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CN108067298B - Catalyst for preparing halogenated methane, preparation method and application thereof - Google Patents

Catalyst for preparing halogenated methane, preparation method and application thereof Download PDF

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CN108067298B
CN108067298B CN201610990970.XA CN201610990970A CN108067298B CN 108067298 B CN108067298 B CN 108067298B CN 201610990970 A CN201610990970 A CN 201610990970A CN 108067298 B CN108067298 B CN 108067298B
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zinc
molecular sieve
solid acid
catalyst
silicon oxide
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CN108067298A (en
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李�杰
张信伟
尹泽群
刘全杰
倪向前
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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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
    • 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
    • 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
    • B01J29/18—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
    • 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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  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

The invention discloses a preparation method and application of a halogenated methane catalyst. The catalyst has a core-shell structure, wherein the core is zinc-containing silicon oxide, the shell is aluminum oxide containing zirconium sulfate solid acid and a molecular sieve, the molecular sieve is at least one of a 5A molecular sieve, a 13X molecular sieve and mordenite, and the weight ratio of the zinc-containing silicon oxide to the aluminum oxide containing the zirconium sulfate solid acid and the molecular sieve is 10:1-2: 1; based on the weight of alumina containing zirconium sulfate solid acid and molecular sieve, the weight content of the zirconium sulfate solid acid is 5-10 wt%, the weight content of the molecular sieve is 1-10 wt%, and the weight content of zinc calculated by oxide is 5-30 wt% based on the weight of zinc-containing silica. The catalyst can simultaneously improve the conversion rate of methane and the selectivity of a target product, namely the halogenated methane, inhibit the deep oxidation of the halogenated methane, and further obviously improve the yield of the halogenated methane.

Description

Catalyst for preparing halogenated methane, preparation method and application thereof
Technical Field
The invention relates to a preparation method and application of a halogenated methane catalyst, in particular to a low-temperature high-activity and selective preparation method and application of a halogenated methane catalyst.
Background
The process of reacting methane with a halogen, not directly but with HCl, HBr or a metal halide as the halogen source, in the presence of oxygen to produce methyl halide is known as oxyhalogenation. The method is firstly applied to the industrial production of preparing chlorine by HCl catalytic oxidation, and is called a Deacon process.
The early methane halogen oxidation reaction mainly uses HCl as halogen source, and the catalystMainly composed of CuCl2As an active ingredient, Bromhead et al (Bromhead J, Font-free J J, Westlake D J. Process for the production of methyl or ethyl mono-chloride or bromide. EP. Patent, 0117731.1984-09-05) loaded CuCl on alumina2To prepare the oxychlorination catalyst. Conner et al (Conner W C Jr, Pieters W J M, Gates W, et al, The oxidative catalysis of methane on fundamental-based Cu, K, La catalysis: II. Gas phase catalysis. Appl Cat, 1984, 11(1): 49-58; Conner W C Jr, Pieters W J M, Signorelli A J. The oxidative catalysis of methane on fundamental-based Cu, K, La catalysis: III. Bulk&surface analysis, appl. Catal., 1984, 11(1): 59-71) in CuCl2On the basis of catalyst the alkali metal chloride KCl or rare earth metal chloride LaCl with high melting point can be added3As an auxiliary agent, it is used for stabilizing the activity of the catalyst, thereby reducing the content of CuCl2The catalyst loss caused by low boiling point can obtain higher methane conversion rate, the catalytic effect is relatively stable, but the polychlorinated methane selectivity is also increased.
US 6452058 discloses as CuCl2Rare earth metal chloride LaCl of main auxiliary agent3The catalyst has good catalytic activity for oxychlorination, synthesizes porous LaOCl, has good catalytic performance, and has the methane conversion rate of 12 percent and the selectivity of methane chloride of 55 percent at the reaction temperature of 400 ℃.
Further studies were made on La-based catalysts, Lercher et al (Podkolzin S G, Stangland E, Lercher J A, et al, Methyl Chloride Production from Methyl over Lanthanum-based catalysts J. Am. chem. Soc., 2007, 129(9): 2569-2576), synthesized catalysts LaOCl/LaCl3Gas composition V at 540 DEG C（CH4）:V（HCl）:V（O2）:V（N2）Under the condition of 2:1:1:0.5, the methane conversion rate is 13.3%, the methane chloride selectivity is 62.6%, and the catalyst has good stability. The reaction mechanism is further researched by Lercher, La is a metal which can enable methane to generate oxychlorination reaction without changing the valence state of La, and the La thinks that the reaction generates redox on the surface of the catalystReaction, O2The Cl on the surface of the activated catalyst forms OCl, the OCl is changed into Cl after activating the methane, and the Cl and the OCl are mutually converted, so that the oxychlorination reaction is carried out.
