WO2018166419A1 - 一种甲烷氧化偶联催化剂及其制备方法和应用 - Google Patents

一种甲烷氧化偶联催化剂及其制备方法和应用 Download PDF

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WO2018166419A1
WO2018166419A1 PCT/CN2018/078709 CN2018078709W WO2018166419A1 WO 2018166419 A1 WO2018166419 A1 WO 2018166419A1 CN 2018078709 W CN2018078709 W CN 2018078709W WO 2018166419 A1 WO2018166419 A1 WO 2018166419A1
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Prior art keywords
manganese
catalyst
weight
parts
tungstate
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English (en)
French (fr)
Inventor
路勇
张鑫
王鹏伟
赵国锋
刘晔
何鸣元
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Zhejiang Jiruitong New Material Co Ltd
East China Normal University
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Zhejiang Jiruitong New Material Co Ltd
East China Normal University
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Priority to SG11201908522P priority Critical patent/SG11201908522PA/en
Priority to EA201992172A priority patent/EA201992172A1/ru
Priority to KR1020197029723A priority patent/KR102339869B1/ko
Priority to EP18768093.9A priority patent/EP3597290A4/en
Priority to CA3056473A priority patent/CA3056473C/en
Priority to US16/494,173 priority patent/US11298684B2/en
Priority to AU2018233329A priority patent/AU2018233329B2/en
Priority to JP2019551373A priority patent/JP6852185B2/ja
Publication of WO2018166419A1 publication Critical patent/WO2018166419A1/zh
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Definitions

  • the invention relates to the technical field of catalysts, in particular to a catalyst, a preparation method and application thereof and a method for oxidative coupling of methane.
  • Methane and olefins are important chemical raw materials.
  • processes in the industry for the preparation of olefins from methane such as Benson, partial oxidation and catalytic pyrolysis (Liaoning Chemical, 1985, 1, 11). ).
  • Benson partial oxidation and catalytic pyrolysis
  • the main research direction of olefins among which methane oxidative coupling method, as one of the effective conversion routes of natural gas, has attracted extensive attention from catalytic scientists all over the world in the past ten years.
  • the catalysts for the oxidative coupling of methane are mainly divided into three categories: alkali metal and alkaline earth metal oxides, rare earth metal oxides and transition metal composite oxides. These catalyst systems are basically the research and development achievements in the 1990s, mainly The problem is that product selectivity is low (generally no higher than 70%) at higher methane conversions (> 25%), making it difficult to meet economic requirements. In addition, the high reaction temperature (>800 ° C) is extremely demanding on the material of the reactor, etc., greatly reducing the economics of the production process. Therefore, the development of low-temperature ( ⁇ 700 ° C) high activity, high selectivity methane oxidative coupling catalyst is currently a challenging and difficult topic.
  • CN02119567.6 discloses a catalyst for SiO 2 supported Mn 2 O 3 , Na 2 WO 4 and SnO 2 , up to 33% of methane can be obtained at a reaction temperature of >700 ° C under pressure (0.6 MPa). Conversion rate and 24% C2+ yield, but the reaction system is pressurized and higher than 700 °C, which increases the risk of explosion and has potential safety hazards, thus greatly restricting its industrial application development.
  • CN201410001437.7 discloses that manganese nitrate (or one of manganese chloride, manganese acetate and manganese sulfate), sodium tungstate and ammonium tungstate are supported on titanium silicalite or pure by using a stepwise impregnation method.
  • a titanium-containing or titanium-free manganese-sodium-tungsten-silicon composite oxide which can be used as a catalyst for methane oxidation coupling can be prepared and obtained by X-ray powder diffraction analysis.
  • the diffraction peak of the vMnO2 ⁇ xNa2O ⁇ yWO3 ⁇ zTiO2 ⁇ (100-vxyz)SiO2 catalyst is exactly the same as that of the titanium silicon molecular sieve or the pure silicon molecular sieve as the carrier, and no phase peak of the active component is observed, indicating that the active component is supported.
  • a first aspect of the present invention provides a methane oxidative coupling catalyst, wherein the methane oxidative coupling catalyst comprises three active components of manganese trioxide, sodium tungstate, and manganese titanate, and a silica carrier.
  • the composition has the following formula: xMn 2 O 3 -yNa 2 WO 4 -zMnTiO 3 -(100-xyz)SiO 2 , wherein: x, y and z represent dimanganese trioxide, sodium tungstate and manganese titanate, respectively The mass fraction occupied by the catalyst, and 0 ⁇ x ⁇ 20, 1 ⁇ y ⁇ 20, 1 ⁇ z ⁇ 40.
  • a second aspect of the present invention provides a method for preparing a methane oxidative coupling catalyst, the preparation method comprising the steps of:
  • step b) adding an aqueous solution of sodium tungstate to the powdery mixture of manganese titanate and silica obtained in step a) at room temperature, then ultrasonically dispersing for 0.5-1 hour and then stirring for 1-3 hours to obtain a paste-like viscosity.
  • step b) adding an aqueous solution of manganese nitrate to the slurry viscous material obtained in the step b) under stirring at room temperature, stirring for further 1-3 hours, and then drying at 80-100 ° C;
  • step c) The dried product obtained in the step c) is ground into a powder and calcined at 500-900 ° C for 1-2 hours in an air atmosphere.
  • the third aspect of the invention provides a preparation method of another methane oxidation coupling catalyst, which comprises the following steps:
  • step B) adding an aqueous solution of manganese nitrate to the slurry viscous material obtained in the step A) under stirring at room temperature, stirring for further 1-3 hours, and then drying at 80-100 ° C;
  • step C) The dried product obtained in the step B) and the manganese titanate are sufficiently ground into a uniform powder, and then calcined at 500 to 900 ° C for 1-2 hours in an air atmosphere.
  • a fourth aspect of the present invention provides a catalyst comprising: dimanganese trioxide, a tungstate, a manganese composite oxide having a perovskite structure and/or a spinel structure, and a carrier, wherein Dimanganese trioxide and tungstate are supported on a support, or the dimanganese trioxide and tungstate are supported on the manganese composite oxide having a perovskite structure and/or a spinel structure and the carrier
  • the content of the dimanganese trioxide is a part by weight based on 100 parts by weight of the catalyst, and the content of the tungstate is b parts by weight, the calcium having The content of the manganese composite oxide of the titanium ore structure and/or the spinel structure is c parts by weight
  • the content of the carrier is d parts by weight, and 0 ⁇ a ⁇ 20, 1 ⁇ b ⁇ 20, 1 ⁇ c ⁇ 40 , 20 ⁇ d ⁇ 98.
  • a fifth aspect of the present invention provides a method for preparing a catalyst, the method comprising the steps of:
  • a manganese composite oxide having a perovskite structure and/or a spinel structure is solid-phase mixed with a carrier to obtain a solid phase mixture A;
  • a sixth aspect of the invention provides a method for preparing another catalyst, the preparation method comprising the steps of:
  • the dry product Y obtained in the step ii) is solid-phase mixed with the manganese composite oxide having a perovskite structure and/or a spinel structure, and then calcined.
  • a seventh aspect of the invention provides the catalyst obtained by the above production method.
  • a ninth aspect of the present invention provides a method for oxidative coupling of methane, comprising: methane oxidative coupling reaction of methane with oxygen under the condition of methane oxidative coupling reaction and the presence of a catalyst, wherein the catalyst It is the aforementioned catalyst or the catalyst obtained by the aforementioned production method.
  • the experimental results show that the catalyst provided by the present invention or the catalyst obtained by the preparation method of the present invention exhibits a manganese composite oxide phase having a perovskite structure and/or a spinel structure in the active component.
  • Unexpected low temperature activity and selectivity for methane oxidative coupling to olefins for up to 27% methane conversion and 76% C2-C3 hydrocarbon selectivity even at lower temperatures of 620-700 °C It can achieve the effect that the prior art needs to be achieved above 750 °C, which is very beneficial to industrial production.
  • existing methane oxidative coupling catalysts have little activity at temperatures below 700 ° C, let alone selectivity.
  • the present invention has also made significant advances over the prior art.
  • Example 1 is an X-ray powder diffraction pattern of a 3Mn 2 O 3 -10Na 2 WO 4 -10MnTiO 3 -77SiO 2 catalyst prepared in Example 1;
  • Example 2 is an X-ray powder diffraction pattern of a 5Mn 2 O 3 -5Na 2 WO 4 -8MnTiO 3 -82SiO 2 catalyst prepared in Example 2;
  • FIG. 3 is an X-ray powder diffraction pattern of a 3Mn 2 O 3 -10Na 2 WO 4 -87SiO 2 catalyst prepared in Comparative Example 1 and a 3Mn 2 O 3 -10Na 2 WO 4 -87 Sillicalite-1 catalyst prepared in Comparative Example 2.
  • the a curve is the catalyst of Comparative Example 1
  • the curve b is the catalyst of Comparative Example 2;
  • Example 4 is a 3Mn 2 O 3 -10Na 2 WO 4 -10MnTiO 3 -77SiO 2 catalyst prepared in Example 1 and a 3Mn 2 O 3 -10Na 2 WO 4 -87SiO 2 catalyst prepared in Comparative Example 1, respectively, in a methane oxidation couple The relationship between methane conversion and C 2 -C 3 hydrocarbon selectivity at different temperatures in the combined reaction;
  • Figure 5 is a 5Mn 2 O 3 -5Na 2 WO 4 -8MnTiO 3 -82SiO 2 catalyst prepared in Example 2 and a 3Mn 2 O 3 -10Na 2 WO 4 -87Sillicalite-1 catalyst prepared in Comparative Example 2 in methane oxidation The relationship between methane conversion and C 2 -C 3 hydrocarbon selectivity at different temperatures in the combined reaction;
  • Fig. 6 is a graph showing the results of the stability test of the 3Mn 2 O 3 -10Na 2 WO 4 -10MnTiO 3 -77SiO 2 catalyst prepared in Example 1 at 650 ° C for 300 hours in the methane oxidative coupling reaction.
  • the first aspect of the present invention provides a methane oxidative coupling catalyst, which is composed of three active components of manganese trioxide, sodium tungstate, and manganese titanate, and a silica carrier.
  • the composition has the following formula: xMn 2 O 3 -yNa 2 WO 4 -zMnTiO 3 -(100-xyz)SiO 2 , wherein: x, y and z represent dimanganese trioxide, sodium tungstate and manganese titanate, respectively The mass fraction occupied by the catalyst, and 0 ⁇ x ⁇ 20, 1 ⁇ y ⁇ 20, 1 ⁇ z ⁇ 40.
  • the symbol of the connection between the components has no particular meaning, and the order of arrangement between the components is not particularly required, and the formula represents only the weight of the catalyst.
  • the invention selects Ti as a modified element by purpose, and can form a TiO 2 auxiliary agent in the intermediate process of catalyzing the methane oxidative coupling reaction, and modify the SiO 2 support-supported components Mn 2 O 3 and Na 2 WO 4 .
  • TiO 2 additive can form MnTiO 3 with Mn 2 O 3 at low temperature, which can effectively reduce the activation temperature of oxygen molecules in the process of oxidative coupling of methane, and obtain "low temperature chemical cycle to activate O 2 molecules to drive low temperature methane oxidative coupling reaction"
  • the effect is that the reaction temperature is greatly reduced from 800-900 ° C to below 700 ° C.
  • the essence of this effect is the low temperature chemical cycle.
  • a methane oxidative coupling catalyst having low temperature, high activity and high selectivity, and manganese dioxide, sodium tungstate and manganese titanate are obtained in the catalyst.
  • the mass fraction is 0 ⁇ x ⁇ 20, 1 ⁇ y ⁇ 20, 1 ⁇ z ⁇ 40, preferably, the contents of the above three components are respectively 1.5 ⁇ x ⁇ 18, 4 ⁇ y ⁇ 18, 2 ⁇ z ⁇ 35.
  • a second aspect of the present invention provides a method for preparing a methane oxidative coupling catalyst, the preparation method comprising the steps of:
  • step b) adding an aqueous solution of sodium tungstate to the powdery mixture of manganese titanate and silica obtained in step a) at room temperature, then ultrasonically dispersing for 0.5-1 hour and then stirring for 1-3 hours to obtain a paste-like viscosity.
  • step b) adding an aqueous solution of manganese nitrate to the slurry viscous material obtained in the step b) under stirring at room temperature, stirring for further 1-3 hours, and then drying at 80-100 ° C;
  • step c) The dried product obtained in the step c) is ground into a powder and calcined at 500-900 ° C for 1-2 hours in an air atmosphere.
  • the third aspect of the invention provides a preparation method of another methane oxidation coupling catalyst, which comprises the following steps:
  • step B) adding an aqueous solution of manganese nitrate to the slurry viscous material obtained in the step A) under stirring at room temperature, stirring for further 1-3 hours, and then drying at 80-100 ° C;
  • step C) The dried product obtained in the step B) and the manganese titanate are sufficiently ground into a uniform powder, and then calcined at 500 to 900 ° C for 1-2 hours in an air atmosphere.
  • a fourth aspect of the present invention provides a catalyst comprising: dimanganese trioxide, a tungstate, a manganese composite oxide having a perovskite structure and/or a spinel structure, and a carrier, wherein Dimanganese trioxide and tungstate are supported on a support, or the dimanganese trioxide and tungstate are supported on the manganese composite oxide and carrier having a perovskite structure and/or a spinel structure, Among them, since the manganese composite oxide having a perovskite structure and/or a spinel structure and a carrier are both large particles, a manganese composite oxide having a perovskite structure and/or a spinel structure is generally considered. It does not exist in the form of a load on a carrier, but coexists in the form of a mixture.
  • the content of dimanganese trioxide is a part by weight based on 100 parts by weight of the weight of the catalyst, and the content of the tungstate is b parts by weight
  • the content of the perovskite structure and/or the spinel structure of the manganese composite oxide is c parts by weight
  • the content of the carrier is d parts by weight, and 0 ⁇ a ⁇ 20, preferably 1.5 ⁇ a ⁇ 18, 1 ⁇ b ⁇ 20, preferably 4 ⁇ b ⁇ 18, 1 ⁇ c ⁇ 40, preferably 2 ⁇ c ⁇ 35, 20 ⁇ d ⁇ 98, preferably 29 ⁇ d ⁇ 92.5.
  • the present invention selectively selects an oxide auxiliary agent capable of forming a specific doping element of a manganese composite oxide having a perovskite structure and/or a spinel structure at a low temperature with a manganese oxide to support a carrier
  • the catalyst formed by the two active components of manganese and tungstate is modified so that the catalyst described in the present invention can form a perovskite structure and/or a spinel structure during the low temperature methane oxidative coupling reaction.
  • a low-temperature chemical cycle in which a manganese composite oxide and a manganese trioxide are mutually converted that is, an oxide promoter of a specific doping element introduced, "low-temperature catalysis", manganese oxide (Mn 2 O 3 ), oxidation activation of methane molecules and generation
  • a manganese composite oxide having a perovskite structure and/or a spinel structure, and a manganese composite oxide having a perovskite structure and/or a spinel structure can also be converted into three at a lower temperature by reacting with oxygen molecules. Dimanganese oxide and an oxide of the specific doping element.
  • the chemical cycle in the catalyst formed by the traditional carrier-loaded di-manganese trioxide and tungstate active components is This cycle can only be achieved under high temperature conditions. Therefore, it is precisely because the formation of the manganese composite oxide having a perovskite structure and/or a spinel structure replaces MnWO 4 , thereby realizing "manganese composite having a perovskite structure and/or a spinel structure.
  • Oxide Low temperature chemical cycle At the same time, the low temperature chemical cycle and the tungstate produce synergistic catalysis, achieving high selectivity control of the target product.
  • the present invention provides a new idea for the direct activation conversion of methane.
  • the modified catalyst can greatly reduce the temperature of methane oxidative coupling reaction, and still obtain higher methane conversion rate and hydrocarbon selectivity such as ethylene.
  • the catalyst provided by the present invention containing manganese dioxide, tungstate, manganese composite oxide having a perovskite structure and/or a spinel structure and a carrier has good stability and can be stabilized at a relatively high temperature. It has been running for hundreds of hours without signs of inactivation, always maintaining a high CH 4 conversion and selectivity for C 2 -C 3 hydrocarbon products.
  • a methane oxidative coupling catalyst having better low temperature, high activity and high selectivity is obtained, and further optimization of dimanganese trioxide, tungstate, and having calcium and titanium is required.
  • the catalyst is composed of dimanganese trioxide, tungstate, having a perovskite structure and/or a spinel.
  • the structure consists of a manganese composite oxide and a carrier.
