CN109289833A - A kind of preparation method of Catalyst for Oxidative Coupling of Methane solid acid catalyst - Google Patents

A kind of preparation method of Catalyst for Oxidative Coupling of Methane solid acid catalyst Download PDF

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CN109289833A
CN109289833A CN201811280546.1A CN201811280546A CN109289833A CN 109289833 A CN109289833 A CN 109289833A CN 201811280546 A CN201811280546 A CN 201811280546A CN 109289833 A CN109289833 A CN 109289833A
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solid acid
catalyst
tio
preparation
methane
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CN109289833B (en
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丑凌军
程飞
杨建�
宋焕玲
赵军
赵华华
闫亮
牛建中
张兵
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Lanzhou Institute of Chemical Physics LICP of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
    • C07C2/82—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
    • C07C2/84—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling catalytic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/32—Manganese, technetium or rhenium
    • C07C2523/34—Manganese
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The present invention relates to a kind of preparation methods of Catalyst for Oxidative Coupling of Methane solid acid catalyst, method includes the following steps: (1) by TiO2It is added in tungsten salt solution after being fully ground to 6000 ~ 7000 mesh, is evaporated through ultrasonic immersing, stirred in water bath, obtain tungsten titanium solid acid precursor；Tungsten titanium solid acid precursor is fired, grind into powder is to get WO3Content is the solid acid WO of the wt% of 5 wt% ~ 153/TiO2Carrier；(2) LiNO is sequentially added in ionized water3、Mn(NO3)2, and make it completely dissolved, then using solid acid WO described in excessive impregnation3/TiO2Carrier obtains dipping object；(3) dipping object is evaporated through stirred in water bath, last roasting of pulverizing is to get solid acid catalyst.Preparation method of the present invention is simple, preparation condition is mild, three industrial wastes are few, and gained catalyst has many advantages, such as better performances, long service life.

Description

A kind of preparation method of Catalyst for Oxidative Coupling of Methane solid acid catalyst
Technical field
The present invention relates to technical field of chemical engineering catalysts more particularly to a kind of Catalyst for Oxidative Coupling of Methane solid acid catalysis The preparation method of agent.
Background technique
Methane oxidation coupling producing light olefins are that Gas Comprehensive is important using one that realizes substitution petroleum cracking route Developing direction industrializes achievable natural gas straight and is bonded into ethylene route, new by providing in the following petroleum resources shortage Ethylene raw source has great strategic significance and great industrial application value.It is related to the text of the catalyst system in the field Offer very more with patent, but for the catalyst system in the current field, there are C for methane oxidative coupling catalyst2Hydrocarbon yield The problems such as not high and reaction required temperature is higher, so that reaction system industrialization is more difficult.
ZL 91104243.1 is disclosed with SiO2For carrier, active component is by 1.9%Mn2O3 And 5%Na2WO4Composition is urged Agent, the catalyst can obtain higher methane conversion and C in oxidative coupling of methane2Selectivity, but it is reacted Process need to carry out at high temperature and (be higher than 800 DEG C).CN1389293A discloses a kind of SiO2For carrier, Mn is loaded2O3、Na2WO4 And SnO2Multicomponent catalyst can get higher methane conversion and C under the conditions of pressurization (0.6 MPa)2Selection Property, but reaction process needs to pressurize, and there are security risks.It is Ag that CN1696084A, which discloses a kind of active component, and carrier is SiO2、Al2O3, SBA-15 etc. catalyst, though oxidative coupling of methane, its C can be carried out at a lower temperature2It receives Rate is lower.102471181 A of CN discloses the methane selective oxidation making catalyst for ethylene of modified MgO of Ba a kind of, can be lower At a temperature of carry out oxidative coupling of methane, but methane conversion is lower.
Summary of the invention
The few methane of simple, mild condition that technical problem to be solved by the invention is to provide a kind of methods, three industrial wastes The preparation method of oxidative coupling ethylene solid acid catalyst.
