CN108067298A - It is a kind of to prepare halide catalyst and its preparation method and application - Google Patents
It is a kind of to prepare halide catalyst and its preparation method and application Download PDFInfo
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- CN108067298A CN108067298A CN201610990970.XA CN201610990970A CN108067298A CN 108067298 A CN108067298 A CN 108067298A CN 201610990970 A CN201610990970 A CN 201610990970A CN 108067298 A CN108067298 A CN 108067298A
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7053—A-type
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/087—X-type faujasite
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/185—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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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, which discloses, a kind of prepares halide catalyst and its preparation method and application.The catalyst has nucleocapsid, core is silica containing zinc, shell is sulfur acid zirconium solid acid and the aluminium oxide of molecular sieve, the molecular sieve is at least one of 5A molecular sieves, 13X molecular sieves and modenite, wherein, silica containing zinc and the weight ratio of sulfur acid zirconium solid acid and the aluminium oxide of molecular sieve are 10:1‑2:1；On the basis of the weight of sulfur acid zirconium solid acid and the aluminium oxide of molecular sieve, zirconium sulfate solid acid weight content is 5wt% 10wt%, and the content of molecular sieve is 1wt% 10wt%, and on the basis of containing zinc silica weight, 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
Halide catalyst and its preparation method and application is prepared the present invention relates to a kind of, is related in particular to a kind of low
Warm high activity, selectivity prepare halide 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, present invention offer is a kind of prepares halide catalyst and preparation method thereof and answers
With.The catalyst can improve the conversion ratio of methane and the selectivity of target product halide simultaneously, it is suppressed that halide
Deep oxidation, and then significantly improve the yield of halide.
A kind of catalyst for preparing halide, the catalyst have nucleocapsid, and core is silica containing zinc, and shell is sulfur-bearing
The aluminium oxide of sour zirconium solid acid and molecular sieve, the molecular sieve are at least one in 5A molecular sieves, 13X molecular sieves and modenite
Kind, wherein, the weight ratio of silica containing zinc and sulfur acid zirconium solid acid and the aluminium oxide of molecular sieve is（That is nucleocapsid weight ratio）10:
1-2:1, it is preferably 8:1-5:1；On the basis of the weight of sulfur acid zirconium solid acid and the aluminium oxide of molecular sieve, zirconium sulfate solid acid
Weight content is 5wt%-10wt%, is preferably 8wt%-15wt%, the content of molecular sieve is 1wt%-10wt%, is preferably 3wt%-
7wt%, on the basis of containing zinc silica weight, 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 silica containing zinc can be spherical or bar shaped, preferably spherical；The oxidation silicon equivalent weight containing zinc is straight
Footpath is 1mm-5mm, preferably 2mm-5mm, preferably 2mm-3mm.
A kind of preparation method for preparing halide catalyst, including following content：By zirconium sulfate solid acid, molecular sieve and
Aluminum hydroxide slurry mixes, and the aluminum hydroxide slurry of sulfur acid zirconium solid acid and molecular sieve is obtained, then with sulfur acid zirconium solid
The aluminum hydroxide slurry of acid and molecular sieve sprays silica containing zinc, and halide catalyst is prepared after drying, roasting.
In the above method, the zirconium sulfate solid acid, molecular sieve are using commercial goods or according to prior art system
It is standby.The aluminum hydroxide slurry generally uses boehmite slurries.Boehmite also known as monohydrate alumina or vacation
Boehmite, molecular formula AlOOHnH2O（n=0.08-0.62）.For the no spy of the preparation method of aluminum hydroxide slurry
Other restriction, can be various methods commonly used in the art, such as can be aluminium alcoholates Hydrolyze method, aluminium salt or aluminate acid system or
Alkaline process, NaA1O2Solution is passed through CO2Carbonizatin method etc..Specific operating method is known to those skilled in the art, herein no longer
It repeats.
In the above method, routine techniques can be used in the preparation of the silica containing zinc, including zinc is supported on appointing on silica
One method.It is specific to can be used zinc compound dip loading in molded silica or by the same silica powder of zinc compound
Then silica containing zinc is made through drying and roasting in kneading and compacting.The silica may be employed commercial goods or according to existing skill
Prepared by art, the zinc compound can be one or more of zinc nitrate, zinc sulfate, zinc bromide, zinc chloride.It is described
Drying time is 1-5h, preferably 2-4h, and drying temperature is 90-150 DEG C, preferably 100-130 DEG C；The roasting time is 3-8h,
It is preferred that 4-6h, temperature is 300-700 DEG C, preferably 400-500 DEG C.