Wang Ye et al (Transformation of methane to propylene: a two step reacted reagent modified CeO2 nanocrystals and zeolites [ J]Angewendte Chemie International Edition, 2012, 51: 2438-; chlorine oxidation reaction of methane on catalyst of palladium oxide and manganese oxide loaded on cerium dioxide nano-rod [ D ]]University of mansion, 2013.) used a catalyst containing a rare earth element Ce as a main component, which has outstanding activity on oxychlorination. The active component of the catalyst is CeO2And the cerium-based bi-component composite oxide which can be prepared by modifying the second component is loaded on different carriers (SiO)2、Al2O3、MgO、ZrO2、TiO2Etc.). At a temperature of 480 ℃ and CH4：HCl：O2：N2: he = 4:2:1:1.5:1.5, space velocity 40mL/min, CH3Cl selectivity and yield reached 66% and 8%, which is better than the LaOCl 55% selectivity of Lercher, and 6.6% yield. The two-component catalyst has the best effect of mixing with iron, and 15 percent wtFeOx-CeO2Nanorod, reaction for 100 h CH4Conversion 23%, CH3Cl selectivity was 74%. Ce in cerium-based catalyst3 +And Ce4+The cyclic conversion of valence states plays an important role in activating HCl in oxychlorination reaction, and HCl passes through O2Activated Cl generated by activation, reaction of the activated Cl and methane to generate methane chloride, and reduced Ce3+And is also O2By oxidation to Ce4+The catalytic cycle is completed. It was also found that the morphology of the catalyst, i.e. the exposed crystal planes, had a significant effect on the activity of the catalyst, the highest being the {100} plane, the next highest being the {110} plane, and the lowest being the {111} plane (epoxidation of propylene with oxygen as oxidant on copper-based catalysts and oxychlorination of methane on cerium-based catalysts [ D)]Building university, 2012).
CN201310216352.6 discloses a catalyst for preparing methyl bromide and CO by methane bromine oxidation, which comprises a main active component and a carrier, wherein the main active component isSelected from FePO4、Fe2P2O7And Fe3(P2O7)2One or more of the carriers are TiC-SiC and TiO2The catalyst is prepared by adopting an impregnation method to load impregnation liquid containing the main active component on a carrier, drying and roasting, and can catalyze the mixture of methane, oxygen and HBr aqueous solution to be converted into methyl bromide and CO at high activity and high selectivity under the reaction conditions of normal pressure and 400-800 ℃. The catalyst has good performance, and has no obvious inactivation and no carbon deposition on the catalyst in the continuous reaction process of more than 1400 hours.
CN201110198638.7 discloses a method for preparing chloromethane by oxychlorination of methane and a method for preparing methyl bromide by bromooxidation of methane. The cerium-based catalyst is suitable for methane oxyhalogenation, and can be CeO2And a cerium-based two-component composite oxide or a supported cerium-based oxide catalyst. The cerium-based catalyst can efficiently and stably catalyze methane oxyhalogen reactions, including oxychlorination and bromooxidation reactions, to generate methyl chloride and methyl bromide. The cerium-based catalyst can efficiently catalyze and convert the reactant CH4，HCl，O2Chlorine oxidation reaction is carried out to generate a product CH3Cl and CH2Cl2(ii) a The cerium-based catalyst can also efficiently convert CH4，HBr(H2O)，O2Carrying out bromine oxidation reaction to generate CH3Br，CH2Br2。
The methane oxyhalogenation reaction in the prior art has the technical problem that the high temperature is favorable for improving the conversion rate of methane, but the generated halogenated methane, particularly monohalogenated methane, can be deeply oxidized to generate CO or CO2The selectivity of the halogenated methane is obviously reduced, so that the yield of the halogenated methane is low, and therefore, the development of the methane oxyhalogenation reaction catalyst with higher methane conversion rate and halogenated methane selectivity has important significance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a halogenated methane catalyst, a preparation method and application thereof. The catalyst can simultaneously improve the conversion rate of methane and the selectivity of a target product, namely the halogenated methane, inhibit the deep oxidation of the halogenated methane, and further obviously improve the yield of the halogenated methane.
A catalyst for preparing halogenated methane has a core-shell structure, wherein the core is zinc-containing silicon oxide, the shell is alumina containing zirconium sulfate solid acid and a molecular sieve, and the molecular sieve is at least one of a 5A molecular sieve, a 13X molecular sieve and mordenite, wherein the weight ratio of the zinc-containing silicon oxide to the alumina containing the zirconium sulfate solid acid and the molecular sieve is (namely the weight ratio of the core to the shell) 10:1-2:1, preferably 8:1-5: 1; the zirconium sulfate solid acid is present in an amount of 5wt% to 15wt%, preferably 8wt% to 10wt%, based on the weight of the alumina containing the zirconium sulfate solid acid and the molecular sieve, and the molecular sieve is present in an amount of 1wt% to 10wt%, preferably 3wt% to 7wt%, based on the weight of the zinc-containing silica, and zinc is present in an amount of 5wt% to 30wt%, preferably 10wt% to 25wt%, based on the weight of the oxide.
In the above catalyst, the thickness of the shell is 5 μm to 200. mu.m, preferably 10 μm to 150. mu.m, and more preferably 15 μm to 100. mu.m.
In the catalyst, the zinc-containing silicon oxide can be spherical or strip-shaped, and is preferably spherical; the zinc-containing silicon oxide has an equivalent diameter of 1mm to 5mm, preferably 2mm to 5mm, and more preferably 2mm to 3 mm.
A preparation method for preparing a halogenated methane catalyst comprises the following steps: mixing zirconium sulfate solid acid, a molecular sieve and aluminum hydroxide slurry to obtain aluminum hydroxide slurry containing the zirconium sulfate solid acid and the molecular sieve, then spraying and soaking zinc-containing silicon oxide by using the aluminum hydroxide slurry containing the zirconium sulfate solid acid and the molecular sieve, drying and roasting to obtain the halogenated methane catalyst.
