaneously,
The deep oxidation of halide is inhibited, and then significantly improves the yield of halide.
A kind of catalyst with core-shell structure, the core of the catalyst are the aluminium oxide of zinc supported, the aluminium oxide L acid
Content is less than 0.2mmol g-1, preferably L acid contents are 0.1mmol g-1~0.05 mmol•g-1；BET specific surfaces for 200~
350m2/ g, preferably BET specific surfaces are 200~300m2/g；Pore volume is 0.3~0.6ml/g, and preferably pore volume is 0.3~0.5ml/g,
Shell is the aluminium oxide of sulfur acid zirconium solid acid, wherein, the weight of the aluminium oxide of zinc supported and the aluminium oxide of sulfur acid zirconium solid acid
Than for 10:1-2:1, it is preferably 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 5wt%-10wt%, is preferably 8wt%-15wt%, on the basis of the alumina weight of zinc supported, zinc is in terms of oxide
Content be 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.
A kind of preparation method with core-shell structure catalyst, including following content：By zirconium sulfate solid acid and hydroxide
Aluminium paste liquid mixes, and the aluminum hydroxide slurry of sulfur acid zirconium solid acid is obtained, then with the hydroxide aluminium paste of sulfur acid zirconium solid acid
Liquid sprays the aluminium oxide of zinc supported, and methane zirconyl oxyhalides reforming catalyst is made after drying, roasting.
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, before spraying the aluminium oxide of zinc supported with the aluminum hydroxide slurry of sulfur acid zirconium solid acid, preferably
Vapor volume content is used as 1%-15%, the vapor nitrogen mixture of preferably 1%-5% to the aluminium oxide of zinc supported at
Reason, treatment temperature are 150-300 DEG C, and preferably 180-200 DEG C, processing time 5-30min, preferably 5-15 min are further excellent
Select 5-10 min.Result of study shows that aluminium oxide can be improved using above-mentioned processing mode the hydroxyl of the oxidation aluminium surface of zinc supported
Base content without the hydroxy radical content inside improving, enables the aluminum hydroxide slurry of sulfur acid zirconium solid acid uniformly to spray simultaneously
Around the aluminium oxide of zinc supported, while the hydroxyl bond that the enough oxidation aluminium surfaces with zinc supported of hydrogen-oxygen bond energy of aluminium hydroxide are rich in
It closes, is that duct is mutually got around regulations, improves the activity of catalyst and the selectivity of target product.
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.
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.
The measure of meleic acid uses U.S. Buddhist nun high-tensile strength IR6700 type Fourier transformation infrared spectrometers.First by sample before measuring
Degassing purification is surface-treated in high vacuum system, and using pyridine as probe molecule, gas-solid suction is carried out under certain vapour pressure
It is attached, then with determination of infrared spectroscopy acidity.Experimental condition：Sample is 500 DEG C in reaction tube, purifies 4h under 60mPa, drops to room
Temperature is evacuated to 0.1mPa Adsorption of Pyridine, and L acid is measured at 160 DEG C.
The measure of specific surface pore volume is measured using the nitrogen absorption under low temperature instrument of Merck ＆ Co., Inc of U.S. ASAP2420 models；Tool
Body process：A small amount of sample 3 ~ 4h of application of vacuum at 300 DEG C is taken, product is finally placed in liquid nitrogen cryogenics（-200℃）Under the conditions of into
Row nitrogen suction-desorption test.
