WO2015101345A1 - Oxidative coupling of methane catalyst and preparation method for same - Google Patents

Oxidative coupling of methane catalyst and preparation method for same Download PDF

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WO2015101345A1
WO2015101345A1 PCT/CN2015/000003 CN2015000003W WO2015101345A1 WO 2015101345 A1 WO2015101345 A1 WO 2015101345A1 CN 2015000003 W CN2015000003 W CN 2015000003W WO 2015101345 A1 WO2015101345 A1 WO 2015101345A1
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manganese
catalyst
sodium
oxide
titanium
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PCT/CN2015/000003
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French (fr)
Chinese (zh)
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路勇
王郁
王鹏伟
何鸣元
徐彬
周晓莹
萧锦诚
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易高环保能源研究院有限公司
华东师范大学
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    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
    • B01J29/0358—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C07C2521/08—Silica
    • 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
    • C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
    • C07C2523/04—Alkali metals
    • 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
    • C07C2523/24—Chromium, molybdenum or tungsten
    • C07C2523/30—Tungsten
    • 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

Definitions

  • the invention relates to a catalyst and a preparation method thereof, in particular to a manganese-sodium-tungsten-silicon composite oxide methane oxidative coupling catalyst containing titanium or not containing titanium and a preparation method thereof.
  • Methane and olefins are important chemical raw materials.
  • processes for the preparation of olefins from methane in the industry such as Benson process, partial oxidation process and catalytic pyrolysis process (Liaoning Chemical Industry 1 (1985) 11) .
  • Benson process the presence of by-product chlorinated hydrocarbons, poses certain difficulties for separation; catalytic pyrolysis produces a large amount of carbon deposits, which seriously affects the stability and service life of the catalyst.
  • methane coupling catalysts Many existing methods use methane coupling catalysts. Therefore, the development of a highly active, highly selective, and stable methane coupling catalyst is of great significance for the development of a low-cost, low-energy methane to olefins process.
  • the catalysts for the oxidative coupling of methane are mainly classified into three types: alkali metal and alkaline earth metal oxides, rare earth metal oxides, and transition metal composite oxides. These catalyst systems were basically developed in the 1990s.
  • the main problem is that the product selectivity is low (generally not higher than 70%) at higher methane conversion rates (>30%), making it difficult to meet economics. Requirements.
  • Alkaline earth metal itself has the catalytic activity of methane oxidative coupling.
  • Alkali metal modification causes lattice distortion of alkaline earth metal, increases active center and reduces surface area, thereby preventing deep oxidation of CH 4 and improving catalyst selectivity.
  • the most active methane oxidative coupling catalysts mostly contain alkali metals, of which Na and Li are the most, and the alkaline earth metal catalysts have the most Mg, Ca and Sr. Such catalysts not only have lower product yields, but also the alkali metal is easily lost resulting in deactivation of the catalyst.
  • Cispray CN1068052A discloses a catalyst comprising an alkaline earth or a rare earth metal fluoride as a main component, a small amount of alkaline earth or rare earth metal oxide or ThO 2 , ZrO 2 , etc., according to the disclosure of the literature, the catalyst application of the document In the methane oxidative coupling reaction, a methane conversion rate of 27 to 34% can be obtained, but the yield of the C 2 + hydrocarbon product is also only 13 to 20%.
  • Cipheral Patent Publication CN 1072615A discloses M 1 OM 2 CO 3 (M 1 , Mg, Sr, Ba; M 2 selected Ca, Sr, Ba) prepared from alkaline earth metal oxides and alkaline earth metal carbonates. Catalyst, according to the disclosure of this document, the catalyst of this document has a maximum methane conversion of 23.9% and a maximum product yield of 17.3%.
  • Rare earth metals have higher catalytic activity and selectivity for oxidative coupling of methane, such as La 2 O 3 , Pr 2 O 3 , Sm 2 O 3 , C e O 2 , YbO.
  • the rare earth catalyst exhibits better catalytic activity and selectivity after being modified with an alkali metal or an alkaline earth metal, and thus has received extensive attention.
  • the activity of the Sm 2 O 3 series catalyst is prominent, and the catalytic activity is further improved after being modified by an alkali metal halide such as LiCl.
  • the transition metal composite oxides for methane oxygen coupling mainly include: Mn, Pb, Zn, Ti, Cr, Fe, Co, Ni, and the like. Although the transition metal oxide has a good activity for the methane oxygen coupling reaction, the reaction selectivity is poor, so its use alone is limited. After modification by alkali metal, alkaline earth metal or halide, the catalytic activity of methane oxidative coupling is greatly improved.
  • Cipheral Patent Publication No. CN 1389293 A discloses a catalyst of SiO 2 supporting Mn 2 O 3 , Na 2 WO 4 and SnO 2 , which can obtain a maximum conversion of methane of 33% and 24% under pressure (0.6 MPa). C 2 + yield.
  • the reaction system needs to be pressurized, which increases the risk of explosion and has potential safety hazards.
  • the object of the present invention is to provide a manganese-sodium-tungsten-silicon composite oxide methane containing titanium or titanium containing no low temperature activity, high selectivity and good reaction stability. Oxidative coupling catalyst and preparation method thereof.
  • An aspect of the present invention provides a manganese-sodium-tungsten-silicon composite oxide catalyst containing or not containing titanium, which has the following formula: vMnO 2 ⁇ xNa 2 O ⁇ yWO 3 ⁇ zTiO 2 ⁇ (100-vxyz) SiO 2 , wherein v, x, y, z represent the mass fraction of metal manganese oxide, sodium oxide, tungsten oxide and titanium oxide, respectively, 0.3 ⁇ v ⁇ 16, 0.1 ⁇ x ⁇ 5, 0.6 ⁇ y ⁇ 21, 0.0 ⁇ z ⁇ 4.
  • the catalyst of the invention can be prepared by loading manganese nitrate (or manganese chloride, manganese acetate, manganese sulfate), sodium tungstate and ammonium tungstate on a titanium silica molecular sieve or a pure silicon molecular sieve by a stepwise impregnation method and calcining.
  • the molecular sieve may be, for example, Ti-MWW, TS-1, Ti-Beta, Silicalite-1, Silicalite-2.
  • the preparation method of the foregoing catalyst mainly comprises the following steps:
  • step b) adding manganese nitrate, manganese chloride, manganese acetate or manganese sulfate aqueous solution to the mixture prepared in step a) dropwise after stirring at room temperature, stirring for 1-3 hours, drying at 80-100 ° C, drying Object
  • step b) The dried product obtained in the step b) is ground into a powder, and calcined at 550 to 800 ° C for 1 to 2 hours in an air atmosphere to obtain the catalyst.
  • a further aspect of the invention is a process for the catalytic coupling of methane (e.g., ethylene, ethane, and propylene) to methane, wherein the reaction temperature is 650 to 800 ° C, and the methane/oxygen volume ratio in the feed gas is 2.5. ⁇ 6, the volume concentration of methane in the raw material gas is 35 to 75%, and the reaction gas has a space velocity of 10,000 to 60000 mL ⁇ g -1 ⁇ h -1 in terms of methane and oxygen.
  • methane e.g., ethylene, ethane, and propylene
  • the catalyst of the invention has the advantages of good low temperature activity, high selectivity, good reaction stability, thermal stability and high chemical stability.
  • the methane conversion rate can reach 30% at a wide gas hourly space velocity of 10,000 to 35,000 mL ⁇ g -1 ⁇ h -1 at 750-800 °C.
  • the selectivity of C2-C3 product can reach 72-81%; when the gas hourly space velocity is 30,000 ⁇ 35000mL ⁇ g -1 ⁇ h -1 , the space-time yield of C2-C3 product can be as high as 140mol ⁇ kg -1 ⁇ h -1 the above.
  • the catalyst of the present invention has significantly better methane oxidative coupling reaction performance than the existing catalyst technology, and its superiority is particularly reflected in the high ethylene/ethane ratio (>2) and apparent propylene formation (selectivity) in the C2 product. Up to 9% or so).
  • Example 1 is an X-ray powder diffraction pattern of a 2.8MnO 2 ⁇ 1.0Na 2 O ⁇ 3.6WO 3 ⁇ 3.0TiO 2 ⁇ 89.6SiO 2 catalyst prepared in Example 1 and a carrier molecular sieve used.
  • Example 2 is an X-ray powder diffraction pattern of a 4.2MnO 2 ⁇ 1.5Na 2 O ⁇ 5.5WO 3 ⁇ 2.9TiO 2 ⁇ 85.9SiO 2 catalyst prepared in Example 2 and a carrier molecular sieve used.
  • Example 3 is an X-ray powder diffraction pattern of a 6.5MnO 2 ⁇ 2.3Na 2 O ⁇ 8.6WO 3 ⁇ 2.7TiO 2 ⁇ 79.9SiO 2 catalyst prepared in Example 3 and a carrier molecular sieve used.
  • Example 4 is an X-ray powder diffraction pattern of a 0.4MnO 2 ⁇ 4.4Na 2 O ⁇ 16.4 WO 3 ⁇ 2.5TiO 2 ⁇ 76.3SiO 2 catalyst prepared in Example 6 and a carrier molecular sieve used.
  • Figure 5 is an X-ray powder diffraction pattern of a 2.8MnO 2 ⁇ 1.0Na 2 O ⁇ 3.2 WO 3 ⁇ 3.9TiO 2 ⁇ 89.1SiO 2 catalyst prepared in Example 8 and a carrier molecular sieve used.
  • Figure 6 is an X-ray powder diffraction pattern of a 2.8MnO 2 ⁇ 1.0Na 2 O ⁇ 3.6WO 3 ⁇ 1.1TiO 2 ⁇ 91.5SiO 2 catalyst prepared in Example 9 and a carrier molecular sieve used.
  • Figure 7 is an X-ray powder diffraction pattern of a 2.8MnO 2 ⁇ 1.0Na 2 O ⁇ 3.6WO 3 ⁇ 3.0TiO 2 ⁇ 89.6SiO 2 catalyst prepared in Example 12 and a carrier molecular sieve used.
  • Figure 8 is an X-ray powder diffraction pattern of a 15.8MnO 2 ⁇ 3.3Na 2 O ⁇ 13.9 WO 3 ⁇ 2.2TiO 2 ⁇ 64.8SiO 2 catalyst prepared in Example 14 and a carrier molecular sieve used.
  • Figure 9 is an X-ray powder diffraction pattern of a 0.5MnO 2 ⁇ 0.2Na 2 O ⁇ 0.7 WO 3 ⁇ 3.2TiO 2 ⁇ 95.4SiO 2 catalyst prepared in Example 15 and a carrier molecular sieve used.
  • Figure 10 is an X-ray powder diffraction pattern of a 2.8MnO 2 ⁇ 0.1Na 2 O ⁇ 3.6 WO 3 ⁇ 3.0TiO 2 ⁇ 90.5SiO 2 catalyst prepared in Example 16 and a carrier molecular sieve used.
  • Figure 11 is a graph showing the effect of methane oxidative coupling reaction temperature and gas hourly space velocity on methane conversion rate on a 2.8MnO 2 ⁇ 1.0Na 2 O ⁇ 3.6WO 3 ⁇ 3.0TiO 2 ⁇ 89.6SiO 2 catalyst prepared in Example 1.
  • Figure 12 is a graph showing the effect of methane oxidative coupling reaction temperature and gas hourly space velocity on product selectivity on a 2.8MnO 2 ⁇ 1.0Na 2 O ⁇ 3.6WO 3 ⁇ 3.0TiO 2 ⁇ 89.6SiO 2 catalyst prepared in Example 1.
  • Figure 13 is a graph showing the results of 100 hours stability test of methane oxidative coupling reaction on a 2.8MnO 2 ⁇ 1.0Na 2 O ⁇ 3.6WO 3 ⁇ 3.0TiO 2 ⁇ 89.6SiO 2 catalyst prepared in Example 1.
  • methane conversion, product selectivity and space time yield are calculated by carbon atom normalization and are defined as:
  • Space time yield (airspeed x methane concentration in the feed) / (gas molar volume in this state x methane conversion x (total ethylene ethylene selectivity in the tail gas / propylene selectivity / 3 in the exhaust gas) /).
  • the purpose of this example was to provide a preparation of a 2.8MnO 2 ⁇ 1.0Na 2 O ⁇ 3.6WO 3 ⁇ 3.0TiO 2 ⁇ 89.6SiO 2 catalyst.
  • XRD X-ray powder diffraction
  • the purpose of this example was to provide a preparation of a catalyst of 4.2MnO 2 ⁇ 1.5Na 2 O ⁇ 5.5WO 3 ⁇ 2.9TiO 2 ⁇ 85.9SiO 2 .
  • XRD X-ray powder diffraction
  • the purpose of this example was to provide a preparation of a 6.5MnO 2 ⁇ 2.3Na 2 O ⁇ 8.6WO 3 ⁇ 2.7TiO 2 ⁇ 79.9SiO 2 catalyst.
  • XRD X-ray powder diffraction
  • the purpose of this example is to provide a preparation of a 3.0MnO 2 ⁇ 0.4Na 2 O ⁇ 1.4 WO 3 ⁇ 3.1TiO 2 -92.1SiO 2 catalyst.
  • the purpose of this example was to provide a preparation of a 8.6MnO 2 ⁇ 3.0Na 2 O ⁇ 11.2 WO 3 ⁇ 2.5TiO 2 ⁇ 74.7SiO 2 catalyst.
  • the purpose of this example was to provide a preparation of a 0.4MnO 2 ⁇ 4.4Na 2 O ⁇ 16.4 WO 3 ⁇ 2.5TiO 2 ⁇ 76.3SiO 2 catalyst.
  • Figure 4 is an X-ray powder diffraction (XRD) pattern of the catalyst prepared in the present example and the supported molecular sieve used; it can be seen from the figure that the catalyst has the same diffraction peak as the Ti-MWW molecular sieve, and no other phase peaks are observed, indicating that the load is The active component is highly dispersed on the surface of the carrier molecular sieve.
  • XRD X-ray powder diffraction
  • the purpose of this example was to provide a preparation of a 2.8MnO 2 ⁇ 1.0Na 2 O ⁇ 3.6WO 3 ⁇ 0.4TiO 2 ⁇ 92.2SiO 2 catalyst.
  • the purpose of this example was to provide a preparation of a 2.8MnO 2 ⁇ 1.0Na 2 O.3.2WO 3 ⁇ 3.9TiO 2 ⁇ 89.1 SiO 2 catalyst.