In the method, the zirconium sulfate solid acid and the molecular sieve can be prepared by using commercial products or according to the prior art. The aluminum hydroxide slurry is generally pseudo-boehmite slurry. The pseudoboehmite is also called alumina monohydrate or pseudoboehmite, and the molecular formula is AlOOH & nH2O (n = 0.08-0.62). For aluminum hydroxide slurryThe method for producing (A) is not particularly limited, and various methods commonly used in the art may be used, and examples thereof include aluminum alkoxide hydrolysis, acid or alkali methods of aluminum salt or aluminate, and NaA1O2Introducing CO into the solution2The carbonization method of (3). The specific operation method is well known to those skilled in the art and will not be described herein.
In the above method, the zinc-containing silica can be prepared by a conventional technique including any method of supporting zinc on silica. Specifically, the zinc-containing compound is impregnated and loaded on the formed silicon oxide or the zinc-containing compound and the silicon oxide are kneaded and formed, and then the zinc-containing silicon oxide is obtained through drying and roasting. The silicon oxide can be prepared by adopting a commercial product or according to the prior art, and the zinc-containing compound can be one or more of zinc nitrate, zinc sulfate, zinc bromide and zinc chloride. The drying time is 1-5h, preferably 2-4h, the drying temperature is 90-150 ℃, preferably 100-130 ℃; the roasting time is 3-8h, preferably 4-6h, and the temperature is 300-700 ℃, preferably 400-500 ℃.
In the method, before the aluminum hydroxide slurry containing zirconium sulfate solid acid and molecular sieve is used for spray soaking of the zinc-containing silicon oxide, the zinc-containing silicon oxide is preferably treated by using a water vapor nitrogen gas mixture with the water vapor volume content of 1-15%, preferably 1-5%, wherein the treatment temperature is 150-300 ℃, preferably 180-200 ℃, and the treatment time is 5-30min, preferably 5-15 min, and further preferably 5-10 min. Research results show that the hydroxyl content of the surface of the zinc-containing silicon oxide can be improved by adopting the treatment mode on the silicon oxide, meanwhile, the internal hydroxyl content is not improved, so that aluminum hydroxide slurry containing zirconium sulfate solid acid and molecular sieve can be uniformly sprayed and soaked around the zinc-containing silicon oxide, meanwhile, the hydroxide-oxygen bond of the aluminum hydroxide can be bonded with the rich hydroxyl on the surface of the zinc-containing silicon oxide, and the aluminum hydroxide is communicated with a pore channel, so that the activity of the catalyst and the selectivity of a target product are improved.
The application of the catalyst in preparing the halogenated methane adopts a fixed bed process, and the halogenated methane is prepared by taking methane, oxygen and halogen acid as reactants or taking a methane, oxygen and halogen acid aqueous solution as reactants under the action of the catalyst, wherein the reaction temperature is 250-600 ℃, preferably 300-450 ℃, the feeding volume ratio of the methane, the halogen acid and the oxygen is (3-5): 1-3):1, and the flow rate of the methane is 10-50ml/min, preferably 20-40 ml/min. The halogenated acid is hydrogen chloride or hydrogen bromide or an aqueous solution thereof, preferably an aqueous hydrogen bromide solution.
Research results show that the preparation of the halogenated methane involves various reactions such as methane steam reforming reaction, methane oxidation reaction and deep oxidation of the halogenated methane, so that the selectivity of the halogenated methane cannot be effectively improved. The catalyst with the core-shell structure, which is prepared by the invention, can realize relative control of the reactions by using the difference of the sensitivity of different components of the core-shell structure to different reactions. Specifically, the zinc-containing silicon oxide of the inner core of the catalyst is more beneficial to the reaction of converting halogen acid into halogen free radicals to generate a small amount of methane halogenation reaction, the zirconium sulfate-containing solid acid and molecular sieve-containing alumina are mainly used for carrying out the methane halogenation reaction, the molecular sieve with methane adsorption performance is contained in the shell, the methane concentration on the outer shell of the catalyst can be improved, the bromination reaction of methane is improved, the halogen free radicals generated by the inner core can be quickly diffused into the outer shell to carry out the methane halogenation reaction, and the halogen free radicals generated by the inner core are quickly diffused to the outside of the catalyst after the halogenated hydrocarbons are generated, so that the further oxidation of the catalyst is prevented, and the selectivity of the halogenated hydrocarbons and the conversion.
Detailed Description
The following examples are provided to further illustrate a method for preparing a methyl halide catalyst, its application and effects, but the following examples are not intended to limit the present invention. The catalyst of the invention can adopt means such as transmission electron microscope observation, electron diffraction analysis, element composition analysis and the like to confirm the core-shell structure and determine the composition of the core and the shell. The determination of the core-shell structure of the catalyst specifically adopts the following method: the sample was sufficiently ground in an agate mortar using a high-resolution transmission electron microscope (JEM 2100 LaB6, JEOL Ltd., Japan) with a resolution of 0.23 nm equipped with an X-ray energy dispersive spectrometer (EDX) from EDAX, and then ultrasonically dispersed in absolute ethanol for 20 min. And (3) dripping 2-3 drops of the suspension liquid on a micro-grid carbon film supported by a copper net, and carrying out TEM observation, electron diffraction analysis and element composition analysis on the sample after the sample is dried.