In the above method, before spraying silica containing zinc with the aluminum hydroxide slurry of sulfur acid zirconium solid acid and molecular sieve,
It is preferred that using vapor volume content as 1%-15%, the vapor nitrogen mixture of preferably 1%-5% is to containing at zinc silica
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.The hydroxyl that result of study shows that silica can be improved using above-mentioned processing mode the silicon oxide surface containing zinc contains
For amount simultaneously without the hydroxy radical content inside improving, the aluminum hydroxide slurry for enabling sulfur acid zirconium solid acid and molecular sieve is uniform
It sprays around silica containing zinc, while the enough hydroxyl bondings being rich in silicon oxide surface containing zinc of hydrogen-oxygen bond energy of aluminium hydroxide,
It 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 halide is prepared, using fixed-bed process, using methane, oxygen, halogen acids as
Reactant carries out preparing halide using methane, oxygen, aqueous solution of halogen acid as reactant under the effect of the catalyst, instead
Answering temperature, methane, halogen acids, the input material volume ratio of oxygen are (3-5) for 250-600 DEG C, preferably 300-450 DEG C:(1-3):1,
The flow of methane is 10-50ml/min, preferably 20-40ml/min.The haloid acid is hydrogen chloride or hydrogen bromide or its is water-soluble
Liquid, preferably aqueous solution of hydrogen bromide.
Result of study shows that preparing halide reaction is related to methane-steam reforming, methane oxidation, halogen
For many reactions of methane deep oxidation, cause the selectivity of halide can not effectively to improve.Prepared by the present invention has core
The catalyst of shell structure can realize the difference of the sensitivity of differential responses with the different component of core-shell structure to above-mentioned anti-
The relation control answered.The kernel silica containing zinc of specifically catalyst is more advantageous to progress halogen acids and is converted into halogen radical
Reaction and a small amount of methane halogenation reaction occurs, shell is substantially carried out methane for the aluminium oxide of sulfur acid zirconium solid acid and molecular sieve
Halogenation, due to the molecular sieve containing methane adsorption in shell, the methane concentration on catalyst shell can be improved, carried
The bromination reaction of high methane, the halogen radical of interior karyogenesis can be diffused rapidly to progress methane halogenating reaction in shell, raw
The outside of catalyst is rapidly diffused into after into halogenated hydrocarbons, it is therefore prevented that it is further aoxidized, and significantly improves the selectivity of halogenated hydrocarbons
With the conversion ratio of methane.
Specific embodiment
Further illustrated the present invention with reference to embodiment it is a kind of prepare halide catalyst and preparation method thereof and
Using functions and effects, but following embodiment is not construed as limiting the invention.Transmission electricity may be employed in the catalyst of the present invention
The means such as sem observation, electron diffraction analysis and Elemental Composition analysis confirm its nucleocapsid structure, and measure the group of its center and shell
Into.Catalyst core shell structure it is definite it is specific with the following method：Use Japanese 2100 LaB6 high-resolution of JEOL companies JEM
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 mortar, then ultrasonic wave disperses 20 min in absolute ethyl alcohol.2-3 drop suspensions is taken to drop in the micro- of copper mesh support
On 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 silica containing zinc：Using equi-volume impregnating in silica（Commercial goods, property are as follows：Specific surface
335m2/ g, pore volume 0.86ml/g）Zinc nitrate solution is impregnated, is dried, roasts after dipping, the drying time is 2h, is done
Dry temperature is 130 DEG C；The roasting time 4h, temperature are 400 DEG C, and the silica containing zinc is spherical shape, and silicon equivalent weight is aoxidized containing zinc
A diameter of 2mm；
Spray process：Suitable zirconium sulfate solid acid, 5A molecular sieves and aluminum hydroxide slurry are mixed, obtain sulfur acid zirconium solid
The aluminum hydroxide slurry of acid and molecular sieve, then sprays oxygen containing zinc with the aluminum hydroxide slurry of sulfur acid zirconium solid acid and molecular sieve