To solve the above problems, a kind of preparation side of Catalyst for Oxidative Coupling of Methane solid acid catalyst of the present invention Method, comprising the following steps:
(1) by TiO2It is added in tungsten salt solution after being fully ground to 6000 ~ 7000 mesh, is steamed through ultrasonic immersing, stirred in water bath It is dry, obtain tungsten titanium solid acid precursor；The tungsten titanium solid acid precursor is fired, grind into powder is to get WO3Content is 5 The solid acid WO of the wt% of wt% ~ 153/TiO2Carrier；
(2) based on by the molar ratio of active component Li, Mn, Ti for 1 ~ 4:1 ~ 4:17.2, LiNO is sequentially added in ionized water3、Mn (NO3)2, and make it completely dissolved, then using solid acid WO described in excessive impregnation3/TiO2Carrier obtains dipping object；
(3) the dipping object is evaporated through stirred in water bath, pulverizes last, in 400 DEG C of 1 ~ 3h of roasting, be then increased to 700 ~ 900 DEG C of 2 ~ 4h of roasting are to get solid acid catalyst.
The step (1) in TiO2For unformed titanium dioxide, plate titanium-type titanium dioxide, anatase titanium dioxide or Any one in rutile titanium dioxide.
The step (1) in tungsten salt solution refer to concentration be the mL ~ 0.375 of 0.112 g/5 g/5 mL ammonium tungstate it is molten Liquid or ammonium metatungstate solution.
The step (1) in ultrasonic immersing condition refer to supersonic frequency be 45 ~ 200KHz, temperature be 20 ~ 60 DEG C, when Between be 20 ~ 60min.
The step (1) in roasting condition refer to temperature be 120 ~ 900 DEG C, the time be 2 ~ 4h.
(1) the step each means that temperature is 80 ~ 120 DEG C with the step condition that (3) middle stirred in water bath is evaporated.
Compared with the prior art, the present invention has the following advantages:
1, the resulting solid acid catalyst of the present invention is with solid acid WO3/TiO2For carrier, alkali metal Li and variable valency metal have been supported Mn has neutralized the excessively high alkalinity of catalyst, it is suppressed that deep oxidation, to improve the reaction result of methane oxidation coupling.
2, the present invention is by first preparing solid acid WO3/TiO2Carrier is equal by active component Li and Mn in conjunction with the method for dipping It is even to be anchored to solid acid WO3/TiO2On carrier, the interaction of active component and carrier is enhanced, enhances the work of catalyst Property.
3, the resulting solid acid catalyst of the present invention can carry out first at 700 ~ 800 DEG C of lower temperature and condition of normal pressure Alkane Selective Oxidation C2Hydrocarbon reaction, catalytic performance are preferable.
Catalyst of the present invention is in 750 DEG C, CH4:O2:N2Under the conditions of=20:8:10 mL/min, it is available most Good result are as follows: 30.54% methane conversion and 59.17% C2Hydrocarbon-selective realizes preferable anti-under lower temperature normal pressure Answer as a result, be more suitable industrial applications popularization.
Compared with catalyst and reaction result disclosed in the ZL 91104243.1 and CN1389293A, the catalyst is more Relatively high catalytic performance is shown under low reaction temperature.With low temperature disclosed in 102471181 A of CN1696084A and CN Catalyst is compared, which shows higher methane conversion and C in Catalyst for Oxidative Coupling of Methane reaction2Hydrocarbon selection Property.
4, preparation method of the present invention is simple, mild condition, three industrial wastes are few, and gained catalyst has long service life etc. excellent Point.
Specific embodiment
Catalyst activity evaluation is carried out on fixed-bed quartz reactor, and reaction product analysis is existed using gas-chromatography Line monitoring.Methane conversion, selectivity of product are calculated using carbon atom normalization method, is defined as:
Conversion ratio=[methane concentration in 1- tail gas/(CO in CO concentration+tail gas in methane concentration+tail gas in tail gas2Concentration+2 × Propylene propane total concentration in+3 × tail gas of ethylene-ethane total concentration in tail gas)] × 100%；
Selectivity=[the concentration of carbonaceous products in n × tail gas/(CO in CO concentration+tail gas in tail gas2Second in concentration+2 × tail gas Propylene propane total concentration in alkene ethane+3 × tail gas of total concentration)] × 100%, wherein n is carbon atom quantity in product.