  • the content of the dimanganese trioxide is from more than 0 parts by weight to less than or equal to 20 parts by weight based on 100 parts by weight of the weight of the catalyst, for example, the content of the dimanganese trioxide may be 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight Parts, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, and any content between any two of the foregoing adjacent contents; the content of the tungstate is from 1 to 20 parts by weight, such as the tungstate,
  • the perovskite structure and/or spinel The content of the manganese composite oxide of the structure is 1 to 40 parts by weight, and for example, the content of the manganese composite oxide having a perovskite structure and/or a spinel structure may be 1 part by weight, 1.5 parts by weight, and 2 parts by weight.
  • the content of dimanganese trioxide is 1.5 to 18 parts by weight based on 100 parts by weight of the weight of the catalyst, and the content of the tungstate is 4 to 18 parts by weight.
  • the content of the manganese composite oxide having a perovskite structure and/or a spinel structure is 2 to 35 parts by weight, with the balance being the carrier.
  • the phase composition of the catalyst is obtained by X-ray powder diffraction test, and the loading amount of each active component in the catalyst is obtained by X-ray powder diffraction standard working curve method.
  • the manganese composite oxide having a perovskite structure and/or a spinel structure contains Titanium, iron, cobalt, nickel, lithium, lead, cadmium, tin, indium, antimony, gallium, antimony, bismuth, antimony, selenium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, niobium, magnesium, At least one of lanthanum, cerium, lanthanum, cerium, lan
  • the manganese composite oxide having a perovskite structure and/or a spinel structure may be a manganese composite oxide having a perovskite structure and/or a manganese composite oxide having a double perovskite structure.
  • the manganese composite oxide when the manganese composite oxide is the manganese composite oxide having a perovskite structure, the manganese composite oxide may be manganese titanate, manganese lead hydride, manganese stannate, manganese indium citrate, lanthanum Manganese acid, manganese gallium, manganese citrate, manganese citrate, manganese citrate, manganese selenate, manganese zirconate, manganese citrate, manganese vanadate, manganese citrate, manganese citrate, manganese chromite, manganese molybdate At least one of manganese tungstate, barium manganate, magnesium manganate, and barium manganate; when the manganese composite oxide is the manganese composite oxide having a double perovskite structure, the manganese composite oxidation
  • the substance may be LnAFeMnO 6 (wherein Ln is one or more of La, Pr, Nd, Sm, Ce
  • the manganese composite oxide having a perovskite structure and/or a spinel structure may also be a manganese composite oxide having a spinel structure.
  • the manganese composite oxide having a spinel structure may be at least one of manganese ferrite, manganese cobalt oxide, manganese nickelate, lithium manganate, manganese cadmium, and lithium nickel cobalt manganese oxide.
  • the support may be various inorganic heat resistant oxides and/or carbides which do not adversely affect the catalyst, including but not limited to SiC, Fe 2 O 3 , Fe 3 O 4 , TiO 2 , ZrO 2 , One of Al 2 O 3 , La 2 O 3 , CaO, SrO, MgO, and SiO 2 . Since the SiO 2 is economically good and crystallized to form cristobalite under the conditions of the oxidative coupling catalytic reaction of methane, it is beneficial to increase the catalytic activity of the catalyst. Therefore, the support is preferably SiO 2 .
  • the carrier preferably has a particle diameter of from 100 to 2000 mesh, more preferably from 100 to 1000 mesh, a specific surface area of preferably from 10 to 1000 m 2 /g, more preferably from 50 to 250 m 2 /g, and the pore volume is preferably 0.1-1.2 mL/g, more preferably 0.5-0.9 mL/g, and most preferably a pore diameter of 2.0-20 nm, more preferably 2.0-10.0 nm, which ensures that the carrier has a high specific surface area and provides A plurality of active sites further enhance the catalytic performance of the catalyst.
  • the specific surface and pore volume refer to the BET specific surface and pore volume
  • the most probable pore diameter is calculated from the adsorption curve by a BJH (Barrett-Joyner-Halenda) model.
  • the manganese composite oxide having a perovskite structure and/or a spinel structure has a particle diameter of from 100 to 2000 mesh, preferably from 100 to 1000 mesh.
  • the manganese composite oxide having a perovskite structure and/or a spinel structure is manganese titanate (MnTiO 3 ), and the catalyst is composed of dimanganese trioxide (Mn 2 O).
  • Manganese manganate (MnTiO 3 ) is selected as the modifying element, and the TiO 2 promoter can be formed in the intermediate process of catalyzing the methane oxidative coupling reaction, and the SiO 2 carrier-supported component Mn 2 O 3 Modified with Na 2 WO 4 , TiO 2 additive can form MnTiO 3 with Mn 2 O 3 at low temperature, which can effectively reduce the activation temperature of oxygen molecules in the process of oxidative coupling of methane, and obtain “low temperature chemical cycle to activate O 2 molecules.
  • the effect of driving the low-temperature methane oxidative coupling reaction is such that the reaction temperature is drastically lowered from the original 800-900 ° C to below 700 ° C.
  • the essence of this effect is the low temperature chemical cycle.
  • Formation that is, the introduction of TiO 2 "low temperature catalysis" Mn 2 O 3 oxidative activation of methane (CH 4 ) molecules to form MnTiO 3
  • the resulting MnTiO 3 can be converted to Mn 2 O at a lower temperature with O 2 molecules. 3 and TiO 2 .
  • the low temperature chemical cycle and Na 2 WO 4 produce synergistic catalysis, achieving high selectivity regulation of the target product.
  • the fifth aspect of the present invention provides a method for preparing a catalyst, which comprises the active component of a dimanganese oxide precursor, a tungstate precursor, and a perovskite structure and/or a tip.
  • the manganese composite oxide of the spar structure is mixed with the carrier, and sequentially dried and calcined.
  • the order in which the dimanganese oxide precursor, the tungstate precursor, and the manganese composite oxide having a perovskite structure and/or a spinel structure are mixed with a carrier may have a perovskite structure and/or a tip.
  • the manganese composite oxide of the spar structure is solid-phase mixed with the carrier, and the mixed product obtained by sequentially mixing the tungstate precursor and the dimanganese trioxide (Mn 2 O 3 ) precursor in the presence of a solvent in the solid phase is continued. Mixing, the mixing order of the mixed product of the tungstate precursor and the dimanganese trioxide (Mn 2 O 3 ) precursor and the solid phase may be exchanged; the tungstate precursor and the trioxide may also be first introduced.
  • the dimanganese (Mn 2 O 3 ) precursor is sequentially mixed with the carrier in the presence of a solvent, and the resulting mixed product is dried and then continuously solid-phase mixed with the manganese composite oxide having a perovskite structure and/or a spinel structure.
  • the order in which the tungstate precursor and the dimanganese trioxide (Mn 2 O 3 ) precursor are mixed with the carrier can be exchanged.
  • the above solid phase mixing is carried out under grinding conditions, and the mixing in the presence of a solvent is carried out under conditions of ultrasonic dispersion and stirring.
  • the liquid material when the liquid material is mixed with the solid material, the liquid material may be added to the solid material in a dropping manner, or the liquid material may be mixed with the solid material in an impregnation manner, wherein the liquid material is a tungstate precursor.
  • the tungstate precursor and the dimanganese trioxide (Mn 2 O 3 ) precursor are both water-soluble a solid material as a carrier and a manganese composite oxide having a perovskite structure and/or a spinel structure, and a tungstate precursor and/or a dimanganese trioxide (Mn 2 O 3 ) precursor and carrier and having A dried product of an intermediate product obtained by mixing a perovskite structure and/or a spinel-structured manganese composite oxide in the presence of a solvent.
  • the dropping method may be a co-current dropping, or another liquid material may be added after the liquid material is completely added;
  • the dripping rate of the liquid material is preferably controlled at a temperature of 10-30 ° C for controlling the temperature of the reaction system;
  • the step dipping may be first
  • the solid material is immersed in a liquid material for first impregnation, and after the first impregnation is completed, the obtained impregnation product is immersed in another liquid material for second impregnation, the first impregnation and the second impregnation
  • the temperature is preferably from 30 to 60 ° C, and the concentration of the liquid material as the impregnation liquid is preferably from 35 to 55% by weight, and the order of the first impregnation and the second impregnation can be reversed.
  • the solid phase mixing refers to physical mixing between solid phase materials in the absence of a solvent.
  • the order of mixing the tungstate precursor and the dimanganese trioxide precursor is not particularly specified as long as the tungstate precursor and the dimanganese trioxide precursor are not previously prepared in the solvent. Mix underneath and mix with other ingredients. Otherwise, the dimanganese oxide precursor and the tungstate precursor are mixed in the presence of a solvent to cause a neutralization reaction, forming a large amount of precipitate, which is disadvantageous to the formation and dispersion of the active component, thereby affecting the tungstate component and the dimanganese trioxide.
  • the crystallinity and dispersibility of the components on the surface of the support ultimately results in a decrease in the catalytic activity of the catalyst.
  • a method for preparing the catalyst may include the following steps:
  • a manganese composite oxide having a perovskite structure and/or a spinel structure is solid-phase mixed with a carrier to obtain a solid phase mixture A;
  • the preparation method may include the following steps:
  • step i) drying the mixture X obtained in step i) to obtain a dried product Y;
  • the dry product Y obtained in the step ii) is solid-phase mixed with the manganese composite oxide having a perovskite structure and/or a spinel structure, and then calcined.
  • the catalyst prepared by the above method, the dimanganese trioxide and the tungstate are supported on a carrier.
  • the preparation method comprises the following steps:
  • a manganese composite oxide having a perovskite structure and/or a spinel structure is solid-phase mixed with a carrier to obtain a solid phase mixture A;
  • step 2) the solid phase mixture A obtained in step 1) and the tungstate precursor are mixed in the presence of a solvent to obtain a slurry viscous material B;
  • the catalyst prepared by the above method, the dimanganese trioxide and the tungstate are supported on the manganese composite oxide having a perovskite structure and/or a spinel structure and a support.
  • the preparation method comprises the following steps:
  • step i) mixing the slurry viscous material X obtained in step i) with the dimanganese trioxide precursor, and drying the obtained product to obtain a dried product Y;
  • the dry product Y obtained in the step ii) is solid-phase mixed with the manganese composite oxide having a perovskite structure and/or a spinel structure, and then calcined.
  • the solid phase mixing is preferred. It is carried out under grinding conditions so that a powdery mixture is obtained after grinding, and more preferably, the powdery mixture has a particle diameter of 200 to 2000 mesh, and more preferably, the powdery mixture has a particle diameter of 200- 1000 mesh.
  • the mixing in the presence of a solvent is preferably carried out under ultrasonic and stirring conditions, respectively.
  • the conditions include an ultrasonic power of 400-2500 W, an ultrasonic frequency of 20-60 kHz, an ultrasonic time of 0.5-1 hour, and a stirring time of 1-3 hours.
  • the drying condition is preferably The drying temperature is 80-100 ° C, and the drying time is 1-2 hours; in order to completely convert the active ingredient in the reaction raw material into an oxide and remove impurities which are inevitably generated such as carbon, the calcination conditions are preferably The method comprises: performing in an oxygen-containing atmosphere, the calcination temperature is 500-900 ° C, and the calcination time is 1-2 hours; more preferably, the oxygen-containing atmosphere is air.
  • the catalytic performance is more excellent, and 100 parts by weight of the dimanganese trioxide precursor based on dimanganese trioxide is used.
  • the total amount of the body, the tungstate precursor, the manganese composite oxide having a perovskite structure and/or a spinel structure, and the carrier, and the amount of the dimanganese trioxide precursor in terms of dimanganese trioxide is more than 0 parts by weight.
  • the tungstate precursor is used in an amount of 1 to 20 parts by weight, preferably 4 to 18 parts by weight;
  • the perovskite structure and/or tip The manganese composite oxide having a spar structure is used in an amount of 1 to 40 parts by weight, preferably 2 to 3 parts by weight; and the carrier is used in an amount of 20 to 98 parts by weight, preferably 29 to 90 parts by weight.
  • the tungstate precursor is a water-soluble salt, and may be, for example, at least one of sodium tungstate, potassium tungstate, and barium tungstate, and a crystalline hydrate thereof.
  • the dimanganese trioxide precursor is a water-soluble salt, and may be, for example, at least one of manganese nitrate, manganese acetate, manganese chloride, manganese sulfate, and a crystalline hydrate thereof.
  • the solvent may be such that the tungstate precursor and the dimanganese trioxide precursor can be dissolved, for example, the solvent may be water.
  • the solvent is present such that the concentration of the tungstate precursor is from 35 to 45% by weight such that the concentration of the dimanganese trioxide precursor is from 45 to 55% by weight.
  • the perovskite structure and/or the spinel structure contains titanium, iron, cobalt, nickel, lithium, lead, cadmium, tin, indium, antimony, gallium, antimony, bismuth, antimony, selenium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, At least one of tungsten, strontium, magnesium, strontium, barium, strontium, strontium, barium, calcium, strontium, barium, and potassium.
  • the manganese composite oxide having a perovskite structure and/or a spinel structure is preferably manganese titanate, manganese ferrite, manganese cobalt oxide, manganese nickel nitrate, and manganese acid.
  • 0.1 ⁇ p ⁇ 0.2, 0 ⁇ q ⁇ 0.25 for example, q may be 0.05, 0.1, 0.12, 0.15, 0.2, 0.22, 0.24, 0.25, and any value between any two of the aforementioned adjacent values, preferably 0.1 ⁇ q ⁇ 0.2, 0 ⁇ n ⁇ 0.25, for example, n may be 0.05, 0.1, 0.12, 0.15, 0.2, 0.22, 0.24, 0.25, and any arbitrary value between any two of the aforementioned adjacent values, preferably 0.1 ⁇ n ⁇ 0.2.
  • the carrier may be various inorganic heat resistant oxides and/or carbides which do not adversely affect the catalyst, including but not limited to SiC, Fe 2 O 3 , Fe 3 O 4 .
  • SiC SiC
  • Fe 2 O 3 Fe 3 O 4
  • the carrier preferably has a particle diameter of 100 to 2000 mesh, more preferably 100 to 1000 mesh, and a specific surface area of preferably 10 to 1000 m 2 /g, more preferably 50 to 250 m 2 .
  • the pore volume is preferably from 0.1 to 1.2 mL/g, more preferably from 0.5 to 0.9 mL/g
  • the most preferred pore diameter is preferably from 2.0 to 20 nm, more preferably from 2.0 to 10.0 nm, which ensures that the carrier has a higher ratio
  • the high specific surface area provides more active sites, which in turn enhances the catalytic performance of the catalyst.
  • the specific surface and pore volume refer to the BET nitrogen adsorption specific surface and pore volume, and the most probable pore diameter is calculated from the adsorption curve by a BJH (Barrett-Joyner-Halenda) model.
  • the manganese composite oxide having a perovskite structure and/or a spinel structure has a particle diameter of 100 to 2000 mesh, preferably 100 to 1000 mesh.
  • the seventh aspect of the present invention also provides a catalyst obtained by the specific method of the above production method.
  • the composition formula of the catalyst may be: xMn 2 O 3 -yR 2 WO 4 -zMn r M 1 s1 M 2 s2 ... M n sn O t -( 100-xyz)Support, wherein R represents an alkali metal element selected from the group consisting of Na, K, and Rb, and Support represents a carrier, and Mn r M 1 s1 M 2 s2 ... M n sn O t represents the perovskite
  • the composition of the structure and/or the spinel structure of the manganese composite oxide, the order of each element is in no particular order, and M 1 , M 2 , ...
  • M n represent the manganese having a perovskite structure and/or a spinel structure.
  • Each of the composite oxides other than the manganese element, and M 1 , M 2 , ..., M n are selected from the group consisting of titanium, iron, cobalt, nickel, lithium, lead, cadmium, tin, indium, antimony, gallium, antimony, One of lanthanum, cerium, selenium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, strontium, magnesium, strontium, strontium, strontium, strontium, strontium, calcium, strontium, strontium, and potassium.
  • r represents the number of manganese atoms
  • s1, s2, ..., sn represent M 1 , M 2 , ..., M n , respectively.
  • Number of atoms t represents the number of oxygen atoms, and 0 ⁇ r ⁇ 1, 0 ⁇ s1 ⁇ 1, 0 ⁇ s2 ⁇ 1, ..., 0 ⁇ sn ⁇ 1, 1 ⁇ t ⁇ 6; x, y and z respectively represent trioxide
  • the symbol of the connection between the points has no particular meaning, and the order of arrangement between the active components is in no particular order, and the formula only represents that the catalyst contains x, y, z and (% by weight, respectively) 100-xyz)
  • Manganese Trioxide Mn 2 O 3
  • the eighth aspect of the present invention also provides the use of the foregoing catalyst or the catalyst obtained by the aforementioned preparation method for oxidative coupling catalytic reaction of methane.
  • the ninth aspect of the invention also provides a method for oxidative coupling of methane, the method comprising: methane oxidative coupling reaction between methane and oxygen under the condition of methane oxidative coupling reaction and the presence of a catalyst, wherein The catalyst is the aforementioned catalyst or the catalyst obtained by the aforementioned production method.