  • Figure 5 is an X-ray powder diffraction (XRD) pattern of the catalyst prepared in the present example and the supported molecular sieve used; it can be seen from the figure that the catalyst has the same diffraction peak as the Ti-MWW molecular sieve, and no other phase peaks are observed, indicating that the load is The active component is highly dispersed on the surface of the carrier molecular sieve.
  • XRD X-ray powder diffraction
  • the purpose of this example was to provide a preparation of a 2.8MnO 2 ⁇ 1.0Na 2 O ⁇ 3.6WO 3 ⁇ 1.1TiO 2 ⁇ 91.5SiO 2 catalyst.
  • Figure 6 is an X-ray powder diffraction (XRD) pattern of the catalyst prepared in the present example and the carrier molecular sieve used; it can be seen from the figure that the catalyst has the same diffraction peak as the Ti-MWW molecular sieve, and no other phase peaks are observed, indicating that the load is The active component is highly dispersed on the surface of the carrier molecular sieve.
  • XRD X-ray powder diffraction
  • the purpose of this example was to provide a preparation of a 2.8MnO 2 ⁇ 1.0Na 2 O ⁇ 3.6 WO 3 ⁇ 92.6SiO 2 catalyst.
  • step b) Weigh 0.104 g of manganese sulfate, dilute to 2 ml with deionized water; add the obtained aqueous manganese nitrate solution dropwise to the slurry viscous mixture obtained in step a) with stirring, continue stirring for 3 hours, at 90 ° C drying;
  • the purpose of this example was to provide a preparation of a 2.8MnO 2 ⁇ 1.0Na 2 O ⁇ 3.6 WO 3 ⁇ 92.6SiO 2 catalyst.
  • the purpose of this example was to provide a preparation of a 2.8MnO 2 ⁇ 1.0Na 2 O ⁇ 3.6WO 3 ⁇ 3.0TiO 2 ⁇ 89.6SiO 2 catalyst.
  • Figure 7 is an X-ray powder diffraction (XRD) pattern of the catalyst prepared in the present example and the supported molecular sieve used; it can be seen from the figure that the catalyst has the same diffraction peak as the TS-1 molecular sieve, and no other phase peak is observed, indicating that the load is The active component is highly dispersed on the surface of the carrier molecular sieve.
  • XRD X-ray powder diffraction
  • the purpose of this example was to provide a preparation of a 15.8MnO 2 ⁇ 1.1Na 2 O ⁇ 20.8 WO 3 ⁇ 2.0TiO 2 ⁇ 60.3 SiO 2 catalyst.
  • the purpose of this example was to provide a preparation of a 15.8MnO 2 ⁇ 3.3Na 2 O ⁇ 13.9 WO 3 ⁇ 2.2TiO 2 ⁇ 64.8 SiO 2 catalyst.
  • Figure 8 is an X-ray powder diffraction (XRD) pattern of the catalyst prepared in the present example and the supported molecular sieve used; it can be seen that the catalyst has the same diffraction peak as the Ti-MWW molecular sieve, and no other phase peaks are observed, indicating that the load is The active component is highly dispersed on the surface of the carrier molecular sieve.
  • XRD X-ray powder diffraction
  • the purpose of this example was to provide a preparation of a 0.5MnO 2 ⁇ 0.2Na 2 O ⁇ 0.7 WO 3 ⁇ 3.2TiO 2 ⁇ 95.4SiO 2 catalyst.
  • Figure 9 is an X-ray powder diffraction (XRD) pattern of the catalyst prepared in the present example and the supported molecular sieve used; it can be seen that the catalyst has the same diffraction peak as the Ti-MWW molecular sieve, and no other phase peaks are observed, indicating that the load is The active component is highly dispersed on the surface of the carrier molecular sieve.
  • XRD X-ray powder diffraction
  • the purpose of this example was to provide a preparation of a 2.8MnO 2 ⁇ 0.1Na 2 O ⁇ 3.6WO 3 ⁇ 3.0TiO 2 ⁇ 90.5SiO 2 catalyst.
  • Figure 10 is an X-ray powder diffraction (XRD) pattern of the catalyst prepared in the present example and the supported molecular sieve used; it can be seen that the catalyst has the same diffraction peak as the Ti-MWW molecular sieve, and no other phase peaks are observed, indicating that the load is The active component is highly dispersed on the surface of the carrier molecular sieve.
  • XRD X-ray powder diffraction
  • the inventors of the present application have found that the performance of the obtained catalyst when using a titanium-containing molecular sieve or a pure silicon molecular sieve containing no titanium as a support is significantly superior to the use of amorphous SiO 2 or amorphous SiO 2 -TiO 2 composite oxide (including Mesoporous SiO 2 ) is the property of the catalyst obtained by the support.
  • amorphous SiO 2 or amorphous SiO 2 -TiO 2 composite oxide including Mesoporous SiO 2
  • This comparative example is to provide an amorphous SiO 2 (Shanghai Sinopharm) supported 2.8MnO 2 ⁇ 1.0Na 2 O ⁇ 3.6WO 3 ⁇ 92.6SiO 2 catalyst.
  • This comparative example was to provide a preparation of a mesoporous SiO 2 supported 2.8MnO 2 ⁇ 1.0Na 2 O ⁇ 3.6 WO 3 ⁇ 92.6SiO 2 catalyst.
  • Catalyst reaction evaluation was carried out on a continuous flow fixed bed microreactor. It adopts a quartz tube reactor with an inner diameter of 16 mm and a length of 400 mm.
  • the catalyst loading was 0.224 g.
  • 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 chilled ethanol-water (30% ethanol) bath, and then quantitatively detected by an online gas chromatograph.
  • C1-C3 hydrocarbon gas was quantified using a 30-m HP Porapak Q capillary column and FID detector.
  • N 2 , O 2 , CO, CO 2 and CH4 were performed using a 2-m ShinCarbon packed column (DIKMA) and a TCD detector. Quantitative analysis.
  • the catalysts of the examples of the present invention have significantly higher catalytic activity and product selectivity than the comparative catalysts. It can be seen from Table 1 that the methane conversion can reach more than 35%, the selectivity of the C2-C3 product can reach more than 80%, and the space-time yield of the C2-C3 product can be as high as 149 mol ⁇ kg -1 ⁇ h -1 .
  • the catalyst of the invention has significantly better methane oxidative coupling reaction performance than the existing catalyst technology; moreover, the catalyst of the invention is superior to the existing catalyst technology in that the ethylene/ethane ratio (>2) and the apparent propylene are high in the C2 product. Generated (selectivity can be as high as 9% or so).
  • the catalyst reaction evaluation and product analysis system were the same as in Application Example 1.
  • the space-time yield of C2-C3 product can be as high as 140 mol ⁇ kg -1 ⁇ h -1 or more.
  • the catalyst reaction evaluation and product analysis system were the same as in Application Example 1.
  • the purpose of this application example is to continue to investigate the effect of reaction temperature and gas hourly space velocity on the performance of the methane oxidative coupling reaction of the catalyst of the example.
  • CH 4 :O 2 :N 2 4:1:1 (volume ratio; CH 4 concentration: 66.7%) of the raw material gas, reaction pressure and reaction evaluated at a temperature of 700 ⁇ 800 °C, the choice of Example 1
  • the prepared catalyst was used in an amount of 0.224 g.
  • the reaction results are shown in Table 4. It can be seen that at the same reaction temperature of 750 ° C and above, the selectivity of the C2-C3 product gradually increases with the increase of the space velocity, but remains substantially within 80%; The increase in the ethylene/ethane ratio of the C2 product is slightly reduced.
  • the ethylene / ethane ratio can reach about 3.0, while about 10% of the propylene product can be produced.
  • the highest C2-C3 product selectivity occurs at 750-760 ° C, and is lower at 700 ° C and 800 ° C; in addition, ethylene / ethane Monotonously increases with temperature.
  • 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 effect of reaction temperature and gas hourly space velocity on the performance of the methane oxidative coupling reaction of the catalyst of the example.
  • the reaction was evaluated under the conditions of g -1 , normal pressure and reaction temperature of 700 to 800 ° C, and the catalyst prepared in Example 1 was used in an amount of 0.224 g.
  • the reaction results are shown in Table 5.
  • the catalyst of the present invention can obtain a higher CH 4 conversion rate at a lower CH 4 /O 2 ratio and a lower CH 4 concentration; the highest C2-C3 product selection The phenotype appeared at 750-760 ° C, and the temperature continued to increase. The selectivity of the C2-C3 product decreased slightly, and a higher product yield and a space-time yield of 70 mol ⁇ kg -1 ⁇ h -1 or more were still obtained.
  • 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 effect of reaction temperature and gas hourly space velocity on the performance of the methane oxidative coupling reaction of the catalyst of the example.
  • the reaction was evaluated under the conditions of g -1 , normal pressure and reaction temperature of 700 to 800 ° C, and the catalyst prepared in Example 1 was used in an amount of 0.224 g.
  • the reaction results are shown in Table 6.
  • the catalyst of the present invention exhibits significant low-temperature activity and selectivity at a higher CH 4 /O 2 ratio and a higher CH 4 concentration, and the reaction temperature is obtained at a reaction temperature of 71 ° C. More than 75% of the C 2 -C 3 products are selective, and the space time yield can reach 85.6 mol ⁇ kg -1 ⁇ h -1 . As the temperature continues to increase, the selectivity does not increase, especially at 800 ° C, the C2-C3 product selectivity is significant. In addition, ethylene/ethane monotonically increases with temperature.
  • the catalyst reaction evaluation and product analysis system were the same as in Application Example 1.
  • the catalyst of the present invention can be applied to the chemical industry.

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Abstract

The present invention discloses a manganese-sodium-tungsten-silicon composite oxide oxidative coupling of methane catalyst containing or not containing titanium, obtained by loading manganese-sodium-tungsten onto a titanium-silicon molecular sieve or a pure silicon molecular sieve by means of a step-by-step impregnation method and calcination. The manganese-sodium-tungsten-silicon composite oxide catalyst containing or not containing titanium has the following structural formula: vMnO2·xNa2O·yWO3·zTiO2·(100-v-x-y-z)SiO2, the v, x, y, and z respectively representing the fractional quality occupied by metal manganese oxide, sodium oxide, tungsten oxide and titanium oxide, 0.3≤v≤16, 0.1≤x≤5, 0.6≤y≤21, 0.0≤z≤4. The manganese-sodium-tungsten-silicon composite oxide catalyst containing or not containing titanium set forth in the present invention is used for oxidative coupling of methane reactions, having excellent low-temperature catalytic activity and ethylene/propylene selectivity generation and reaction stability.

Description

一种甲烷氧化偶联催化剂及其制备方法Methane oxidation coupling catalyst and preparation method thereof 技术领域Technical field
本发明涉及一种催化剂及其制备方法，特别地涉及一种含钛或不含钛的锰-钠-钨-硅复合氧化物甲烷氧化偶联催化剂及其制备方法。The invention relates to a catalyst and a preparation method thereof, in particular to a manganese-sodium-tungsten-silicon composite oxide methane oxidative coupling catalyst containing titanium or not containing titanium and a preparation method thereof.
背景技术Background technique
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1(1985)11)。传统的本森法，存在副产物氯代烃，对分离造成一定的困难；催化热解法产生大量积碳，严重影响了催化剂的稳定性和使用寿命。Methane and olefins (such as ethylene) are important chemical raw materials. There are processes for the preparation of olefins from methane in the industry, such as Benson process, partial oxidation process and catalytic pyrolysis process (Liaoning Chemical Industry 1 (1985) 11) . The traditional Benson method, the presence of by-product chlorinated hydrocarbons, poses certain difficulties for separation; catalytic pyrolysis produces a large amount of carbon deposits, which seriously affects the stability and service life of the catalyst.
众多已有方法使用了甲烷偶联催化剂，因此，开发高活性、高选择性、稳定性良好的甲烷偶联催化剂对发展低成本低耗能的甲烷制烯烃工艺具有重要意义。Many existing methods use methane coupling catalysts. Therefore, the development of a highly active, highly selective, and stable methane coupling catalyst is of great significance for the development of a low-cost, low-energy methane to olefins process.
目前，用于甲烷氧化偶联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在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(＞30％)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。At present, the catalysts for the oxidative coupling of methane are mainly classified into three types: alkali metal and alkaline earth metal oxides, rare earth metal oxides, and transition metal composite oxides. These catalyst systems were basically developed in the 1990s. The main problem is that the product selectivity is low (generally not higher than 70%) at higher methane conversion rates (>30%), making it difficult to meet economics. Requirements.
(一)碱金属与碱土金属氧化物(1) Alkali metal and alkaline earth metal oxides
碱土金属本身具有甲烷氧化偶联催化活性，碱金属改性会引起碱土金属晶格畸变，增加活性中心，减少表面积，从而防止CH4的深度氧化，提高催化剂的选择性。目前，活性最高的甲烷氧化偶联催化剂大多含有碱金属，其中以Na，Li最多，而碱土金属催化剂中以Mg，Ca，Sr最多。此类催化剂不仅产物收率较低，而且碱金属容易流失导致催化剂的失活。Alkaline earth metal itself has the catalytic activity of methane oxidative coupling. Alkali metal modification causes lattice distortion of alkaline earth metal, increases active center and reduces surface area, thereby preventing deep oxidation of CH 4 and improving catalyst selectivity. At present, the most active methane oxidative coupling catalysts mostly contain alkali metals, of which Na and Li are the most, and the alkaline earth metal catalysts have the most Mg, Ca and Sr. Such catalysts not only have lower product yields, but also the alkali metal is easily lost resulting in deactivation of the catalyst.
中国专利公开CN1068052A公开了一种以碱土或稀土金属氟化物为主要成分，配以少量碱土或稀土金属氧化物或ThO2、ZrO2等组成的催化剂，根据此文献的披露，该文献的催化剂应用于甲烷氧化偶联反应，可以获得27～34％的甲烷转化率，但C2 +烃类产物的收率也仅为13～20％。Chinese Patent Publication CN1068052A discloses a catalyst comprising an alkaline earth or a rare earth metal fluoride as a main component, a small amount of alkaline earth or rare earth metal oxide or ThO 2 , ZrO 2 , etc., according to the disclosure of the literature, the catalyst application of the document In the methane oxidative coupling reaction, a methane conversion rate of 27 to 34% can be obtained, but the yield of the C 2 + hydrocarbon product is also only 13 to 20%.