A kind of preparation method of the Catalyst for Oxidative Coupling of Methane solid acid catalyst of embodiment 1, comprising the following steps:
(1) by 2 g Detitanium-ore-type TiO2It is molten that the mL ammonium metatungstate of 0.112 g/5 is added to after being fully ground to 6000 ~ 7000 mesh In liquid, then ultrasonic immersing 20min under conditions of supersonic frequency is 45KHz, temperature is 20 DEG C is stirred in 80 DEG C of water-baths It mixes and is evaporated, obtain tungsten titanium solid acid precursor；Tungsten titanium solid acid precursor is added in Muffle furnace with the heating rate of 4 DEG C/min Grind into powder is after heat to 800 DEG C of roasting 3h to get WO3Content is the solid acid WO of 5 wt%3/TiO2Carrier.
(2) 0.138 g LiNO is sequentially added in 10 mL ionized waters3、0.358 g Mn(NO3)2(50%), and keep its complete Then 1.448 g solid acid WO are added in fully dissolved3/TiO2Carrier obtains dipping object using excessive impregnation；
(3) will impregnate 80 DEG C of object of stirred in water bath be evaporated, pulverize it is last, with the heating speed of 4 DEG C/min in Muffle furnace Rate is heated to 400 DEG C of roasting 1h, is increased to 800 DEG C of roasting 2h then to get solid acid catalyst.
The catalyst is in CH4:O2:N2Catalytic perfomance data under=20:8:10 mL/min are shown in Table 1.
Table 1
A kind of preparation method of the Catalyst for Oxidative Coupling of Methane solid acid catalyst of embodiment 2, comprising the following steps:
(1) by 2 g Detitanium-ore-type TiO2It is molten that the mL ammonium metatungstate of 0.185 g/5 is added to after being fully ground to 6000 ~ 7000 mesh In liquid, ultrasonic immersing 20min under conditions of supersonic frequency is 200KHz, temperature is 60 DEG C, then in 80 DEG C of stirred in water bath It is evaporated, obtains tungsten titanium solid acid precursor；Tungsten titanium solid acid precursor is heated in Muffle furnace with the heating rate of 4 DEG C/min Grind into powder is after to 800 DEG C of roasting 3h to get WO3Content is the solid acid WO of 8 wt%3/TiO2Carrier.
(2) 0.138 g LiNO is sequentially added in 10 mL ionized waters3、0.358 g Mn(NO3)2(50%), and keep its complete Then 1.493 g solid acid WO are added in fully dissolved3/TiO2Carrier obtains dipping object using excessive impregnation；
(3) will impregnate 80 DEG C of object of stirred in water bath be evaporated, pulverize it is last, with the heating speed of 4 DEG C/min in Muffle furnace Rate is heated to 400 DEG C of roasting 1h, is increased to 800 DEG C of roasting 2h then to get solid acid catalyst.
Catalytic perfomance data of the catalyst at 750 DEG C are shown in Table 2.
Table 2
A kind of preparation method of the Catalyst for Oxidative Coupling of Methane solid acid catalyst of embodiment 3, comprising the following steps:
(1) by 2 g Detitanium-ore-type TiO2It is molten that the mL ammonium metatungstate of 0.112 g/5 is added to after being fully ground to 6000 ~ 7000 mesh In liquid, then ultrasonic immersing 20min under conditions of supersonic frequency is 45KHz, temperature is 20 DEG C is stirred in 80 DEG C of water-baths It mixes and is evaporated, obtain tungsten titanium solid acid precursor；Tungsten titanium solid acid precursor is added in Muffle furnace with the heating rate of 4 DEG C/min Grind into powder is after heat to 800 DEG C of roasting 2h to get WO3Content is the solid acid WO of 5 wt%3/TiO2Carrier.