Example 1
Preparing aluminum hydroxide slurry by adopting an aluminum isopropoxide hydrolysis method: mixing water and aluminum isopropoxide according to a molar ratio of 120:1, controlling the hydrolysis temperature at 80-85 ℃, hydrolyzing the aluminum isopropoxide for 1.5h, and then aging at 90-95 ℃ for 18h to obtain aluminum hydroxide slurry with the solid content of 21.3 wt%.
Preparing zinc-containing silicon oxide: an isovolumetric impregnation method was used to impregnate silica (commercially available, having the following properties: specific surface 335 m)2Per g, the pore volume is 0.86 ml/g), drying and roasting are carried out after impregnation, the drying time is 2 hours, and the drying temperature is 130 ℃; the roasting time is 4 hours, the temperature is 400 ℃, the zinc-containing silicon oxide is spherical, and the equivalent diameter of the zinc-containing silicon oxide is 2 mm;
spray soaking process: mixing a proper amount of zirconium sulfate solid acid, a 5A molecular sieve and aluminum hydroxide slurry to obtain aluminum hydroxide slurry containing the zirconium sulfate solid acid and the molecular sieve, then spray-soaking zinc-containing silicon oxide in the aluminum hydroxide slurry containing the zirconium sulfate solid acid and the molecular sieve, and drying and roasting to obtain the halogenated methane catalyst, wherein the drying time is 4 hours, and the drying temperature is 100 ℃; the roasting time is 6h, and the temperature is 400 ℃.
The catalyst properties were as follows: the catalyst has a core-shell structure, wherein the core is zinc-containing silicon oxide, and the shell is aluminum oxide containing zirconium sulfate solid acid and a molecular sieve, wherein the weight ratio of the zinc-containing silicon oxide to the aluminum oxide containing the zirconium sulfate solid acid and the molecular sieve is 8: 1; based on the weight of alumina containing zirconium sulfate solid acid and molecular sieve, the content of zirconium sulfate solid acid is 8wt%, the content of molecular sieve is 3wt%, and based on the weight of zinc-containing silica, the content of zinc is 25wt% calculated by oxide; the thickness of the shell is 15 μm.
The above catalyst was evaluated for the oxyhalogenation of methane under the following conditions: the methane oxybromination reaction is carried out in a fixed bed microreactor at normal pressure. 10ml of 20-40 mesh catalyst is loaded into a quartz reaction tube, a catalyst bed layer is positioned in the middle of a heating furnace, and quartz sand is filled above and below the catalyst bed layer. The reaction gas flow rate was adjusted by a mass flow meter, and the hydrobromic acid flow rate was controlled by a peristaltic pump. And (2) under the protection of nitrogen, raising the temperature to 350 ℃, and after the temperature is constant, mixing methane, halogen acid, oxygen and nitrogen according to a volume ratio of 4:2:1:1 was passed into the reactor at a flow rate of methane of 30 ml/min. After reacting for 2h, the tail gas is washed by water, dried and analyzed on line by north SP-3420A type gas chromatography. The evaluation results are shown in Table 1
Example 2
Preparing aluminum hydroxide slurry by adopting an aluminum isopropoxide hydrolysis method: mixing water and aluminum isopropoxide according to a molar ratio of 120:1, controlling the hydrolysis temperature at 80-85 ℃, hydrolyzing the aluminum isopropoxide for 1.5h, and then aging at 90-95 ℃ for 18h to obtain aluminum hydroxide slurry with the solid content of 21.3 wt%.
Preparing zinc-containing silicon oxide: an isovolumetric impregnation method was used to impregnate silica (commercially available, having the following properties: specific surface 335 m)2Per g, the pore volume is 0.86 ml/g), drying and roasting are carried out after dipping, the drying time is 3h, and the drying temperature is 120 ℃; the roasting time is 5 hours, the temperature is 450 ℃, the zinc-containing silicon oxide is spherical, and the equivalent diameter of the zinc-containing silicon oxide is 2 mm;
spray soaking process: mixing a proper amount of zirconium sulfate solid acid, a mordenite molecular sieve and aluminum hydroxide slurry to obtain aluminum hydroxide slurry containing the zirconium sulfate solid acid and the molecular sieve, then spraying and soaking zinc-containing silicon oxide in the aluminum hydroxide slurry containing the zirconium sulfate solid acid and the molecular sieve, and drying and roasting to obtain a halogenated methane catalyst, wherein the drying time is 3 hours, and the drying temperature is 100 ℃; the roasting time is 4 hours, and the temperature is 450 ℃.
The catalyst properties were as follows: the catalyst has a core-shell structure, wherein the core is zinc-containing silicon oxide, and the shell is aluminum oxide containing zirconium sulfate solid acid and a molecular sieve, wherein the weight ratio of the zinc-containing silicon oxide to the aluminum oxide containing the zirconium sulfate solid acid and the molecular sieve is 7: 1; based on the weight of alumina containing zirconium sulfate solid acid and molecular sieve, the content of zirconium sulfate solid acid is 11wt%, the content of molecular sieve is 7wt%, and based on the weight of zinc-containing silica, the content of zinc calculated as oxide is 15 wt%; the thickness of the shell was 30 μm.
