WO2021004424A1 - Molybdenum-based catalyst, preparation method therefor and use thereof - Google Patents

Molybdenum-based catalyst, preparation method therefor and use thereof Download PDF

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WO2021004424A1
WO2021004424A1 PCT/CN2020/100410 CN2020100410W WO2021004424A1 WO 2021004424 A1 WO2021004424 A1 WO 2021004424A1 CN 2020100410 W CN2020100410 W CN 2020100410W WO 2021004424 A1 WO2021004424 A1 WO 2021004424A1
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molybdenum
carrier
based catalyst
active component
catalyst according
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PCT/CN2020/100410
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Chinese (zh)
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WO2021004424A9 (en
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王勇
吕国锋
马啸
王哲
于丽丽
唐静思
陈志荣
李浩然
王志轩
毛建拥
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浙江新和成股份有限公司
浙江大学
山东新和成氨基酸有限公司
山东新和成维生素有限公司
上虞新和成生物化工有限公司
山东新和成药业有限公司
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Priority to DE112020000197.0T priority Critical patent/DE112020000197T5/en
Publication of WO2021004424A1 publication Critical patent/WO2021004424A1/en
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    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • 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
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    • B01J23/28—Molybdenum
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    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8898—Manganese, technetium or rhenium containing also molybdenum
    • B01J35/23—
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
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    • C07C46/06—Preparation of quinones by oxidation giving rise to quinoid structures of at least one hydroxy group on a six-membered aromatic ring
    • C07C46/08—Preparation of quinones by oxidation giving rise to quinoid structures of at least one hydroxy group on a six-membered aromatic ring with molecular oxygen
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    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
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    • C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
    • C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
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    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the invention relates to the technical field of catalysts, in particular to a molybdenum-based catalyst and a preparation method and application thereof.
  • Molybdenum-based catalysts are a typical catalyst in propylene oxidation and ammoxidation reactions, and are also used in oxidative dehydrogenation reactions of some hydrocarbons. Since most of the oxidation reactions are exothermic, the hot spot temperature of the catalyst bed during the reaction is too high, which is easy to cause the agglomeration and loss of active centers, and eventually the catalyst is gradually deactivated and regeneration is difficult.
  • Molybdenum-based catalysts are divided into unsupported and supported catalysts.
  • the active components of unsupported catalysts are easy to agglomerate and have poor stability. Therefore, most of the current molybdenum-based catalysts are supported catalysts.
  • the traditional preparation methods of supported catalysts include impregnation method, kneading method, co-precipitation method, ion exchange method, etc.
  • impregnation method and kneading method are mostly used in industry.
  • the kneading method is an early catalyst preparation method. The method is to mix the metal and auxiliary component compounds, the carrier powder and the binder together, and then knead, shape, dry and roast to prepare the catalyst.
  • the advantage of this method is that the preparation process is simple, but the disadvantage is that the active metal component is poorly dispersed.
  • the impregnation method is currently the most commonly used method for preparing supported catalysts. This method first prepares the support, then impregnates the solution containing the active components on the support, and finally prepares the catalyst through steps such as drying and roasting.
  • the catalyst prepared by this method has relatively good metal dispersibility, but the interaction between the active metal component and the carrier is weak, and there are still disadvantages such as the active component being easy to aggregate and sinter at high temperature.
  • a molybdenum-based catalyst and a preparation method and application thereof are provided.
  • the molybdenum-based catalyst includes an active component molybdenum and a carrier.
  • the active component molybdenum exists in the form of elemental Mo and MoO x , where 0 ⁇ x ⁇ 3, the carrier is a metal oxide, and the surface has oxygen vacancies.
  • the elemental Mo in the active component molybdenum combines with the oxygen vacancy to form a Mo-[O]-M structure, where [O] represents the oxygen vacancy, M is the metal element in the carrier, and the active group Molybdenum is distributed on the surface of the carrier in the form of nanoparticles.
  • a carrier with oxygen vacancies is used to support the active component molybdenum.