(2) 0.138 g LiNO is sequentially added in 10 mL ionized waters3、0.358 g Mn(NO3)2(50%), and keep its complete Then 1.448 g solid acid WO are added in fully dissolved3/TiO2Carrier obtains dipping object using excessive impregnation；
(3) will impregnate 80 DEG C of object of stirred in water bath be evaporated, pulverize it is last, with the heating speed of 4 DEG C/min in Muffle furnace Rate is heated to 400 DEG C of roasting 1h, is increased to 840 DEG C of roasting 2h then to get solid acid catalyst.
The catalyst is at 750 DEG C, CH4:O2:N2Catalytic perfomance data under=20:8:10 mL/min are shown in Table 3.
Table 3
A kind of preparation method of the Catalyst for Oxidative Coupling of Methane solid acid catalyst of embodiment 4, comprising the following steps:
(1) by 2 g Detitanium-ore-type TiO2It is molten that the mL ammonium metatungstate of 0.112 g/5 is added to after being fully ground to 6000 ~ 7000 mesh In liquid, then ultrasonic immersing 20min under conditions of supersonic frequency is 150KHz, temperature is 50 DEG C is stirred in 80 DEG C of water-baths It mixes and is evaporated, obtain tungsten titanium solid acid precursor；Tungsten titanium solid acid precursor is added in Muffle furnace with the heating rate of 4 DEG C/min Grind into powder is after heat to 800 DEG C of roasting 3h to get WO3Content is the solid acid WO of 5 wt%3/TiO2Carrier.
(2) 0.138 g LiNO is sequentially added in 10 mL ionized waters3、0.358 g Mn(NO3)2(50%), and keep its complete Then 1.448 g solid acid WO are added in fully dissolved3/TiO2Carrier obtains dipping object using excessive impregnation；
(3) will impregnate 80 DEG C of object of stirred in water bath be evaporated, pulverize it is last, with the heating speed of 4 DEG C/min in Muffle furnace Rate is heated to 400 DEG C of roasting 1h, is increased to 900 DEG C of roasting 2h then to get solid acid catalyst.
The catalyst is at 750 DEG C, CH4:O2:N2Catalytic perfomance data under=20:8:10 mL/min are shown in Table 4.
Table 4
A kind of preparation method of the Catalyst for Oxidative Coupling of Methane solid acid catalyst of embodiment 5, comprising the following steps:
(1) by 2 g Detitanium-ore-type TiO2It is molten that the mL ammonium metatungstate of 0.375 g/5 is added to after being fully ground to 6000 ~ 7000 mesh In liquid, ultrasonic immersing 20min under conditions of supersonic frequency is 80KHz, temperature is 30 DEG C, then in 80 DEG C of stirred in water bath It is evaporated, obtains tungsten titanium solid acid precursor；Tungsten titanium solid acid precursor is heated in Muffle furnace with the heating rate of 4 DEG C/min Grind into powder is after to 800 DEG C of roasting 3h to get WO3Content is the solid acid WO of 15 wt%3/TiO2Carrier.
(2) 0.138 g LiNO is sequentially added in 10 mL ionized waters3、0.358 g Mn(NO3)2(50%), and keep its complete Then 1.619 g solid acid WO are added in fully dissolved3/TiO2Carrier obtains dipping object using excessive impregnation；
(3) will impregnate 80 DEG C of object of stirred in water bath be evaporated, pulverize it is last, with the heating speed of 4 DEG C/min in Muffle furnace Rate is heated to 400 DEG C of roasting 1h, is increased to 800 DEG C of roasting 3h then to get solid acid catalyst.
The catalyst is at 750 DEG C, CH4:O2:N2Catalytic perfomance data under=20:8:10 mL/min are shown in Table 5.