  • the method for oxidative coupling of methane provided by the present invention, wherein the volume ratio of methane to oxygen can be from 3 to 8:1, and the reaction temperature can be from 620 to 900 ° C, for example, 620 ° C, 630 ° C, 640 ° C, 650 °C, 660 ° C, 670 ° C, 680 ° C, 690 ° C, 700 ° C, 720 ° C, 750 ° C, 780 ° C, 800 ° C, 820 ° C, 850 ° C, 880 ° C and 900 ° C, and any two of the aforementioned adjacent temperatures Any temperature between them is preferably 620-800 ° C; the reaction pressure may be 0.1-2 MPa, preferably 0.1-1 MPa; and the gas hourly space velocity may be 3000-50000 mL ⁇ h -1 ⁇ g based on the total amount of methane and oxygen -1 , preferably 4000-8500 mL ⁇ h -1 ⁇ g
  • the methane oxidative coupling reaction between methane and oxygen may further contain an inert gas to dilute the raw material gas composed of methane and oxygen to prevent the methane oxidative coupling reaction process from heating up too fast and eliminating the thermal effect.
  • the inert gas may be nitrogen or argon, preferably nitrogen; more preferably, the volume ratio of methane, oxygen and the inert gas may be from 3 to 8:1:3.5 to 4.5.
  • the method for oxidative coupling of methane provided according to the present invention wherein the catalyst used in the oxidative coupling reaction of the methane is effective for reducing methane by the foregoing catalyst provided by the present invention or the catalyst obtained by the aforementioned preparation method provided by the present invention
  • the oxygen molecule activation temperature during the oxidative coupling process so the reaction temperature can be drastically reduced from the conventional 800-900 ° C methane oxidative coupling temperature to below 700 ° C, preferably 620-700 ° C.
  • the diameter of manganese titanate is 500 mesh
  • the particle size of manganese ferrite is 200 mesh
  • the particle size of manganese cobalt oxide is 200 mesh
  • Ca 0.2 La 0.2 K 0.6 Mn 0.78 Fe 0.22 The particle size of O 3 was 325 mesh.
  • the carrier is SiO 2
  • the carrier has a particle diameter of 200 mesh, a specific surface area of 50-250 m 2 /g, a pore volume of 0.5-0.9 mL/g, and a maximum pore diameter of 2.0- 10.0 nm.
  • reaction product components were carried out on a gas chromatograph available from Agilent Model No. 7820A.
  • ultrasonic dispersion was performed using an ultrasonic system model SK-12C purchased from Shanghai Science and Technology Ultrasonic Instrument Co., Ltd., with an ultrasonic power of 400-500 W and an ultrasonic frequency of 25 kHz.
  • the purpose of this embodiment is to provide a catalyst: 3Mn 2 O 3 -10Na 2 WO 4 -10MnTiO 3 -77SiO 2 , and the preparation method thereof is as follows:
  • the temperature of the system is maintained between 10 and 30 ° C, and after ultrasonic dispersion for 1 hour, stirring is continued for 3 hours to obtain a slurry-like viscous material;
  • step 2) Weigh 0.272 g of a 50% by weight aqueous solution of manganese nitrate, dilute to 5 ml with deionized water; add the obtained aqueous solution of manganese nitrate to the slurry viscous material obtained in step 1) with stirring, and control the dropwise addition. During the process, the temperature of the system is maintained between 10-30 ° C, stirring is continued for 3 hours, and then dried at 100 ° C;
  • Fig. 1 is an X-ray powder diffraction (XRD) pattern of the catalyst prepared in the present example; it can be seen from Fig. 1 that the catalyst contains three phases of Mn 2 O 3 , Na 2 WO 4 and MnTiO 3 .
  • XRD X-ray powder diffraction
  • Object of the present embodiment is to provide a catalyst: 5Mn 2 O 3 -5Na 2 WO 4 -8MnTiO 3 -82SiO 2, which is prepared as follows:
  • XRD X-ray powder diffraction
  • the purpose of this embodiment is to provide a catalyst: 1.5Mn 2 O 3 -8Na 2 WO 4 -4MnTiO 3 -86.5SiO 2 , and the preparation method thereof is as follows:
  • step 2) Weigh 0.136 g of a 50% by weight aqueous solution of manganese nitrate, dilute to 5 ml with deionized water; add the obtained aqueous solution of manganese nitrate to the slurry viscous material obtained in step 1) with stirring, and control the dropwise addition. During the process, the temperature of the system is maintained between 10-30 ° C, stirring is continued for 2 hours, and then drying at 80 ° C;
  • X-ray powder diffraction analysis showed that the X-ray powder diffraction (XRD) pattern of the catalyst prepared in the present example contained three phases of Mn 2 O 3 , Na 2 WO 4 and MnTiO 3 .
  • the purpose of this embodiment is to provide a catalyst: 10Mn 2 O 3 -4Na 2 WO 4 -5MnTiO 3 -83SiO 2 , and the preparation method thereof is as follows:
  • step 2) Weigh 0.906 g of 50% by weight aqueous solution of manganese nitrate, dilute to 5 ml with deionized water; add the obtained aqueous solution of manganese nitrate to the slurry viscous material obtained in step 1) with stirring, and control the dropwise addition. During the process, the temperature of the system is maintained between 10-30 ° C, stirring is continued for 3 hours, and then dried at 100 ° C;
  • X-ray powder diffraction analysis showed that the X-ray powder diffraction (XRD) pattern of the catalyst prepared in the present example contained three phases of Mn 2 O 3 , Na 2 WO 4 and MnTiO 3 .
  • the purpose of this embodiment is to provide a catalyst: 15Mn 2 O 3 -12Na 2 WO 4 -20MnTiO 3 -53SiO 2 , and the preparation method thereof is as follows:
  • step 2) Weigh 1.360g of a 50% by weight aqueous solution of manganese nitrate, dilute to 5 ml with deionized water; add the obtained aqueous solution of manganese nitrate to the viscous viscous mixture obtained in step 1) with stirring, and control the dropwise addition. During the process, the temperature of the system is maintained between 10-30 ° C, stirring is continued for 1.5 hours, and then drying at 85 ° C;
  • the sample prepared in the step 2) was sufficiently ground with 0.4 g of manganese titanate powder, and calcined at 800 ° C for 1 hour in an air atmosphere to obtain a catalyst of this example.
  • X-ray powder diffraction analysis showed that the X-ray powder diffraction (XRD) pattern of the catalyst prepared in the present example contained three phases of Mn 2 O 3 , Na 2 WO 4 and MnTiO 3 .
  • the purpose of this embodiment is to provide a catalyst: 18Mn 2 O 3 -15Na 2 WO 4 -15MnTiO 3 -52SiO 2 , and the preparation method thereof is as follows:
  • step 2) Weigh 1.632 g of 50% by weight aqueous solution of manganese nitrate, dilute to 5 ml with deionized water; add the obtained aqueous solution of manganese nitrate to the viscous viscous mixture obtained in step 1) with stirring, and control the dropwise addition.
  • the temperature of the system is maintained at 10-30 ° C, and after stirring for 1 hour, it is dried at 100 ° C;
  • the sample prepared in the step 2) was sufficiently ground with 0.3 g of manganese titanate powder, and calcined at 800 ° C for 2.5 hours in an air atmosphere to obtain a catalyst of this example.
  • X-ray powder diffraction analysis showed that the X-ray powder diffraction (XRD) pattern of the catalyst prepared in the present example contained three phases of Mn 2 O 3 , Na 2 WO 4 and MnTiO 3 .
  • Object of the present embodiment is to provide a catalyst: 2Mn 2 O 3 -18Na 2 WO 4 -7MnTiO 3 -73SiO 2, which is prepared as follows:
  • the temperature of the system is maintained between 10 and 30 ° C, and after ultrasonic dispersion for 0.8 hours, stirring is continued for 3 hours to obtain a slurry-like viscous material;
  • step 2) Weigh 0.181 g of 50% by weight aqueous solution of manganese nitrate, dilute to 5 ml with deionized water; add the obtained aqueous solution of manganese nitrate to the slurry viscous material obtained in step 1) with stirring, and control the dropwise addition. During the process, the temperature of the system is maintained between 10-30 ° C, stirring is continued for 1.5 hours, and then drying at 90 ° C;
  • X-ray powder diffraction analysis showed that the X-ray powder diffraction (XRD) pattern of the catalyst prepared in the present example contained three phases of Mn 2 O 3 , Na 2 WO 4 and MnTiO 3 .
  • Object of the present embodiment is to provide a catalyst: 12Mn 2 O 3 -10Na 2 WO 4 -2MnTiO 3 -76SiO 2, which is prepared as follows:
  • step 2) Weigh 1.088 g of 50% by weight aqueous solution of manganese nitrate, dilute to 5 ml with deionized water; add the obtained aqueous solution of manganese nitrate to the slurry viscous material obtained in step 1) with stirring, and control the dropwise addition. During the process, the temperature of the system is maintained between 10-30 ° C, stirring is continued for 2.5 hours, and then drying at 85 ° C;
  • X-ray powder diffraction analysis showed that the X-ray powder diffraction (XRD) pattern of the catalyst prepared in the present example contained three phases of Mn 2 O 3 , Na 2 WO 4 and MnTiO 3 .
  • the purpose of this embodiment is to provide a catalyst: 8Mn 2 O 3 -12Na 2 WO 4 -28MnTiO 3 -52SiO 2 , and the preparation method thereof is as follows:
  • the temperature of the system is maintained between 10 and 30 ° C, and after ultrasonic dispersion for 0.5 hours, stirring is continued for 1.5 hours to obtain a slurry-like viscous material;
  • step 2) Weigh 0.725 g of a 50% by weight aqueous solution of manganese nitrate, dilute to 5 ml with deionized water; add the obtained aqueous solution of manganese nitrate to the slurry viscous material obtained in step 1) with stirring, and control the dropwise addition. During the process, the temperature of the system is maintained between 10-30 ° C, stirring is continued for 2 hours, and then dried at 100 ° C;
  • X-ray powder diffraction analysis showed that the X-ray powder diffraction (XRD) pattern of the catalyst prepared in the present example contained three phases of Mn 2 O 3 , Na 2 WO 4 and MnTiO 3 .
  • the purpose of this embodiment is to provide a catalyst: 18Mn 2 O 3 -18Na 2 WO 4 -35MnTiO 3 -29SiO 2 , and the preparation method thereof is as follows:
  • step 2) Weigh 1.632 g of 50% by weight aqueous solution of manganese nitrate, dilute to 5 ml with deionized water; add the obtained aqueous solution of manganese nitrate to the slurry viscous material obtained in step 1) with stirring, and control the dropwise addition. During the process, the temperature of the system is maintained between 10-30 ° C, stirring is continued for 2 hours, and then drying at 95 ° C;
  • the sample prepared in the step 2) was sufficiently ground with 0.7 g of manganese titanate powder, and calcined at 850 ° C for 2 hours in an air atmosphere to obtain a catalyst of this example.
  • X-ray powder diffraction analysis showed that the X-ray powder diffraction (XRD) pattern of the catalyst prepared in the present example contained three phases of Mn 2 O 3 , Na 2 WO 4 and MnTiO 3 .
  • the purpose of this embodiment is to provide a catalyst: 3Mn 2 O 3 -10Na 2 WO 4 -10MnFe 2 O 4 -77SiO 2 , and the preparation method thereof is as follows:
  • the temperature of the system is maintained between 10-30 ° C, and after ultrasonic dispersion for 1 hour, stirring is continued for 3 hours to obtain a slurry-like viscous material;
  • step 2) Weigh 0.272 g of a 50% by weight aqueous solution of manganese nitrate, dilute to 5 ml with deionized water; add the obtained aqueous solution of manganese nitrate to the slurry viscous material obtained in step 1) with stirring, and control the dropwise addition. During the process, the temperature of the system is maintained between 10-30 ° C, stirring is continued for 3 hours, and then dried at 100 ° C;
  • X-ray powder diffraction analysis showed that the X-ray powder diffraction (XRD) pattern of the catalyst prepared in the present example contained three phases of Mn 2 O 3 , Na 2 WO 4 and MnFe 2 O 4 .
  • the purpose of this embodiment is to provide a catalyst: 5Mn 2 O 3 -5Na 2 WO 4 -8MnCo 2 O 4 -82SiO 2 , and the preparation method thereof is as follows:
  • the X-ray powder diffraction (XRD) pattern of the catalyst prepared in the present example contained three phases of Mn 2 O 3 , Na 2 WO 4 and MnCo 2 O 4 .
  • the purpose of this embodiment is to provide a catalyst: 1.5Mn 2 O 3 -8K 2 WO 4 -4MnLi 2 O 4 -86.5SiO 2 , and the preparation method thereof is as follows:
  • step 2) Weigh 0.136 g of a 50% by weight aqueous solution of manganese acetate, dilute to 5 ml with deionized water; add the obtained aqueous solution of manganese acetate to the slurry viscous material obtained in step 1) with stirring, and control the dropwise addition. During the process, the temperature of the system is maintained between 10-30 ° C, stirring is continued for 2 hours, and then drying at 80 ° C;
  • X-ray powder diffraction analysis showed that the X-ray powder diffraction (XRD) pattern of the catalyst prepared in the present example contained three phases of Mn 2 O 3 , K 2 WO 4 and MnLi 2 O 4 .
  • the purpose of this embodiment is to provide a catalyst: 3Mn 2 O 3 -10Na 2 WO 4 -10Ca 0.2 La 0.2 K 0.6 Mn 0.78 Fe 0.22 O 3 -77SiO 2 , and the preparation method thereof is as follows:
  • step 2) Weigh 0.272 g of a 50% by weight aqueous solution of manganese nitrate, dilute to 5 ml with deionized water; add the obtained aqueous solution of manganese nitrate to the slurry viscous material obtained in step 1) with stirring, and control the dropwise addition. During the process, the temperature of the system is maintained between 10-30 ° C, stirring is continued for 3 hours, and then dried at 100 ° C;
  • X-ray powder diffraction analysis showed that the X-ray powder diffraction (XRD) pattern of the catalyst prepared in this example contained Mn 2 O 3 , Na 2 WO 4 and Ca 0.2 La 0.2 K 0.6 Mn 0.78 Fe 0.22 O 3 . Phase.
  • the purpose of the present comparative example is to provide a catalyst: 3Mn 2 O 3 -10Na 2 WO 4 -87SiO 2 , prepared according to the method of Example 1, except that manganese titanate is not added during the preparation, and the preparation method thereof is specifically as follows :
  • step 2) Weigh 0.272 g of 50% by weight aqueous solution of manganese nitrate, dilute to 2 ml with deionized water; add the obtained aqueous solution of manganese nitrate to the slurry viscous material obtained in step 1) with stirring, and control the dropwise addition. During the process, the temperature of the system is maintained between 10-30 ° C, stirring is continued for 3 hours, and then dried at 100 ° C;
  • This comparative example is to provide a catalyst: 3Mn 2 O 3 -10Na 2 WO 4 -87Sillicalite-1, prepared according to the method of Example 1, except that manganese titanate is not added during the preparation, and the carrier used
  • the MFI type all-silica molecular sieve Sillicalite-1 carrier is prepared as follows:
  • step 2) Weigh 0.272 g of 50% by weight aqueous solution of manganese nitrate, dilute to 2 ml with deionized water; add the obtained aqueous solution of manganese nitrate to the slurry viscous material obtained in step 1) with stirring, and control the dropwise addition.
  • the temperature of the system is maintained between 10-30 ° C, and after stirring for 1 hour, it is dried at 90 ° C;
  • XRD 3 is an X-ray powder diffraction (XRD) pattern of the catalysts prepared in Comparative Example 1 and Comparative Example 2, and it can be seen from FIG. 3 that only the X-ray powder diffraction (XRD) patterns of the catalysts prepared in Comparative Examples 1 and 2 were only The Mn 2 O 3 and Na 2 WO 4 phases have no MnTiO 3 phase.
  • a catalyst was prepared in accordance with Example 2 of CN201410001437.7: 4.2MnO 2 ⁇ 1.5Na 2 O ⁇ 5.5WO 3 ⁇ 2.9TiO 2 ⁇ 85.9SiO 2 .
  • X-ray powder diffraction analysis showed that the X-ray powder diffraction (XRD) pattern of the catalyst prepared in the present comparative example had the same diffraction peak as that of the Ti-MWW molecular sieve, and no other phase peak was observed.
  • XRD X-ray powder diffraction
  • Catalyst reaction evaluation was carried out on a continuous flow fixed bed microreactor.
  • a quartz tube reactor was used with an inner diameter of 16 mm and a length of 400 mm.
  • the catalyst bed height is 10 mm.
  • the catalyst does not need to be pretreated, and is directly heated to a set reaction temperature, and then cut into a reaction mixture to carry out a reaction.