  • the active component molybdenum exists in the form of elemental Mo and MoO x (0 ⁇ x ⁇ 3). There is a strong relationship between elemental Mo and oxygen vacancies. The interface effect can make the active component molybdenum and the surface of the carrier bond more firmly, and at the same time make the molybdenum-based catalyst have excellent catalytic activity.
  • the active component molybdenum in the molybdenum-based catalyst can be distributed on the surface of the carrier in the form of highly dispersed nanoparticles, and its particle size It can reach 5nm or even below 1nm, so the highly dispersed state of the catalyst active site exposure rate is extremely high, with excellent catalytic activity and selectivity.
  • the ultrafine nanoparticles can be effectively stabilized to prevent their agglomeration and loss.
  • the particle size of the active component molybdenum is less than or equal to 5 nm.
  • the molar content of the elemental Mo in the existence form of the active component molybdenum is 60% to 100%.
  • the carrier includes a first carrier selected from Ti, Zr, Ce, V, Cr, Mn, Fe, Zn, Ga, Ge, Sn, Bi, Y, Nb, Oxides of one element or multiple elements in La and Re.
  • the carrier further includes a second carrier, and the second carrier has an oxygen vacancy concentration lower than the oxygen vacancy concentration of the first carrier.
  • the second carrier is selected from one element or oxides of multiple elements among Al, Mg, and Ca.
  • the second carrier accounts for 0.5% to 30% of the mass of the carrier.
  • the loading amount of the active component molybdenum is recorded as 0.1% to 50% by mass percentage.
  • the preparation method of the molybdenum-based catalyst includes the following steps:
  • the second solid is placed in a reducing gas for a second calcination to obtain a molybdenum-based catalyst.
  • a carrier capable of forming oxygen vacancies is used to support the active component molybdenum, and a highly dispersed molybdenum-based catalyst is prepared by two calcinations.
  • the first time is calcined in air or inert gas, and the second time Calcined in reducing gas, after two calcinations, a molybdenum-based catalyst with elemental Mo as the main active component is obtained.
  • the preparation method makes a large number of oxygen vacancies formed on the surface of the carrier, the elemental Mo in the active component molybdenum and the oxygen vacancies on the surface of the carrier form a Mo-[O]-M structure, so that a strong interface between the active component molybdenum and the carrier is formed
  • the active component molybdenum can be distributed on the surface of the carrier in the form of nanoparticles, and its particle size can reach 5nm or even below 1nm.
  • the active component of the catalyst is not easy to agglomerate and lose, and it has excellent catalytic activity. .
  • the calcination temperature is 600° C. to 1000° C.
  • the calcination time is 0.1 hour to 12 hours.
  • the calcination temperature is 300° C. to 800° C.
  • the calcination time is 0.1 hour to 24 hours.
  • the carrier contains intrinsic oxygen vacancies.
  • the precursor of molybdenum is molybdic acid or soluble molybdate.
  • the precursor of molybdenum is selected from (NH 4 ) 2 Mo 2 O 7 , (NH 4 ) 2 Mo 4 O 13. 2H 2 O, H 2 MoO 4 , K 2 MoO 4 , ( One or more of NH 4 ) 6 Mo 7 O 24 ⁇ 4H 2 O and Na 2 MoO 4 ⁇ 2H 2 O.
  • the mass ratio of the precursor of the molybdenum to the carrier is 1-30.
  • the reducing gas includes hydrogen, methane, ethane, ethylene, acetylene, propane, propylene, propyne, propadiene, n-butane, isobutane, 1-butene, 2- One or more of butene, isobutene, 1,3-butadiene, and carbon monoxide.
  • the oxidation reaction includes ammoxidation of methanol to prepare hydrocyanic acid, ammoxidation of propylene to prepare acrylonitrile, oxidation of propylene to prepare acrolein, oxidation of butane to prepare maleic anhydride, oxidation of cyclohexane to prepare cyclohexanone, and One or more of cyclohexanol and o-xylene are oxidized to prepare phthalic anhydride, p-xylene is oxidized to prepare terephthalic acid, hydroxymethyl furfural is oxidized to prepare furandicarboxylic acid, and trimethylbenzoquinone is prepared in the production of vitamin E.