The above catalyst was evaluated for the oxyhalogenation of methane under the same conditions as in example 1, and the evaluation results are shown in Table 1.
Example 3
Preparing aluminum hydroxide slurry by adopting an aluminum isopropoxide hydrolysis method: mixing water and aluminum isopropoxide according to a molar ratio of 120:1, controlling the hydrolysis temperature at 80-85 ℃, hydrolyzing the aluminum isopropoxide for 1.5h, and then aging at 90-95 ℃ for 18h to obtain aluminum hydroxide slurry with the solid content of 21.3 wt%.
Preparing zinc-containing silicon oxide: an isovolumetric impregnation method was used to impregnate silica (commercially available, having the following properties: specific surface 335 m)2Per g, the pore volume is 0.86 ml/g), drying and roasting are carried out after impregnation, the drying time is 4 hours, and the drying temperature is 100 ℃; the roasting time is 4 hours, the temperature is 500 ℃, the zinc-containing silicon oxide is spherical, and the equivalent diameter of the zinc-containing silicon oxide is 3 mm;
spray soaking process: mixing a proper amount of zirconium sulfate solid acid, a 13X molecular sieve and aluminum hydroxide slurry to obtain aluminum hydroxide slurry containing the zirconium sulfate solid acid and the molecular sieve, then spray-soaking zinc-containing silicon oxide in the aluminum hydroxide slurry containing the zirconium sulfate solid acid and the molecular sieve, and drying and roasting to obtain the halogenated methane catalyst, wherein the drying time is 3 hours, and the drying temperature is 100 ℃; the roasting time is 4 hours, and the temperature is 450 ℃.
The catalyst properties were as follows: the catalyst has a core-shell structure, wherein the core is zinc-containing silicon oxide, and the shell is aluminum oxide containing zirconium sulfate solid acid and a molecular sieve, wherein the weight ratio of the zinc-containing silicon oxide to the aluminum oxide containing the zirconium sulfate solid acid and the molecular sieve is 5: 1; based on the weight of alumina containing zirconium sulfate solid acid and molecular sieve, the content of zirconium sulfate solid acid is 15wt%, the content of molecular sieve is 5wt%, and based on the weight of zinc-containing silica, the content of zinc is 10wt% calculated by oxide; the thickness of the shell was 60 μm.
The above catalyst was evaluated for the oxyhalogenation of methane under the same conditions as in example 1, and the evaluation results are shown in Table 1.
Example 4
Preparing aluminum hydroxide slurry by adopting an aluminum isopropoxide hydrolysis method: mixing water and aluminum isopropoxide according to a molar ratio of 120:1, controlling the hydrolysis temperature at 80-85 ℃, hydrolyzing the aluminum isopropoxide for 1.5h, and then aging at 90-95 ℃ for 18h to obtain aluminum hydroxide slurry with the solid content of 21.3 wt%.
Preparing zinc-containing silicon oxide: an isovolumetric impregnation method was used to impregnate silica (commercially available, having the following properties: specific surface 335 m)2Per g, the pore volume is 0.86 ml/g), drying and roasting are carried out after dipping, the drying time is 3h, and the drying temperature is 120 ℃; the roasting time is 5 hours, the temperature is 450 ℃, the zinc-containing silicon oxide is spherical, and the equivalent diameter of the zinc-containing silicon oxide is 2 mm; carrying out hydro-thermal treatment on the zinc-containing silicon oxide by adopting water vapor nitrogen mixed gas with the volume content of 1%, wherein the treatment temperature is 200 ℃, and the treatment time is 10 min.
Spray soaking process: mixing a proper amount of zirconium sulfate solid acid, mordenite and aluminum hydroxide slurry to obtain aluminum hydroxide slurry containing the zirconium sulfate solid acid and a molecular sieve, then spraying and soaking zinc-containing silicon oxide in the aluminum hydroxide slurry containing the zirconium sulfate solid acid and the molecular sieve, and drying and roasting to obtain a halogenated methane catalyst, wherein the drying time is 3 hours, and the drying temperature is 100 ℃; the roasting time is 4 hours, and the temperature is 450 ℃.
The catalyst properties were as follows: the catalyst has a core-shell structure, wherein the core is zinc-containing silicon oxide, and the shell is aluminum oxide containing zirconium sulfate solid acid and a molecular sieve, wherein the weight ratio of the zinc-containing silicon oxide to the aluminum oxide containing the zirconium sulfate solid acid and the molecular sieve is 7: 1; based on the weight of alumina containing zirconium sulfate solid acid and molecular sieve, the content of zirconium sulfate solid acid is 11wt%, the content of molecular sieve is 1wt%, and based on the weight of zinc-containing silica, the content of zinc calculated as oxide is 15 wt%; the thickness of the shell was 30 μm.
The above catalyst was evaluated for the oxyhalogenation of methane under the same conditions as in example 1, and the evaluation results are shown in Table 1.