  • the reaction tail gas was condensed and separated by a frozen ethanol-water bath (30% ethanol), and then quantitatively detected by an online gas chromatograph.
  • N 2 , O 2 , CO, CO 2 , CH 4 , and C 2 -C 3 were quantitatively analyzed using a 5A capillary column and a PQ packed column (DIKMA) in parallel and a TCD detector.
  • DIKMA PQ packed column
  • the purpose of this application example was to investigate the methane oxidative coupling reaction performance of the examples and comparative catalysts at different reaction temperatures.
  • the catalytic performance of the Comparative Example 3 catalyst was also tested at 750 ° C while maintaining other conditions.
  • the methane oxidative coupling catalyst provided by the present invention exhibits an unexpected result because the active component contains a manganese composite oxide phase having a perovskite structure and/or a spinel structure.
  • the active component contains a manganese composite oxide phase having a perovskite structure and/or a spinel structure.
  • methane oxidative coupling to olefins can achieve methane conversion of up to 27% and C 2 -C 3 hydrocarbon selectivity at lower temperatures and pressures of 620-700 ° C
  • the catalyst provided in the comparative example is almost inactive at less than 700 ° C, let alone selectivity. It is to be noted that the present invention achieves significant advances and unexpected effects over the prior art.
  • Example 5 is prepared in Example 2 of the embodiment 5Mn 2 O 3 -5Na 2 WO 4 -8MnTiO 3 -82SiO 2 catalyst
  • the catalyst of the present invention has good low temperature activity and selectivity compared to conventional catalysts, and has made significant progress over the prior art.
  • the catalyst reaction evaluation and product analysis system were the same as in Application Example 1.
  • the purpose of this application example is to investigate the stability of the catalyst of the examples in the methane oxidative coupling reaction.
  • the reaction stability test was carried out for 300 hours under the conditions of g -1 , normal pressure and reaction temperature at 650 ° C.
  • the 3Mn 2 O 3 -10Na 2 WO 4 -10MnTiO 3 -77SiO 2 catalyst prepared in Example 1 was used in an amount of 0.8 g.
  • the reaction results are shown in Fig. 6.
  • the catalyst of the present invention has good reaction stability. In the 300-hour stability test, the conversion rate was always maintained at about 24%, and the selectivity was maintained at about 67%.

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Abstract

一种甲烷氧化偶联催化剂及其制备方法和应用。该催化剂的组成包括：三氧化二锰、钨酸盐、具有钙钛矿结构和/或尖晶石结构的锰复合氧化物和载体，其中，三氧化二锰和钨酸盐负载在具有钙钛矿结构和/或尖晶石结构的锰复合氧化物和载体上，在该催化剂中，以100重量份催化剂的重量为基准，三氧化二锰的含量为a重量份，钨酸盐的含量为b重量份，具有钙钛矿结构和/或尖晶石结构的锰复合氧化物的含量为c重量份，载体的含量为d重量份，且0＜a≤20，1≤b≤20，1≤c≤40，20≤d＜98。该催化剂用于甲烷氧化偶联反应时，具有良好的低温活性和选择性。

Description

[根据细则37.2由ISA制定的发明名称]　一种甲烷氧化偶联催化剂及其制备方法和应用 技术领域
本发明涉及催化剂技术领域，具体涉及一种催化剂及其制备方法和应用以及甲烷氧化偶联的方法。
背景技术
甲烷和烯烃(例如乙烯)都是重要的化学原料，工业上已有通过甲烷制备烯烃的工艺，例如本森法、部分氧化法和催化热解法等合成工艺(辽宁化工，1985，1，11)。由于传统的本森法存在副产物氯代烃，对分离造成一定的困难，而催化热解法会产生大量积碳，严重影响了催化剂的稳定性和使用寿命，因此，部分氧化法成为目前制备烯烃的主要研究方向，其中，甲烷氧化偶联法作为天然气的有效转化途径之一，在过去的十几年里引起了世界各国催化科学工作者的广泛关注。
目前，用于甲烷氧化偶联的催化剂主要分为三类：碱金属与碱土金属氧化物、稀土金属氧化物以及过渡金属复合氧化物，这些催化剂体系基本上是20世纪90年代的研发成果，主要的问题是在较高甲烷转化率(＞25％)下时产物选择性偏低(一般不高于70％)，因而难以满足经济性的要求。另外，高反应温度(＞800℃)对反应器材质等的要求极为苛刻，极大地降低了生产过程的经济性。因此，研制开发低温(＜700℃)高活性、高选择性甲烷氧化偶联催化剂是当前极具挑战的难点课题。
虽然CN02119567.6公开了一种SiO 2负载Mn 2O 3、Na 2WO 4和SnO 2的催化剂，在加压(0.6MPa)条件下，反应温度＞700℃时，最高可获得33％的甲烷转化率和24％的C2+收率，但此反应体系在加压和高于700℃的高温，增加了爆炸风险，存在安全隐患，因此极大地制约了其工业化应用开发。
为了解决上述问题，CN201410001437.7公开了通过采用分步浸渍法将硝酸锰(或氯化锰、醋酸锰和硫酸锰中的一种)、钨酸钠和钨酸氨负载于钛硅分子筛或纯硅分子筛上并经焙烧，可制备得到一种可用作甲烷氧化偶联催化剂的含钛或不含钛的锰-钠-钨-硅复合氧化物，通过X射线粉末衍射分析得知所得到的vMnO2·xNa2O·yWO3·zTiO2·(100-v-x-y-z)SiO2催化剂的衍射峰与作为载体的钛硅分子筛或纯硅分子筛完全相同，未观察到活性组分的物相峰，表明所负载的活性组分均高度分散在载体分子筛的表面；虽然实验证明：所述催化剂在常压下、750-800℃时，在 10000-35000mL·g -1·h -1的很宽气时空速范围内，甲烷转化率可达25％以上，C2-C3产物选择性可达72-81％，但所述催化剂仍然需要在高于700℃的较高温度(750-800℃)下才具有较好的活性和选择性，在低于700℃时几乎没有活性，因此仍然不能满足低温工业化生产要求。
发明内容
针对现有技术存在的上述问题和需求，本发明的目的是提供一种催化剂及其制备方法和应用以及甲烷氧化偶联的方法。
为了实现上述目的，本发明第一方面提供一种甲烷氧化偶联催化剂，所述甲烷氧化偶联催化剂是由三氧化二锰、钨酸钠和钛酸锰三种活性组分与二氧化硅载体组成，具有如下通式：xMn 2O 3-yNa 2WO 4-zMnTiO 3-(100-x-y-z)SiO 2，其中：x、y和z分别表示三氧化二锰、钨酸钠和钛酸锰在所述催化剂中所占的质量分数，且0＜x≤20，1≤y≤20，1≤z≤40。
作为较佳方案，其中的1.5≤x≤18，4≤y≤18，2≤z≤35。
本发明第二方面提供一种甲烷氧化偶联催化剂的制备方法，该制备方法包括如下步骤：
a)将钛酸锰与二氧化硅充分研磨，形成均匀粉状混合物；
b)室温下，将钨酸钠水溶液滴加到步骤a)得到的钛酸锰与二氧化硅的粉状混合物中，然后超声分散0.5-1小时之后再搅拌1-3小时，得浆状粘稠物；
c)室温搅拌下，将硝酸锰水溶液滴加到步骤b)制得的浆状粘稠物中，继续搅拌1-3小时，然后在80-100℃下烘干；
d)将步骤c)制得的烘干物研磨成粉末，在空气氛中于500-900℃焙烧1-2小时。
本发明第三方面提供另一种甲烷氧化偶联催化剂的制备方法，该制备方法包括如下步骤：
A)室温下，将钨酸钠水溶液滴加到二氧化硅中，超声分散0.5-1小时之后再搅拌1-3小时，得浆状粘稠物；
B)室温搅拌下，将硝酸锰水溶液滴加到步骤A)制得的浆状粘稠物中，继续搅拌1-3小时，然后在80-100℃下烘干；
C)将步骤B)制得的烘干物与钛酸锰充分研磨成均匀粉末，然后在空气氛中于500-900℃焙烧1-2小时。
本发明第四方面提供一种催化剂，所述催化剂的组成包括：三氧化二锰、钨酸盐、 具有钙钛矿结构和/或尖晶石结构的锰复合氧化物和载体，其中，所述三氧化二锰和钨酸盐负载在载体上，或者，所述三氧化二锰和钨酸盐负载在所述具有钙钛矿结构和/或尖晶石结构的锰复合氧化物和所述载体上，在所述催化剂中，以100重量份的所述催化剂的重量为基准，所述三氧化二锰的含量为a重量份，所述钨酸盐的含量为b重量份，所述具有钙钛矿结构和/或尖晶石结构的锰复合氧化物的含量为c重量份，所述载体的含量为d重量份，且0＜a≤20，1≤b≤20，1≤c≤40，20≤d＜98。
本发明第五方面提供一种催化剂的制备方法，该制备方法包括如下步骤：
1)将具有钙钛矿结构和/或尖晶石结构的锰复合氧化物与载体进行固相混合，得到固相混合物A；
2)将步骤1)得到的固相混合物A与钨酸盐前驱体和三氧化二锰前驱体在溶剂存在下进行混合，得到混合产物B；
3)将步骤2)得到的混合产物B依次进行干燥和焙烧。
本发明第六方面提供另一种催化剂的制备方法，该制备方法包括如下步骤：
i)将钨酸盐前驱体和三氧化二锰前驱体与载体在溶剂存在下混合，得到混合物X；
ii)将步骤i)得到的混合物X与三氧化二锰前驱体混合，并对混合得到的产物进行干燥，得到干燥产物Y；
iii)将步骤ii)得到的干燥产物Y与具有钙钛矿结构和/或尖晶石结构的锰复合氧化物进行固相混合后焙烧。
本发明第七方面提供由上述制备方法得到的催化剂。
本发明第八方面提供一种前述催化剂或由前述制备方法得到的催化剂在甲烷氧化偶联催化反应的应用。
本发明第九方面提供一种甲烷氧化偶联的方法，所述方法包括：在甲烷氧化偶联反应条件下以及催化剂的存在下，使甲烷与氧气进行甲烷氧化偶联反应，其中，所述催化剂为前述催化剂或由前述制备方法得到的催化剂。
实验结果表明，本发明提供的催化剂或由本发明所述的制备方法得到的催化剂，因活性组分中含有具有钙钛矿结构和/或尖晶石结构的锰复合氧化物物相，因而体现出出乎意料的低温活性和选择性，使甲烷氧化偶联制烯烃反应即使在620-700℃的较低温度下也可实现高达27％的甲烷转化率和76％的C2-C3烃类选择性，达到现有技术需要在高于750℃下才能实现的效果，非常有利于工业化生产。尤其是，现有的甲烷氧化偶联催化剂在低于700℃时几乎不具有活性，更谈不上选择性。因此，本发明相对于现有技术， 也取得了显著性进步。
附图说明
图1为实施例1所制备的3Mn 2O 3-10Na 2WO 4-10MnTiO 3-77SiO 2催化剂的X射线粉末衍射图谱；
图2为实施例2所制备的5Mn 2O 3-5Na 2WO 4-8MnTiO 3-82SiO 2催化剂的X射线粉末衍射图谱；
图3为对比例1所制备的3Mn 2O 3-10Na 2WO 4-87SiO 2催化剂和对比例2所制备的3Mn 2O 3-10Na 2WO 4-87Sillicalite-1催化剂的X射线粉末衍射图谱，其中，a曲线为对比例1催化剂，b曲线为对比例2催化剂；
图4为实施例1所制备的3Mn 2O 3-10Na 2WO 4-10MnTiO 3-77SiO 2催化剂和对比例1所制备的3Mn 2O 3-10Na 2WO 4-87SiO 2催化剂分别在甲烷氧化偶联反应中于不同温度下的甲烷转化率和C 2-C 3烃类选择性的关系曲线；
图5为实施例2所制备的5Mn 2O 3-5Na 2WO 4-8MnTiO 3-82SiO 2催化剂和对比例2所制备的3Mn 2O 3-10Na 2WO 4-87Sillicalite-1催化剂在甲烷氧化偶联反应中于不同温度下的甲烷转化率和C 2-C 3烃类选择性的关系曲线；
图6为实施例1所制备的3Mn 2O 3-10Na 2WO 4-10MnTiO 3-77SiO 2催化剂在甲烷氧化偶联反应中于650℃时300小时的稳定性实验结果。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
如前所述，本发明第一方面提供一种甲烷氧化偶联催化剂，所述甲烷氧化偶联催化剂是由三氧化二锰、钨酸钠和钛酸锰三种活性组分与二氧化硅载体组成，具有如下通式：xMn 2O 3-yNa 2WO 4-zMnTiO 3-(100-x-y-z)SiO 2，其中：x、y和z分别表示三氧化二锰、钨酸钠和钛酸锰在所述催化剂中所占的质量分数，且0＜x≤20，1≤y≤20，1≤z≤40。
根据本发明，在所述通式中，各组分之间的连接符号没有特别的含义，各组分之间的排列顺序没有特殊的要求，所述通式仅代表所述催化剂中含有重量百分含量分别为 x、y、z以及(100-x-y-z)的三氧化二锰(Mn 2O 3)、钨酸钠(Na 2WO 4)、钛酸锰(MnTiO 3)以及二氧化硅(SiO 2)。