中国专利公开CN 1072615A公开了由碱土金属氧化物及碱土金属碳酸盐制备而成的M1O-M2CO3(M1选用Mg、Ca、Sr、Ba；M2选用Ca、Sr、Ba)类型催化剂，根据此文献的披露，该文献的催化剂的最高甲烷转化率为23.9％、最高产物收率为17.3％。Chinese Patent Publication CN 1072615A discloses M 1 OM 2 CO 3 (M 1 , Mg, Sr, Ba; M 2 selected Ca, Sr, Ba) prepared from alkaline earth metal oxides and alkaline earth metal carbonates. Catalyst, according to the disclosure of this document, the catalyst of this document has a maximum methane conversion of 23.9% and a maximum product yield of 17.3%.
(二)稀土金属氧化物 (2) Rare earth metal oxides
稀土金属具有较高的甲烷氧化偶联的催化活性和选择性，如La2O3、Pr2O3、Sm2O3、CeO2、YbO。稀土催化剂经碱金属或碱土金属改性后表现出更好的催化活性和选择性，因而受到广泛关注。其中Sm2O3系列催化剂的活性比较突出，并且经LiCl等碱金属卤化物改性后，催化活性进一步提高。Rare earth metals have higher catalytic activity and selectivity for oxidative coupling of methane, such as La 2 O 3 , Pr 2 O 3 , Sm 2 O 3 , C e O 2 , YbO. The rare earth catalyst exhibits better catalytic activity and selectivity after being modified with an alkali metal or an alkaline earth metal, and thus has received extensive attention. Among them, the activity of the Sm 2 O 3 series catalyst is prominent, and the catalytic activity is further improved after being modified by an alkali metal halide such as LiCl.
(三)复合氧化物和卤化物(3) Composite oxides and halides
用于甲烷临氧偶联的过渡金属复合氧化物主要有：Mn、Pb、Zn、Ti、Cr、Fe、Co、Ni等。过渡金属氧化物对甲烷临氧偶联反应虽然具有较好的活性，但反应选择性较差，因此其单独使用受到一定限制。经过碱金属、碱土金属或卤化物进行改性之后，其甲烷氧化偶联的催化活性得到大大提高。The transition metal composite oxides for methane oxygen coupling mainly include: Mn, Pb, Zn, Ti, Cr, Fe, Co, Ni, and the like. Although the transition metal oxide has a good activity for the methane oxygen coupling reaction, the reaction selectivity is poor, so its use alone is limited. After modification by alkali metal, alkaline earth metal or halide, the catalytic activity of methane oxidative coupling is greatly improved.
中国专利公开CN 1389293A公开了一种SiO2负载Mn2O3、Na2WO4和SnO2的催化剂，在加压(0.6MPa)条件下，最高可获得33％的甲烷转化率和24％的C2 +收率。但反应体系需要加压，会增加爆炸风险、存在安全隐患。Chinese Patent Publication No. CN 1389293 A discloses a catalyst of SiO 2 supporting Mn 2 O 3 , Na 2 WO 4 and SnO 2 , which can obtain a maximum conversion of methane of 33% and 24% under pressure (0.6 MPa). C 2 + yield. However, the reaction system needs to be pressurized, which increases the risk of explosion and has potential safety hazards.
发明内容Summary of the invention
针对以上现有催化剂技术的问题和不足，本发明的目的是提供一种低温活性好、选择性高、反应稳定性好的含钛或不含钛的锰-钠-钨-硅复合氧化物甲烷氧化偶联催化剂及其制备方法。In view of the problems and deficiencies of the above existing catalyst technology, the object of the present invention is to provide a manganese-sodium-tungsten-silicon composite oxide methane containing titanium or titanium containing no low temperature activity, high selectivity and good reaction stability. Oxidative coupling catalyst and preparation method thereof.
本发明的一方面是提供一种含钛或不含钛的锰-钠-钨-硅复合氧化物催化剂，其特征在于，具有如下通式：vMnO2·xNa2O·yWO3·zTiO2·(100-v-x-y-z)SiO2，其中v、x、y、z分别表示金属氧化锰、氧化钠、氧化钨和氧化钛所占的质量分数，0.3≤v≤16，0.1≤x≤5，0.6≤y≤21，0.0≤z≤4。An aspect of the present invention provides a manganese-sodium-tungsten-silicon composite oxide catalyst containing or not containing titanium, which has the following formula: vMnO 2 ·xNa 2 O·yWO 3 ·zTiO 2 · (100-vxyz) SiO 2 , wherein v, x, y, z represent the mass fraction of metal manganese oxide, sodium oxide, tungsten oxide and titanium oxide, respectively, 0.3 ≤ v ≤ 16, 0.1 ≤ x ≤ 5, 0.6 ≤ y ≤ 21, 0.0 ≤ z ≤ 4.
本发明的催化剂可以通过分步浸渍法将硝酸锰(或氯化锰、醋酸锰、硫酸锰)、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制备得到。所述分子筛例如可以为Ti-MWW、TS-1、Ti-Beta、Silicalite-1、Silicalite-2。The catalyst of the invention can be prepared by loading manganese nitrate (or manganese chloride, manganese acetate, manganese sulfate), sodium tungstate and ammonium tungstate on a titanium silica molecular sieve or a pure silicon molecular sieve by a stepwise impregnation method and calcining. The molecular sieve may be, for example, Ti-MWW, TS-1, Ti-Beta, Silicalite-1, Silicalite-2.
本发明的另一方面是前述催化剂的制备方法主要包括如下步骤：Another aspect of the present invention is that the preparation method of the foregoing catalyst mainly comprises the following steps:
a)室温下将干燥的分子筛粉末浸渍于钨酸钠水溶液或钨酸钠与钨酸铵的混合水溶液中，经超声分散0.5～1小时后搅拌1～3小时，得到浆状黏稠混合物；a) immersing the dried molecular sieve powder in a mixed aqueous solution of sodium tungstate or sodium tungstate and ammonium tungstate at room temperature, after ultrasonic dispersion for 0.5 to 1 hour, and then stirring for 1 to 3 hours to obtain a viscous viscous mixture;
b)室温搅拌下，将硝酸锰、氯化锰、醋酸锰或硫酸锰水溶液逐滴加入到步骤a)制得的混合物后，继续搅拌1～3小时后80～100℃烘干，得烘干物；b) adding manganese nitrate, manganese chloride, manganese acetate or manganese sulfate aqueous solution to the mixture prepared in step a) dropwise after stirring at room temperature, stirring for 1-3 hours, drying at 80-100 ° C, drying Object
c)将步骤b)制得的烘干物研磨成粉末，在空气氛中于550～800℃下焙烧1～2小时，即得到所述的催化剂。c) The dried product obtained in the step b) is ground into a powder, and calcined at 550 to 800 ° C for 1 to 2 hours in an air atmosphere to obtain the catalyst.
本发明的再一方面是将前述催化剂用于甲烷氧化偶联制备烯烃(例如乙烯、乙烷和丙 烯)的方法，其特征在于：反应温度650～800℃，原料气中甲烷/氧气体积比2.5～6，原料气中甲烷体积浓度35～75％，以甲烷和氧气计的反应气时空速10000～60000mL·g-1·h-1。A further aspect of the invention is a process for the catalytic coupling of methane (e.g., ethylene, ethane, and propylene) to methane, wherein the reaction temperature is 650 to 800 ° C, and the methane/oxygen volume ratio in the feed gas is 2.5. ～6, the volume concentration of methane in the raw material gas is 35 to 75%, and the reaction gas has a space velocity of 10,000 to 60000 mL·g -1 ·h -1 in terms of methane and oxygen.
与现有技术相比，本发明的催化剂具有低温活性好、选择性高、反应稳定性好、热稳定及化学稳定性高等优点。例如，以空气中含40％的甲烷混合气为原料，在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30％以上，C2-C3产物选择性可达72～81％；在气时空速30000～35000mL·g-1·h-1时，C2-C3产物时空产率可高达140mol·kg-1·h-1以上。可以看出，本发明催化剂具有明显优于现有催化剂技术的甲烷氧化偶联反应性能，其优越性尤其体现在C2产物中高的乙烯/乙烷比(>2)以及明显的丙烯生成(选择性可达9％左右)。Compared with the prior art, the catalyst of the invention has the advantages of good low temperature activity, high selectivity, good reaction stability, thermal stability and high chemical stability. For example, with a 40% methane mixture in the air as a raw material, the methane conversion rate can reach 30% at a wide gas hourly space velocity of 10,000 to 35,000 mL·g -1 ·h -1 at 750-800 °C. Above, the selectivity of C2-C3 product can reach 72-81%; when the gas hourly space velocity is 30,000~35000mL·g -1 ·h -1 , the space-time yield of C2-C3 product can be as high as 140mol·kg -1 ·h -1 the above. It can be seen that the catalyst of the present invention has significantly better methane oxidative coupling reaction performance than the existing catalyst technology, and its superiority is particularly reflected in the high ethylene/ethane ratio (>2) and apparent propylene formation (selectivity) in the C2 product. Up to 9% or so).
附图说明DRAWINGS
图1为实施例1所制2.8MnO2·1.0Na2O·3.6WO3·3.0TiO2·89.6SiO2催化剂及所用载体分子筛的X射线粉末衍射图。1 is an X-ray powder diffraction pattern of a 2.8MnO 2 ·1.0Na 2 O·3.6WO 3 ·3.0TiO 2 ·89.6SiO 2 catalyst prepared in Example 1 and a carrier molecular sieve used.
图2为实施例2所制4.2MnO2·1.5Na2O·5.5WO3·2.9TiO2·85.9SiO2催化剂及所用载体分子筛的X射线粉末衍射图。2 is an X-ray powder diffraction pattern of a 4.2MnO 2 ·1.5Na 2 O·5.5WO 3 ·2.9TiO 2 ·85.9SiO 2 catalyst prepared in Example 2 and a carrier molecular sieve used.
图3为实施例3所制6.5MnO2·2.3Na2O·8.6WO3·2.7TiO2·79.9SiO2催化剂及所用载体分子筛的X射线粉末衍射图。3 is an X-ray powder diffraction pattern of a 6.5MnO 2 ·2.3Na 2 O·8.6WO 3 ·2.7TiO 2 ·79.9SiO 2 catalyst prepared in Example 3 and a carrier molecular sieve used.
图4为实施例6所制0.4MnO2·4.4Na2O·16.4WO3·2.5TiO2·76.3SiO2催化剂及所用载体分子筛的X射线粉末衍射图。4 is an X-ray powder diffraction pattern of a 0.4MnO 2 ·4.4Na 2 O·16.4 WO 3 ·2.5TiO 2 ·76.3SiO 2 catalyst prepared in Example 6 and a carrier molecular sieve used.
图5为实施例8所制2.8MnO2·1.0Na2O·3.2WO3·3.9TiO2·89.1SiO2催化剂及所用载体分子筛的X射线粉末衍射图。Figure 5 is an X-ray powder diffraction pattern of a 2.8MnO 2 ·1.0Na 2 O·3.2 WO 3 ·3.9TiO 2 ·89.1SiO 2 catalyst prepared in Example 8 and a carrier molecular sieve used.
图6为实施例9所制2.8MnO2·1.0Na2O·3.6WO3·1.1TiO2·91.5SiO2催化剂及所用载体分子筛的X射线粉末衍射图。Figure 6 is an X-ray powder diffraction pattern of a 2.8MnO 2 ·1.0Na 2 O·3.6WO 3 ·1.1TiO 2 ·91.5SiO 2 catalyst prepared in Example 9 and a carrier molecular sieve used.
图7为实施例12所制2.8MnO2·1.0Na2O·3.6WO3·3.0TiO2·89.6SiO2催化剂及所用载体分子筛的X射线粉末衍射图。Figure 7 is an X-ray powder diffraction pattern of a 2.8MnO 2 ·1.0Na 2 O·3.6WO 3 ·3.0TiO 2 ·89.6SiO 2 catalyst prepared in Example 12 and a carrier molecular sieve used.
图8为实施例14所制15.8MnO2·3.3Na2O·13.9WO3·2.2TiO2·64.8SiO2催化剂及所用载体分子筛的X射线粉末衍射图。Figure 8 is an X-ray powder diffraction pattern of a 15.8MnO 2 ·3.3Na 2 O·13.9 WO 3 ·2.2TiO 2 ·64.8SiO 2 catalyst prepared in Example 14 and a carrier molecular sieve used.
图9为实施例15所制0.5MnO2·0.2Na2O·0.7WO3·3.2TiO2·95.4SiO2催化剂及所用载体分子筛的X射线粉末衍射图。Figure 9 is an X-ray powder diffraction pattern of a 0.5MnO 2 ·0.2Na 2 O·0.7 WO 3 ·3.2TiO 2 ·95.4SiO 2 catalyst prepared in Example 15 and a carrier molecular sieve used.
图10为实施例16所制2.8MnO2·0.1Na2O·3.6WO3·3.0TiO2·90.5SiO2催化剂及所用载体分子筛的X射线粉末衍射图。Figure 10 is an X-ray powder diffraction pattern of a 2.8MnO 2 ·0.1Na 2 O·3.6 WO 3 ·3.0TiO 2 ·90.5SiO 2 catalyst prepared in Example 16 and a carrier molecular sieve used.
图11为实施例1所制2.8MnO2·1.0Na2O·3.6WO3·3.0TiO2·89.6SiO2催化剂上甲烷氧化偶联反应温度和气时空速对甲烷转化率的影响。Figure 11 is a graph showing the effect of methane oxidative coupling reaction temperature and gas hourly space velocity on methane conversion rate on a 2.8MnO 2 ·1.0Na 2 O·3.6WO 3 ·3.0TiO 2 ·89.6SiO 2 catalyst prepared in Example 1.
图12为实施例1所制2.8MnO2·1.0Na2O·3.6WO3·3.0TiO2·89.6SiO2催化剂上甲烷氧化偶联反应温度和气时空速对产物选择性的影响。Figure 12 is a graph showing the effect of methane oxidative coupling reaction temperature and gas hourly space velocity on product selectivity on a 2.8MnO 2 ·1.0Na 2 O·3.6WO 3 ·3.0TiO 2 ·89.6SiO 2 catalyst prepared in Example 1.
图13为实施例1所制2.8MnO2·1.0Na2O·3.6WO3·3.0TiO2·89.6SiO2催化剂上甲烷氧化偶联反应100小时稳定性实验结果。 Figure 13 is a graph showing the results of 100 hours stability test of methane oxidative coupling reaction on a 2.8MnO 2 ·1.0Na 2 O·3.6WO 3 ·3.0TiO 2 ·89.6SiO 2 catalyst prepared in Example 1.
具体实施方式detailed description
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。The present invention will be further described in detail below in conjunction with the embodiments and the accompanying drawings.