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 and aluminum hydroxide slurry are mixed, obtain the hydrogen-oxygen of sulfur acid zirconium solid acid
Change aluminium paste liquid, the aluminium oxide of zinc supported is then sprayed with the aluminum hydroxide slurry of sulfur acid zirconium solid acid, made after drying, roasting
Methane zirconyl oxyhalides reforming catalyst is obtained, the drying time is 4h, and drying temperature is 100 DEG C；The roasting time 6h, temperature are
400℃。
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 and aluminum hydroxide slurry are mixed, obtain the hydrogen-oxygen of sulfur acid zirconium solid acid
Change aluminium paste liquid, the aluminium oxide of zinc supported is then sprayed with the aluminum hydroxide slurry of sulfur acid zirconium solid acid, made after drying, roasting
Methane zirconyl oxyhalides reforming catalyst is obtained, the drying time is 3h, and drying temperature is 100 DEG C；The roasting time 4h, temperature are
450℃。
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 and aluminum hydroxide slurry are mixed, obtain the hydrogen-oxygen of sulfur acid zirconium solid acid
Change aluminium paste liquid, the aluminium oxide of zinc supported is then sprayed with the aluminum hydroxide slurry of sulfur acid zirconium solid acid, made after drying, roasting
Methane zirconyl oxyhalides reforming catalyst is obtained, the drying time is 3h, and drying temperature is 100 DEG C；The roasting time 4h, temperature are
450℃。
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 and aluminum hydroxide slurry are mixed, obtain sulfur acid zirconium solid acid
Then aluminum hydroxide slurry sprays the aluminium oxide of zinc supported with the aluminum hydroxide slurry of sulfur acid zirconium solid acid, through drying, roasting
Methane zirconyl oxyhalides reforming catalyst is made afterwards, the drying time is 3h, and drying temperature is 100 DEG C；The roasting time 4h, temperature
It spends for 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 and aluminum hydroxide slurry are mixed, obtain the hydrogen-oxygen of sulfur acid zirconium solid acid
Change aluminium paste liquid, the aluminium oxide of zinc supported is then sprayed with the aluminum hydroxide slurry of sulfur acid zirconium solid acid, made after drying, roasting
Methane zirconyl oxyhalides reforming catalyst is obtained, the drying time is 4h, and drying temperature is 100 DEG C；The roasting time 6h, temperature are
400℃。
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 and aluminum hydroxide slurry are mixed, obtain the hydrogen-oxygen of sulfur acid zirconium solid acid
Change aluminium paste liquid, the aluminium oxide of zinc supported is then sprayed with the aluminum hydroxide slurry of sulfur acid zirconium solid acid, made after drying, roasting
Methane zirconyl oxyhalides reforming catalyst is obtained, the drying time is 3h, and drying temperature is 100 DEG C；The roasting time 4h, temperature are
450℃。
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 and aluminum hydroxide slurry are mixed, obtain the hydrogen-oxygen of sulfur acid zirconium solid acid
Change aluminium paste liquid, the aluminium oxide of zinc supported is then sprayed with the aluminum hydroxide slurry of sulfur acid zirconium solid acid, made after drying, roasting
Methane zirconyl oxyhalides reforming catalyst is obtained, the drying time is 3h, and drying temperature is 100 DEG C；The roasting time 4h, temperature are
450℃。
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 and aluminum hydroxide slurry are mixed, obtain sulfur acid zirconium solid acid
Then aluminum hydroxide slurry sprays the aluminium oxide of zinc supported with the aluminum hydroxide slurry of sulfur acid zirconium solid acid, through drying, roasting
Methane zirconyl oxyhalides reforming catalyst is made afterwards, the drying time is 3h, and drying temperature is 100 DEG C；The roasting time 4h, temperature
It spends for 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 made and urge through drying, roasting
Agent.The weight ratio of the aluminium oxide of zinc supported and the aluminium oxide of sulfur acid zirconium solid acid is 8 in catalyst：1；Consolidated with sulfur acid zirconium
On the basis of the weight of the aluminium oxide of body acid, zirconium sulfate solid acid weight content is 8wt%, using the alumina weight of zinc supported as base
Standard, zinc is using the content that oxide is counted as 25wt%, and the composition of catalyst is the same as 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 (15)
1. a kind of catalyst with core-shell structure, it is characterised in that：The core of the catalyst is the aluminium oxide of zinc supported, described
Aluminium oxide L acid contents are less than 0.2mmol g-1；BET specific surfaces are 200~350m2/g；Pore volume is 0.3~0.6ml/g；Shell is
The aluminium oxide of sulfur acid zirconium solid acid, wherein, the weight ratio of the aluminium oxide and the aluminium oxide of sulfur acid zirconium solid acid of zinc supported is
10:1-2:1；On the basis of the weight of the aluminium oxide of sulfur acid zirconium solid acid, zirconium sulfate solid acid weight content is 5wt%-
10wt%, on the basis of the alumina weight of zinc supported, zinc is using the content that oxide is counted as 5wt%-30wt%.