SiClx prepares halide catalyst 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 silica containing zinc, and shell is sulfur acid zirconium solid acid
With the aluminium oxide of molecular sieve, wherein, the weight ratio of the aluminium oxide of silica containing zinc and sulfur acid zirconium solid acid and molecular sieve is 8：
1；On the basis of the weight of sulfur acid zirconium solid acid and the aluminium oxide of molecular sieve, zirconium sulfate solid acid weight content is 8wt%, point
The content of son sieve is 3wt%, and on the basis of containing zinc silica weight, zinc is using the content that oxide is counted as 25wt%；The thickness of the shell
It spends for 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 silica containing zinc：Using equi-volume impregnating in silica（Commercial goods, property are as follows：Specific surface
335m2/ g, pore volume 0.86ml/g）Solution of zinc sulfate is impregnated, is dried, roasts after dipping, the drying time is 3h, is done
Dry temperature is 120 DEG C；The roasting time 5h, temperature are 450 DEG C, and the silica containing zinc is spherical shape, and silicon equivalent weight is aoxidized containing zinc
A diameter of 2mm；
Spray process：Suitable zirconium sulfate solid acid, mordenite molecular sieve and aluminum hydroxide slurry are mixed, obtain sulfur acid
Then the aluminum hydroxide slurry of zirconium solid acid and molecular sieve is sprayed with the aluminum hydroxide slurry of sulfur acid zirconium solid acid and molecular sieve
Silica containing zinc prepares halide 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 silica containing zinc, and shell is sulfur acid zirconium solid acid
With the aluminium oxide of molecular sieve, wherein, the weight ratio of the aluminium oxide of silica containing zinc and sulfur acid zirconium solid acid and molecular sieve is 7：
1；On the basis of the weight of sulfur acid zirconium solid acid and the aluminium oxide of molecular sieve, zirconium sulfate solid acid weight content is 11wt%, point
The content of son sieve is 7wt%, and on the basis of containing zinc silica weight, zinc is using the content that oxide is counted as 15wt%；The thickness of the shell
It spends for 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 silica containing zinc：Using equi-volume impregnating in silica（Commercial goods, property are as follows：Specific surface
335m2/ g, pore volume 0.86ml/g）Bromide solutions are impregnated, is dried, roasts after dipping, the drying time is 4h, is done
Dry temperature is 100 DEG C；The roasting time 4h, temperature are 500 DEG C, and the silica containing zinc is spherical shape, and silicon equivalent weight is aoxidized containing zinc
A diameter of 3mm；
Spray process：Suitable zirconium sulfate solid acid, 13X molecular sieves and aluminum hydroxide slurry are mixed, sulfur acid zirconium is obtained and consolidates
The aluminum hydroxide slurry of body acid and molecular sieve, is then sprayed with the aluminum hydroxide slurry of sulfur acid zirconium solid acid and molecular sieve containing zinc
Silica prepares halide catalyst after drying, roasting, and the drying time is 3h, and drying temperature is 100 DEG C；
The roasting time 4h, temperature are 450 DEG C.
Catalyst property is as follows：The catalyst has nucleocapsid, and core is silica containing zinc, and shell is sulfur acid zirconium solid acid
With the aluminium oxide of molecular sieve, wherein, the weight ratio of the aluminium oxide of silica containing zinc and sulfur acid zirconium solid acid and molecular sieve is 5：
1；On the basis of the weight of sulfur acid zirconium solid acid and the aluminium oxide of molecular sieve, zirconium sulfate solid acid weight content is 15wt%, point
The content of son sieve is 5wt%, and on the basis of containing zinc silica weight, zinc is using the content that oxide is counted as 10wt%；The thickness of the shell
It spends for 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 silica containing zinc：Using equi-volume impregnating in silica（Commercial goods, property are as follows：Specific surface
335m2/ g, pore volume 0.86ml/g）Solution of zinc sulfate is impregnated, is dried, roasts after dipping, the drying time is 3h, is done
Dry temperature is 120 DEG C；The roasting time 5h, temperature are 450 DEG C, and the silica containing zinc is spherical shape, and silicon equivalent weight is aoxidized containing zinc
A diameter of 2mm；Volume content is used to carry out hydro-thermal process, treatment temperature to containing zinc silica for 1% vapor nitrogen mixture
For 200 DEG C, processing time 10min.