在本申请中，甲烷转化率、产物选择性和时空产率采用碳原子归一法进行计算，定义为：In the present application, methane conversion, product selectivity and space time yield are calculated by carbon atom normalization and are defined as:
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CO2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％；Conversion rate = [1 - methane concentration in the tail gas / (methane concentration in the tail gas + CO concentration in the tail gas + CO 2 concentration in the tail gas + 2 × total ethylene ethylene concentration in the exhaust gas + 3 × total concentration of propylene and propane in the exhaust gas)] × 100 %;
选择性＝[n×尾气中含碳产物的浓度/(尾气中CO浓度+尾气中CO2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；Selectivity = [n × concentration of carbonaceous product in the tail gas / (CO concentration in the tail gas + CO 2 concentration in the tail gas + 2 × total ethylene ethylene concentration in the exhaust gas + 3 × total concentration of propylene and propane in the exhaust gas)] × 100%, Wherein n is the number of carbon atoms in the product;
时空产率＝(空速×原料中甲烷浓度)/(该状态下气体摩尔体积×甲烷转化率×(尾气中乙烯乙烷总选择性/2+尾气中丙烯选择性/3))。Space time yield = (airspeed x methane concentration in the feed) / (gas molar volume in this state x methane conversion x (total ethylene ethylene selectivity in the tail gas / propylene selectivity / 3 in the exhaust gas) /).
实施例1Example 1
本实施例的目的是提供2.8MnO2·1.0Na2O·3.6WO3·3.0TiO2·89.6SiO2催化剂的制备。The purpose of this example was to provide a preparation of a 2.8MnO 2 ·1.0Na 2 O·3.6WO 3 ·3.0TiO 2 ·89.6SiO 2 catalyst.
a)称取0.11克钨酸钠(Na2WO4·2H2O)溶于2.5毫升去离子水中配成钨酸钠的水溶液；称取2.00克干燥的Ti-MWW分子筛(Si/Ti比40)移入100毫升烧杯中，先加入5.0毫升去离子水使分子筛分散后，逐滴加入上述配制的钨酸钠水溶液，超声分散0.5小时后继续搅拌3小时，得浆状粘稠混合物；a) Weigh 0.11 g of sodium tungstate (Na 2 WO 4 · 2H 2 O) dissolved in 2.5 ml of deionized water to prepare an aqueous solution of sodium tungstate; weigh 2.00 g of dry Ti-MWW molecular sieve (Si/Ti ratio 40 Transfer into a 100 ml beaker, first add 5.0 ml of deionized water to disperse the molecular sieve, then add the above prepared sodium tungstate aqueous solution dropwise, ultrasonically disperse for 0.5 hour, and continue to stir for 3 hours to obtain a viscous viscous mixture;
b)称取0.247克50％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逐滴加入到步骤a)所得浆状粘稠混合物中，继续搅拌3小时后，于90℃烘干；b) Weigh 0.247 g of 50% aqueous manganese nitrate solution, dilute to 2 ml with deionized water; add the obtained aqueous manganese nitrate solution dropwise to the slurry viscous mixture obtained in step a) with stirring, and continue stirring for 3 hours. Dry at 90 ° C;
c)将步骤b)制得的样品研磨成粉末，在空气氛中于550℃下焙烧2小时，即得本发明实施例催化剂。c) The sample obtained in the step b) was ground into a powder and calcined at 550 ° C for 2 hours in an air atmosphere to obtain a catalyst of the examples of the present invention.
图1为本实施例所制催化剂及所用载体分子筛的X射线粉末衍射(XRD)图谱；由图可知，催化剂具有与Ti-MWW分子筛相同的衍射峰，未观察到其他物相峰，表明负载的活性组分高度分散在载体分子筛表面。1 is an X-ray powder diffraction (XRD) pattern of the catalyst prepared in the present example and the carrier molecular sieve used; it can be seen from the figure that the catalyst has the same diffraction peak as the Ti-MWW molecular sieve, and no other phase peaks are observed, indicating that the load is The active component is highly dispersed on the surface of the carrier molecular sieve.
实施例2Example 2
本实施例的目的是提供4.2MnO2·1.5Na2O·5.5WO3·2.9TiO2·85.9SiO2催化剂的制备。The purpose of this example was to provide a preparation of a catalyst of 4.2MnO 2 ·1.5Na 2 O·5.5WO 3 ·2.9TiO 2 ·85.9SiO 2 .
a)称取0.177克钨酸钠(Na2WO4·2H2O)溶于2.5毫升去离子水中配成钨酸钠的水溶液；称取2.00克干燥的Ti-MWW分子筛(Si/Ti比40)移入100毫升烧杯中，先加入5.0毫升去离子水使分子筛分散后，逐滴加入上述配制的钨酸钠水溶液，超声分散1小时后继续搅拌1小时，得浆状粘稠混合物；a) Weigh 0.177 g of sodium tungstate (Na 2 WO 4 ·2H 2 O) dissolved in 2.5 ml of deionized water to prepare an aqueous solution of sodium tungstate; weigh 2.00 g of dried Ti-MWW molecular sieve (Si/Ti ratio 40 Transfer into a 100 ml beaker, first add 5.0 ml of deionized water to disperse the molecular sieve, then add the above prepared sodium tungstate aqueous solution dropwise, and stir for 1 hour after ultrasonic dispersion for 1 hour to obtain a viscous viscous mixture;
b)称取0.391克50％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逐滴加入到步骤a)所得浆状粘稠混合物中，继续搅拌1小时后，于80℃烘干； b) Weigh 0.391 g of 50% manganese nitrate aqueous solution, dilute to 2 ml with deionized water; add the obtained manganese nitrate aqueous solution dropwise to the slurry viscous mixture obtained in the step a) with stirring, and continue stirring for 1 hour. Dry at 80 ° C;
c)将步骤b)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。c) The sample obtained in the step b) was ground into a powder and calcined at 650 ° C for 2 hours in an air atmosphere to obtain a catalyst of this example.
图2为本实施例所制催化剂及所用载体分子筛的X射线粉末衍射(XRD)图谱；由图可知，催化剂具有与Ti-MWW分子筛相同的衍射峰，未观察到其他物相峰，表明负载的活性组分高度分散在载体分子筛表面。2 is an X-ray powder diffraction (XRD) pattern of the catalyst prepared in the present example and the carrier molecular sieve used; it can be seen from the figure that the catalyst has the same diffraction peak as the Ti-MWW molecular sieve, and no other phase peak is observed, indicating that the load is The active component is highly dispersed on the surface of the carrier molecular sieve.
实施例3Example 3
本实施例的目的是提供6.5MnO2·2.3Na2O·8.6WO3·2.7TiO2·79.9SiO2催化剂的制备。The purpose of this example was to provide a preparation of a 6.5MnO 2 ·2.3Na 2 O·8.6WO 3 ·2.7TiO 2 ·79.9SiO 2 catalyst.
a)称取0.295克钨酸钠(Na2WO4·2H2O)溶于2.5毫升去离子水中配成钨酸钠的水溶液；称取2.00克干燥的Ti-MWW分子筛(Si/Ti比40)移入100毫升烧杯中，先加入5.0毫升去离子水使分子筛分散后，逐滴加入上述配制的钨酸钠水溶液，超声分散0.5小时后继续搅拌2小时，得浆状粘稠混合物；a) Weigh 0.295 g of sodium tungstate (Na 2 WO 4 ·2H 2 O) dissolved in 2.5 ml of deionized water to form an aqueous solution of sodium tungstate; weigh 2.00 g of dry Ti-MWW molecular sieve (Si/Ti ratio 40 Transfer into a 100 ml beaker, first add 5.0 ml of deionized water to disperse the molecular sieve, then add the above prepared sodium tungstate aqueous solution dropwise, ultrasonically disperse for 0.5 hour, and continue to stir for 2 hours to obtain a viscous viscous mixture;
b)称取0.651克50％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逐滴加入到步骤a)所得浆状粘稠混合物中，继续搅拌3小时后，于100℃烘干；b) Weigh 0.651 g of 50% manganese nitrate aqueous solution, dilute to 2 ml with deionized water; add the obtained manganese nitrate aqueous solution dropwise to the slurry-like viscous mixture obtained in the step a), and continue stirring for 3 hours. Dry at 100 ° C;
c)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，即得本发明实施例催化剂。c) The sample obtained in the step b) was ground into a powder and calcined at 700 ° C for 2 hours in an air atmosphere to obtain a catalyst of the examples of the present invention.
图3为本实施例所制催化剂及所用载体分子筛的X射线粉末衍射(XRD)图谱；由图可知，催化剂具有与Ti-MWW分子筛相同的衍射峰，未观察到其他物相峰，表明负载的活性组分高度分散在载体分子筛表面。3 is an X-ray powder diffraction (XRD) pattern of the catalyst prepared in the present example and the carrier molecular sieve used; it can be seen from the figure that the catalyst has the same diffraction peak as the Ti-MWW molecular sieve, and no other phase peak is observed, indicating that the load is The active component is highly dispersed on the surface of the carrier molecular sieve.
实施例4Example 4
本实施例的目的是提供3.0MnO2·0.4Na2O·1.4WO3·3.1TiO2-92.1SiO2催化剂的制备。The purpose of this example is to provide a preparation of a 3.0MnO 2 ·0.4Na 2 O·1.4 WO 3 ·3.1TiO 2 -92.1SiO 2 catalyst.
a)称取0.043克钨酸钠(Na2WO4·2H2O)溶于2.5毫升去离子水中配成钨酸钠的水溶液；称取2.00克干燥的Ti-Beta分子筛(Si/Ti比40)移入100毫升烧杯中，先加入5.0毫升去离子水使分子筛分散后，逐滴加入上述配制的钨酸钠水溶液，超声分散0.5小时后继续搅拌3小时，得浆状粘稠混合物；a) Weigh 0.043 g of sodium tungstate (Na 2 WO 4 ·2H 2 O) dissolved in 2.5 ml of deionized water to prepare an aqueous solution of sodium tungstate; weigh 2.00 g of dry Ti-Beta molecular sieve (Si/Ti ratio 40 Transfer into a 100 ml beaker, first add 5.0 ml of deionized water to disperse the molecular sieve, then add the above prepared sodium tungstate aqueous solution dropwise, ultrasonically disperse for 0.5 hour, and continue to stir for 3 hours to obtain a viscous viscous mixture;
b)称取0.169克四水合醋酸锰，加去离子水稀释至2毫升；在搅拌下将所得硝酸锰水溶液逐滴加入到步骤a)所得浆状粘稠混合物中，继续搅拌3小时后，于100℃烘干；b) Weigh 0.169 g of manganese acetate tetrahydrate, dilute to 2 ml with deionized water; add the obtained aqueous manganese nitrate solution dropwise to the viscous viscous mixture obtained in step a) with stirring, and continue stirring for 3 hours. Drying at 100 ° C;
c)将步骤b)制得的样品研磨成粉末，在空气氛中于800℃下焙烧1小时，即得本实施例催化剂。c) The sample obtained in the step b) was ground into a powder and calcined at 800 ° C for 1 hour in an air atmosphere to obtain a catalyst of this example.
实施例5Example 5
本实施例的目的是提供8.6MnO2·3.0Na2O·11.2WO3·2.5TiO2·74.7SiO2催化剂的制备。 The purpose of this example was to provide a preparation of a 8.6MnO 2 ·3.0Na 2 O·11.2 WO 3 ·2.5TiO 2 ·74.7SiO 2 catalyst.
a)称取0.414克钨酸钠(Na2WO4·2H2O)溶于2.5毫升去离子水中配成钨酸钠的水溶液；称取2.00克干燥的Ti-MWW分子筛(Si/Ti比40)移入100毫升烧杯中，先加入5.0毫升去离子水使分子筛分散后，逐滴加入上述配制的钨酸钠水溶液，超声分散1小时后继续搅拌3小时，得浆状粘稠混合物；a) Weigh 0.414 g of sodium tungstate (Na 2 WO 4 · 2H 2 O) dissolved in 2.5 ml of deionized water to prepare an aqueous solution of sodium tungstate; weigh 2.00 g of dry Ti-MWW molecular sieve (Si/Ti ratio 40 Transfer into a 100 ml beaker, first add 5.0 ml of deionized water to disperse the molecular sieve, then add the above prepared sodium tungstate aqueous solution dropwise, and ultrasonically disperse for 1 hour and then continue to stir for 3 hours to obtain a viscous viscous mixture;
b)称取0.911克50％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逐滴加入到步骤a)所得浆状粘稠混合物中，继续搅拌3小时后，于100℃烘干；b) Weigh 0.911 g of 50% aqueous manganese nitrate solution, dilute to 2 ml with deionized water; add the obtained aqueous manganese nitrate solution dropwise to the slurry-like viscous mixture obtained in the step a), and continue stirring for 3 hours. Dry at 100 ° C;
c)将步骤b)制得的样品研磨成粉末，在空气氛中于600℃下焙烧1小时，即得本实施例催化剂。c) The sample obtained in the step b) was ground into a powder and calcined at 600 ° C for 1 hour in an air atmosphere to obtain a catalyst of this example.
实施例6Example 6
本实施例的目的是提供0.4MnO2·4.4Na2O·16.4WO3·2.5TiO2·76.3SiO2催化剂的制备。The purpose of this example was to provide a preparation of a 0.4MnO 2 · 4.4Na 2 O·16.4 WO 3 ·2.5TiO 2 ·76.3SiO 2 catalyst.
a)称取0.591克钨酸钠(Na2WO4·2H2O)溶于2.5毫升去离子水中配成钨酸钠的水溶液；称取2.00克干燥的Ti-MWW分子筛(Si/Ti比40)移入100毫升烧杯中，先加入5.0毫升去离子水使分子筛分散后，逐滴加入上述配制的钨酸钠水溶液，超声分散1小时后继续搅拌3小时，得浆状粘稠混合物；a) Weigh 0.591 g of sodium tungstate (Na 2 WO 4 · 2H 2 O) in 2.5 ml of deionized water formulated into an aqueous solution of sodium tungstate; drying weighed 2.00 g of Ti-MWW zeolite (Si / Ti ratio of 40 Transfer into a 100 ml beaker, first add 5.0 ml of deionized water to disperse the molecular sieve, then add the above prepared sodium tungstate aqueous solution dropwise, and ultrasonically disperse for 1 hour and then continue to stir for 3 hours to obtain a viscous viscous mixture;
b)称取0.030克50％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逐滴加入到步骤a)所得浆状粘稠混合物中，继续搅拌3小时后，于100℃烘干；b) Weigh 0.030 g of a 50% aqueous solution of manganese nitrate, dilute to 2 ml with deionized water; add the obtained aqueous solution of manganese nitrate dropwise to the viscous viscous mixture obtained in the step a), and continue stirring for 3 hours. Dry at 100 ° C;
c)将步骤b)制得的样品研磨成粉末，在空气氛中于600℃下焙烧1小时，即得本发明实施例催化剂。c) The sample obtained in the step b) was ground into a powder and calcined at 600 ° C for 1 hour in an air atmosphere to obtain a catalyst of the examples of the present invention.