  • Figure 1 is a scanning electron microscope photograph of the molybdenum-based catalyst prepared in Example 5 of the present invention.
  • Figure 2 is a scanning electron microscope photograph of the molybdenum-based catalyst prepared in Comparative Example 1 of the present invention.
  • the embodiment of the present invention provides a molybdenum-based catalyst, comprising an active component molybdenum and a carrier, the active component molybdenum exists in the form of elemental Mo and MoO x , where 0 ⁇ x ⁇ 3, and the carrier is a metal oxide, The surface has oxygen vacancies.
  • the elemental Mo in the active component molybdenum combines with the oxygen vacancies to form a Mo-[O]-M structure, where [O] represents the oxygen vacancies, and M is the oxide carrier
  • the active component molybdenum is distributed on the surface of the carrier in the form of nanoparticles.
  • the molybdenum-based catalyst provided by the embodiment of the present invention adopts a carrier with oxygen vacancies to support the active component molybdenum.
  • the active component molybdenum exists in the form of elemental Mo and MoO x (0 ⁇ x ⁇ 3). There is a strong interface effect between the active component molybdenum and the surface of the carrier more firmly, and at the same time, the molybdenum-based catalyst has excellent catalytic activity.
  • the active component molybdenum in the molybdenum-based catalyst can be distributed on the surface of the carrier in the form of highly dispersed nanoparticles, such a highly dispersed state
  • the catalyst has a very high exposure rate of active sites and has excellent catalytic activity and selectivity.
  • the ultrafine nanoparticles can be effectively stabilized and prevented from agglomeration and loss.
  • the particle size of the active component molybdenum is less than or equal to 5 nm, preferably less than or equal to 1 nm. The smaller the particle size of the active component molybdenum, the more the number of atoms exposed on the surface, the more active sites, and the higher the catalyst activity.
  • the MoO x in the active component molybdenum includes one or more of MoO, MoO 2 , and MoO 3 .
  • the active component molybdenum exists in the form of elemental Mo and MoO x .
  • elemental Mo has a strong interfacial effect with the oxygen vacancies on the surface of the carrier, and can form a Mo-[O]-M structure to improve the active composition.
  • the degree of dispersion of molybdenum is 60% to 100%.
  • the surface of the carrier has a large number of oxygen vacancies.
  • the carrier includes a first carrier, and the first carrier is a metal oxide, which may be selected from Ti, Zr, Ce, V, Cr, Mn, Fe, Zn, Ga, Ge, One element or oxides of multiple elements among Sn, Bi, Y, Nb, La, and Re.
  • a metal oxide which may be selected from Ti, Zr, Ce, V, Cr, Mn, Fe, Zn, Ga, Ge, One element or oxides of multiple elements among Sn, Bi, Y, Nb, La, and Re.
  • the oxide surface of one or more elements of Ti, Zr, Ce, Mn, Fe, Zn, Ga, Sn, Bi, La, and Re may contain a higher concentration of oxygen vacancies, which is different from the elemental Mo There is a stronger interfacial effect between them, and the combination is firmer and stable, and the dispersion of the active component molybdenum can be higher.
  • the metal oxide is selected from oxides of one or more elements of Ti, Zr, Ce, Mn, Fe, Zn, Ga, Sn, Bi, La, and Re.
  • the carrier further includes a second carrier mixed with the first carrier, and the surface of the second carrier may contain a lower concentration of oxygen vacancies, and the interface between the carrier and the elemental Mo Weaker, the cooperation of the first carrier and the second carrier can make the carrier have a better oxygen vacancy concentration and better loading effect, wherein the second carrier accounts for 0.5% to 30% of the carrier mass %.
  • the second carrier may be selected from one element or oxides of multiple elements among Al, Mg, and Ca.
  • the particle size and specific surface area of the catalyst are not particularly limited.
  • the particle size of the catalyst may preferably be 0.03 ⁇ m To 0.5 ⁇ m, the specific surface area is preferably 20m 2 /g to 230m 2 /g.