2. catalyst according to claim 1, it is characterised in that：The aluminium oxide L acid contents are 0.1mmol g-1~
0.05 mmol•g-1；BET specific surfaces are 200~300m2/g；Pore volume be 0.3~0.5ml/g, the aluminium oxide and sulfur-bearing of zinc supported
The weight ratio of the aluminium oxide of sour zirconium solid acid is 8:1-5:1；Zirconium sulfate solid acid weight content is 8wt%-15wt%, and zinc is to aoxidize
The content of object meter is 10 wt%-25wt%.
3. catalyst according to claim 1, it is characterised in that：The thickness of the shell is 5 μm -200 μm, the zinc supported
Aluminium oxide equivalent diameter be 1mm-5mm.
4. catalyst according to claim 1, it is characterised in that：The thickness of the shell is 15 μm -100 μm, the load
The aluminium oxide equivalent diameter of zinc is 2mm-5mm.
5. the preparation method of any catalyst of Claims 1-4, it is characterised in that：Including following content：By zirconium sulfate solid acid
It is mixed with aluminum hydroxide slurry, the aluminum hydroxide slurry of sulfur acid zirconium solid acid is obtained, then with the hydrogen of sulfur acid zirconium solid acid
Aluminium oxide slurries spray the aluminium oxide of zinc supported, and methane zirconyl oxyhalides reforming catalyst is made after drying, roasting.
6. according to the method described in claim 5, it is characterized in that：The zirconium sulfate solid acid using commercial goods or according to
It is prepared by the prior art.
7. according to the method described in claim 5, it is characterized in that：The aluminum hydroxide slurry uses boehmite slurries.
8. according to the method described in claim 5, 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 negative through drying and roasting
Carry the aluminium oxide of zinc.
9. according to the method described in claim 8, it is characterized in that：The aluminium oxide is using commercial goods or according to the prior art
It is prepared, the zinc compound can be one or more of zinc nitrate, zinc sulfate, zinc bromide, zinc chloride.
10. according to the method described in claim 8, 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.
11. according to the method described in claim 10, it is characterized in that：The drying time is 2-4h, drying temperature 100-
130℃；The roasting time is 4-6h, and temperature is 400-500 DEG C.
12. according to the method described in claim 5, it is characterized in that：It is sprayed with the aluminum hydroxide slurry of sulfur acid zirconium solid acid
Before the aluminium oxide of zinc supported, vapor volume content is used as oxidation of the vapor nitrogen mixture of 1%-15% to zinc supported
Aluminium is handled.
13. according to the method for claim 12, it is characterised in that：Treatment temperature is 150-300 DEG C, processing time 5-
30min。
14. according to the method for claim 13, it is characterised in that：Treatment temperature is 180-200 DEG C, processing time 5-
10 min。
15. application of any catalyst of Claims 1-4 in the conversion of methane zirconyl oxyhalides, it is characterised in that：Using fixed bed work
Skill carries out methane oxyhalogen using methane, oxygen, halogen acids as reactant or using methane, oxygen, aqueous solution of halogen acid as reactant
Change conversion, reaction temperature is 250-600 DEG C, and methane, halogen acids, the input material volume ratio of oxygen are (3-5):(1-3):1, methane
Flow is 10-50ml/min.
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| CN111889114A (en) * | 2019-05-05 | 2020-11-06 | 中国石油化工股份有限公司 | Catalyst with shell-core structure and preparation method and application thereof |
| CN111889116A (en) * | 2019-05-05 | 2020-11-06 | 中国石油化工股份有限公司 | Catalytic combustion catalyst and preparation method thereof |
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