Table 5
A kind of preparation method of the Catalyst for Oxidative Coupling of Methane solid acid catalyst of embodiment 6, comprising the following steps:
(1) by 2 g Detitanium-ore-type TiO2It is molten that the mL ammonium metatungstate of 0.112 g/5 is added to after being fully ground to 6000 ~ 7000 mesh In liquid, then ultrasonic immersing 20min under conditions of supersonic frequency is 120KHz, temperature is 50 DEG C is stirred in 80 DEG C of water-baths It mixes and is evaporated, obtain tungsten titanium solid acid precursor；Tungsten titanium solid acid precursor is added in Muffle furnace with the heating rate of 4 DEG C/min Grind into powder is after heat to 800 DEG C of roasting 3h to get WO3Content is the solid acid WO of 5 wt%3/TiO2Carrier.
(2) 0.276 g LiNO is sequentially added in 10 mL ionized waters3、0.358 g Mn(NO3)2(50%), and keep its complete Then 1.448 g solid acid WO are added in fully dissolved3/TiO2Carrier obtains dipping object using excessive impregnation；
(3) will impregnate 80 DEG C of object of stirred in water bath be evaporated, pulverize it is last, with the heating speed of 4 DEG C/min in Muffle furnace Rate is heated to 400 DEG C of roasting 1h, is increased to 800 DEG C of roasting 2h then to get solid acid catalyst.
The catalyst is at 750 DEG C, CH4:O2:N2Catalytic perfomance data under=20:8:10 mL/min are shown in Table 6.
Table 6
A kind of preparation method of the Catalyst for Oxidative Coupling of Methane solid acid catalyst of embodiment 7, comprising the following steps:
(1) by 2 g Detitanium-ore-type TiO2The mL ammonium tungstate solution of 0.112 g/5 is added to after being fully ground to 6000 ~ 7000 mesh In, ultrasonic immersing 60min under conditions of supersonic frequency is 100KHz, temperature is 40 DEG C, then in 80 DEG C of stirred in water bath It is evaporated, obtains tungsten titanium solid acid precursor；Tungsten titanium solid acid precursor is heated in Muffle furnace with the heating rate of 4 DEG C/min Grind into powder is after to 800 DEG C of roasting 3h to get WO3Content is the solid acid WO of 5 wt%3/TiO2Carrier.
(2) 0.069 g LiNO is sequentially added in 10 mL ionized waters3、1.432 g Mn(NO3)2(50%), and keep its complete Then 1.448 g solid acid WO are added in fully dissolved3/TiO2Carrier obtains dipping object using excessive impregnation；
(3) will impregnate 80 DEG C of object of stirred in water bath be evaporated, pulverize it is last, with the heating speed of 4 DEG C/min in Muffle furnace Rate is heated to 400 DEG C of roasting 1h, is increased to 800 DEG C of roasting 2h then to get solid acid catalyst.
CH4:O2:N2Catalytic perfomance data under=20:8:10 mL/min are shown in Table 7.
Table 7
A kind of preparation method of the Catalyst for Oxidative Coupling of Methane solid acid catalyst of embodiment 8, comprising the following steps:
(1) by 2 g Detitanium-ore-type TiO2It is molten that the mL ammonium metatungstate of 0.112 g/5 is added to after being fully ground to 6000 ~ 7000 mesh In liquid, ultrasonic immersing 20min under conditions of supersonic frequency is 45KHz, temperature is 20 DEG C, then in 80 DEG C of stirred in water bath It is evaporated, obtains tungsten titanium solid acid precursor；Tungsten titanium solid acid precursor is heated in Muffle furnace with the heating rate of 4 DEG C/min Grind into powder is after to 800 DEG C of roasting 2h to get WO3Content is the solid acid WO of 5 wt%3/TiO2Carrier.