  • the loading amount of the active component molybdenum is recorded as 0.1% to 50% by mass percentage.
  • the embodiment of the present invention also provides a method for preparing a molybdenum-based catalyst, which includes the following steps:
  • the preparation method of the molybdenum-based catalyst provided by the embodiment of the present invention adopts a carrier capable of forming oxygen vacancies to support the active component molybdenum, and prepares a highly dispersed molybdenum-based catalyst through two calcinations, and the first calcination is in air or inert gas ,
  • the second calcination in reducing gas after two calcinations to obtain a molybdenum-based catalyst with elemental Mo as the main active component, and the preparation method makes a large number of oxygen vacancies formed on the surface of the carrier, the elemental Mo in the active component and the carrier
  • the oxygen vacancies on the surface form a Mo-[O]-M structure, which makes the active component and the carrier form a strong interface, so that the active component can be distributed on the surface of the carrier in the form of nanoparticles, and the particle size can be Reaching 5nm, even below 1nm, at the same time makes the active components of the catalyst difficult to agglomerate and lose,
  • the carrier may contain intrinsic oxygen vacancies or may not contain intrinsic oxygen vacancies, and oxygen vacancies will be formed during the subsequent first calcination or the second calcination.
  • the method of loading the precursor of molybdenum on the carrier and drying is an immersion method, which includes dispersing and immersing the carrier in the solution of the precursor of molybdenum to make the molybdenum
  • the forebody is loaded on the carrier.
  • the impregnation can adopt the excessive impregnation method.
  • the carrier is immersed in an excessive amount of the precursor solution of molybdenum and stirred, and then the excess solvent is evaporated to dryness.
  • the temperature when the solvent is evaporated is not particularly limited, but it is further considered Time cost and impregnation efficiency. In one or more embodiments, the temperature when the solvent is evaporated to dryness is 60°C to 80°C. In this step, the excessive impregnation method can make the molybdenum precursor more uniformly dispersed on the surface of the carrier.
  • the type of the precursor of molybdenum is not particularly limited, and can be conventionally selected.
  • the precursor of molybdenum may be various substances that are soluble in water at 25° C. and can provide Mo in ionic form, for example, may be molybdic acid or soluble molybdate.
  • the precursor of molybdenum may be selected from (NH 4 ) 2 Mo 2 O 7 , (NH 4 ) 2 Mo 4 O 13. 2H 2 O, H 2 MoO 4 , K 2 MoO 4.
  • the support may include a first support or a first support and a second support
  • the first support may be selected from Ti, Zr, Ce, V, Cr, Mn, Fe Oxides of one element or multiple elements among Zn, Ga, Ge, Sn, Bi, Y, Nb, La, Re, preferably Ti, Zr, Ce, Mn, Fe, Zn, Ga, Sn, Bi
  • An oxide of one or more elements of La, La and Re, and the second support is selected from an oxide of one or more elements of Al, Mg, and Ca.
  • the mass ratio of the precursor of the molybdenum to the carrier is 1-30.
  • step S20 the first solid is placed in air or inert gas for the first calcination.
  • the molybdenum precursor can be calcined into oxides, and on the other hand, oxygen vacancies can be formed on the surface of the carrier.
  • the calcination temperature of the first calcination is 600°C to 1000°C, and the calcination time is 0.1 hour to 12 hours.
  • the inert gas may include one or more of nitrogen, argon, helium, neon, krypton, and xenon.
  • step S30 the second solid is placed in a reducing gas for a second calcination.
  • oxygen vacancies can continue to be generated on the surface of the carrier to further increase the concentration of oxygen vacancies on the surface of the carrier.
  • the oxide formed after the first calcination can be reduced to elemental Mo and oxides of various oxidation states, and the elemental Mo can bind to the oxygen vacancies on the surface of the carrier.
  • the formation of Mo-[O]-M changes the crystal form of the carrier, induces the molybdenum particles of the active component to disperse on the surface of the carrier, further improves the dispersion of the active component molybdenum, and makes the active component Molybdenum is distributed on the surface of the carrier in the form of nanoparticles.