Example 5
Preparing aluminum hydroxide slurry by adopting a carbonization method of introducing carbon dioxide gas into sodium metaaluminate solution: will contain 30wt% CO2CO of2/N2Introducing the mixed gas into a sodium metaaluminate solution, carrying out gelling reaction at 30 ℃, controlling the pH of the reaction end point to be 10.5-11.0, aging after the reaction is finished, and washing the mixture by deionized water at 60 ℃ until the pH of the filtrate is 6.5 to obtain aluminum hydroxide slurry with the solid content of 31.2 wt%;
preparing zinc-containing silicon oxide: an isovolumetric impregnation method was used to impregnate silica (commercially available, having the following properties: specific surface 335 m)2Per g, the pore volume is 0.86 ml/g), drying and roasting are carried out after impregnation, the drying time is 2 hours, and the drying temperature is 130 ℃; the roasting time is 4 hours, the temperature is 400 ℃, the zinc-containing silicon oxide is spherical, and the equivalent diameter of the zinc-containing silicon oxide is 2 mm;
spray soaking process: mixing a proper amount of zirconium sulfate solid acid, a 5A molecular sieve and aluminum hydroxide slurry to obtain aluminum hydroxide slurry containing the zirconium sulfate solid acid and the molecular sieve, then spray-soaking zinc-containing silicon oxide in the aluminum hydroxide slurry containing the zirconium sulfate solid acid and the molecular sieve, and drying and roasting to obtain the halogenated methane catalyst, wherein the drying time is 4 hours, and the drying temperature is 100 ℃; the roasting time is 6h, and the temperature is 400 ℃.
The catalyst properties were as follows: the catalyst has a core-shell structure, wherein the core is zinc-containing silicon oxide, and the shell is aluminum oxide containing zirconium sulfate solid acid and a molecular sieve, wherein the weight ratio of the zinc-containing silicon oxide to the aluminum oxide containing the zirconium sulfate solid acid and the molecular sieve is 8: 1; based on the weight of alumina containing zirconium sulfate solid acid and molecular sieve, the content of zirconium sulfate solid acid is 8wt%, the content of molecular sieve is 10wt%, and based on the weight of zinc-containing silica, the content of zinc calculated as oxide is 25 wt%; the thickness of the shell is 15 μm.
The above catalyst was evaluated for the oxyhalogenation of methane under the same conditions as in example 1, and the evaluation results are shown in Table 1.
Example 6
Preparing aluminum hydroxide slurry by adopting a carbonization method of introducing carbon dioxide gas into sodium metaaluminate solution: will contain 30wt% CO2CO of2/N2Introducing the mixed gas into sodium metaaluminate solution, carrying out gelling reaction at 30 ℃, and controlling the pH value of the reaction end point to be 10.511.0, aging after the reaction is finished, washing the mixture by deionized water at 60 ℃ until the pH of the filtrate is 6.5, and obtaining aluminum hydroxide slurry with the solid content of 31.2 wt%;
preparing zinc-containing silicon oxide: an isovolumetric impregnation method was used to impregnate silica (commercially available, having the following properties: specific surface 335 m)2Per g, the pore volume is 0.86 ml/g), drying and roasting are carried out after dipping, the drying time is 3h, and the drying temperature is 120 ℃; the roasting time is 5 hours, the temperature is 450 ℃, the zinc-containing silicon oxide is spherical, and the equivalent diameter of the zinc-containing silicon oxide is 2 mm;
spray soaking process: mixing a proper amount of zirconium sulfate solid acid, a 13X molecular sieve and aluminum hydroxide slurry to obtain aluminum hydroxide slurry containing the zirconium sulfate solid acid and the molecular sieve, then spray-soaking zinc-containing silicon oxide in the aluminum hydroxide slurry containing the zirconium sulfate solid acid and the molecular sieve, and drying and roasting to obtain the halogenated methane catalyst, wherein the drying time is 3 hours, and the drying temperature is 100 ℃; the roasting time is 4 hours, and the temperature is 450 ℃.
The catalyst properties were as follows: the catalyst has a core-shell structure, wherein the core is zinc-containing silicon oxide, and the shell is aluminum oxide containing zirconium sulfate solid acid and a molecular sieve, wherein the weight ratio of the zinc-containing silicon oxide to the aluminum oxide containing the zirconium sulfate solid acid and the molecular sieve is 7: 1; based on the weight of alumina containing zirconium sulfate solid acid and molecular sieve, the content of zirconium sulfate solid acid is 11wt%, the content of molecular sieve is 5%, based on the weight of silicon oxide containing zinc, the content of zinc calculated as oxide is 15 wt%; the thickness of the shell was 30 μm.
The above catalyst was evaluated for the oxyhalogenation of methane under the same conditions as in example 1, and the evaluation results are shown in Table 1.