本发明通过目标性地选取Ti作为改性元素，在催化甲烷氧化偶联反应的中间过程可以形成TiO 2助剂，对SiO 2载体负载的组分Mn 2O 3和Na 2WO 4进行改性，TiO 2助剂在低温下能同Mn 2O 3形成MnTiO 3，可以有效降低甲烷氧化偶联过程中氧气分子活化温度，获得“低温化学循环活化O 2分子以驱动低温甲烷氧化偶联反应”的效果，使反应温度由原来的800-900℃大幅下降至700℃以下。产生此效果的本质在于低温化学循环
Figure PCTCN2018078709-appb-000001
的形成，即引入的TiO 2“低温催化”Mn 2O 3对甲烷(CH 4)分子的氧化活化而生成MnTiO 3，生成的MnTiO 3可在较低温度与O 2分子反应转化为Mn 2O 3和TiO 2。同时，该低温化学循环与Na 2WO 4产生协同催化作用，实现了目标产物的高选择性调控。
根据本发明，为了有效发挥各组分的协同作用，获得具有低温高活性、高选择性的甲烷氧化偶联催化剂，三氧化二锰、钨酸钠和钛酸锰在所述催化剂中所占的质量分数分别为0＜x≤20，1≤y≤20，1≤z≤40，优选地，上述三种组分的含量分别为1.5≤x≤18，4≤y≤18，2≤z≤35。
本发明第二方面提供一种甲烷氧化偶联催化剂的制备方法，该制备方法包括如下步骤：
a)将钛酸锰与二氧化硅充分研磨，形成均匀粉状混合物；
b)室温下，将钨酸钠水溶液滴加到步骤a)得到的钛酸锰与二氧化硅的粉状混合物中，然后超声分散0.5-1小时之后再搅拌1-3小时，得浆状粘稠物；
c)室温搅拌下，将硝酸锰水溶液滴加到步骤b)制得的浆状粘稠物中，继续搅拌1-3小时，然后在80-100℃下烘干；
d)将步骤c)制得的烘干物研磨成粉末，在空气氛中于500-900℃焙烧1-2小时。
本发明第三方面提供另一种甲烷氧化偶联催化剂的制备方法，该制备方法包括如下步骤：
A)室温下，将钨酸钠水溶液滴加到二氧化硅中，超声分散0.5-1小时之后再搅拌1-3小时，得浆状粘稠物；
B)室温搅拌下，将硝酸锰水溶液滴加到步骤A)制得的浆状粘稠物中，继续搅拌1-3小时，然后在80-100℃下烘干；
C)将步骤B)制得的烘干物与钛酸锰充分研磨成均匀粉末，然后在空气氛中于500-900℃焙烧1-2小时。
本发明第四方面提供一种催化剂，所述催化剂的组成包括：三氧化二锰、钨酸盐、具有钙钛矿结构和/或尖晶石结构的锰复合氧化物和载体，其中，所述三氧化二锰和钨酸盐负载在载体上，或者，所述三氧化二锰和钨酸盐负载在所述具有钙钛矿结构和/或尖晶石结构的锰复合氧化物和载体上，其中，由于所述具有钙钛矿结构和/或尖晶石结构的锰复合氧化物与载体均为较大的颗粒，因此一般认为钙钛矿结构和/或尖晶石结构的锰复合氧化物不是以负载在载体上的形式存在，而是以混合物的形式共存。
优选地，在所述催化剂中，以100重量份的所述催化剂的重量为基准，所述三氧化二锰的含量为a重量份，所述钨酸盐的含量为b重量份，所述具有钙钛矿结构和/或尖晶石结构的锰复合氧化物的含量为c重量份，所述载体的含量为d重量份，且0＜a≤20，优选1.5≤a≤18，1≤b≤20，优选4≤b≤18，1≤c≤40，优选2≤c≤35，20≤d＜98，优选29≤d≤92.5。
本发明由于目标性地选取在低温下能同锰的氧化物形成具有钙钛矿结构和/或尖晶石结构的锰复合氧化物的特定掺杂元素的氧化物助剂对载体负载三氧化二锰和钨酸盐两种活性组分形成的催化剂进行改性，使得在本发明中所述的催化剂在低温甲烷氧化偶联反应过程中可以形成具有钙钛矿结构和/或尖晶石结构的锰复合氧化物与三氧化二锰相互转化的低温化学循环，即引入的特定掺杂元素的氧化物助剂“低温催化”三氧化二锰(Mn 2O 3)对甲烷分子的氧化活化并生成具有钙钛矿结构和/或尖晶石结构的锰复合氧化物，生成的具有钙钛矿结构和/或尖晶石结构的锰复合氧化物也可在较低温度与氧气分子反应转化为三氧化二锰和该特定掺杂元素的氧化物。而传统载体负载三氧化二锰和钨酸盐两种活性组分形成的催化剂中的化学循环为
Figure PCTCN2018078709-appb-000002
该循环只能在高温条件下实现。因此，正是由于所述具有钙钛矿结构和/或尖晶石结构的锰复合氧化物的生成代替了MnWO 4，从而实现了“具有钙钛矿结构和/或尖晶石结构的锰复合氧化物
Figure PCTCN2018078709-appb-000003
低温化学循环。同时，该低温化学循环与钨酸盐产生协同催化作用，实现了目标产物的高选择性调控。而且本发明为甲烷直接活化转化提供了新的思路，改性后的催化剂可使甲烷氧化偶联反应温度大幅降低，并仍可获得较高的甲烷转化率和乙烯等烃类选择性。另外，本发明提供的含有三氧化二锰、钨酸盐、具有钙钛矿结构和/或尖晶石结构的锰复合氧化物和载体的催化剂具有良好的稳定性，可以在较高温度下稳定运行数百小时无失活迹象，始终保持较高的CH 4转化率和C 2-C 3烃类产物的选择性。
根据本发明，为了更好地发挥各组分的协同作用，获得具有更优的低温高活性、高选择性的甲烷氧化偶联催化剂，需要进一步优化三氧化二锰、钨酸盐和具有钙钛矿结构和/或尖晶石结构的锰复合氧化物三种组分的用量配比，优选地，所述催化剂由三氧化 二锰、钨酸盐、具有钙钛矿结构和/或尖晶石结构的锰复合氧化物和载体组成。
在所述催化剂中，以100重量份的所述催化剂的重量为基准，所述三氧化二锰的含量为大于0重量份至小于等于20重量份，例如所述三氧化二锰的含量可以为0.1重量份、0.2重量份、0.3重量份、0.4重量份、0.5重量份、1重量份、1.5重量份、2重量份、2.5重量份、3重量份、3.5重量份、4重量份、4.5重量份、5重量份、6重量份、7重量份、8重量份、9重量份、10重量份、11重量份、12重量份、13重量份、14重量份、15重量份、16重量份、17重量份、18重量份、19重量份、20重量份，以及任意两个前述相邻含量之间的任意含量；所述钨酸盐的含量为1-20重量份，例如所述钨酸盐的含量可以为1重量份、1.5重量份、2重量份、2.5重量份、3重量份、3.5重量份、4重量份、4.5重量份、5重量份、6重量份、7重量份、8重量份、9重量份、10重量份、11重量份、12重量份、13重量份、14重量份、15重量份、16重量份、17重量份、18重量份、19重量份、20重量份，以及任意两个前述相邻含量之间的任意含量；所述具有钙钛矿结构和/或尖晶石结构的锰复合氧化物的含量为1-40重量份，例如所述具有钙钛矿结构和/或尖晶石结构的锰复合氧化物的含量可以为1重量份、1.5重量份、2重量份、2.5重量份、3重量份、3.5重量份、4重量份、4.5重量份、5重量份、6重量份、7重量份、8重量份、9重量份、10重量份、11重量份、12重量份、13重量份、14重量份、15重量份、16重量份、17重量份、18重量份、19重量份、20重量份、21重量份、22重量份、23重量份、24重量份、25重量份、26重量份、27重量份、28重量份、29重量份、30重量份、31重量份、32重量份、33重量份、34重量份、35重量份、36重量份、37重量份、38重量份、39重量份、40重量份，以及任意两个前述相邻含量之间的任意含量；余量为所述载体。
进一步优选地，在所述催化剂中，以100重量份的所述催化剂的重量为基准，所述三氧化二锰的含量为1.5-18重量份，所述钨酸盐的含量为4-18重量份，所述具有钙钛矿结构和/或尖晶石结构的锰复合氧化物的含量为2-35重量份，余量为所述载体。
本发明中，所述催化剂的物相组成通过X射线粉末衍射测试得出，所述催化剂中的各活性组分的负载量通过X射线粉末衍射标准工作曲线法表征测试获得。
根据本发明，为了使所述具有钙钛矿结构和/或尖晶石结构的锰复合氧化物在低温甲烷氧化偶联反应过程中更容易形成低温化学循环“具有钙钛矿结构和/或尖晶石结构的锰复合氧化物
Figure PCTCN2018078709-appb-000004
”，优选地，在所述具有钙钛矿结构和/或尖晶石结构的锰复合氧化物的组成中，所述具有钙钛矿结构和/或尖晶石结构的锰复合氧化物中含有钛、铁、钴、 镍、锂、铅、镉、锡、铟、锗、镓、锑、铋、碲、硒、锆、铪、钒、铌、钽、铬、钼、钨、钡、镁、铈、镧、镨、钕、钐、钙、锶、钡、钾中的至少一种元素。
根据本发明，所述具有钙钛矿结构和/或尖晶石结构的锰复合氧化物可以为具有钙钛矿结构的锰复合氧化物和/或具有双钙钛矿结构的锰复合氧化物。具体地，当所述锰复合氧化物为所述具有钙钛矿结构的锰复合氧化物时，所述锰复合氧化物可以为钛酸锰、铅酸锰、锡酸锰、铟酸锰、锗酸锰、镓酸锰、锑酸锰、铋酸锰、碲酸锰、硒酸锰、锆酸锰、铪酸锰、钒酸锰、铌酸锰、钽酸锰、铬酸锰、钼酸锰、钨酸锰、锰酸钡、锰酸镁、锰酸铈中的至少一种；当所述锰复合氧化物为所述具有双钙钛矿结构的锰复合氧化物时，所述锰复合氧化物可以为LnAFeMnO 6(其中Ln为La，Pr，Nd，Sm中的一种或多种，Ce；A为Ca，Sr，Ba中的一种或多种)、La 0.5Sr 0.5Mn 1-mFe mO 3、Ca αLa βK 1-α-βMn 0.5Fe 0.5O 3、Ca pLa qK 1-p-qMn 0.78Fe 0.22O 3、Bi 0.5Ca 0.5-nLa nFe 0.3Mn 0.7O 3中的至少一种，其中，0＜m≤0.25，例如，m可以为0.05、0.1、0.12、0.15、0.2、0.22、0.24、0.25，以及任意两个前述相邻数值之间的任意数值，优选0.1≤m≤0.22，0＜α≤0.25，例如，α可以为0.05、0.1、0.12、0.15、0.2、0.22、0.24、0.25，以及任意两个前述相邻数值之间的任意数值，优选0.1≤α≤0.2，0＜β≤0.25，例如，β可以为0.05、0.1、0.12、0.15、0.2、0.22、0.24、0.25，以及任意两个前述相邻数值之间的任意数值，优选0.1≤β≤0.2，0＜p≤0.25，例如，p可以为0.05、0.1、0.12、0.15、0.2、0.22、0.24、0.25，以及任意两个前述相邻数值之间的任意数值，优选0.1≤p≤0.2，0＜q≤0.25，例如，q可以为0.05、0.1、0.12、0.15、0.2、0.22、0.24、0.25，以及任意两个前述相邻数值之间的任意数值，优选0.1≤q≤0.2，0＜n≤0.25，例如，n可以为0.05、0.1、0.12、0.15、0.2、0.22、0.24、0.25，以及任意两个前述相邻数值之间的任意数值，优选0.1≤n≤0.2。
根据本发明，所述具有钙钛矿结构和/或尖晶石结构的锰复合氧化物还可以为具有尖晶石结构的锰复合氧化物。具体地，所述具有尖晶石结构的锰复合氧化物可以为铁酸锰、钴酸锰、镍酸锰、锰酸锂、镉酸锰和镍钴锰酸锂中的至少一种。
根据本发明，所述载体可以为各种不对催化剂造成不良影响的无机耐热氧化物和/或碳化物，包括但不限于SiC、Fe 2O 3、Fe 3O 4、TiO 2、ZrO 2、Al 2O 3、La 2O 3、CaO、SrO、MgO和SiO 2中的一种。由于SiO 2经济性好，且在甲烷氧化偶联催化反应条件下会发生转晶形成方石英，有益于提高所述催化剂的催化活性，因此，所述载体优选为SiO 2。
根据本发明，所述载体的粒径优选为100-2000目，更优选为100-1000目，比表面积优选为10-1000m 2/g，更优选为50-250m 2/g，孔体积优选为0.1-1.2mL/g，更优选为 0.5-0.9mL/g，最可几孔径优选为2.0-20nm，更优选为2.0-10.0nm，这样可以保障所述载体具有较高的比表面积并提供较多的活性位点，进而增强所述催化剂的催化性能。本发明中，所述比表面和孔体积是指BET比表面和孔体积、最可几孔径采用BJH(Barrett-Joyner-Halenda)模型由吸附曲线计算得到。
根据本发明，所述具有钙钛矿结构和/或尖晶石结构的锰复合氧化物的粒径为100-2000目，优选为100-1000目。
根据本发明一种优选的实施方式，所述具有钙钛矿结构和/或尖晶石结构的锰复合氧化物为钛酸锰(MnTiO 3)，所述催化剂由三氧化二锰(Mn 2O 3)、钨酸钠(Na 2WO 4)、钛酸锰(MnTiO 3)和二氧化硅(SiO 2)载体组成，当所述具有钙钛矿结构和/或尖晶石结构的锰复合氧化物为钛酸锰(MnTiO 3)时，目标性地选取Ti作为改性元素，在催化甲烷氧化偶联反应的中间过程可以形成TiO 2助剂，对SiO 2载体负载的组分Mn 2O 3和Na 2WO 4进行改性，TiO 2助剂在低温下能同Mn 2O 3形成MnTiO 3，可以有效降低甲烷氧化偶联过程中氧气分子活化温度，获得“低温化学循环活化O 2分子以驱动低温甲烷氧化偶联反应”的效果，使反应温度由原来的800-900℃大幅下降至700℃以下。产生此效果的本质在于低温化学循环
Figure PCTCN2018078709-appb-000005
的形成，即引入的TiO 2“低温催化”Mn 2O 3对甲烷(CH 4)分子的氧化活化而生成MnTiO 3，生成的MnTiO 3可在较低温度与O 2分子反应转化为Mn 2O 3和TiO 2。同时，该低温化学循环与Na 2WO 4产生协同催化作用，实现了目标产物的高选择性调控。
如前所述，本发明第五方面提供了一种催化剂的制备方法，所述制备方法包括将活性组分三氧化二锰前驱体、钨酸盐前驱体与具有钙钛矿结构和/或尖晶石结构的锰复合氧化物和载体混合，并依次进行干燥和焙烧。所述三氧化二锰前驱体、钨酸盐前驱体与具有钙钛矿结构和/或尖晶石结构的锰复合氧化物和载体混合的顺序可以为先将具有钙钛矿结构和/或尖晶石结构的锰复合氧化物与载体进行固相混合，再将钨酸盐前驱体和三氧化二锰(Mn 2O 3)前驱体在溶剂存在下依次与前述固相混合得到的混合产物继续混合，所述钨酸盐前驱体和三氧化二锰(Mn 2O 3)前驱体与所述固相混合得到的混合产物的混合顺序可以调换；也可以先将钨酸盐前驱体和三氧化二锰(Mn 2O 3)前驱体在溶剂存在下依次与载体混合，再将所得混合产物干燥后与具有钙钛矿结构和/或尖晶石结构的锰复合氧化物继续进行固相混合，所述钨酸盐前驱体和三氧化二锰(Mn 2O 3)前驱体与载体进行混合的顺序可以调换。优选情况下，上述固相混合在研磨的条件下进行，在溶剂存在下的混合在超声分散和搅拌的条件下进行。更优选地，液态物料与固态物料混合时，可以以 滴加的方式将液态物料加入至固态物料，也可以以浸渍的方式将液态物料与固态物料混合，其中，液态物料为钨酸盐前驱体和溶剂形成的溶液以及三氧化二锰(Mn 2O 3)前驱体和溶剂形成的溶液，所述钨酸盐前驱体和所述三氧化二锰(Mn 2O 3)前驱体均为水溶性盐；固态物料为载体和具有钙钛矿结构和/或尖晶石结构的锰复合氧化物，以及钨酸盐前驱体和/或三氧化二锰(Mn 2O 3)前驱体与载体以及具有钙钛矿结构和/或尖晶石结构的锰复合氧化物在溶剂存在下混合时得到的中间产物的干燥产物。当液态物料与固态物料混合的方式为滴加的方式时，所述滴加方式可以为并流滴加，也可以待一种液态物料滴加完全之后再滴加另一种液态物料；所述液态物料的滴速以控制所述反应体系的温度保持在10-30℃为宜；当液态物料与固态物料混合的方式为浸渍时，优选为分步浸渍，所述分步浸渍可以为先将固态物料浸渍在一种液态物料中进行第一浸渍，待所述第一浸渍完成，再将得到的浸渍产物浸渍在另一种液态物料中进行第二浸渍，所述第一浸渍和第二浸渍的温度均优选为30-60℃，作为浸渍液的液态物料的浓度均优选为35-55重量％，所述第一浸渍和第二浸渍的顺序可以调换。
本发明中，所述固相混合是指固相物料之间在不存在溶剂情况下的物理混合。