Spray process：Suitable zirconium sulfate solid acid, modenite and aluminum hydroxide slurry are mixed, obtain sulfur acid zirconium
Then the aluminum hydroxide slurry of solid acid and molecular sieve is sprayed with the aluminum hydroxide slurry of sulfur acid zirconium solid acid and molecular sieve and contained
Zinc silica prepares halide 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 silica containing zinc, and shell is sulfur acid zirconium solid acid
With the aluminium oxide of molecular sieve, wherein, the weight ratio of the aluminium oxide of silica containing zinc and sulfur acid zirconium solid acid and molecular sieve is 7：
1；On the basis of the weight of sulfur acid zirconium solid acid and the aluminium oxide of molecular sieve, zirconium sulfate solid acid weight content is 11wt%, point
The content of son sieve is 1wt%, and on the basis of containing zinc silica weight, zinc is using the content that oxide is counted as 15wt%；The thickness of the shell
It spends for 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 silica containing zinc：Using equi-volume impregnating in silica（Commercial goods, property are as follows：Specific surface 335m2/ g,
Pore volume is 0.86ml/g）Zinc nitrate solution is impregnated, is dried, roasts after dipping, the drying time is 2h, and drying temperature is
130℃；The roasting time 4h, temperature are 400 DEG C, and the silica containing zinc is spherical shape, and the equivalent diameter of silica containing zinc is
2mm；
Spray process：Suitable zirconium sulfate solid acid, 5A molecular sieves and aluminum hydroxide slurry are mixed, obtain sulfur acid zirconium solid
The aluminum hydroxide slurry of acid and molecular sieve, then sprays oxygen containing zinc with the aluminum hydroxide slurry of sulfur acid zirconium solid acid and molecular sieve
SiClx prepares halide catalyst 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 silica containing zinc, and shell is sulfur acid zirconium solid acid
With the aluminium oxide of molecular sieve, wherein, the weight ratio of the aluminium oxide of silica containing zinc and sulfur acid zirconium solid acid and molecular sieve is 8：
1；On the basis of the weight of sulfur acid zirconium solid acid and the aluminium oxide of molecular sieve, zirconium sulfate solid acid weight content is 8wt%, point
The content of son sieve is 10wt%, and on the basis of containing zinc silica weight, zinc is using the content that oxide is counted as 25wt%；The thickness of the shell
It spends for 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 silica containing zinc：Using equi-volume impregnating in silica（Commercial goods, property are as follows：Specific surface 335m2/ g,
Pore volume is 0.86ml/g）Solution of zinc sulfate is impregnated, is dried, roasts after dipping, the drying time is 3h, and drying temperature is
120℃；The roasting time 5h, temperature are 450 DEG C, and the silica containing zinc is spherical shape, and the equivalent diameter of silica containing zinc is
2mm；
Spray process：Suitable zirconium sulfate solid acid, 13X molecular sieves and aluminum hydroxide slurry are mixed, sulfur acid zirconium is obtained and consolidates
The aluminum hydroxide slurry of body acid and molecular sieve, is then sprayed with the aluminum hydroxide slurry of sulfur acid zirconium solid acid and molecular sieve containing zinc
Silica prepares halide catalyst after drying, roasting, and the drying time is 3h, and drying temperature is 100 DEG C；
The roasting time 4h, temperature are 450 DEG C.