(2) 0.069 g LiNO is sequentially added in 10 mL ionized waters3、0.358 g Mn(NO3)2(50%), and keep its complete Then 1.448 g solid acid WO are added in fully dissolved3/TiO2Carrier obtains dipping object using excessive impregnation；
(3) will impregnate 80 DEG C of object of stirred in water bath be evaporated, pulverize it is last, with the heating speed of 4 DEG C/min in Muffle furnace Rate is heated to 400 DEG C of roasting 1h, is increased to 800 DEG C of roasting 2h then to get solid acid catalyst.
The catalyst is at 750 DEG C, CH4:O2:N2Catalytic perfomance data under=20:8:10 mL/min are shown in Table 8.
Table 8
A kind of preparation method of the Catalyst for Oxidative Coupling of Methane solid acid catalyst of embodiment 9, comprising the following steps:
(1) by 2 g Detitanium-ore-type TiO2The mL ammonium metatungstate solution of 0.112 g/5 is added to after being fully ground to 6000 ~ 7000 mesh In, ultrasonic immersing 20min under conditions of supersonic frequency is 45KHz, temperature is 20 DEG C, then in 80 DEG C of stirred in water bath It is evaporated, obtains tungsten titanium solid acid precursor；Tungsten titanium solid acid precursor is heated in Muffle furnace with the heating rate of 4 DEG C/min Grind into powder is after to 800 DEG C of roasting 2h to get WO3Content is the solid acid WO of 5 wt%3/TiO2Carrier.
(2) 0.276 g LiNO is sequentially added in 10 mL ionized waters3、1.432 g Mn(NO3)2(50%), and keep its complete Then 1.448 g solid acid WO are added in fully dissolved3/TiO2Carrier obtains dipping object using excessive impregnation；
(3) will impregnate 80 DEG C of object of stirred in water bath be evaporated, pulverize it is last, with the heating speed of 4 DEG C/min in Muffle furnace Rate is heated to 400 DEG C of roasting 1h, is increased to 800 DEG C of roasting 2h then to get solid acid catalyst.
The catalyst is at 750 DEG C, CH4:O2:N2Catalytic perfomance data under=20:8:10 mL/min are shown in Table 9.
Table 9
A kind of preparation method of the Catalyst for Oxidative Coupling of Methane solid acid catalyst of embodiment 10, comprising the following steps:
(1) by the unformed TiO of 2 g2The mL ammonium metatungstate solution of 0.112 g/5 is added to after being fully ground to 6000 ~ 7000 mesh In, ultrasonic immersing 20min under conditions of supersonic frequency is 160KHz, temperature is 45 DEG C, then in 80 DEG C of stirred in water bath It is evaporated, obtains tungsten titanium solid acid precursor；Tungsten titanium solid acid precursor is heated in Muffle furnace with the heating rate of 4 DEG C/min Grind into powder is after to 800 DEG C of roasting 3h to get WO3Content is the solid acid WO of 5 wt%3/TiO2Carrier.
(2) 0.138 g LiNO is sequentially added in 10 mL ionized waters3、0.358 g Mn(NO3)2(50%), and keep its complete Then 1.448 g solid acid WO are added in fully dissolved3/TiO2Carrier obtains dipping object using excessive impregnation；
(3) will impregnate 80 DEG C of object of stirred in water bath be evaporated, pulverize it is last, with the heating speed of 4 DEG C/min in Muffle furnace Rate is heated to 400 DEG C of roasting 1h, is increased to 800 DEG C of roasting 2h then to get solid acid catalyst.
The catalyst is at 750 DEG C, CH4:O2:N2Catalytic perfomance data under=20:8:10 mL/min are shown in Table 10.
Table 10
A kind of preparation method of the Catalyst for Oxidative Coupling of Methane solid acid catalyst of embodiment 11, comprising the following steps:
(1) by 2 g rutile TiOs2The mL ammonium metatungstate solution of 0.112g/5 is added to after being fully ground to 6000 ~ 7000 mesh In, ultrasonic immersing 20min under conditions of supersonic frequency is 45KHz, temperature is 20 DEG C, then in 80 DEG C of stirred in water bath It is evaporated, obtains tungsten titanium solid acid precursor；Tungsten titanium solid acid precursor is heated in Muffle furnace with the heating rate of 4 DEG C/min Grind into powder is after to 800 DEG C of roasting 3h to get WO3Content is the solid acid WO of 5 wt%3/TiO2Carrier.