在本发明中，在所述制备方法中，钨酸盐前驱体和三氧化二锰前驱体的混合顺序没有特别的规定，只要不是事先将钨酸盐前驱体和三氧化二锰前驱体在溶剂下进行混合，再与其他原料混合即可。否则三氧化二锰前驱体与钨酸盐前驱体在溶剂存在下混合会发生中和反应，形成大量沉淀，不利于活性组分的形成和分散，进而影响钨酸盐组分和三氧化二锰组分在载体表面的结晶度和分散性，最终导致所述催化剂的催化活性降低。
根据本发明第五方面提供的一种所述催化剂的制备方法，该制备方法可以包括如下步骤：
1)将具有钙钛矿结构和/或尖晶石结构的锰复合氧化物与载体进行固相混合，得到固相混合物A；
2)将步骤1)得到的固相混合物A与钨酸盐前驱体和三氧化二锰前驱体在溶剂存在下进行混合，得到混合产物B；
3)将步骤2)得到的混合产物B依次进行干燥和焙烧。
根据本发明第六方面提供的另一种所述催化剂的制备方法，该制备方法可以包括如下步骤：
i)将钨酸盐前驱体和三氧化二锰前驱体与载体在溶剂存在下混合，得到混合物X；
ii)将步骤i)得到的混合物X进行干燥，得到干燥产物Y；
iii)将步骤ii)得到的干燥产物Y与具有钙钛矿结构和/或尖晶石结构的锰复合氧化物进行固相混合后焙烧。
采用上述方法制得的催化剂，所述三氧化二锰和钨酸盐负载在载体上。
根据本发明一种具体的实施方式，所述制备方法包括如下步骤：
1)将具有钙钛矿结构和/或尖晶石结构的锰复合氧化物与载体进行固相混合，得到固相混合物A；
2)将步骤1)得到的固相混合物A与钨酸盐前驱体在溶剂存在下混合，得到浆状粘稠物B；
3)将步骤2)得到的浆状粘稠物B与三氧化二锰前驱体混合，并将混合得到的产物依次进行干燥和焙烧。
采用上述方法制得的催化剂，所述三氧化二锰和钨酸盐负载在所述具有钙钛矿结构和/或尖晶石结构的锰复合氧化物和载体上。
根据本发明另一种具体的实施方式，所述制备方法包括如下步骤：
i)将钨酸盐前驱体与载体在溶剂存在下混合，得到浆状粘稠物X；
ii)将步骤i)得到的浆状粘稠物X与三氧化二锰前驱体混合，并对混合得到的产物进行干燥，得到干燥产物Y；
iii)将步骤ii)得到的干燥产物Y与具有钙钛矿结构和/或尖晶石结构的锰复合氧化物进行固相混合后焙烧。
在本发明提供的所述制备方法中，为了使所述固相混合过程中的各物料混合均匀，并保障所述混响混合后得到的物料具有较高的比表面积，所述固相混合优选在研磨条件下进行，使得研磨后得到粉状混合物料，更优选地，所述粉状混合物料的粒径为200-2000目，进一步优选地，所述粉状混合物料的粒径为200-1000目。
在本发明提供的所述制备方法中，为了使所述在溶剂存在下的混合过程中的各物料混合均匀，所述在溶剂存在下的混合优选依次在超声波和搅拌条件下进行，所述超声的条件包括超声功率为400-2500W，超声频率为20-60kHz，超声时间为0.5-1小时，所述搅拌的时间为1-3小时。
在本发明提供的所述制备方法中，为了使所述浆状粘稠物B或所述浆状粘稠物X与三氧化二锰前驱体混合得到的产物充分干燥，所述干燥的条件优选包括：干燥温度为80-100℃，干燥时间为1-2小时；为了使所述反应原料中的有效成分完全转变为氧化物，并除去碳等不可避免产生的杂质，所述焙烧的条件优选包括：在含氧气氛中进行，焙烧 温度为500-900℃，焙烧时间为1-2小时；更优选地，所述含氧气氛为空气。
根据本发明提供的前述催化剂的制备方法，为了使获得的催化剂中各组分充分发挥协同作用，具有更优异的催化性能，相对于100重量份的以三氧化二锰计的三氧化二锰前驱体、钨酸盐前驱体、具有钙钛矿结构和/或尖晶石结构的锰复合氧化物和载体的总用量，三氧化二锰前驱体以三氧化二锰计的用量为大于0重量份至小于等于20重量份，优选为1.5-18重量份；所述钨酸盐前驱体的用量为1-20重量份，优选为4-18重量份；所述具有钙钛矿结构和/或尖晶石结构的锰复合氧化物的用量为1-40重量份，优选为2-35重量份；所述载体的用量为20-98重量份，优选为29-90重量份。
在本发明提供的所述制备方法中，所述钨酸盐前驱体为水溶性盐，例如可以为钨酸钠、钨酸钾、钨酸铷中的至少一种及其结晶水合物。
在本发明提供的所述制备方法中，所述三氧化二锰前驱体为水溶性盐，例如可以为硝酸锰、醋酸锰、氯化锰、硫酸锰中的至少一种及其结晶水合物。
在本发明提供的所述制备方法中，所述溶剂只要可以将钨酸盐前驱体和三氧化二锰前驱体溶解即可，例如所述溶剂可以为水。优选地，所述溶剂的存在，使得所述钨酸盐前驱体的浓度为35-45重量％，使得所述三氧化二锰前驱体的浓度为45-55重量％。
在本发明提供的所述制备方法中，在所述具有钙钛矿结构和/或尖晶石结构的锰复合氧化物的组成中，所述具有钙钛矿结构和/或尖晶石结构的锰复合氧化物中含有钛、铁、钴、镍、锂、铅、镉、锡、铟、锗、镓、锑、铋、碲、硒、锆、铪、钒、铌、钽、铬、钼、钨、钡、镁、铈、镧、镨、钕、钐、钙、锶、钡、钾中的至少一种元素。
在本发明提供的所述制备方法中，所述具有钙钛矿结构和/或尖晶石结构的锰复合氧化物优选为钛酸锰、铁酸锰、钴酸锰、镍酸锰、锰酸锂、镍钴锰酸锂、铅酸锰、镉酸锰、锡酸锰、铟酸锰、锗酸锰、镓酸锰、锑酸锰、铋酸锰、碲酸锰、硒酸锰、锆酸锰、铪酸锰、钒酸锰、铌酸锰、钽酸锰、铬酸锰、钼酸锰、钨酸锰、锰酸钡、锰酸镁、锰酸铈、LnAFeMnO 6(Ln＝La，Pr，Nd，Sm，Ce；A＝Ca，Sr，Ba)、La 0.5Sr 0.5Mn 1-mFe mO 3、Ca αLa βK 1-α-βMn 0.5Fe 0.5O 3、Ca pLa qK 1-p-qMn 0.78Fe 0.22O 3、Bi 0.5Ca 0.5-nLa nFe 0.3Mn 0.7O 3中的至少一种，其中，0＜m≤0.25，例如，m可以为0.05、0.1、0.12、0.15、0.2、0.22、0.24、0.25，以及任意两个前述相邻数值之间的任意数值，优选0.1≤m≤0.22，0＜α≤0.25，例如，α可以为0.05、0.1、0.12、0.15、0.2、0.22、0.24、0.25，以及任意两个前述相邻数值之间的任意数值，优选0.1≤α≤0.2，0＜β≤0.25，例如，β可以为0.05、0.1、0.12、0.15、0.2、0.22、0.24、0.25，以及任意两个前述相邻数值之间的任意数值，优选0.1≤β≤0.2，0＜p≤0.25， 例如，p可以为0.05、0.1、0.12、0.15、0.2、0.22、0.24、0.25，以及任意两个前述相邻数值之间的任意数值，优选0.1≤p≤0.2，0＜q≤0.25，例如，q可以为0.05、0.1、0.12、0.15、0.2、0.22、0.24、0.25，以及任意两个前述相邻数值之间的任意数值，优选0.1≤q≤0.2，0＜n≤0.25，例如，n可以为0.05、0.1、0.12、0.15、0.2、0.22、0.24、0.25，以及任意两个前述相邻数值之间的任意数值，优选0.1≤n≤0.2。
在本发明提供的所述制备方法中，所述载体可以为各种不对催化剂造成不良影响的无机耐热氧化物和/或碳化物，包括但不限于SiC、Fe 2O 3、Fe 3O 4、TiO 2、ZrO 2、Al 2O 3、La 2O 3、CaO、SrO、MgO和SiO 2中的一种。由于SiO 2经济性好，且在甲烷氧化偶联催化反应条件下会发生转晶形成方石英，有益于提高所述催化剂的催化活性，因此，所述载体优选为SiO 2。
在本发明提供的所述制备方法中，所述载体的粒径优选为100-2000目，更优选为100-1000目，比表面积优选为10-1000m 2/g，更优选为50-250m 2/g，孔体积优选为0.1-1.2mL/g，更优选为0.5-0.9mL/g，最可几孔径优选为2.0-20nm，更优选为2.0-10.0nm，这样可以保障所述载体具有较高的比表面积并提供较多的活性位点，进而增强所述催化剂的催化性能。本发明中，所述比表面和孔体积是指BET氮吸附比表面和孔体积、最可几孔径采用BJH(Barrett-Joyner-Halenda)模型由吸附曲线计算得到。
在本发明提供的所述制备方法中，所述具有钙钛矿结构和/或尖晶石结构的锰复合氧化物的粒径为100-2000目，优选为100-1000目。
本发明第七方面还提供了由上述制备方法的具体实施方法得到的催化剂。
根据本发明提供的所述制备方法得到的催化剂，表示所述催化剂的组成通式可以为：xMn 2O 3-yR 2WO 4-zMn rM 1 s1M 2 s2…M n snO t-(100-x-y-z)Support，其中，R表示选自Na、K、Rb中的一种碱金属元素，Support表示载体，Mn rM 1 s1M 2 s2…M n snO t表示所述具有钙钛矿结构和/或尖晶石结构的锰复合氧化物的组成，各元素排列顺序不分先后，M 1、M 2、…M n表示所述具有钙钛矿结构和/或尖晶石结构的锰复合氧化物中除锰元素之外的其他各元素，且M 1、M 2、…M n选自钛、铁、钴、镍、锂、铅、镉、锡、铟、锗、镓、锑、铋、碲、硒、锆、铪、钒、铌、钽、铬、钼、钨、钡、镁、铈、镧、镨、钕、钐、钙、锶、钡、钾中的一种，在所述具有钙钛矿结构和/或尖晶石结构的锰复合氧化物的组成通式中，r代表锰原子的个数，s1、s2、…sn分别代表M 1、M 2、…M n各原子的个数，t代表氧原子的个数，且0＜r≤1，0≤s1≤1，0≤s2≤1，…，0≤sn≤1，1≤t≤6；x、y和z分别表示三氧化二锰、钨酸盐和具有钙钛矿结构和/或尖晶石结构的锰复合氧化物三 种组分在所述催化剂中所占的重量百分含量，在所述通式中，各组分之间的连接符号没有特别的含义，各活性组分之间的排列顺序不分先后，所述通式仅代表所述所述催化剂中含有重量百分含量分别为x、y、z以及(100-x-y-z)的三氧化二锰(Mn 2O 3)、钨酸盐(R 2WO 4)、具有钙钛矿结构和/或尖晶石结构的锰复合氧化物(Mn rM 1 s1M 2 s2…M n snO t)以及载体(Support)。由于催化剂的制备过程中形成的各组分不涉及损失的环节发生，因此，各组分的重量百分含量根据各组分的原料来源的投料量计算得到。
本发明第八方面还提供了一种前述催化剂或由前述制备方法得到的催化剂在甲烷氧化偶联催化反应的应用。
本发明第九方面还提供了一种甲烷氧化偶联的方法，所述方法包括：在甲烷氧化偶联反应条件下以及催化剂的存在下，使甲烷与氧气进行甲烷氧化偶联反应，其中，所述催化剂为前述催化剂或由前述制备方法得到的催化剂。
根据本发明提供的甲烷氧化偶联的方法，其中，甲烷和氧气的用量的体积比可以为3-8∶1，反应温度可以为620-900℃，例如620℃、630℃、640℃、650℃、660℃、670℃、680℃、690℃、700℃、720℃、750℃、780℃、800℃、820℃、850℃、880℃和900℃，以及以及任意两个前述相邻温度之间的任意温度，优选为620-800℃；反应压力可以为0.1-2MPa，优选为0.1-1MPa；以甲烷和氧气的总量计，气时空速可以为3000-50000mL·h -1·g -1，优选为4000-8500mL·h -1·g -1。
根据本发明，甲烷与氧气进行甲烷氧化偶联反应的过程中还可以含有惰性气体对甲烷和氧气组成的原料气进行稀释，避免所述甲烷氧化偶联反应过程升温过快，消除热效应，所述惰性气体可以为氮气或氩气，优选为氮气；更优选地，甲烷、氧气和所述惰性气体的用量的体积比可以为3-8∶1∶3.5-4.5。
根据本发明提供的甲烷氧化偶联的方法，其中，由于所述甲烷氧化偶联反应过程中使用的催化剂为本发明提供的前述催化剂或由本发明提供的前述制备方法得到的催化剂，可以有效降低甲烷氧化偶联过程中氧气分子活化温度，因此所述反应温度可以由传统的800-900℃的甲烷氧化偶联温度大幅下降至700℃以下，优选为620-700℃。
下面结合实施例和附图对本发明做进一步详细、完整地说明。
以下实验实施例和实验对比例中，钛酸锰的粒径为500目，铁酸锰的粒径为200目，钴酸锰的粒径为200目，Ca 0.2La 0.2K 0.6Mn 0.78Fe 0.22O 3的粒径为325目。
以下实验实施例和实验对比例中，载体为SiO 2，载体的粒径为200目，比表面积 为50-250m 2/g，孔体积为0.5-0.9mL/g，最可几孔径为2.0-10.0nm。
以下实验实施例和实验对比例中，X射线衍射分析在购自日本理学公司的型号为Rigaku Uitima IV的X射线衍射仪上进行；载体的孔结构参数分析在美国康塔公司生产的Autosorb-3B型吸附仪上进行；样品的比表面积和孔体积计算采用BET氮吸附方法测得；最可几孔径采用BJH(Barrett-Joyner-Halenda)模型由吸附曲线计算得到；催化剂的活性组分负载量在购自日本理学公司的型号为Rigaku Uitima IV的X射线衍射仪上，通过标准工作曲线法分析测定。
以下各应用例中，反应产物成分的分析在购自安捷伦公司型号为7820A的气相色谱仪上进行。
以下实验实施例和实验对比例中，超声分散使用购自于上海科导超声仪器有限公司的型号为SK-12C的超声仪进行，超声功率为400-500W，超声频率为25kHz。
以下实验实施例和实验对比例中，各物料的混合在室温下进行。
以下实验实施例和实验对比例中，甲烷转化率和产物选择性采用碳原子归一法进行计算，具体定义为：
转化率＝[1-尾气中甲烷浓度/(尾气中甲烷浓度+尾气中CO浓度+尾气中CO 2浓度+2×尾气中乙烯乙烷总浓度+3×尾气中丙烯丙烷总浓度)]×100％；
选择性＝[n×尾气中含碳产物的浓度/(尾气中CO浓度+尾气中CO 2浓度+2×尾气中乙烯乙烷总浓度+3×尾气中丙烯丙烷总浓度)]×100％，其中n为产物中含碳原子数。
实施例1
本实施例的目的是提供一种催化剂：3Mn 2O 3-10Na 2WO 4-10MnTiO 3-77SiO 2，其制备方法具体如下：
1)分别称取1.54克干燥的SiO 2粉末(粒径为200目，比表面积为200m 2/g，孔体积为0.9mL/g，最可几孔径为2nm)和0.2克钛酸锰粉末，充分研磨后移入100毫升烧杯中；再称取0.2克钨酸钠(Na 2WO 4·2H 2O)溶于5.0毫升去离子水中配成钨酸钠水溶液，然后滴加到干燥的钛酸锰与SiO 2的混合粉末中，控制滴加过程中，体系温度保持在10-30℃之间，超声分散1小时后继续搅拌3小时，得浆状粘稠物；
2)称取0.272克浓度为50重量％的硝酸锰水溶液，加去离子水稀释至5毫升；在搅拌下将所得硝酸锰水溶液滴加入到步骤1)所得浆状粘稠物中，控制滴加过程中，体系温度保持在10-30℃之间，继续搅拌3小时后，于100℃烘干；
3)将步骤2)制得的样品研磨成粉末，在空气氛中于550℃下焙烧2小时，即得本实施例催化剂。
图1为本实施例所制催化剂的X射线粉末衍射(XRD)图谱；由图1可见：所述催化剂中含有Mn 2O 3、Na 2WO 4和MnTiO 3三种物相。
实施例2
本实施例的目的是提供一种催化剂：5Mn 2O 3-5Na 2WO 4-8MnTiO 3-82SiO 2，其制备方法具体如下：
1)称取1.64克干燥的SiO 2粉末(粒径为200目，比表面积为235m 2/g，孔体积为0.8mL/g，最可几孔径为6nm)移入100毫升烧杯中；称取0.1克钨酸钠(Na 2WO 4·2H 2O)溶于5.0毫升去离子水中配成钨酸钠水溶液，然后滴加到干燥的SiO 2粉末中，控制滴加过程中，体系温度保持在10-30℃之间，超声分散0.6小时后继续搅拌2小时，得浆状粘稠物；
2)称取0.453克浓度为50重量％的硝酸锰水溶液，加去离子水稀释至5毫升；在搅拌下将所得硝酸锰水溶液滴加入到步骤1)所得浆状粘稠物中，控制滴加过程中，体系温度保持在10-30℃之间，继续搅拌1小时后，于90℃烘干；
3)将步骤2)制得的样品与0.16克钛酸锰粉末充分研磨后，在空气氛中于650℃下焙烧2小时，即得本实施例催化剂。