Example 7
Preparing aluminum hydroxide slurry by adopting a carbonization method of introducing carbon dioxide gas into sodium metaaluminate solution: will contain 30wt% CO2CO of2/N2Introducing the mixed gas into sodium metaaluminate solution, carrying out gelling reaction at 30 ℃, controlling the pH of the reaction end point to be 10.5-11.0, aging after the reaction is finished, washing with deionized water at 60 ℃ until the pH of the filtrate is 6.5, and obtaining the sodium hydroxide with the solid content of 31.2wt%Aluminum slurry;
preparing zinc-containing silicon oxide: an isovolumetric impregnation method was used to impregnate silica (commercially available, having the following properties: specific surface 335 m)2Per g, the pore volume is 0.86 ml/g), drying and roasting are carried out after impregnation, the drying time is 4 hours, and the drying temperature is 100 ℃; the roasting time is 4 hours, the temperature is 500 ℃, the zinc-containing silicon oxide is spherical, and the equivalent diameter of the zinc-containing silicon oxide is 3 mm;
spray soaking process: mixing a proper amount of zirconium sulfate solid acid, mordenite and aluminum hydroxide slurry to obtain aluminum hydroxide slurry containing the zirconium sulfate solid acid and a molecular sieve, then spraying and soaking zinc-containing silicon oxide in the aluminum hydroxide slurry containing the zirconium sulfate solid acid and the molecular sieve, and drying and roasting to obtain a halogenated methane catalyst, wherein the drying time is 3 hours, and the drying temperature is 100 ℃; the roasting time is 4 hours, and the temperature is 450 ℃.
The catalyst properties were as follows: the catalyst has a core-shell structure, wherein the core is zinc-containing silicon oxide, and the shell is aluminum oxide containing zirconium sulfate solid acid and a molecular sieve, wherein the weight ratio of the zinc-containing silicon oxide to the aluminum oxide containing the zirconium sulfate solid acid and the molecular sieve is 5: 1; based on the weight of alumina containing zirconium sulfate solid acid and molecular sieve, the content of zirconium sulfate solid acid is 15wt%, the content of molecular sieve is 10wt%, and based on the weight of zinc-containing silica, the content of zinc is 10wt% calculated by oxide; the thickness of the shell was 60 μm.
The above catalyst was evaluated for the oxyhalogenation of methane under the same conditions as in example 1, and the evaluation results are shown in Table 1.
Example 8
Preparing aluminum hydroxide slurry by adopting a carbonization method of introducing carbon dioxide gas into sodium metaaluminate solution: will contain 30wt% CO2CO of2/N2Introducing the mixed gas into a sodium metaaluminate solution, carrying out gelling reaction at 30 ℃, controlling the pH of the reaction end point to be 10.5-11.0, aging after the reaction is finished, and washing the mixture by deionized water at 60 ℃ until the pH of the filtrate is 6.5 to obtain aluminum hydroxide slurry with the solid content of 31.2 wt%;
preparing zinc-containing silicon oxide: by an isovolumetric impregnation method on silica (commercially available product)The properties are as follows: specific surface 335m2Per g, the pore volume is 0.86 ml/g), drying and roasting are carried out after dipping, the drying time is 3h, and the drying temperature is 120 ℃; the roasting time is 5 hours, the temperature is 450 ℃, the zinc-containing silicon oxide is spherical, and the equivalent diameter of the zinc-containing silicon oxide is 2 mm; carrying out hydro-thermal treatment on the zinc-containing silicon oxide by adopting water vapor nitrogen mixed gas with the volume content of 5%, wherein the treatment temperature is 200 ℃, and the treatment time is 10 min.
Spray soaking process: mixing a proper amount of zirconium sulfate solid acid, mordenite and aluminum hydroxide slurry to obtain aluminum hydroxide slurry containing the zirconium sulfate solid acid and a molecular sieve, then spraying and soaking zinc-containing silicon oxide in the aluminum hydroxide slurry containing the zirconium sulfate solid acid and the molecular sieve, and drying and roasting to obtain a halogenated methane catalyst, wherein the drying time is 3 hours, and the drying temperature is 100 ℃; the roasting time is 4 hours, and the temperature is 450 ℃.
The catalyst properties were as follows: the catalyst has a core-shell structure, wherein the core is zinc-containing silicon oxide, and the shell is aluminum oxide containing zirconium sulfate solid acid and a molecular sieve, wherein the weight ratio of the zinc-containing silicon oxide to the aluminum oxide containing the zirconium sulfate solid acid and the molecular sieve is 7: 1; based on the weight of alumina containing zirconium sulfate solid acid and molecular sieve, the content of zirconium sulfate solid acid is 11wt%, the content of molecular sieve is 5wt%, and based on the weight of zinc-containing silica, the content of zinc calculated as oxide is 15 wt%; the thickness of the shell was 30 μm.
Comparative example 1
Preparing alumina containing a zirconium sulfate solid acid 5A molecular sieve by adopting an aluminum isopropoxide hydrolysis method: mixing water and aluminum isopropoxide according to a molar ratio of 120:1, controlling the hydrolysis temperature at 80-85 ℃, hydrolyzing the aluminum isopropoxide for 1.5h, aging at 90-95 ℃ for 18h to obtain aluminum hydroxide slurry with a solid content of 21.3wt%, mixing a proper amount of zirconium sulfate solid acid, a 5A molecular sieve and the aluminum hydroxide slurry to obtain aluminum hydroxide slurry containing the zirconium sulfate solid acid and the molecular sieve, filtering, drying and roasting to obtain aluminum oxide containing the zirconium sulfate solid acid 5A molecular sieve;
preparing zinc-containing silicon oxide: by an equal volume impregnation methodOn silica (commercially available, properties are as follows: specific surface 335 m)2Per g, the pore volume is 0.86 ml/g), drying and roasting are carried out after impregnation, the drying time is 2 hours, and the drying temperature is 130 ℃; the roasting time is 4 hours, the temperature is 400 ℃, and the zinc-containing silicon oxide is in a powder shape;
the catalyst is prepared by kneading and molding aluminum oxide containing a zirconium sulfate solid acid 5A molecular sieve and zinc-containing silicon oxide powder, drying and roasting. The weight ratio of the zinc-containing silicon oxide to the aluminum oxide containing the zirconium sulfate solid acid and the molecular sieve in the catalyst is 8: 1; the catalyst was prepared in the same manner as in example 1 except that the catalyst contained 8wt% of solid zirconium sulfate acid and 3wt% of molecular sieve, based on the weight of alumina containing solid zirconium sulfate acid and molecular sieve, and 25wt% of zinc, calculated as oxide, based on the weight of zinc-containing silica.