(2) 0.138 g LiNO is sequentially added in 10 mL ionized waters3、0.358 g Mn(NO3)2(50%), and keep its complete Then 1.448 g solid acid WO are added in fully dissolved3/TiO2Carrier obtains dipping object using excessive impregnation；
(3) will impregnate 80 DEG C of object of stirred in water bath be evaporated, pulverize it is last, with the heating speed of 4 DEG C/min in Muffle furnace Rate is heated to 400 DEG C of roasting 1h, is increased to 700 DEG C of roasting 2h then to get solid acid catalyst.
CH4:O2:N2Catalytic perfomance data under=20:8:10 mL/min are shown in Table 11.
Table 11
A kind of preparation method of the Catalyst for Oxidative Coupling of Methane solid acid catalyst of embodiment 12, comprising the following steps:
(1) by 2 g Detitanium-ore-type TiO2The mL ammonium metatungstate solution of 0.112g/5 is added to after being fully ground to 6000 ~ 7000 mesh In, ultrasonic immersing 20min under conditions of supersonic frequency is 130KHz, temperature is 35 DEG C, then in 80 DEG C of stirred in water bath It is evaporated, obtains tungsten titanium solid acid precursor；Tungsten titanium solid acid precursor is heated in Muffle furnace with the heating rate of 4 DEG C/min Grind into powder is after to 120 DEG C of roasting 4h to get WO3Content is the solid acid WO of 5 wt%3/TiO2Carrier.
(2) 0.138g LiNO is sequentially added in 10 mL ionized waters3、0.358 g Mn(NO3)2(50%), and make it completely Dissolution, is then added 1.448 g solid acid WO3/TiO2Carrier obtains dipping object using excessive impregnation；
(3) will impregnate 80 DEG C of object of stirred in water bath be evaporated, pulverize it is last, with the heating speed of 4 DEG C/min in Muffle furnace Rate is heated to 400 DEG C of roasting 1h, is increased to 800 DEG C of roasting 2h then to get solid acid catalyst.
The catalyst is at 750 DEG C, CH4:O2:N2Catalytic perfomance data under=20:8:10 mL/min are shown in Table 12.
Table 12
A kind of preparation method of the Catalyst for Oxidative Coupling of Methane solid acid catalyst of embodiment 13, comprising the following steps:
(1) by 2 g plate titanium-type TiO2It is added to after being fully ground to 6000 ~ 7000 mesh in the mL ammonium tungstate solution of 0.112g/5, Then ultrasonic immersing 20min under conditions of supersonic frequency is 45KHz, temperature is 20 DEG C is steamed in 120 DEG C of stirred in water bath It is dry, obtain tungsten titanium solid acid precursor；Tungsten titanium solid acid precursor is heated in Muffle furnace with the heating rate of 4 DEG C/min Grind into powder is after 800 DEG C of roasting 2h to get WO3Content is the solid acid WO of 5wt%3/TiO2Carrier.
(2) 0.138 g LiNO is sequentially added in 10 mL ionized waters3、0.358 g Mn(NO3)2(50%), and keep its complete Then 1.448g solid acid WO is added in fully dissolved3/TiO2Carrier obtains dipping object using excessive impregnation；
(3) will impregnate 120 DEG C of object of stirred in water bath be evaporated, pulverize it is last, with the heating speed of 4 DEG C/min in Muffle furnace Rate is heated to 400 DEG C of roasting 3h, is increased to 800 DEG C of roasting 4h then to get solid acid catalyst.
The catalyst is at 750 DEG C, CH4:O2:N2Catalytic perfomance data under=20:8:10 mL/min are shown in Table 13.