图4是本实施例所制催化剂及所用载体分子筛的X射线粉末衍射(XRD)图谱；由图可知，催化剂具有与Ti-MWW分子筛相同的衍射峰，未观察到其他物相峰，表明负载的活性组分高度分散在载体分子筛表面。Figure 4 is an X-ray powder diffraction (XRD) pattern of the catalyst prepared in the present example and the supported molecular sieve used; it can be seen from the figure that the catalyst has the same diffraction peak as the Ti-MWW molecular sieve, and no other phase peaks are observed, indicating that the load is The active component is highly dispersed on the surface of the carrier molecular sieve.
实施例7Example 7
本实施例的目的是提供2.8MnO2·1.0Na2O·3.6WO3·0.4TiO2·92.2SiO2催化剂的制备。The purpose of this example was to provide a preparation of a 2.8MnO 2 ·1.0Na 2 O·3.6WO 3 ·0.4TiO 2 ·92.2SiO 2 catalyst.
a)称取0.11克钨酸钠(Na2WO4·2H2O)溶于2.5毫升去离子水中配成钨酸钠的水溶液；称取2.00克干燥的Ti-MWW分子筛(Si/Ti比300)移入100毫升烧杯中，先加入5.0毫升去离子水使分子筛分散后，逐滴加入上述配制的钨酸钠水溶液，超声分散0.5小时后继续搅拌3小时，得浆状粘稠混合物；a) Weigh 0.11 g of sodium tungstate (Na 2 WO 4 ·2H 2 O) dissolved in 2.5 ml of deionized water to prepare an aqueous solution of sodium tungstate; weigh 2.00 g of dry Ti-MWW molecular sieve (Si/Ti ratio 300) Transfer into a 100 ml beaker, first add 5.0 ml of deionized water to disperse the molecular sieve, then add the above prepared sodium tungstate aqueous solution dropwise, ultrasonically disperse for 0.5 hour, and continue to stir for 3 hours to obtain a viscous viscous mixture;
b)称取0.247克50％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逐滴加入到步骤a)所得浆状粘稠混合物中，继续搅拌3小时后，于90℃烘干；b) Weigh 0.247 g of 50% aqueous manganese nitrate solution, dilute to 2 ml with deionized water; add the obtained aqueous manganese nitrate solution dropwise to the slurry viscous mixture obtained in step a) with stirring, and continue stirring for 3 hours. Dry at 90 ° C;
c)将步骤b)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。 c) The sample obtained in the step b) was ground into a powder and calcined at 550 ° C for 2 hours in an air atmosphere to obtain a catalyst of this example.
实施例8Example 8
本实施例的目的是提供2.8MnO2·1.0Na2O·3.2WO3·3.9TiO2·89.1SiO2催化剂的制备。The purpose of this example was to provide a preparation of a 2.8MnO 2 ·1.0Na 2 O.3.2WO 3 ·3.9TiO 2 ·89.1 SiO 2 catalyst.
a)称取0.11克钨酸钠(Na2WO4·2H2O)溶于2.5毫升去离子水中配成钨酸钠的水溶液；称取2.00克干燥的Ti-MWW分子筛(Si/Ti比30)移入100毫升烧杯中，先加入5.0毫升去离子水使分子筛分散后，逐滴加入上述配制的钨酸钠水溶液，超声分散0.5小时后继续搅拌3小时，得浆状粘稠混合物；a) Weigh 0.11 g of sodium tungstate (Na 2 WO 4 ·2H 2 O) dissolved in 2.5 ml of deionized water to prepare an aqueous solution of sodium tungstate; weigh 2.00 g of dry Ti-MWW molecular sieve (Si/Ti ratio 30 Transfer into a 100 ml beaker, first add 5.0 ml of deionized water to disperse the molecular sieve, then add the above prepared sodium tungstate aqueous solution dropwise, ultrasonically disperse for 0.5 hour, and continue to stir for 3 hours to obtain a viscous viscous mixture;
b)称取0.247克50％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逐滴加入到步骤a)所得浆状粘稠混合物中，继续搅拌3小时后，于90℃烘干；b) Weigh 0.247 g of 50% aqueous manganese nitrate solution, dilute to 2 ml with deionized water; add the obtained aqueous manganese nitrate solution dropwise to the slurry viscous mixture obtained in step a) with stirring, and continue stirring for 3 hours. Dry at 90 ° C;
c)将步骤b)制得的样品研磨成粉末，在空气氛中于550℃下焙烧2小时，即得本发明实施例催化剂。c) The sample obtained in the step b) was ground into a powder and calcined at 550 ° C for 2 hours in an air atmosphere to obtain a catalyst of the examples of the present invention.
图5是本实施例所制催化剂及所用载体分子筛的X射线粉末衍射(XRD)图谱；由图可知，催化剂具有与Ti-MWW分子筛相同的衍射峰，未观察到其他物相峰，表明负载的活性组分高度分散在载体分子筛表面。Figure 5 is an X-ray powder diffraction (XRD) pattern of the catalyst prepared in the present example and the supported molecular sieve used; it can be seen from the figure that the catalyst has the same diffraction peak as the Ti-MWW molecular sieve, and no other phase peaks are observed, indicating that the load is The active component is highly dispersed on the surface of the carrier molecular sieve.
实施例9Example 9
本实施例的目的是提供2.8MnO2·1.0Na2O·3.6WO3·1.1TiO2·91.5SiO2催化剂的制备。The purpose of this example was to provide a preparation of a 2.8MnO 2 ·1.0Na 2 O·3.6WO 3 ·1.1TiO 2 ·91.5SiO 2 catalyst.
a)称取0.11克钨酸钠(Na2WO4·2H2O)溶于2.5毫升去离子水中配成钨酸钠的水溶液；称取2.00克干燥的Ti-MWW分子筛(Si/Ti比110)移入100毫升烧杯中，先加入5.0毫升去离子水使分子筛分散后，逐滴加入上述配制的钨酸钠水溶液，超声分散0.5小时后继续搅拌3小时，得浆状粘稠混合物；a) Weigh 0.11 g of sodium tungstate (Na 2 WO 4 ·2H 2 O) dissolved in 2.5 ml of deionized water to prepare an aqueous solution of sodium tungstate; weigh 2.00 g of dry Ti-MWW molecular sieve (Si/Ti ratio 110) Transfer into a 100 ml beaker, first add 5.0 ml of deionized water to disperse the molecular sieve, then add the above prepared sodium tungstate aqueous solution dropwise, ultrasonically disperse for 0.5 hour, and continue to stir for 3 hours to obtain a viscous viscous mixture;
b)称取0.247克50％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逐滴加入到步骤a)所得浆状粘稠混合物中，继续搅拌3小时后，于90℃烘干；b) Weigh 0.247 g of 50% aqueous manganese nitrate solution, dilute to 2 ml with deionized water; add the obtained aqueous manganese nitrate solution dropwise to the slurry viscous mixture obtained in step a) with stirring, and continue stirring for 3 hours. Dry at 90 ° C;
c)将步骤b)制得的样品研磨成粉末，在空气氛中于550℃下焙烧2小时，即得本发明实施例催化剂。c) The sample obtained in the step b) was ground into a powder and calcined at 550 ° C for 2 hours in an air atmosphere to obtain a catalyst of the examples of the present invention.
图6是本实施例所制催化剂及所用载体分子筛的X射线粉末衍射(XRD)图谱；由图可知，催化剂具有与Ti-MWW分子筛相同的衍射峰，未观察到其他物相峰，表明负载的活性组分高度分散在载体分子筛表面。Figure 6 is an X-ray powder diffraction (XRD) pattern of the catalyst prepared in the present example and the carrier molecular sieve used; it can be seen from the figure that the catalyst has the same diffraction peak as the Ti-MWW molecular sieve, and no other phase peaks are observed, indicating that the load is The active component is highly dispersed on the surface of the carrier molecular sieve.
实施例10Example 10
本实施例的目的是提供2.8MnO2·1.0Na2O·3.6WO3·92.6SiO2催化剂的制备。The purpose of this example was to provide a preparation of a 2.8MnO 2 ·1.0Na 2 O·3.6 WO 3 ·92.6SiO 2 catalyst.
a)称取0.11克钨酸钠(Na2WO4·2H2O)溶于2.5毫升去离子水中配成钨酸钠的水溶液；称取2.00克干燥的纯硅Silicalite-1分子筛移入100毫升烧杯中，先加入5.0毫升去离子水使分子筛分散后，逐滴加入上述配制的钨酸钠水溶液，超声分散0.5小时后继续搅拌3小时，得浆状粘稠混合物； a) Weigh 0.11 g of sodium tungstate (Na 2 WO 4 · 2H 2 O) dissolved in 2.5 ml of deionized water to prepare an aqueous solution of sodium tungstate; weigh 2.00 g of dry pure silicon Silicalite-1 molecular sieve into a 100 ml beaker After adding 5.0 ml of deionized water to disperse the molecular sieve, the above prepared sodium tungstate aqueous solution was added dropwise, ultrasonically dispersed for 0.5 hour, and stirring was continued for 3 hours to obtain a viscous viscous mixture;
b)称取0.104克硫酸锰，加去离子水稀释至2毫升；在搅拌下将所得硝酸锰水溶液逐滴加入到步骤a)所得浆状粘稠混合物中，继续搅拌3小时后，于90℃烘干；b) Weigh 0.104 g of manganese sulfate, dilute to 2 ml with deionized water; add the obtained aqueous manganese nitrate solution dropwise to the slurry viscous mixture obtained in step a) with stirring, continue stirring for 3 hours, at 90 ° C drying;
c)将步骤b)制得的样品研磨成粉末，在空气氛中于550℃下焙烧2小时，即得本发明实施例催化剂。c) The sample obtained in the step b) was ground into a powder and calcined at 550 ° C for 2 hours in an air atmosphere to obtain a catalyst of the examples of the present invention.
实施例11Example 11
本实施例的目的是提供2.8MnO2·1.0Na2O·3.6WO3·92.6SiO2催化剂的制备。The purpose of this example was to provide a preparation of a 2.8MnO 2 ·1.0Na 2 O·3.6 WO 3 ·92.6SiO 2 catalyst.
a)称取0.11克钨酸钠(Na2WO4·2H2O)溶于2.5毫升去离子水中配成钨酸钠的水溶液；称取2.00克干燥的纯硅Silicalite-2分子筛移入100毫升烧杯中，先加入5.0毫升去离子水使分子筛分散后，逐滴加入上述配制的钨酸钠水溶液，超声分散0.5小时后继续搅拌3小时，得浆状粘稠混合物；a) Weigh 0.11 g of sodium tungstate (Na 2 WO 4 ·2H 2 O) dissolved in 2.5 ml of deionized water to prepare an aqueous solution of sodium tungstate; weigh 2.00 g of dry pure silicon Silicalite-2 molecular sieve into 100 ml beaker After adding 5.0 ml of deionized water to disperse the molecular sieve, the above prepared sodium tungstate aqueous solution was added dropwise, ultrasonically dispersed for 0.5 hour, and stirring was continued for 3 hours to obtain a viscous viscous mixture;
b)称取0.247克50％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逐滴加入到步骤a)所得浆状粘稠混合物中，继续搅拌3小时后，于90℃烘干；b) Weigh 0.247 g of 50% aqueous manganese nitrate solution, dilute to 2 ml with deionized water; add the obtained aqueous manganese nitrate solution dropwise to the slurry viscous mixture obtained in step a) with stirring, and continue stirring for 3 hours. Dry at 90 ° C;
c)将步骤b)制得的样品研磨成粉末，在空气氛中于550℃下焙烧2小时，即得本发明实施例催化剂。c) The sample obtained in the step b) was ground into a powder and calcined at 550 ° C for 2 hours in an air atmosphere to obtain a catalyst of the examples of the present invention.
实施例12Example 12
本实施例的目的是提供2.8MnO2·1.0Na2O·3.6WO3·3.0TiO2·89.6SiO2催化剂的制备。The purpose of this example was to provide a preparation of a 2.8MnO 2 ·1.0Na 2 O·3.6WO 3 ·3.0TiO 2 ·89.6SiO 2 catalyst.
a)称取0.11克钨酸钠(Na2WO4·2H2O)溶于2.5毫升去离子水中配成钨酸钠的水溶液；称取2.00克干燥的TS-1分子筛(Si/Ti比40)移入100毫升烧杯中，先加入5.0毫升去离子水使分子筛分散后，逐滴加入上述配制的钨酸钠水溶液，超声分散0.5小时后继续搅拌3小时，得浆状粘稠混合物；a) Weigh 0.11 g of sodium tungstate (Na 2 WO 4 · 2H 2 O) dissolved in 2.5 ml of deionized water to prepare an aqueous solution of sodium tungstate; weigh 2.00 g of dried TS-1 molecular sieve (Si/Ti ratio 40 Transfer into a 100 ml beaker, first add 5.0 ml of deionized water to disperse the molecular sieve, then add the above prepared sodium tungstate aqueous solution dropwise, ultrasonically disperse for 0.5 hour, and continue to stir for 3 hours to obtain a viscous viscous mixture;
b)称取0.136克四水合氯化锰，加去离子水稀释至2毫升；在搅拌下将所得硝酸锰水溶液逐滴加入到步骤a)所得浆状粘稠混合物中，继续搅拌3小时后，于90℃烘干；b) Weigh 0.136 g of manganese chloride tetrahydrate, dilute to 2 ml with deionized water; add the obtained aqueous manganese nitrate solution dropwise to the viscous viscous mixture obtained in step a) with stirring, and continue stirring for 3 hours. Dry at 90 ° C;
c)将步骤b)制得的样品研磨成粉末，在空气氛中于550℃下焙烧2小时，即得本发明实施例催化剂。c) The sample obtained in the step b) was ground into a powder and calcined at 550 ° C for 2 hours in an air atmosphere to obtain a catalyst of the examples of the present invention.
图7是本实施例所制催化剂及所用载体分子筛的X射线粉末衍射(XRD)图谱；由图可知，催化剂具有与TS-1分子筛相同的衍射峰，未观察到其他物相峰，表明负载的活性组分高度分散在载体分子筛表面。Figure 7 is an X-ray powder diffraction (XRD) pattern of the catalyst prepared in the present example and the supported molecular sieve used; it can be seen from the figure that the catalyst has the same diffraction peak as the TS-1 molecular sieve, and no other phase peak is observed, indicating that the load is The active component is highly dispersed on the surface of the carrier molecular sieve.