Catalyst property is as follows：The catalyst has nucleocapsid, and core is silica containing zinc, and shell is sulfur acid zirconium solid acid
With the aluminium oxide of molecular sieve, wherein, the weight ratio of the aluminium oxide of silica containing zinc and sulfur acid zirconium solid acid and molecular sieve is 7：
1；On the basis of the weight of sulfur acid zirconium solid acid and the aluminium oxide of molecular sieve, zirconium sulfate solid acid weight content is 11wt%, point
The content of son sieve is 5%, and on the basis of containing zinc silica weight, zinc is using the content that oxide is counted as 15wt%；The thickness of the shell
For 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 silica containing zinc：Using equi-volume impregnating in silica（Commercial goods, property are as follows：Specific surface 335m2/ g,
Pore volume is 0.86ml/g）Bromide solutions are impregnated, is dried, roasts after dipping, the drying time is 4h, and drying temperature is
100℃；The roasting time 4h, temperature are 500 DEG C, and the silica containing zinc is spherical shape, and the equivalent diameter of silica containing zinc is
3mm；
Spray process：Suitable zirconium sulfate solid acid, modenite and aluminum hydroxide slurry are mixed, obtain sulfur acid zirconium solid
The aluminum hydroxide slurry of acid and molecular sieve, then sprays oxygen containing zinc with the aluminum hydroxide slurry of sulfur acid zirconium solid acid and molecular sieve
SiClx prepares halide catalyst 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 silica containing zinc, and shell is sulfur acid zirconium solid acid
With the aluminium oxide of molecular sieve, wherein, the weight ratio of the aluminium oxide of silica containing zinc and sulfur acid zirconium solid acid and molecular sieve is 5：
1；On the basis of the weight of sulfur acid zirconium solid acid and the aluminium oxide of molecular sieve, zirconium sulfate solid acid weight content is 15wt%, point
The content of son sieve is 10wt%, and on the basis of containing zinc silica weight, zinc is using the content that oxide is counted as 10wt%；The thickness of the shell
It spends for 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 silica containing zinc：Using equi-volume impregnating in silica（Commercial goods, property are as follows：Specific surface 335m2/ g,
Pore volume is 0.86ml/g）Solution of zinc sulfate is impregnated, is dried, roasts after dipping, the drying time is 3h, and drying temperature is
120℃；The roasting time 5h, temperature are 450 DEG C, and the silica containing zinc is spherical shape, and the equivalent diameter of silica containing zinc is
2mm；Volume content is used to carry out hydro-thermal process, treatment temperature 200 to containing zinc silica for 5% vapor nitrogen mixture
DEG C, processing time 10min.
Spray process：Suitable zirconium sulfate solid acid, modenite and aluminum hydroxide slurry are mixed, obtain sulfur acid zirconium
Then the aluminum hydroxide slurry of solid acid and molecular sieve is sprayed with the aluminum hydroxide slurry of sulfur acid zirconium solid acid and molecular sieve and contained
Zinc silica prepares halide 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 silica containing zinc, and shell is sulfur acid zirconium solid acid
With the aluminium oxide of molecular sieve, wherein, the weight ratio of the aluminium oxide of silica containing zinc and sulfur acid zirconium solid acid and molecular sieve is 7：
1；On the basis of the weight of sulfur acid zirconium solid acid and the aluminium oxide of molecular sieve, zirconium sulfate solid acid weight content is 11wt%, point
The content of son sieve is 5wt%, and on the basis of containing zinc silica weight, zinc is using the content that oxide is counted as 15wt%；The thickness of the shell
It spends for 30 μm.
Comparative example 1
The aluminium oxide of sulfur acid zirconium solid acid 5A molecular sieves is prepared using aluminium isopropoxide Hydrolyze method：By water and aluminium isopropoxide by mole
Than 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 control
System obtains the aluminum hydroxide slurry that solid content is 21.3wt%, by suitable zirconium sulfate at 90 DEG C -95 DEG C, ageing time 18h
Solid acid, 5A molecular sieves and aluminum hydroxide slurry mixing, obtain the aluminum hydroxide slurry of sulfur acid zirconium solid acid and molecular sieve, pass through
Filtering, dry, obtained sulfur acid zirconium solid acid 5A molecular sieves after roasting aluminium oxide；
Prepare silica containing zinc：Using equi-volume impregnating in silica（Commercial goods, property are as follows：Specific surface 335m2/ g,
Pore volume is 0.86ml/g）Zinc nitrate solution is impregnated, is dried, roasts after dipping, the drying time is 2h, and drying temperature is
130℃；The roasting time 4h, temperature are 400 DEG C, and the silica containing zinc is powder shape；
It is made by the aluminium oxide of sulfur acid zirconium solid acid 5A molecular sieves and the kneading and compacting of silica powder containing zinc, through drying, roasting