图2为本实施例所制催化剂的X射线粉末衍射(XRD)图谱；由图2可见：所述催化剂中含有Mn 2O 3、Na 2WO 4和MnTiO 3三种物相。
实施例3
本实施例的目的是提供一种催化剂：1.5Mn 2O 3-8Na 2WO 4-4MnTiO 3-86.5SiO 2，其制备方法具体如下：
1)分别称取1.73克干燥的SiO 2粉末(粒径为200目，比表面积为220m 2/g，孔体积为0.9mL/g，最可几孔径为7nm)和0.8克钛酸锰粉末移入100毫升烧杯中；称取0.16克钨酸钠(Na 2WO 4·2H 2O)溶于5.0毫升去离子水中配成钨酸钠水溶液，然后滴加到干燥的钛酸锰与SiO 2的混合粉末中，控制滴加过程中，体系温度保持在10-30℃之间，超声分散1小时后继续搅拌1小时，得浆状粘稠物；
2)称取0.136克浓度为50重量％的硝酸锰水溶液，加去离子水稀释至5毫升；在 搅拌下将所得硝酸锰水溶液滴加入到步骤1)所得浆状粘稠物中，控制滴加过程中，体系温度保持在10-30℃之间，继续搅拌2小时后，于80℃烘干；
3)将步骤2)制得的样品研磨成粉末，在空气氛中于500℃下焙烧1.5小时，即得本实施例催化剂。
经X射线粉末衍射分析得知，本实施例所制催化剂的X射线粉末衍射(XRD)图谱中含有Mn 2O 3、Na 2WO 4和MnTiO 3三种物相。
实施例4
本实施例的目的是提供一种催化剂：10Mn 2O 3-4Na 2WO 4-5MnTiO 3-83SiO 2，其制备方法具体如下：
1)分别称取1.66克干燥的SiO 2粉末(粒径为200目，比表面积为225m 2/g，孔体积为0.5mL/g，最可几孔径为10nm)和0.1克钛酸锰粉末移入100毫升烧杯中；称取0.08克钨酸钠(Na 2WO 4·2H 2O)溶于5.0毫升去离子水中配成钨酸钠水溶液，然后滴加到干燥的钛酸锰与SiO 2的混合粉末中，控制滴加过程中，体系温度保持在10-30℃之间，超声分散0.6小时后继续搅拌2.5小时，得浆状粘稠物；
2)称取0.906克浓度为50重量％的硝酸锰水溶液，加去离子水稀释至5毫升；在搅拌下将所得硝酸锰水溶液滴加入到步骤1)所得浆状粘稠物中，控制滴加过程中，体系温度保持在10-30℃之间，继续搅拌3小时后，于100℃烘干；
3)将步骤b)制得的样品研磨成粉末，在空气氛中于700℃下焙烧2小时，即得本实施例催化剂。
经X射线粉末衍射分析得知，本实施例所制催化剂的X射线粉末衍射(XRD)图谱中含有Mn 2O 3、Na 2WO 4和MnTiO 3三种物相。
实施例5
本实施例的目的是提供一种催化剂：15Mn 2O 3-12Na 2WO 4-20MnTiO 3-53SiO 2，其制备方法具体如下：
1)称取1.06克干燥的SiO 2粉末(粒径为200目，比表面积为210m 2/g，孔体积为0.6mL/g，最可几孔径为5.5nm)移入100毫升烧杯中；称取0.24克钨酸钠(Na 2WO 4·2H 2O)溶于5.0毫升去离子水中配成钨酸钠水溶液，然后滴加到SiO 2粉末中，控制滴加过程中，体系温度保持在10-30℃之间，超声分散0.7小时后继续搅拌2小时，得浆状粘稠混合 物；
2)称取1.360克浓度为50重量％的硝酸锰水溶液，加去离子水稀释至5毫升；在搅拌下将所得硝酸锰水溶液滴加入到步骤1)所得浆状粘稠混合物中，控制滴加过程中，体系温度保持在10-30℃之间，继续搅拌1.5小时后，于85℃烘干；
3)将步骤2)制得的样品与0.4克钛酸锰粉末充分研磨，在空气氛中于800℃下焙烧1小时，即得本实施例催化剂。
经X射线粉末衍射分析得知，本实施例所制催化剂的X射线粉末衍射(XRD)图谱中含有Mn 2O 3、Na 2WO 4和MnTiO 3三种物相。
实施例6
本实施例的目的是提供一种催化剂：18Mn 2O 3-15Na 2WO 4-15MnTiO 3-52SiO 2，其制备方法具体如下：
1)称取1.04克干燥的SiO 2粉末(粒径为200目，比表面积为205m 2/g，孔体积为0.75mL/g，最可几孔径为2.5nm)移入100毫升烧杯中；称取0.3克钨酸钠(Na 2WO 4·2H 2O)溶于5.0毫升去离子水中配成钨酸钠水溶液，然后滴加到SiO 2粉末中，控制滴加过程中，体系温度保持在10-30℃之间，超声分散0.9小时后继续搅拌2.5小时，得浆状粘稠物；
2)称取1.632克浓度为50重量％的硝酸锰水溶液，加去离子水稀释至5毫升；在搅拌下将所得硝酸锰水溶液滴加入到步骤1)所得浆状粘稠混合物中，控制滴加过程中，体系温度保持在10-30℃之间，继续搅拌1小时后，于100℃烘干；
3)将步骤2)制得的样品与0.3克钛酸锰粉末充分研磨，在空气氛中于800℃下焙烧2.5小时，即得本实施例催化剂。
经X射线粉末衍射分析得知，本实施例所制催化剂的X射线粉末衍射(XRD)图谱中含有Mn 2O 3、Na 2WO 4和MnTiO 3三种物相。
实施例7
本实施例的目的是提供一种催化剂：2Mn 2O 3-18Na 2WO 4-7MnTiO 3-73SiO 2，其制备方法具体如下：
1)分别称取1.46克干燥的SiO 2粉末(粒径为200目，比表面积为215m 2/g，孔体积为0.69mL/g，最可几孔径为4.5nm)和0.14克钛酸锰粉末，充分研磨后移入100毫升烧杯中；称取0.36克钨酸钠(Na 2WO 4·2H 2O)溶于5.0毫升去离子水中配成钨酸钠水溶液， 然后滴加到干燥的钛酸锰与SiO 2的混合粉末中，控制滴加过程中，体系温度保持在10-30℃之间，超声分散0.8小时后继续搅拌3小时，得浆状粘稠物；
2)称取0.181克浓度为50重量％的硝酸锰水溶液，加去离子水稀释至5毫升；在搅拌下将所得硝酸锰水溶液滴加入到步骤1)所得浆状粘稠物中，控制滴加过程中，体系温度保持在10-30℃之间，继续搅拌1.5小时后，于90℃烘干；
3)将步骤2)制得的样品研磨成粉末，在空气氛中于650℃下焙烧2小时，即得本实施例催化剂。
经X射线粉末衍射分析得知，本实施例所制催化剂的X射线粉末衍射(XRD)图谱中含有Mn 2O 3、Na 2WO 4和MnTiO 3三种物相。
实施例8
本实施例的目的是提供一种催化剂：12Mn 2O 3-10Na 2WO 4-2MnTiO 3-76SiO 2，其制备方法具体如下：
1)称取1.52克干燥的SiO 2粉末(粒径为200目，比表面积为212m 2/g，孔体积为0.7mL/g，最可几孔径为2.3nm)移入100毫升烧杯中；称取0.2克钨酸钠(Na 2WO 4·2H 2O)溶于5.0毫升去离子水中配成钨酸钠水溶液，然后滴加到SiO 2粉末中，控制滴加过程中，体系温度保持在10-30℃之间，超声分散0.9小时后继续搅拌1.5小时，得浆状粘稠物；
2)称取1.088克浓度为50重量％的硝酸锰水溶液，加去离子水稀释至5毫升；在搅拌下将所得硝酸锰水溶液滴加入到步骤1)所得浆状粘稠物中，控制滴加过程中，体系温度保持在10-30℃之间，继续搅拌2.5小时后，于85℃烘干；
3)将步骤b)制得的样品与0.04克钛酸锰粉末充分研磨，在空气氛中于900℃下焙烧2小时，即得本实施例催化剂。
经X射线粉末衍射分析得知，本实施例所制催化剂的X射线粉末衍射(XRD)图谱中含有Mn 2O 3、Na 2WO 4和MnTiO 3三种物相。
实施例9
本实施例的目的是提供一种催化剂：8Mn 2O 3-12Na 2WO 4-28MnTiO 3-52SiO 2，其制备方法具体如下：
1)分别称取1.24克干燥的SiO 2粉末(粒径为200目，比表面积为300m 2/g，孔体积为1.2mL/g，最可几孔径为12nm)和0.56克钛酸锰粉末，充分研磨后移入100毫升烧杯 中；称取0.24克钨酸钠(Na 2WO 4·2H 2O)溶于5.0毫升去离子水中配成钨酸钠水溶液，然后滴加到干燥的钛酸锰与SiO 2的混合粉末中，控制滴加过程中，体系温度保持在10-30℃之间，超声分散0.5小时后继续搅拌1.5小时，得浆状粘稠物；
2)称取0.725克浓度为50重量％的硝酸锰水溶液，加去离子水稀释至5毫升；在搅拌下将所得硝酸锰水溶液滴加入到步骤1)所得浆状粘稠物中，控制滴加过程中，体系温度保持在10-30℃之间，继续搅拌2小时后，于100℃烘干；
3)将步骤2)制得的样品研磨成粉末，在空气氛中于750℃下焙烧2小时，即得本实施例催化剂。
经X射线粉末衍射分析得知，本实施例所制催化剂的X射线粉末衍射(XRD)图谱中含有Mn 2O 3、Na 2WO 4和MnTiO 3三种物相。
实施例10
本实施例的目的是提供一种催化剂：18Mn 2O 3-18Na 2WO 4-35MnTiO 3-29SiO 2，其制备方法具体如下：
1)称取0.58克干燥的SiO 2粉末(粒径为200目，比表面积为245m 2/g，孔体积为0.6mL/g，最可几孔径为12nm)移入100毫升烧杯中；称取0.36克钨酸钠(Na 2WO 4·2H 2O)溶于5.0毫升去离子水中配成钨酸钠水溶液，然后滴加到SiO 2粉末中，控制滴加过程中，体系温度保持在10-30℃之间，超声分散0.6小时后继续搅拌2.5小时，得浆状粘稠物；
2)称取1.632克浓度为50重量％的硝酸锰水溶液，加去离子水稀释至5毫升；在搅拌下将所得硝酸锰水溶液滴加入到步骤1)所得浆状粘稠物中，控制滴加过程中，体系温度保持在10-30℃之间，继续搅拌2小时后，于95℃烘干；
3)将步骤2)制得的样品与0.7克钛酸锰粉末充分研磨，在空气氛中于850℃下焙烧2小时，即得本实施例催化剂。
经X射线粉末衍射分析得知，本实施例所制催化剂的X射线粉末衍射(XRD)图谱中含有Mn 2O 3、Na 2WO 4和MnTiO 3三种物相。
实施例11
本实施例的目的是提供一种催化剂：3Mn 2O 3-10Na 2WO 4-10MnFe 2O 4-77SiO 2，其制备方法具体如下：
1)分别称取1.54克干燥的SiO 2粉末(粒径为200目，比表面积为205m 2/g，孔体积 为1.1mL/g，最可几孔径为6.5nm)和0.2克铁酸锰粉末，充分研磨后移入100毫升烧杯中；再称取0.2克钨酸钠(Na 2WO 4·2H 2O)溶于5.0毫升去离子水中配成钨酸钠水溶液，然后滴加到干燥的铁酸锰与SiO 2的混合粉末中，控制滴加过程中，体系温度保持在10-30℃之间，超声分散1小时后继续搅拌3小时，得浆状粘稠物；
2)称取0.272克浓度为50重量％的硝酸锰水溶液，加去离子水稀释至5毫升；在搅拌下将所得硝酸锰水溶液滴加入到步骤1)所得浆状粘稠物中，控制滴加过程中，体系温度保持在10-30℃之间，继续搅拌3小时后，于100℃烘干；
3)将步骤2)制得的样品研磨成粉末，在空气氛中于550℃下焙烧2小时，即得本实施例催化剂。
经X射线粉末衍射分析得知，本实施例所制催化剂的X射线粉末衍射(XRD)图谱中含有Mn 2O 3、Na 2WO 4和MnFe 2O 4三种物相。
实施例12
本实施例的目的是提供一种催化剂：5Mn 2O 3-5Na 2WO 4-8MnCo 2O 4-82SiO 2，其制备方法具体如下：
1)称取1.64克干燥的SiO 2粉末(粒径为200目，比表面积为234m 2/g，孔体积为0.8mL/g，最可几孔径为5.5nm)移入100毫升烧杯中；称取0.1克钨酸钠(Na 2WO 4·2H 2O)溶于5.0毫升去离子水中配成钨酸钠水溶液，然后滴加到干燥的SiO 2粉末中，控制滴加过程中，体系温度保持在10-30℃之间，超声分散0.6小时后继续搅拌2小时，得浆状粘稠物；
2)称取0.453克浓度为50重量％的硝酸锰水溶液，加去离子水稀释至5毫升；在搅拌下将所得硝酸锰水溶液滴加入到步骤1)所得浆状粘稠物中，控制滴加过程中，体系温度保持在10-30℃之间，继续搅拌1小时后，于90℃烘干；
3)将步骤2)制得的样品与0.16克钴酸锰粉末充分研磨后，在空气氛中于650℃下焙烧2小时，即得本实施例催化剂。
经X射线粉末衍射分析得知，本实施例所制催化剂的X射线粉末衍射(XRD)图谱中含有Mn 2O 3、Na 2WO 4和MnCo 2O 4三种物相。
实施例13
本实施例的目的是提供一种催化剂：1.5Mn 2O 3-8K 2WO 4-4MnLi 2O 4-86.5SiO 2，其制 备方法具体如下：
1)分别称取1.73克干燥的SiO 2粉末(粒径为200目，比表面积为234m 2/g，孔体积为0.8mL/g，最可几孔径为5.5nm)和0.8克锰酸锂粉末移入100毫升烧杯中；称取0.16克钨酸钾(K 2WO 4·2H 2O)溶于5.0毫升去离子水中配成钨酸钾水溶液，然后滴加到干燥的锰酸锂与SiO 2的混合粉末中，控制滴加过程中，体系温度保持在10-30℃之间，超声分散1小时后继续搅拌1小时，得浆状粘稠物；
2)称取0.136克浓度为50重量％的醋酸锰水溶液，加去离子水稀释至5毫升；在搅拌下将所得醋酸锰水溶液滴加入到步骤1)所得浆状粘稠物中，控制滴加过程中，体系温度保持在10-30℃之间，继续搅拌2小时后，于80℃烘干；
3)将步骤2)制得的样品研磨成粉末，在空气氛中于500℃下焙烧1.5小时，即得本实施例催化剂。
经X射线粉末衍射分析得知，本实施例所制催化剂的X射线粉末衍射(XRD)图谱中含有Mn 2O 3、K 2WO 4和MnLi 2O 4三种物相。
实施例14
本实施例的目的是提供一种催化剂：3Mn 2O 3-10Na 2WO 4-10Ca 0.2La 0.2K 0.6Mn 0.78Fe 0.22O 3-77SiO 2，其制备方法具体如下：
1)分别称取1.54克干燥的SiO 2粉末(粒径为200目，比表面积为228m 2/g，孔体积为0.9mL/g，最可几孔径为7.5nm)和0.22克Ca 0.2La 0.2K 0.6Mn 0.78Fe 0.22O 3粉末(参照文献(Journal of Materials Science 2014，49：6883-6891)，采用溶胶-凝胶法得到)，充分研磨后移入100毫升烧杯中；再称取0.2克钨酸钠(Na 2WO 4·2H 2O)溶于5.0毫升去离子水中配成钨酸钠水溶液，然后滴加到干燥的Ca 0.2La 0.2K 0.6Mn 0.78Fe 0.22O 3与SiO 2的混合粉末中，控制滴加过程中，体系温度保持在10-30℃之间，超声分散1小时后继续搅拌3小时，得浆状粘稠物；
2)称取0.272克浓度为50重量％的硝酸锰水溶液，加去离子水稀释至5毫升；在搅拌下将所得硝酸锰水溶液滴加入到步骤1)所得浆状粘稠物中，控制滴加过程中，体系温度保持在10-30℃之间，继续搅拌3小时后，于100℃烘干；
3)将步骤2)制得的样品研磨成粉末，在空气氛中于550℃下焙烧2小时，即得本实施例催化剂。
经X射线粉末衍射分析得知，本实施例所制催化剂的X射线粉末衍射(XRD)图谱 中含有Mn 2O 3、Na 2WO 4和Ca 0.2La 0.2K 0.6Mn 0.78Fe 0.22O 3三种物相。
对比例1
本对比例的目的是提供一种催化剂：3Mn 2O 3-10Na 2WO 4-87SiO 2，按照实施例1的方法制备，不同的是，制备过程中未加入钛酸锰，其制备方法具体如下：
1)称取1.74克干燥的无定形SiO 2(粒径为200目，比表面积为200m 2/g，孔体积为0.9mL/g，最可几孔径为2nm)移入100毫升烧杯中；称取0.2克钨酸钠(Na 2WO 4·2H 2O)溶于5.0毫升去离子水中配成钨酸钠水溶液，然后滴加到无定形SiO 2中，超声分散1小时后继续搅拌3小时，得浆状粘稠物；
2)称取0.272克浓度为50重量％的硝酸锰水溶液，加去离子水稀释至2毫升；在搅拌下将所得硝酸锰水溶液滴加入到步骤1)所得浆状粘稠物中，控制滴加过程中，体系温度保持在10-30℃之间，继续搅拌3小时后，于100℃烘干；