实施例13Example 13
本实施例的目的是提供15.8MnO2·1.1Na2O·20.8WO3·2.0TiO2·60.3SiO2催化剂的制备。The purpose of this example was to provide a preparation of a 15.8MnO 2 ·1.1Na 2 O·20.8 WO 3 ·2.0TiO 2 ·60.3 SiO 2 catalyst.
a)分别称取0.11克钨酸钠(Na2WO4·2H2O)和0.367克钨酸铵(N10H40O41W12·xH2O；WO3含量：72％)溶于2.5毫升去离子水中配成钨酸钠和钨酸铵的混合水溶液；称取2.00克干燥的Ti-MWW分子筛(Si/Ti比40)移入100毫升烧杯中，先加入5.0毫升去离子水 使分子筛分散后，逐滴加入上述配制的钨酸钠水溶液，超声分散0.5h后继续搅拌3h，得浆状粘稠混合物；a) 0.11 g of sodium tungstate (Na 2 WO 4 ·2H 2 O) and 0.367 g of ammonium tungstate (N 10 H 40 O 41 W 12 ·xH 2 O; WO 3 content: 72%) were respectively dissolved in 2.5. A mixed aqueous solution of sodium tungstate and ammonium tungstate is prepared in milliliters of deionized water; 2.00 g of dried Ti-MWW molecular sieve (Si/Ti ratio 40) is weighed into a 100 ml beaker, and 5.0 ml of deionized water is added to disperse the molecular sieve. After that, the sodium tungstate aqueous solution prepared above was added dropwise, and after ultrasonic dispersion for 0.5 h, stirring was continued for 3 hours to obtain a viscous viscous mixture;
b)称取1.30克50％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逐滴加入到步骤a)所得浆状粘稠混合物中，继续搅拌3h后，于100℃烘干；b) Weigh 1.30 g of 50% aqueous manganese nitrate solution, dilute to 2 ml with deionized water; add the obtained aqueous solution of manganese nitrate dropwise to the viscous viscous mixture obtained in step a), and continue stirring for 3 h. Drying at 100 ° C;
c)将步骤b)制得的样品研磨成粉末，在空气氛中于600℃下焙烧1小时，即得本发明实施例催化剂。c) The sample obtained in the step b) was ground into a powder and calcined at 600 ° C for 1 hour in an air atmosphere to obtain a catalyst of the examples of the present invention.
实施例14Example 14
本实施例的目的是提供15.8MnO2·3.3Na2O·13.9WO3·2.2TiO2·64.8SiO2催化剂的制备。The purpose of this example was to provide a preparation of a 15.8MnO 2 ·3.3Na 2 O·13.9 WO 3 ·2.2TiO 2 ·64.8 SiO 2 catalyst.
a)分别称取0.532克钨酸钠(Na2WO4·2H2O)和0.045克钨酸铵溶于2.5毫升去离子水中配成钨酸钠和钨酸铵的混合水溶液；称取2.00克干燥的Ti-MWW分子筛(Si/Ti比40)移入100毫升烧杯中，先加入5.0毫升去离子水使分子筛分散后，逐滴加入上述配制的钨酸钠水溶液，超声分散0.5h后继续搅拌3h，得浆状粘稠混合物；a) Weigh 0.532 g of sodium tungstate (Na 2 WO 4 ·2H 2 O) and 0.045 g of ammonium tungstate dissolved in 2.5 ml of deionized water to prepare a mixed aqueous solution of sodium tungstate and ammonium tungstate; weigh 2.00 g The dried Ti-MWW molecular sieve (Si/Ti ratio 40) was transferred into a 100 ml beaker. After adding 5.0 ml of deionized water to disperse the molecular sieve, the above prepared sodium tungstate aqueous solution was added dropwise, and ultrasonically dispersed for 0.5 h and then stirred for 3 hours. a viscous mixture;
b)称取1.95克50％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逐滴加入到步骤a)所得浆状粘稠混合物中，继续搅拌3h后，于100℃烘干；b) Weigh 1.95 g of 50% aqueous manganese nitrate solution, dilute to 2 ml with deionized water; add the obtained aqueous solution of manganese nitrate dropwise to the viscous viscous mixture obtained in step a), and continue stirring for 3 h. Drying at 100 ° C;
c)将步骤b)制得的样品研磨成粉末，在空气氛中于600℃下焙烧1小时，即得本发明实施例催化剂。c) The sample obtained in the step b) was ground into a powder and calcined at 600 ° C for 1 hour in an air atmosphere to obtain a catalyst of the examples of the present invention.
图8是本实施例所制催化剂及所用载体分子筛的X射线粉末衍射(XRD)图谱；可以看出，催化剂具有与Ti-MWW分子筛相同的衍射峰，未观察到其他物相峰，表明负载的活性组分高度分散在载体分子筛表面。Figure 8 is an X-ray powder diffraction (XRD) pattern of the catalyst prepared in the present example and the supported molecular sieve used; it can be seen that the catalyst has the same diffraction peak as the Ti-MWW molecular sieve, and no other phase peaks are observed, indicating that the load is The active component is highly dispersed on the surface of the carrier molecular sieve.
实施例15Example 15
本实施例的目的是提供0.5MnO2·0.2Na2O·0.7WO3·3.2TiO2·95.4SiO2催化剂的制备。The purpose of this example was to provide a preparation of a 0.5MnO 2 ·0.2Na 2 O·0.7 WO 3 ·3.2TiO 2 ·95.4SiO 2 catalyst.
a)称取0.019克钨酸钠(Na2WO4·2H2O)溶于2.5毫升去离子水中配成钨酸钠的水溶液；称取2.00克干燥的Ti-MWW分子筛(Si/Ti比40)移入100毫升烧杯中，先加入5.0毫升去离子水使分子筛分散后，逐滴加入上述配制的钨酸钠水溶液，超声分散1小时后继续搅拌1小时，得浆状粘稠混合物；a) Weigh 0.019 g of sodium tungstate (Na 2 WO 4 ·2H 2 O) dissolved in 2.5 ml of deionized water to prepare an aqueous solution of sodium tungstate; weigh 2.00 g of dry Ti-MWW molecular sieve (Si/Ti ratio 40 Transfer into a 100 ml beaker, first add 5.0 ml of deionized water to disperse the molecular sieve, then add the above prepared sodium tungstate aqueous solution dropwise, and stir for 1 hour after ultrasonic dispersion for 1 hour to obtain a viscous viscous mixture;
b)称取0.042克50％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逐滴加入到步骤a)所得浆状粘稠混合物中，继续搅拌1小时后，于80℃烘干；b) Weigh 0.042 g of 50% aqueous manganese nitrate solution, dilute to 2 ml with deionized water; add the obtained aqueous manganese nitrate solution dropwise to the viscous viscous mixture obtained in the step a), and continue stirring for 1 hour. Dry at 80 ° C;
c)将步骤b)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。c) The sample obtained in the step b) was ground into a powder and calcined at 650 ° C for 2 hours in an air atmosphere to obtain a catalyst of this example.
图9是本实施例所制催化剂及所用载体分子筛的X射线粉末衍射(XRD)图谱；可以看出，催化剂具有与Ti-MWW分子筛相同的衍射峰，未观察到其他物相峰，表明负载的活性组分高度分散在载体分子筛表面。 Figure 9 is an X-ray powder diffraction (XRD) pattern of the catalyst prepared in the present example and the supported molecular sieve used; it can be seen that the catalyst has the same diffraction peak as the Ti-MWW molecular sieve, and no other phase peaks are observed, indicating that the load is The active component is highly dispersed on the surface of the carrier molecular sieve.
实施例16Example 16
本实施例的目的是提供2.8MnO2·0.1Na2O·3.6WO3·3.0TiO2·90.5SiO2催化剂的制备。The purpose of this example was to provide a preparation of a 2.8MnO 2 ·0.1Na 2 O·3.6WO 3 ·3.0TiO 2 ·90.5SiO 2 catalyst.
a)称取0.011克钨酸钠(Na2WO4·2H2O)和0.078克钨酸铵(N10H40O41W12·xH2O；WO3含量：72％)溶于2.5毫升去离子水中配成钨酸钠的水溶液；称取2.00克干燥的Ti-MWW分子筛(Si/Ti比40)移入100毫升烧杯中，先加入5.0毫升去离子水使分子筛分散后，逐滴加入上述配制的钨酸钠水溶液，超声分散1小时后继续搅拌1小时，得浆状粘稠混合物；a) Weigh 0.011 g of sodium tungstate (Na 2 WO 4 ·2H 2 O) and 0.078 g of ammonium tungstate (N 10 H 40 O 41 W 12 ·xH 2 O; WO 3 content: 72%) dissolved in 2.5 ml An aqueous solution of sodium tungstate is prepared in deionized water; 2.00 g of dried Ti-MWW molecular sieve (Si/Ti ratio 40) is weighed into a 100 ml beaker, and then 5.0 ml of deionized water is added to disperse the molecular sieve, and then added dropwise. The prepared sodium tungstate aqueous solution was ultrasonically dispersed for 1 hour and then stirred for 1 hour to obtain a viscous viscous mixture;
b)称取0.247克50％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逐滴加入到步骤a)所得浆状粘稠混合物中，继续搅拌1小时后，于80℃烘干；b) Weigh 0.247 g of 50% manganese nitrate aqueous solution, dilute to 2 ml with deionized water; add the obtained manganese nitrate aqueous solution dropwise to the slurry viscous mixture obtained in the step a) with stirring, and continue stirring for 1 hour. Dry at 80 ° C;
c)将步骤b)制得的样品研磨成粉末，在空气氛中于650℃下焙烧2小时，即得本发明实施例催化剂。c) The sample obtained in the step b) was ground into a powder and calcined at 650 ° C for 2 hours in an air atmosphere to obtain a catalyst of the examples of the present invention.
图10是本实施例所制催化剂及所用载体分子筛的X射线粉末衍射(XRD)图谱；可以看出，催化剂具有与Ti-MWW分子筛相同的衍射峰，未观察到其他物相峰，表明负载的活性组分高度分散在载体分子筛表面。Figure 10 is an X-ray powder diffraction (XRD) pattern of the catalyst prepared in the present example and the supported molecular sieve used; it can be seen that the catalyst has the same diffraction peak as the Ti-MWW molecular sieve, and no other phase peaks are observed, indicating that the load is The active component is highly dispersed on the surface of the carrier molecular sieve.
本申请的发明人发现，本发明在选用含钛分子筛或不含钛的纯硅分子筛作为载体时所得催化剂的性能明显优于用无定形SiO2或无定形SiO2-TiO2复合氧化物(包括介孔SiO2)为载体所得催化剂的性能。下面是本申请的发明人所做的若干用于对比的实验。The inventors of the present application have found that the performance of the obtained catalyst when using a titanium-containing molecular sieve or a pure silicon molecular sieve containing no titanium as a support is significantly superior to the use of amorphous SiO 2 or amorphous SiO 2 -TiO 2 composite oxide (including Mesoporous SiO 2 ) is the property of the catalyst obtained by the support. The following are some experiments for comparison by the inventors of the present application.
对比例1Comparative example 1
本对比例的目的是提供一种无定形SiO2(上海国药)负载的2.8MnO2·1.0Na2O·3.6WO3·92.6SiO2催化剂的制备。The purpose of this comparative example is to provide an amorphous SiO 2 (Shanghai Sinopharm) supported 2.8MnO 2 ·1.0Na 2 O·3.6WO 3 ·92.6SiO 2 catalyst.
a)称取0.11克钨酸钠(Na2WO4·2H2O)溶于2.5毫升去离子水中配成钨酸钠的水溶液；称取2.00克干燥的无定形SiO2(上海国药)移入100毫升烧杯中，先加入5.0毫升去离子水使分子筛分散后，逐滴加入上述配制的钨酸钠水溶液，超声分散0.5小时后继续搅拌3小时，得浆状粘稠混合物；a) Weigh 0.11 g of sodium tungstate (Na 2 WO 4 · 2H 2 O) dissolved in 2.5 ml of deionized water to prepare an aqueous solution of sodium tungstate; weigh 2.00 g of dried amorphous SiO 2 (Shanghai Sinopharm) into 100 In a milliliter beaker, after adding 5.0 ml of deionized water to disperse the molecular sieve, the above prepared sodium tungstate aqueous solution was added dropwise, ultrasonically dispersed for 0.5 hour, and stirring was continued for 3 hours to obtain a viscous viscous mixture;
b)称取0.247克50％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逐滴加入到步骤a)所得浆状粘稠混合物中，继续搅拌3小时后，于90℃烘干；b) Weigh 0.247 g of 50% aqueous manganese nitrate solution, dilute to 2 ml with deionized water; add the obtained aqueous manganese nitrate solution dropwise to the slurry viscous mixture obtained in step a) with stirring, and continue stirring for 3 hours. Dry at 90 ° C;
c)将步骤b)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。c) The sample prepared in the step b) was ground into a powder and calcined at 550 ° C for 2 hours in an air atmosphere to obtain the catalyst of the comparative example.
对比例2Comparative example 2
本对比例的目的是提供一种用无定形介孔TiO2-SiO2(Si/Ti比＝40)氧化物为载体的2.8MnO2·1.0Na2O·3.6WO3·3.0TiO2-89.6SiO2催化剂的制备。 The purpose of this comparative example is to provide a 2.8MnO 2 ·1.0Na 2 O·3.6WO 3 ·3.0TiO 2 -89.6 with an amorphous mesoporous TiO 2 -SiO 2 (Si/Ti ratio=40) oxide as a support. Preparation of a SiO 2 catalyst.