The above catalyst was evaluated for the oxyhalogenation of methane under the same conditions as in example 1, and the evaluation results are shown in Table 1.
TABLE 1 results of different catalysts used in the bromination of methane
Figure 899742DEST_PATH_IMAGE001

Claims (15)

1. A process for preparing a methyl halide catalyst, comprising: the catalyst has a core-shell structure, wherein the core is zinc-containing silicon oxide, the shell is aluminum oxide containing zirconium sulfate solid acid and a molecular sieve, the molecular sieve is at least one of a 5A molecular sieve, a 13X molecular sieve and mordenite, and the weight ratio of the zinc-containing silicon oxide to the aluminum oxide containing the zirconium sulfate solid acid and the molecular sieve is 10:1-2: 1; based on the weight of alumina containing zirconium sulfate solid acid and molecular sieve, the weight content of the zirconium sulfate solid acid is 5-15 wt%, the weight content of the molecular sieve is 1-10 wt%, and the weight content of zinc calculated by oxide is 5-30 wt% based on the weight of zinc-containing silica.
2. The catalyst of claim 1, wherein: the weight ratio of the zinc-containing silicon oxide to the zirconium sulfate-containing solid acid and molecular sieve-containing aluminum oxide is 8:1-5: 1; based on the weight of alumina containing zirconium sulfate solid acid and molecular sieve, the weight content of the zirconium sulfate solid acid is 8-10 wt%, the weight content of the molecular sieve is 3-7 wt%, and the weight content of zinc calculated by oxide is 10-25 wt% based on the weight of zinc-containing silica.
3. The catalyst of claim 1, wherein: the shell has a thickness of 5-200 μm, and the zinc-containing silicon oxide has an equivalent diameter of 1-5 mm.
4. The catalyst of claim 1, wherein: the shell has a thickness of 15-100 μm, and the zinc-containing silicon oxide has an equivalent diameter of 2-5 mm.
5. A process for the preparation of a catalyst according to any one of claims 1 to 4, characterized in that: the method comprises the following steps: mixing at least one of a 5A molecular sieve, a 13X molecular sieve and mordenite, zirconium sulfate solid acid and aluminum hydroxide slurry to obtain aluminum hydroxide slurry containing the zirconium sulfate solid acid and the molecular sieve, then spraying zinc-containing silicon oxide in the aluminum hydroxide slurry containing the zirconium sulfate solid acid and the molecular sieve, drying and roasting to obtain the halogenated methane catalyst.
6. The method of claim 5, wherein: the zirconium sulfate solid acid and the molecular sieve are prepared by adopting commercial products or according to the prior art.
7. The method of claim 5, wherein: the aluminum hydroxide slurry is pseudo-boehmite slurry.
8. The method of claim 5, wherein: the zinc-containing silicon oxide is prepared by impregnating and loading a zinc-containing compound on the formed silicon oxide or kneading the zinc-containing compound and silicon oxide powder for forming, and then drying and roasting.
9. The method of claim 8, wherein: the silicon oxide is prepared by adopting a commercial product or according to the prior art, and the zinc-containing compound can be one or more of zinc nitrate, zinc sulfate, zinc bromide and zinc chloride.
10. The method of claim 8, wherein: the drying time is 1-5h, and the drying temperature is 90-150 ℃; the roasting time is 3-8h, and the temperature is 300-700 ℃.
11. The method of claim 10, wherein: the drying time is 2-4h, and the drying temperature is 100-130 ℃; the roasting time is 4-6h, and the temperature is 400-500 ℃.
12. The method of claim 5, wherein: before the aluminum hydroxide slurry containing zirconium sulfate solid acid and molecular sieve is sprayed and soaked in the zinc-containing silicon oxide, the zinc-containing silicon oxide is treated by adopting water vapor nitrogen mixed gas with the water vapor volume content of 1-15%.
13. The method of claim 12, wherein: the treatment temperature is 150 ℃ and 300 ℃, and the treatment time is 5-30 min.
14. The method of claim 13, wherein: the treatment temperature is 180 ℃ and 200 ℃, and the treatment time is 5-10 min.
15. Use of a catalyst according to any one of claims 1 to 4 for the preparation of methyl halide, characterized in that: the method adopts a fixed bed process, and takes methane, oxygen and halogen acid as reactants or aqueous solution of methane, oxygen and halogen acid as reactants to prepare halogenated methane, wherein the reaction temperature is 250-600 ℃, the feeding volume ratio of the methane, the halogen acid and the oxygen is (3-5): 1-3) and the flow rate of the methane is 10-50 ml/min.
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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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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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