  • the particle diameter of the active component molybdenum in the molybdenum-based catalyst prepared by the preparation method is less than or equal to 5 nm, and further less than or equal to 1 nm.
  • the reducing gas may include hydrogen, methane, ethane, ethylene, acetylene, propane, propylene, propyne, propadiene, n-butane, isobutane, 1-butene, 2-butene, isobutene, 1 , One or more of 3-butadiene and carbon monoxide.
  • the preparation method of the molybdenum-based catalyst provided by the embodiments of the present invention has low raw material price, simple preparation method, and easy large-scale production.
  • the molybdenum-based catalyst prepared has a high degree of dispersion of the active component molybdenum, which can make the active component molybdenum
  • the particle size reaches 5nm or even below 1nm, and the active component molybdenum contains elemental molybdenum, which has excellent catalytic activity and selectivity.
  • the active component molybdenum has a strong binding effect with the carrier, and the active component molybdenum is not easy to agglomerate and lose.
  • the stability of the catalyst is better.
  • the embodiment of the present invention further provides the application of the molybdenum-based catalyst or the molybdenum-based catalyst obtained by the preparation method in the oxidation reaction of alcohols and hydrocarbons.
  • the oxidation reaction may include the ammoxidation of methanol to prepare hydrocyanic acid, the ammoxidation of propylene to prepare acrylonitrile, the oxidation of propylene to prepare acrolein, the oxidation of butane to prepare maleic anhydride, the oxidation of cyclohexane to prepare cyclohexanone and cyclohexanol, and two One or more of phthalic anhydride prepared by oxidation of toluene, terephthalic acid prepared by oxidation of p-xylene, furandicarboxylic acid prepared by oxidation of hydroxymethyl furfural, and trimethylbenzoquinone prepared in the production of vitamin E.
  • the second solid is reduced under a hydrogen atmosphere for 8 hours at a temperature of 500°C, a heating rate of 3°C/min, and naturally cooled to room temperature to obtain a molybdenum-based catalyst.
  • the active component is determined by X-ray photoelectron spectroscopy.
  • the molar content of elemental Mo in the existing form of molybdenum is 62.3%.
  • the preparation method is basically the same as in Example 1, except that the carrier is cerium oxide.
  • the preparation method is basically the same as that of Example 1, except that the support is titanium oxide.
  • the preparation method is basically the same as that of Example 1, except that the carrier is niobium oxide.
  • the preparation method is basically the same as in Example 1, except that the carrier is a mixed oxide of iron oxide, aluminum oxide, manganese oxide, and zirconium oxide.
  • the preparation method is basically the same as that of Example 1, except that the carrier is a mixed oxide of titanium oxide and silicon oxide.
  • the preparation method is basically the same as that of Example 1, except that the carrier is a mixed oxide of bismuth oxide, vanadium pentoxide and aluminum oxide.
  • step S30 the second solid is not calcined in a reducing gas, but is still calcined in a nitrogen atmosphere for the same time, the temperature is also 500°C, and the heating rate is also 3°C/ Min, the molybdenum-based catalyst can be obtained by natural cooling to room temperature.
  • the specific reaction conditions are: a fixed bed reactor is used, 80g of catalyst is loaded, the mass space velocity is 0.34h -1 , the molar ratio of ammonia to methanol is 1.03:1, the molar ratio of air to methanol is 290:1, and the reaction temperature is set Set at 390°C.
  • the molybdenum-based catalyst prepared in Example 5 and Comparative Example 1 was used to catalyze the oxidation of propylene to produce acrolein.
  • the reaction equation is as follows:
  • the specific reaction conditions are: a fixed bed reactor is used, 50g of catalyst is filled, the reaction raw material is a mixed gas containing 15vol.% (volume ratio) propylene and 85vol.% (volume ratio) air, the mass space velocity is 1500h -1 , the reaction temperature Set to 320°C.
  • the specific reaction conditions are: a 40mL fluidized bed reactor is used, propylene is fed at a space velocity of 0.07h -1 , the molar ratio of ammonia to propylene is 1.04, the molar ratio of air to propylene is 10, and the reaction temperature is set to 430 °C.