无定形TiO2-SiO2(Si/Ti比＝40)氧化物的制备参照专利CN 102614857 B公开的金属原子掺杂的单分散介孔二氧化硅球形纳米颗粒的制备方法进行合成。The preparation of an amorphous TiO 2 -SiO 2 (Si/Ti ratio = 40) oxide is carried out by referring to the preparation method of metal atom-doped monodisperse mesoporous silica spherical nanoparticles disclosed in the patent CN 102614857 B.
a)称取0.11克钨酸钠(Na2WO4·2H2O)溶于2.5毫升去离子水中配成钨酸钠的水溶液；称取2.00克干燥的无定形介孔TiO2-SiO2移入100毫升烧杯中，先加入5.0毫升去离子水使分子筛分散后，逐滴加入上述配制的钨酸钠水溶液，超声分散0.5小时后继续搅拌3小时，得浆状粘稠混合物；a) Weigh 0.11 g of sodium tungstate (Na 2 WO 4 · 2H 2 O) dissolved in 2.5 ml of deionized water to prepare an aqueous solution of sodium tungstate; weigh 2.00 g of dry amorphous mesoporous TiO 2 -SiO 2 into the solution In a 100 ml beaker, after adding 5.0 ml of deionized water to disperse the molecular sieve, the above prepared sodium tungstate aqueous solution was added dropwise, ultrasonically dispersed for 0.5 hour, and stirring was continued for 3 hours to obtain a viscous viscous mixture;
b)称取0.247克50％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逐滴加入到步骤a)所得浆状粘稠混合物中，继续搅拌3小时后，于90℃烘干；b) Weigh 0.247 g of 50% aqueous manganese nitrate solution, dilute to 2 ml with deionized water; add the obtained aqueous manganese nitrate solution dropwise to the slurry viscous mixture obtained in step a) with stirring, and continue stirring for 3 hours. Dry at 90 ° C;
c)将步骤b)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。c) The sample prepared in the step b) was ground into a powder and calcined at 550 ° C for 2 hours in an air atmosphere to obtain the catalyst of the comparative example.
对比例3Comparative example 3
本对比例的目的是提供一种介孔SiO2负载的2.8MnO2·1.0Na2O·3.6WO3·92.6SiO2催化剂的制备。The purpose of this comparative example was to provide a preparation of a mesoporous SiO 2 supported 2.8MnO 2 ·1.0Na 2 O·3.6 WO 3 ·92.6SiO 2 catalyst.
a)称取0.11克钨酸钠(Na2WO4·2H2O)溶于2.5毫升去离子水中配成钨酸钠的水溶液；称取2.00克干燥的介孔SiO2移入100毫升烧杯中，先加入5.0毫升去离子水使分子筛分散后，逐滴加入上述配制的钨酸钠水溶液，超声分散0.5小时后继续搅拌3小时，得浆状粘稠混合物；a) Weigh 0.11 g of sodium tungstate (Na 2 WO 4 · 2H 2 O) dissolved in 2.5 ml of deionized water to prepare an aqueous solution of sodium tungstate; weigh 2.00 g of dry mesoporous SiO 2 into a 100 ml beaker. After adding 5.0 ml of deionized water to disperse the molecular sieve, the above prepared sodium tungstate aqueous solution was added dropwise, ultrasonically dispersed for 0.5 hour, and stirring was continued for 3 hours to obtain a viscous viscous mixture;
b)称取0.247克50％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逐滴加入到步骤a)所得浆状粘稠混合物中，继续搅拌3小时后，于90℃烘干；b) Weigh 0.247 g of 50% aqueous manganese nitrate solution, dilute to 2 ml with deionized water; add the obtained aqueous manganese nitrate solution dropwise to the slurry viscous mixture obtained in step a) with stirring, and continue stirring for 3 hours. Dry at 90 ° C;
c)将步骤b)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。c) The sample prepared in the step b) was ground into a powder and calcined at 550 ° C for 2 hours in an air atmosphere to obtain the catalyst of the comparative example.
对比例4Comparative example 4
本对比例的目的是提供一种具有与Ti-MWW相同晶体结构的硅铝分子筛MCM-22分子筛(Si/Al比＝15)负载的MnO2-Na2O-WO3催化剂的制备；所得催化剂组成：2.8MnO2·1.0Na2O·3.6WO3·92.6MCM-22。The purpose of this comparative example is to provide a preparation of a MnO 2 -Na 2 O-WO 3 catalyst supported by a silica-alumina molecular sieve MCM-22 molecular sieve (Si/Al ratio = 15) having the same crystal structure as Ti-MWW; Composition: 2.8MnO 2 ·1.0Na 2 O·3.6WO 3 ·92.6MCM-22.
a)称取0.11克钨酸钠(Na2WO4·2H2O)溶于2.5毫升去离子水中配成钨酸钠的水溶液；称取2.00克干燥的MCM-22分子筛(Si/Al比＝15)移入100毫升烧杯中，先加入5.0毫升去离子水使分子筛分散后，逐滴加入上述配制的钨酸钠水溶液，超声分散0.5小时后继续搅拌3小时，得浆状粘稠混合物；a) Weigh 0.11 g of sodium tungstate (Na 2 WO 4 ·2H 2 O) dissolved in 2.5 ml of deionized water to prepare an aqueous solution of sodium tungstate; weigh 2.00 g of dried MCM-22 molecular sieve (Si/Al ratio = 15) Transfer into a 100 ml beaker, first add 5.0 ml of deionized water to disperse the molecular sieve, then add the above prepared sodium tungstate aqueous solution dropwise, ultrasonically disperse for 0.5 hour, and continue to stir for 3 hours to obtain a viscous viscous mixture;
b)称取0.247克50％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逐滴加入到步骤a)所得浆状粘稠混合物中，继续搅拌3小时后，于90℃烘干；b) Weigh 0.247 g of 50% aqueous manganese nitrate solution, dilute to 2 ml with deionized water; add the obtained aqueous manganese nitrate solution dropwise to the slurry viscous mixture obtained in step a) with stirring, and continue stirring for 3 hours. Dry at 90 ° C;
c)将步骤b)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。c) The sample prepared in the step b) was ground into a powder and calcined at 550 ° C for 2 hours in an air atmosphere to obtain the catalyst of the comparative example.
对比例5 Comparative example 5
本对比例的目的是提供一种具有与Silicalite-1相同晶体结构的硅铝分子筛ZSM-5分子筛(Si/Al比＝30)负载的MnO2-Na2O-WO3催化剂的制备；所得催化剂组成：2.8MnO2·1.0Na2O·3.6WO3·92.6ZSM-5。The purpose of this comparative example is to provide a preparation of a MnO 2 -Na 2 O-WO 3 catalyst supported by a silica-alumina molecular sieve ZSM-5 molecular sieve (Si/Al ratio = 30) having the same crystal structure as Silicalite-1; Composition: 2.8MnO 2 ·1.0Na 2 O·3.6WO 3 ·92.6ZSM-5.
a)称取0.11克钨酸钠(Na2WO4·2H2O)溶于2.5毫升去离子水中配成钨酸钠的水溶液；称取2.00克干燥的ZSM-5分子筛(Si/Al比＝30)移入100毫升烧杯中，先加入5.0毫升去离子水使分子筛分散后，逐滴加入上述配制的钨酸钠水溶液，超声分散0.5小时后继续搅拌3小时，得浆状粘稠混合物；a) Weigh 0.11 g of sodium tungstate (Na 2 WO 4 ·2H 2 O) dissolved in 2.5 ml of deionized water to prepare an aqueous solution of sodium tungstate; weigh 2.00 g of dried ZSM-5 molecular sieve (Si/Al ratio = 30) Transfer into a 100 ml beaker, first add 5.0 ml of deionized water to disperse the molecular sieve, then add the above prepared sodium tungstate aqueous solution dropwise, ultrasonically disperse for 0.5 hour, and continue to stir for 3 hours to obtain a viscous viscous mixture;
b)称取0.247克50％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逐滴加入到步骤a)所得浆状粘稠混合物中，继续搅拌3小时后，于90℃烘干；b) Weigh 0.247 g of 50% aqueous manganese nitrate solution, dilute to 2 ml with deionized water; add the obtained aqueous manganese nitrate solution dropwise to the slurry viscous mixture obtained in step a) with stirring, and continue stirring for 3 hours. Dry at 90 ° C;
c)将步骤b)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。c) The sample prepared in the step b) was ground into a powder and calcined at 550 ° C for 2 hours in an air atmosphere to obtain the catalyst of the comparative example.
应用例1Application example 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16mm、长400mm。催化剂装量0.224克。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(30％乙醇)浴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。C1-C3烃气体采用30-m HP Porapak Q毛细管色谱柱和FID检测器进行定量分析，N2、O2、CO、CO2和CH4采用2-m ShinCarbon填充柱(DIKMA)和TCD检测器进行定量分析。Catalyst reaction evaluation was carried out on a continuous flow fixed bed microreactor. It adopts a quartz tube reactor with an inner diameter of 16 mm and a length of 400 mm. The catalyst loading was 0.224 g. 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 chilled ethanol-water (30% ethanol) bath, and then quantitatively detected by an online gas chromatograph. C1-C3 hydrocarbon gas was quantified using a 30-m HP Porapak Q capillary column and FID detector. N 2 , O 2 , CO, CO 2 and CH4 were performed using a 2-m ShinCarbon packed column (DIKMA) and a TCD detector. Quantitative analysis.
本应用例的目的是考察实施例和对比例催化剂的甲烷氧化偶联反应性能。采用CH4∶O2∶N2＝3.2∶1∶3.7(体积比；CH4浓度：40％)的原料气，在以CH4和O2计的气时空速GHSV＝30,000ml·h-1·g-1、常压和反应温度700～800℃条件下进行反应评价。实施例催化剂和对比例催化剂的甲烷氧化偶联反应结果分别见表1和表2。由表1和表2结果可以看出，本发明实施例催化剂具有明显高于对比例催化剂的催化活性和产物选择性。由表1可见，甲烷转化可达35％以上，C2-C3产物选择性可达80％以上，C2-C3产物时空产率可高达149mol·kg-1·h-1。本发明催化剂具有明显优于现有催化剂技术的甲烷氧化偶联反应性能；而且，本发明催化剂优于现有催化剂技术还体现在C2产物中高的乙烯/乙烷比(>2)以及明显的丙烯生成(选择性可高达9％左右)。 The purpose of this application example was to investigate the methane oxidative coupling reaction performance of the examples and comparative catalysts. Using CH 4 :O 2 :N 2 = 3.2:1:3.7 ( volume ratio; CH 4 concentration: 40%) of the raw-material gas of CH 4 and O in terms of gas hourly space velocity 2 GHSV = 30,000ml · h -1 · Evaluation of the reaction under the conditions of g -1 , normal pressure and reaction temperature of 700 to 800 °C. The results of the methane oxidative coupling reaction of the example catalyst and the comparative catalyst are shown in Tables 1 and 2, respectively. As can be seen from the results of Tables 1 and 2, the catalysts of the examples of the present invention have significantly higher catalytic activity and product selectivity than the comparative catalysts. It can be seen from Table 1 that the methane conversion can reach more than 35%, the selectivity of the C2-C3 product can reach more than 80%, and the space-time yield of the C2-C3 product can be as high as 149 mol·kg -1 ·h -1 . The catalyst of the invention has significantly better methane oxidative coupling reaction performance than the existing catalyst technology; moreover, the catalyst of the invention is superior to the existing catalyst technology in that the ethylene/ethane ratio (>2) and the apparent propylene are high in the C2 product. Generated (selectivity can be as high as 9% or so).
表1 实施例催化剂的甲烷氧化偶联反应性能Table 1 Performance of methane oxidative coupling reaction of the catalysts of the examples
Figure PCTCN2015000003-appb-000001
Figure PCTCN2015000003-appb-000001
Figure PCTCN2015000003-appb-000002
Figure PCTCN2015000003-appb-000002
表2 对比例催化剂的甲烷氧化偶联反应性能Table 2 Performance of methane oxidative coupling reaction of comparative catalyst
Figure PCTCN2015000003-appb-000003
Figure PCTCN2015000003-appb-000003
应用例2Application example 2
催化剂反应评价和产物分析系统同应用例1。 The catalyst reaction evaluation and product analysis system were the same as in Application Example 1.
本应用例的目的是考察反应温度和气时空速对实施例催化剂的甲烷氧化偶联反应性能影响。分别采用CH4∶O2∶N2＝3.2∶1∶3.7(体积比；CH4浓度：40％)的原料气，在常压和反应温度700～800℃条件下进行反应评价，选用实施例1制备的催化剂，用量0.224克。反应结果见表3、图11和图12，可以看出，在较低的空速下，可以得到较高的转化率，特别是，10000ml·kg-1·h-1空速时，700℃下甲烷转化率可达24％但选择性较低(C2-C3选择性～67％)；另外，在较低空速下，随反应温度升高至800℃，产物选择性仍较低。当空速大于25000ml·kg-1·h-1和反应温度750℃及以上时，均能得到较高的甲烷转化率和产物选择性。在相同反应温度下，C2-C3产物选择性随着空速的增大而逐渐提高但甲烷转化率则随之有所降低；另外，C2产物的乙烯/乙烷比随之也略有下降。在相同空速下，反应温度从700℃增加至750℃时，C2-C3产物选择性陡然增加至～80％，然后随温度继续升高会略有降低；但乙烯/乙烷则随温度单调增加。随着空速的提高，C2-C3产物时空产率可高达140mol·kg-1·h-1以上。 The purpose of this application example is to investigate the effect of reaction temperature and gas hourly space velocity on the performance of the methane oxidative coupling reaction of the catalyst of the example. Respectively CH 4 :O 2 :N 2 = 3.2:1:3.7 ( volume ratio; CH 4 concentration: 40%) of the raw material gas, reaction pressure and reaction evaluated at a temperature of 700 ~ 800 ℃, selection Example 1 prepared catalyst, the amount of 0.224 grams. The reaction results are shown in Table 3, Figure 11 and Figure 12. It can be seen that at a lower space velocity, a higher conversion rate can be obtained, in particular, at a space velocity of 10000 ml·kg -1 ·h -1 , 700 ° C The methane conversion rate can reach 24% but the selectivity is low (C2-C3 selectivity ~67%); in addition, at lower space velocity, the product selectivity is still lower as the reaction temperature increases to 800 °C. When the space velocity is greater than 25000 ml·kg -1 ·h -1 and the reaction temperature is 750 ° C and above, higher methane conversion rate and product selectivity can be obtained. At the same reaction temperature, the selectivity of C2-C3 product gradually increased with the increase of space velocity, but the methane conversion rate decreased accordingly. In addition, the ethylene/ethane ratio of C2 product decreased slightly. At the same space velocity, when the reaction temperature is increased from 700 °C to 750 °C, the selectivity of C2-C3 product increases sharply to ～80%, and then decreases slightly with increasing temperature; however, ethylene/ethane is monotonous with temperature. increase. With the increase of space velocity, the space-time yield of C2-C3 product can be as high as 140 mol·kg -1 ·h -1 or more.
表3 反应温度和气时空速对实施例催化剂的甲烷氧化偶联反应性能的影响Table 3 Effect of reaction temperature and gas hourly space velocity on the performance of methane oxidative coupling reaction of the catalysts of the examples
Figure PCTCN2015000003-appb-000004
Figure PCTCN2015000003-appb-000004
应用例3Application Example 3
催化剂反应评价和产物分析系统同应用例1。The catalyst reaction evaluation and product analysis system were the same as in Application Example 1.