3)将步骤2)制得的样品研磨成粉末，在空气氛中于550℃下焙烧2小时，即得本对比例催化剂。
对比例2
本对比例的目的是提供一种催化剂：3Mn 2O 3-10Na 2WO 4-87Sillicalite-1，按照实施例1的方法制备，不同的是，制备过程中未加入钛酸锰，且使用的载体为MFI型全硅分子筛Sillicalite-1载体，其制备方法具体如下：
1)称取1.74克干燥的MFI型全硅分子筛Sillicalite-1(粒径为1000目，比表面积为320m 2/g，孔体积为0.2mL/g)移入100毫升烧杯中；称取0.2克钨酸钠(Na 2WO 4·2H 2O)溶于5.0毫升去离子水中配成钨酸钠水溶液，然后滴加到干燥的MFI型全硅分子筛Sillicalite-1中，控制滴加过程中，体系温度保持在10-30℃之间，超声分散0.6小时后继续搅拌2小时，得浆状粘稠物；
2)称取0.272克浓度为50重量％的硝酸锰水溶液，加去离子水稀释至2毫升；在搅拌下将所得硝酸锰水溶液滴加入到步骤1)所得浆状粘稠物中，控制滴加过程中，体系温度保持在10-30℃之间，继续搅拌1小时后，于90℃烘干；
3)将步骤2)制得的样品研磨成粉末，在空气氛中于650℃下焙烧2小时，即得本对比例催化剂。
图3为对比例1和对比例2所制催化剂的X射线粉末衍射(XRD)图谱，由图3可 见：对比例1和对比例2所制催化剂的X射线粉末衍射(XRD)图谱中均只有Mn 2O 3和Na 2WO 4物相，均没有MnTiO 3物相。
对比例3
参照CN201410001437.7实施例2制备一种催化剂：4.2MnO 2·1.5Na 2O·5.5WO 3·2.9TiO 2·85.9SiO 2。
经X射线粉末衍射分析得知，本对比例所制催化剂的X射线粉末衍射(XRD)图谱具有与Ti-MWW分子筛相同的衍射峰，未观察到其他物相峰。
应用例1
催化剂反应评价在连续流固定床微反装置上进行。采用石英管反应器，内径16毫米、长400毫米。催化剂床层高度10毫米。催化剂无需前处理，直接加热到设定反应温度后切入反应混合气进行反应。反应尾气经冷冻的乙醇-水浴(30％乙醇)对可凝产物进行冷凝分离后，采用在线气相色谱仪进行定量检测。N 2、O 2、CO、CO 2、CH 4、C 2-C 3采用5A毛细管柱和PQ填充柱(DIKMA)并联和TCD检测器进行定量分析。
本应用例的目的是考察实施例和对比例催化剂在不同反应温度下的甲烷氧化偶联反应性能。采用体积比为CH 4∶O 2∶N 2＝5∶1∶4(CH 4浓度：50％)的原料气，以CH 4和O 2计，气时空速GHSV＝8000mL·h -1·g -1、常压和反应温度为620-700℃条件下进行反应评价。还在750℃、保持其他条件不变时，测试了对比例3催化剂的催化性能。
有关实施例催化剂和对比例催化剂在甲烷氧化偶联反应中的催化效果分别见表1所示。
表1
Figure PCTCN2018078709-appb-000006
Figure PCTCN2018078709-appb-000007
由表1实验结果可见：本发明提供的甲烷氧化偶联催化剂，因活性组分中含有具有钙钛矿结构和/或尖晶石结构的锰复合氧化物物相，因而体现出出乎意料的低温活性和选择性，使甲烷氧化偶联制烯烃反应在620-700℃的较低温度和常压下就可实现高达27％的甲烷转化率和76％的C 2-C 3烃类选择性；而对比例提供的催化剂在低于700℃时几乎不具有活性，更谈不上选择性。说明本发明相对于现有技术，取得了显著性进步和出乎意料的效果。
图4为实施例1所制备的3Mn 2O 3-10Na 2WO 4-10MnTiO 3-77SiO 2催化剂和对比例1所制备的3Mn 2O 3-10Na 2WO 4-87SiO 2催化剂分别在甲烷氧化偶联反应中于不同温度下的甲烷转化率和C 2-C 3烃类选择性的关系曲线；图5为实施例2所制备的5Mn 2O 3-5Na 2WO 4-8MnTiO 3-82SiO 2催化剂和对比例2所制备的3Mn 2O 3-10Na 2WO 4-87Sillicalite-1催化剂在甲烷氧化偶联反应中于不同温度下的甲烷转化率和C 2-C 3烃类选择性的关系曲线。结合图4和图5可见：本发明催化剂相较于传统催化剂，具有良好的低温活性和选择性，相对于现有技术取得了显著性进步。
应用例2
催化剂反应评价和产物分析系统同应用例1。
本应用例的目的是考察实施例催化剂在甲烷氧化偶联反应中的稳定性。采用体积比为CH 4∶O 2∶N 2＝5∶1∶4(CH 4浓度：50％)的原料气，在以CH 4和O 2计的气时空速GHSV＝8000mL·h -1·g -1、常压和反应温度650℃条件下进行300小时的反应稳定性测试，选用实施例1制备的3Mn 2O 3-10Na 2WO 4-10MnTiO 3-77SiO 2催化剂，用量0.8克。反应结果见图6所示。由图6可以看出，本发明催化剂具有良好的反应稳定性，在300小时稳定性测试中，转化率始终保持在24％左右，选择性保持在67％左右。
最后需要指出的是：以上仅是本发明的部分优选实施例，不能理解为对本发明保护范围的限制，本领域的技术人员根据本发明的上述内容做出的一些非本质的改进和调整均属于本发明的保护范围。

Claims (23)

  1. 一种甲烷氧化偶联催化剂，其特征在于，所述甲烷氧化偶联催化剂是由三氧化二锰、钨酸钠和钛酸锰三种活性组分与二氧化硅载体组成，具有如下通式：xMn 2O 3-yNa 2WO 4-zMnTiO 3-(100-x-y-z)SiO 2，其中：x、y和z分别表示三氧化二锰、钨酸钠和钛酸锰在所述催化剂中所占的质量分数，且0＜x≤20，1≤y≤20，1≤z≤40。
  2. 根据权利要求1所述的甲烷氧化偶联催化剂，其中，在所述通式中，1.5≤x≤18，4≤y≤18，2≤z≤35。
  3. 一种甲烷氧化偶联催化剂的制备方法，其特征在于，该制备方法包括如下步骤：
    a)将钛酸锰与二氧化硅充分研磨，形成均匀粉状混合物；
    b)室温下，将钨酸钠水溶液滴加到步骤a)得到的钛酸锰与二氧化硅的粉状混合物中，然后超声分散0.5-1小时之后再搅拌1-3小时，得浆状粘稠物；
    c)室温搅拌下，将硝酸锰水溶液滴加到步骤b)制得的浆状粘稠物中，继续搅拌1-3小时，然后在80-100℃下烘干；
    d)将步骤c)制得的烘干物研磨成粉末，在空气氛中于500-900℃焙烧1-2小时。
  4. 一种甲烷氧化偶联催化剂的制备方法，其特征在于，该制备方法包括如下步骤：
    A)室温下，将钨酸钠水溶液滴加到二氧化硅中，超声分散0.5-1小时之后再搅拌1-3小时，得浆状粘稠物；
    B)室温搅拌下，将硝酸锰水溶液滴加到步骤A)制得的浆状粘稠物中，继续搅拌1-3小时，然后在80-100℃下烘干；
    C)将步骤B)制得的烘干物与钛酸锰充分研磨成均匀粉末，然后在空气氛中于500-900℃焙烧1-2小时。
  5. 一种催化剂，其特征在于，所述催化剂的组成包括：三氧化二锰、钨酸盐、具有钙钛矿结构和/或尖晶石结构的锰复合氧化物和载体，其中，所述三氧化二锰和钨酸盐负载在载体上，或者，所述三氧化二锰和钨酸盐负载在所述具有钙钛矿结构和/或尖晶石结构的锰复合氧化物和所述载体上，在所述催化剂中，以100重量份的所述催化剂的重量为基准，所述三氧化二锰的含量为a重量份，所述钨酸盐的含量为b重量份，所述具 有钙钛矿结构和/或尖晶石结构的锰复合氧化物的含量为c重量份，所述载体的含量为d重量份，且0＜a≤20，1≤b≤20，1≤c≤40，20≤d＜98。
  6. 根据权利要求5所述的催化剂，其中，所述催化剂由三氧化二锰、钨酸盐、具有钙钛矿结构和/或尖晶石结构的锰复合氧化物和载体组成，在所述催化剂中，以100重量份的所述催化剂的重量为基准，所述三氧化二锰的含量为大于0重量份至小于等于20重量份，优选为1.5-18重量份；所述钨酸盐的含量为1-20重量份，优选为4-18重量份；所述具有钙钛矿结构和/或尖晶石结构的锰复合氧化物的含量为1-40重量份，优选为2-35重量份，余量为所述载体。
  7. 根据权利要求5或6所述的催化剂，其中，所述具有钙钛矿结构和/或尖晶石结构的锰复合氧化物中含有钛、铁、钴、镍、锂、铅、镉、锡、铟、锗、镓、锑、铋、碲、硒、锆、铪、钒、铌、钽、铬、钼、钨、钡、镁、铈、镧、镨、钕、钐、钙、锶、钡、钾中的至少一种元素。
  8. 根据权利要求5-7中任意一项所述的催化剂，其中，所述具有钙钛矿结构和/或尖晶石结构的锰复合氧化物为钛酸锰、铁酸锰、钴酸锰、镍酸锰、锰酸锂、镍钴锰酸锂、铅酸锰、镉酸锰、锡酸锰、铟酸锰、锗酸锰、镓酸锰、锑酸锰、铋酸锰、碲酸锰、硒酸锰、锆酸锰、铪酸锰、钒酸锰、铌酸锰、钽酸锰、铬酸锰、钼酸锰、钨酸锰、锰酸钡、锰酸镁、锰酸铈、LnAFeMnO 6(Ln＝La，Pr，Nd，Sm，Ce；A＝Ca，Sr，Ba)、La 0.5Sr 0.5Mn 1-mFe mO 3、Ca αLa βK 1-α-βMn 0.5Fe 0.5O 3、Ca pLa qK 1-p-qMn 0.78Fe 0.22O 3、Bi 0.5Ca 0.5-nLa nFe 0.3Mn 0.7O 3中的至少一种，其中，0＜m≤0.25，0＜α≤0.25，0＜β≤0.25，0＜p≤0.25，0＜q≤0.25，0＜n≤0.25；
    优选地，所述具有钙钛矿结构和/或尖晶石结构的锰复合氧化物的粒径为100-2000目，优选为100-1000目。
  9. 根据权利要求5-8中任意一项所述的催化剂，其中，所述载体为SiC、Fe 2O 3、Fe 3O 4、TiO 2、ZrO 2、Al 2O 3、La 2O 3、CaO、SrO、MgO和SiO 2中的至少一种，优选为SiO 2；
    优选地，所述载体的粒径为100-2000目，优选为100-1000目，比表面积为 10-1000m 2/g，优选为50-250m 2/g，孔体积为0.1-1.2mL/g，优选为0.5-0.9mL/g，最可几孔径为2.0-20.0nm，优选为2.0-10.0nm。
  10. 一种催化剂的制备方法，其特征在于，该制备方法包括如下步骤：
    1)将具有钙钛矿结构和/或尖晶石结构的锰复合氧化物与载体进行固相混合，得到固相混合物A；
    2)将步骤1)得到的固相混合物A与钨酸盐前驱体和三氧化二锰前驱体在溶剂存在下进行混合，得到混合产物B；
    3)将步骤2)得到的混合产物B依次进行干燥和焙烧。
  11. 一种催化剂的制备方法，其特征在于，该制备方法包括如下步骤：
    i)将钨酸盐前驱体和三氧化二锰前驱体与载体在溶剂存在下混合，得到混合物X；
    ii)将步骤i)得到的混合物X进行干燥，得到干燥产物Y；
    iii)将步骤ii)得到的干燥产物Y与具有钙钛矿结构和/或尖晶石结构的锰复合氧化物进行固相混合后焙烧。
  12. 根据权利要求10或11所述的制备方法，其中，所述固相混合在研磨条件下进行，使得研磨后的物料的粒径为200-2000目，优选为200-1000目。
  13. 根据权利要求10或11所述的制备方法，其中，所述在溶剂存在下的混合为分步浸渍混合或超声搅拌混合；优选为超声搅拌混合，更优选地，所述超声搅拌混合的方式包括依次在超声波和搅拌条件下进行混合，所述超声波的功率为400-2500W，频率为20-60kHz，在超声波下进行混合的时间为0.5-1小时，在搅拌条件下进行混合的时间为1-3小时。
  14. 根据权利要求10或11所述的制备方法，其中，所述溶剂为水，所述钨酸盐前驱体和三氧化二锰前驱体为水溶性盐。
  15. 根据权利要求10或11所述的制备方法，其中，所述干燥的条件包括：干燥温度为80-100℃，干燥时间为1-2小时；所述焙烧的条件包括：在含氧气氛中进行，焙烧温度为500-900℃，焙烧时间为1-2小时。
  16. 根据权利要求10-15中任意一项所述的制备方法，其中，分别以三氧化二锰、钨酸盐、具有钙钛矿结构和/或尖晶石结构的锰复合氧化物和载体计，相对于100重量份的三氧化二锰前驱体、钨酸盐前驱体、具有钙钛矿结构和/或尖晶石结构的锰复合氧化物和载体的总用量，三氧化二锰前驱体的用量为大于0重量份至小于等于20重量份，优选为1.5-18重量份；所述钨酸盐前驱体的用量为1-20重量份，优选为4-18重量份；所述具有钙钛矿结构和/或尖晶石结构的锰复合氧化物的用量为1-40重量份，优选为2-35重量份；所述载体的用量为20-98重量份，优选为29-90重量份。
  17. 根据权利要求10-16中任意一项所述的制备方法，其中，所述具有钙钛矿结构和/或尖晶石结构的锰复合氧化物中含有钛、铁、钴、镍、锂、铅、镉、锡、铟、锗、镓、锑、铋、碲、硒、锆、铪、钒、铌、钽、铬、钼、钨、钡、镁、铈、镧、镨、钕、钐、钙、锶、钡、钾中的至少一种元素。
  18. 根据权利要求17所述的制备方法，其中，所述具有钙钛矿结构和/或尖晶石结构的锰复合氧化物为钛酸锰、铁酸锰、钴酸锰、镍酸锰、锰酸锂、镍钴锰酸锂、铅酸锰、镉酸锰、锡酸锰、铟酸锰、锗酸锰、镓酸锰、锑酸锰、铋酸锰、碲酸锰、硒酸锰、锆酸锰、铪酸锰、钒酸锰、铌酸锰、钽酸锰、铬酸锰、钼酸锰、钨酸锰、锰酸钡、锰酸镁、锰酸铈、LnAFeMnO 6(Ln＝La，Pr，Nd，Sm，Ce；A＝Ca，Sr，Ba)、La 0.5Sr 0.5Mn 1-mFe mO 3、Ca αLa βK 1-α-βMn 0.5Fe 0.5O 3、Ca pLa qK 1-p-qMn 0.78Fe 0.22O 3、Bi 0.5Ca 0.5-nLa nFe 0.3Mn 0.7O 3中的至少一种，其中，0＜m≤0.25，0＜α≤0.25，0＜β≤0.25，0＜p≤0.25，0＜q≤0.25，0＜n≤0.25；
    优选地，所述具有钙钛矿结构和/或尖晶石结构的锰复合氧化物的粒径为100-2000目，优选为100-1000目。
  19. 根据权利要求10-18中任意一项所述的制备方法，其中，载体为SiC、Fe 2O 3、Fe 3O 4、TiO 2、ZrO 2、Al 2O 3、La 2O 3、CaO、SrO、MgO和SiO 2中的至少一种，优选为SiO 2；
    优选地，所述载体的粒径为100-2000目，优选为100-1000目，比表面积为10-1000m 2/g，优选为50-250m 2/g，孔体积为0.1-1.2mL/g，优选为0.5-0.9mL/g，最可几孔径为2.0-20.0nm，优选为2.0-10.0nm。
  20. 由权利要求3、4和10-19中任意一项所述的制备方法得到的催化剂。
  21. 一种权利要求1-2、5-9和20中任意一项所述的催化剂在甲烷氧化偶联催化反应的应用。
  22. 一种甲烷氧化偶联的方法，所述方法包括：在甲烷氧化偶联反应条件下以及催化剂的存在下，使甲烷与氧气进行甲烷氧化偶联反应，其特征在于，所述催化剂为权利要求1-2、5-9和20中任意一项所述的催化剂。
  23. 根据权利要求22所述的方法，其中，所述甲烷和氧气的用量的体积比为3-8∶1，反应温度为620-900℃，优选为620-800℃；反应压力为0.1-2MPa，优选为0.1-1MPa；以甲烷和氧气的总量计，气时空速为3000-50000mL·h -1·g -1，优选为4000-8500mL·h -1·g -1。
PCT/CN2018/078709 2017-03-13 2018-03-12 一种甲烷氧化偶联催化剂及其制备方法和应用 Ceased WO2018166419A1 (zh)

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