Table 13
A kind of preparation method of the Catalyst for Oxidative Coupling of Methane solid acid catalyst of embodiment 14, comprising the following steps:
(1) by 2 g plate titanium-type TiO2It is added to after being fully ground to 6000 ~ 7000 mesh in the mL ammonium tungstate solution of 0.185 g/5, Then ultrasonic immersing 40min under conditions of supersonic frequency is 130KHz, temperature is 35 DEG C is steamed in 100 DEG C of stirred in water bath It is dry, obtain tungsten titanium solid acid precursor；Tungsten titanium solid acid precursor is heated in Muffle furnace with the heating rate of 4 DEG C/min Grind into powder is after 900 DEG C of roasting 2h to get WO3Content is the solid acid WO of 8 wt%3/TiO2Carrier.
(2) 0.138 g LiNO is sequentially added in 10 mL ionized waters3、0.358 g Mn(NO3)2(50%), and keep its complete Then 1.493 g solid acid WO are added in fully dissolved3/TiO2Carrier obtains dipping object using excessive impregnation；
(3) will impregnate 100 DEG C of object of stirred in water bath be evaporated, pulverize it is last, with the heating speed of 4 DEG C/min in Muffle furnace Rate is heated to 400 DEG C of roasting 2h, is increased to 800 DEG C of roasting 3h then to get solid acid catalyst.
The catalyst is at 750 DEG C, CH4:O2:N2Catalytic perfomance data under=20:8:10 mL/min are shown in Table 14.
Table 14

Claims (6)

1. a kind of preparation method of Catalyst for Oxidative Coupling of Methane solid acid catalyst, comprising the following steps:
(1) by TiO2It is added in tungsten salt solution after being fully ground to 6000 ~ 7000 mesh, is evaporated through ultrasonic immersing, stirred in water bath, Obtain tungsten titanium solid acid precursor；The tungsten titanium solid acid precursor is fired, grind into powder is to get WO3Content is 5 wt% The solid acid WO of ~ 15 wt%3/TiO2Carrier；
(2) based on by the molar ratio of active component Li, Mn, Ti for 1 ~ 4:1 ~ 4:17.2, LiNO is sequentially added in ionized water3、Mn (NO3)2, and make it completely dissolved, then using solid acid WO described in excessive impregnation3/TiO2Carrier obtains dipping object；
(3) the dipping object is evaporated through stirred in water bath, pulverizes last, in 400 DEG C of 1 ~ 3h of roasting, be then increased to 700 ~ 900 DEG C of 2 ~ 4h of roasting are to get solid acid catalyst.
2. a kind of preparation method of Catalyst for Oxidative Coupling of Methane solid acid catalyst as described in claim 1, feature exist In: the step (1) in TiO2For unformed titanium dioxide, plate titanium-type titanium dioxide, anatase titanium dioxide or rutile Any one in type titanium dioxide.
3. a kind of preparation method of Catalyst for Oxidative Coupling of Methane solid acid catalyst as described in claim 1, feature exist In: the step (1) in tungsten salt solution refer to ammonium tungstate solution that concentration is the mL ~ 0.375 of 0.112 g/5 g/5 mL or Ammonium metatungstate solution.
4. a kind of preparation method of Catalyst for Oxidative Coupling of Methane solid acid catalyst as described in claim 1, feature exist In: the step (1) in ultrasonic immersing condition refer to that supersonic frequency is 45 ~ 200KHz, temperature is 20 ~ 60 DEG C, the time 20 ~60min。
5. a kind of preparation method of Catalyst for Oxidative Coupling of Methane solid acid catalyst as described in claim 1, feature exist In: the step (1) in roasting condition refer to that temperature is 120 ~ 900 DEG C, the time is 2 ~ 4h.
6. a kind of preparation method of Catalyst for Oxidative Coupling of Methane solid acid catalyst as described in claim 1, feature exist In: (1) the step each means that temperature is 80 ~ 120 DEG C with the step condition that (3) middle stirred in water bath is evaporated.
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