本应用例的目的是继续考察反应温度和气时空速对实施例催化剂的甲烷氧化偶联反应性能影响。采用CH4∶O2∶N2＝4∶1∶1(体积比；CH4浓度：66.7％)的原料气，在常压和反 应温度700～800℃条件下进行反应评价，选用实施例1制备的催化剂，用量0.224克。反应结果见表4，可以看出，在750℃及以上的相同反应温度下，C2-C3产物的选择性随着空速的增大而逐渐，但基本保持在80％以内；随着空速的增大，C2产物乙烯/乙烷比略有降低。800℃下，乙烯/乙烷比均可达3.0左右，同时可生成约10％的丙烯产物。在相同空速下，反应温度从700℃增加至800℃时，最高的C2-C3产物选择性出现在750-760℃，而700℃和800℃下均较低；另外，乙烯/乙烷则随温度单调增加。与现有技术的催化剂相比，上述数据(以及下文其他应用例所得数据)表明本发明的催化剂在更宽的反应条件下具有更优的催化性能。The purpose of this application example is to continue to investigate the effect of reaction temperature and gas hourly space velocity on the performance of the methane oxidative coupling reaction of the catalyst of the example. Using CH 4 :O 2 :N 2 = 4:1:1 ( volume ratio; CH 4 concentration: 66.7%) of the raw material gas, reaction pressure and reaction evaluated at a temperature of 700 ~ 800 ℃, the choice of Example 1 The prepared catalyst was used in an amount of 0.224 g. The reaction results are shown in Table 4. It can be seen that at the same reaction temperature of 750 ° C and above, the selectivity of the C2-C3 product gradually increases with the increase of the space velocity, but remains substantially within 80%; The increase in the ethylene/ethane ratio of the C2 product is slightly reduced. At 800 ° C, the ethylene / ethane ratio can reach about 3.0, while about 10% of the propylene product can be produced. At the same space velocity, when the reaction temperature is increased from 700 ° C to 800 ° C, the highest C2-C3 product selectivity occurs at 750-760 ° C, and is lower at 700 ° C and 800 ° C; in addition, ethylene / ethane Monotonously increases with temperature. The above data (and data from other application examples below) indicate that the catalyst of the present invention has superior catalytic performance over a wider range of reaction conditions than prior art catalysts.
表4 反应温度和气时空速对实施例催化剂的甲烷氧化偶联反应性能的影响Table 4 Effect of reaction temperature and gas hourly space velocity on the performance of methane oxidative coupling reaction of the catalysts of the examples
Figure PCTCN2015000003-appb-000005
Figure PCTCN2015000003-appb-000005
应用例4Application Example 4
催化剂反应评价和产物分析系统同应用例1。The catalyst reaction evaluation and product analysis system were the same as in Application Example 1.
本应用例的目的是考察反应温度和气时空速对实施例催化剂的甲烷氧化偶联反应性能影响。采用CH4∶O2∶N2＝2.6∶1∶3.7(体积比；CH4浓度：35％)的原料气，在以CH4和O2计的气时空速GHSV＝30,000ml·h-1·g-1、常压和反应温度700～800℃条件下进行反应评价，选用实施例1制备的催化剂，用量0.224克。反应结果见表5，可以看出，本发明催化剂在较低的CH4/O2比和较低的CH4浓度条件下，可以得到较高的CH4转化率；最高的C2-C3产物选择性出现在750-760℃，温度继续升高C2-C3产物选择性略有下降，仍然可以获得较高的产物收率和70mol·kg-1·h-1以上的时空产率。The purpose of this application example is to investigate the effect of reaction temperature and gas hourly space velocity on the performance of the methane oxidative coupling reaction of the catalyst of the example. Using CH 4 :O 2 :N 2 = 2.6:1:3.7 ( volume ratio; CH 4 concentration: 35%) of the raw-material gas of CH 4 and O 2 in terms of gas hourly space velocity GHSV = 30,000ml · h -1 The reaction was evaluated under the conditions of g -1 , normal pressure and reaction temperature of 700 to 800 ° C, and the catalyst prepared in Example 1 was used in an amount of 0.224 g. The reaction results are shown in Table 5. It can be seen that the catalyst of the present invention can obtain a higher CH 4 conversion rate at a lower CH 4 /O 2 ratio and a lower CH 4 concentration; the highest C2-C3 product selection The phenotype appeared at 750-760 ° C, and the temperature continued to increase. The selectivity of the C2-C3 product decreased slightly, and a higher product yield and a space-time yield of 70 mol·kg -1 ·h -1 or more were still obtained.
表5 反应温度对实施例催化剂的甲烷氧化偶联反应性能的影响Table 5 Effect of reaction temperature on the performance of methane oxidative coupling reaction of the catalyst of the example
Figure PCTCN2015000003-appb-000006
Figure PCTCN2015000003-appb-000006
应用例5Application Example 5
催化剂反应评价和产物分析系统同应用例1。The catalyst reaction evaluation and product analysis system were the same as in Application Example 1.
本应用例的目的是考察反应温度和气时空速对实施例催化剂的甲烷氧化偶联反应性能影响。采用CH4∶O2∶N2＝6∶1∶1(体积比；CH4浓度：75％)的原料气，在以CH4和O2计的气时空速GHSV＝30,000ml·h-1·g-1、常压和反应温度700～800℃条件下进行反应评价，选用实施例1制备的催化剂，用量0.224克。反应结果见表6，由表可知，在较高的CH4/O2比和较高的CH4浓度条件下，本发明催化剂表现出明显的低温活性和选择性，反应温度71O℃时即获得75％以上的C2-C3产物选择性，时空产率可达85.6mol·kg-1·h-1。随温度继续升高选择性并没有随之升高，特别是800℃时，C2-C3产物选择性明显。另外，乙烯/乙烷则随温度单调增加。 The purpose of this application example is to investigate the effect of reaction temperature and gas hourly space velocity on the performance of the methane oxidative coupling reaction of the catalyst of the example. Using CH 4 :O 2 :N 2 = 6:1:1 ( volume ratio; CH 4 concentration: 75%) of the raw-material gas of CH 4 and O in terms of gas hourly space velocity 2 GHSV = 30,000ml · h -1 The reaction was evaluated under the conditions of g -1 , normal pressure and reaction temperature of 700 to 800 ° C, and the catalyst prepared in Example 1 was used in an amount of 0.224 g. The reaction results are shown in Table 6. It can be seen from the table that the catalyst of the present invention exhibits significant low-temperature activity and selectivity at a higher CH 4 /O 2 ratio and a higher CH 4 concentration, and the reaction temperature is obtained at a reaction temperature of 71 ° C. More than 75% of the C 2 -C 3 products are selective, and the space time yield can reach 85.6 mol·kg -1 ·h -1 . As the temperature continues to increase, the selectivity does not increase, especially at 800 ° C, the C2-C3 product selectivity is significant. In addition, ethylene/ethane monotonically increases with temperature.
表6 反应温度对实施例催化剂的甲烷氧化偶联反应性能的影响Table 6 Effect of reaction temperature on the performance of methane oxidative coupling reaction of the catalysts of the examples
Figure PCTCN2015000003-appb-000007
Figure PCTCN2015000003-appb-000007
应用例6Application Example 6
催化剂反应评价和产物分析系统同应用例1。The catalyst reaction evaluation and product analysis system were the same as in Application Example 1.
本应用例的目的是考察实施例催化剂的甲烷氧化偶联反应的稳定性。采用CH4∶O2∶N2＝3.2∶1∶3.7(体积比；CH4浓度：40％)的原料气，在以CH4和O2计的气时空速GHSV＝30,000ml·h-1·g-1、常压和反应温度700～800℃条件下进行反应评价，选用实施例1制备的催化剂，用量0.224克。反应结果见图13，可以看出，催化剂具有良好的反应稳定性。The purpose of this application example was to investigate the stability of the methane oxidative coupling reaction of the catalysts of the examples. Using CH 4 :O 2 :N 2 = 3.2:1:3.7 ( volume ratio; CH 4 concentration: 40%) of the raw-material gas of CH 4 and O in terms of gas hourly space velocity 2 GHSV = 30,000ml · h -1 The reaction was evaluated under the conditions of g -1 , normal pressure and reaction temperature of 700 to 800 ° C, and the catalyst prepared in Example 1 was used in an amount of 0.224 g. The results of the reaction are shown in Figure 13, and it can be seen that the catalyst has good reaction stability.
工业实用性Industrial applicability
本发明所涉及的催化剂可以应用于化工领域。 The catalyst of the present invention can be applied to the chemical industry.

Claims (8)

  1. 一种含钛或不含钛的锰-钠-钨-硅复合氧化物催化剂，其特征在于，具有如下通式：vMnO2·xNa2O·yWO3·zTiO2·(100-v-x-y-z)SiO2，其中v、x、y、z分别表示氧化锰、氧化钠、氧化钨和氧化钛所占的质量分数，0.3≤v≤16，0.1≤x≤5，0.6≤y≤21，0.0≤z≤4。A manganese-sodium-tungsten-silicon composite oxide catalyst containing or not containing titanium, which has the following formula: vMnO2·xNa2O·yWO3·zTiO2·(100-vxyz)SiO2, wherein v, x, Y and z respectively represent the mass fraction of manganese oxide, sodium oxide, tungsten oxide and titanium oxide, 0.3 ≤ v ≤ 16, 0.1 ≤ x ≤ 5, 0.6 ≤ y ≤ 21, 0.0 ≤ z ≤ 4.
  2. 根据权利要求1所述含钛或不含钛的锰-钠-钨-硅复合氧化物催化剂，其中，所述催化剂通过浸渍法使氧化锰、氧化钠和氧化钨负载于钛硅分子筛或纯硅分子筛上并经焙烧制备得到。The titanium-containing or titanium-free manganese-sodium-tungsten-silicon composite oxide catalyst according to claim 1, wherein said catalyst supports manganese oxide, sodium oxide and tungsten oxide on titanium silicon molecular sieve or pure silicon by a dipping method It is prepared by molecular sieve and calcined.
  3. 根据权利要求2所述含钛或不含钛的锰-钠-钨-硅复合氧化物催化剂，其中，所述分子筛为Ti-MWW、TS-1、Ti-Beta、Silicalite-1、Silicalite-2中的任一种。The titanium-containing or titanium-free manganese-sodium-tungsten-silicon composite oxide catalyst according to claim 2, wherein the molecular sieve is Ti-MWW, TS-1, Ti-Beta, Silicalite-1, Silicalite-2 Any of them.
  4. 根据权利要求2所述含钛或不含钛的锰-钠-钨-硅复合氧化物催化剂，其中，所述氧化锰的前体是硝酸锰、醋酸锰、氯化锰或硫酸锰，所述氧化钠和氧化钨的前体是钨酸钠、钨酸钠与钨酸铵的混合物。The titanium-containing or titanium-free manganese-sodium-tungsten-silicon composite oxide catalyst according to claim 2, wherein the manganese oxide precursor is manganese nitrate, manganese acetate, manganese chloride or manganese sulfate, The precursors of sodium oxide and tungsten oxide are a mixture of sodium tungstate, sodium tungstate and ammonium tungstate.
  5. 一种用于制备含钛或不含钛的锰-钠-钨-硅复合氧化物催化剂的方法，包括如下步骤：A method for preparing a manganese-sodium-tungsten-silicon composite oxide catalyst containing or not containing titanium, comprising the steps of:
    a)室温下将干燥的分子筛粉末浸渍于钨酸钠水溶液或钨酸钠与钨酸铵的混合水溶液中，经超声分散0.5～1小时后搅拌1～3小时，得到混合物；a) immersing the dried molecular sieve powder in a mixed aqueous solution of sodium tungstate or sodium tungstate and ammonium tungstate at room temperature, after ultrasonic dispersion for 0.5 to 1 hour, and then stirring for 1 to 3 hours to obtain a mixture;
    b)室温搅拌下，将硝酸锰、氯化锰、醋酸锰或硫酸锰水溶液逐滴加入到步骤a)制得的混合物后，继续搅拌1～3小时后80～100℃烘干，得到烘干物；b) adding manganese nitrate, manganese chloride, manganese acetate or manganese sulfate aqueous solution to the mixture obtained in step a) dropwise after stirring at room temperature, stirring for 1 to 3 hours, drying at 80 to 100 ° C, and drying. Object
    c)将步骤b)制得的烘干物研磨成粉末，在空气氛中于550～800℃下焙烧1～2小时，即得到所述的催化剂。c) The dried product obtained in the step b) is ground into a powder, and calcined at 550 to 800 ° C for 1 to 2 hours in an air atmosphere to obtain the catalyst.
  6. 根据权利要求5的方法，其中步骤c)所得到的催化剂具有如下通式：vMnO2·xNa2O·yWO3·zTiO2·(100-v-x-y-z)SiO2，其中v、x、y、z分别表示氧化锰、氧化钠、氧化钨和氧化钛所占的质量分数，0.3≤v≤16，0.1≤x≤5，0.6≤y≤21，0.0≤z≤4。The method according to claim 5, wherein the catalyst obtained in the step c) has the following formula: vMnO 2 · xNa 2 O · yWO 3 · zTiO 2 · (100-vxyz) SiO 2 , wherein v, x, y, z respectively It represents the mass fraction of manganese oxide, sodium oxide, tungsten oxide and titanium oxide, 0.3 ≤ v ≤ 16, 0.1 ≤ x ≤ 5, 0.6 ≤ y ≤ 21, 0.0 ≤ z ≤ 4.
  7. 一种采用甲烷氧化偶联工艺来制备烯烃的方法，其特征在于使用根据权利要求1所述的含钛或不含钛的锰-钠-钨-硅复合氧化物催化剂。A method for producing an olefin by a methane oxidative coupling process, characterized in that the titanium-containing or titanium-free manganese-sodium-tungsten-silicon composite oxide catalyst according to claim 1 is used.
  8. 根据权利要求7的方法，其中：反应温度650～800℃，原料气中甲烷/氧气体积比2.5～6，原料气中甲烷体积浓度35～75％，以甲烷和氧气计的反应气时空速10000～60000mL·g-1·h-1。 The method according to claim 7, wherein the reaction temperature is 650 to 800 ° C, the methane/oxygen volume ratio in the raw material gas is 2.5 to 6, the methane volume concentration in the raw material gas is 35 to 75%, and the reaction gas hour and space velocity in terms of methane and oxygen is 10,000. ~60000mL·g -1 ·h -1 .
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