Catalyst.Silica containing zinc and the weight ratio of sulfur acid zirconium solid acid and the aluminium oxide of molecular sieve are 8 in catalyst：1；With sulfur-bearing
On the basis of the weight of the aluminium oxide of sour zirconium solid acid and molecular sieve, zirconium sulfate solid acid weight content is 8wt%, and molecular sieve contains
It measures as 3wt%, on the basis of containing zinc silica weight, zinc is using the content that oxide is counted as 25wt%, and the composition of catalyst is the same as implementing
Example 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 prepare halide catalyst, it is characterised in that：The catalyst has nucleocapsid, and core is to be aoxidized containing zinc
Silicon, shell are sulfur acid zirconium solid acid and the aluminium oxide of molecular sieve, and the molecular sieve is 5A molecular sieves, 13X molecular sieves and mercerising boil
At least one of stone, wherein, silica containing zinc is 10 with the weight ratio of sulfur acid zirconium solid acid and the aluminium oxide of molecular sieve:1-
2:1；On the basis of the weight of sulfur acid zirconium solid acid and the aluminium oxide of molecular sieve, zirconium sulfate solid acid weight content is 5wt%-
10wt%, the content of molecular sieve is 1wt%-10wt%, and on the basis of containing zinc silica weight, content of the zinc in terms of oxide is
5wt%-30wt%。
2. catalyst according to claim 1, it is characterised in that：Silica containing zinc and sulfur acid zirconium solid acid and molecule
The weight ratio of the aluminium oxide of sieve is 8:1-5:1；Zirconium sulfate solid acid weight content is 8wt%-15wt%, and the content of molecular sieve is
3wt%-7wt%, zinc is using the content that oxide is counted as 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 oxygen containing zinc
SiClx equivalent diameter is 1mm-5mm.
4. catalyst according to claim 1, it is characterised in that：The thickness of the shell is 15 μm -100 μm, described to contain zinc
Silica equivalent diameter is 2mm-5mm.
5. the preparation method of any catalyst of Claims 1-4, it is characterised in that：Including following content：By 5A molecular sieves, 13X
At least one of molecular sieve and modenite, zirconium sulfate solid acid and aluminum hydroxide slurry mixing, obtain sulfur acid zirconium solid
The aluminum hydroxide slurry of acid and molecular sieve, then sprays oxygen containing zinc with the aluminum hydroxide slurry of sulfur acid zirconium solid acid and molecular sieve
SiClx prepares halide catalyst after drying, roasting.
6. according to the method described in claim 5, it is characterized in that：The zirconium sulfate solid acid, molecular sieve use commercial goods
Or it is prepared according to 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 silica containing zinc, which uses, impregnates zinc compound
It is supported on molded silica or by zinc compound with silica powder kneading and compacting, oxygen containing zinc then is made through drying and roasting
SiClx.
9. according to the method described in claim 8, it is characterized in that：The silica 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：With sulfur acid zirconium solid acid and the aluminium hydroxide of molecular sieve
Before slurries spray silica containing zinc, the vapor nitrogen mixture that vapor volume content is 1%-15% is used to be aoxidized to containing zinc
Silicon 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 halide is prepared, it is characterised in that：Using fixed bed work
Skill using methane, oxygen, halogen acids as reactant or using methane, oxygen, aqueous solution of halogen acid as reactant prepare halogenated
Methane, reaction temperature are 250-600 DEG C, and methane, halogen acids, the input material volume ratio of oxygen are (3-5):(1-3):1, the stream of methane
It measures as 10-50ml/min.
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| 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 |
| CN103331179A (en) * | 2013-07-08 | 2013-10-02 | 河北科技大学 | Catalyst used for synthesizing methyl chloride by gas-solid phase reaction and preparation method thereof |
| 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 |
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| EP0575915A1 (en) * | 1992-06-19 | 1993-12-29 | Asahi Glass Company | Method for producing methyl chloride |
| 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 |
| CN103331179A (en) * | 2013-07-08 | 2013-10-02 | 河北科技大学 | Catalyst used for synthesizing methyl chloride by gas-solid phase reaction and preparation method thereof |
| 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 |
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| CN112717986A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Compound and preparation method thereof |
| CN112717986B (en) * | 2019-10-28 | 2022-08-12 | 中国石油化工股份有限公司 | Compound and preparation method thereof |
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