  • the molybdenum-based catalyst prepared in Example 7 and Comparative Example 1 was used to catalyze the oxidation of n-butane to prepare maleic anhydride.
  • the reaction equation is as follows:
  • reaction conditions were: a fixed-bed reactor, the catalyst packed 50g, reaction feed containing 1.7vol% (by volume) n-butane, a mixed gas 98.3vol% (by volume) of air, WHSV is 1500h -.. 1. Set the reaction temperature to 400°C.
  • the molybdenum-based catalyst prepared in Example 7 and Comparative Example 1 was used to catalyze the oxidation of o-xylene to prepare phthalic anhydride.
  • the reaction equation is as follows:
  • reaction conditions were: a fixed-bed reactor, the catalyst packed 50g, reaction feed containing 3.3vol% (by volume) n-butane, a mixed gas 96.7vol% (by volume) of air, WHSV is 1500h -.. 1.
  • the reaction temperature is set to 360°C.
  • reaction conditions were: stainless steel autoclave, the catalyst was added 100mg, 100mg hydroxymethyl furfural, 5 mL methanol, and then charged into 3MPa standard air (mixed gas of 79vol% N 2 and 21vol% O 2 of, vol volume ratio), It was heated to 120°C under a stirring speed of 800 rpm, and the reaction time was 5 hours.
  • Catalyst type The molar yield of dimethyl furandicarboxylate (%) The molybdenum-based catalyst prepared in Example 1 86.6 Molybdenum-based catalyst prepared in Example 2 84.7 Molybdenum-based catalyst prepared in Comparative Example 1 43.6%
  • the molybdenum-based catalyst prepared in Example 1-2 and Comparative Example 1 was used to catalyze the oxidation of p-xylene to prepare terephthalic acid and its esters.
  • the reaction equation is as follows:
  • the specific reaction conditions are: using a stainless steel autoclave, adding 100mg catalyst, 100mg p-xylene, 5mL methanol, and then filling 3MPa standard air (79vol% N 2 and 21vol% O 2 mixed gas, vol is the volume ratio), Heat to 120°C under 800rpm stirring speed, reaction time 5 hours.
  • Catalyst type The molar yield of dimethyl terephthalate (%) The molybdenum-based catalyst prepared in Example 1 89.4 Molybdenum-based catalyst prepared in Example 2 88.6 Molybdenum-based catalyst prepared in Comparative Example 1 60.3%
  • the specific reaction conditions are: using a 25mL three-necked flask, adding 50mg of catalyst, 200mg of 2,5,6-trimethylphenol, 5mL of ethanol, 2mL of hydrogen peroxide (30wt% H 2 O 2 ), heating to 30°C at a stirring speed of 800 rpm, The reaction time is 3 hours.

Abstract

Disclosed are a molybdenum-based catalyst, a preparation method therefor and the use thereof. The molybdenum-based catalyst comprises an active component molybdenum and a carrier, wherein the active component molybdenum is present in the form of elementary Mo and MoOx, where 0 < x ≤ 3, and the carrier is a metal oxide having an oxygen vacancy on the surface thereof; the elementary Mo in the active component molybdenum is combined with the oxygen vacancy to form a Mo-[O]-M structure, wherein [O] represents the oxygen vacancy, and M is a metal element in the carrier, and the active component molybdenum is distributed on the surface of the carrier in the form of nanoparticles.

Description

钼基催化剂及其制备方法和应用Molybdenum-based catalyst and its preparation method and application
相关申请Related application
本申请要求2019年7月8日申请的，申请号为201910611495.4，发明名称为“钼基催化剂及其制备方法和应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application filed on July 8, 2019 with the application number 201910611495.4 and the invention title "Molybdenum-based catalyst and its preparation method and application", the entire content of which is incorporated into this application by reference.
技术领域Technical field
本发明涉及催化剂技术领域，特别是涉及一种钼基催化剂及其制备方法和应用。The invention relates to the technical field of catalysts, in particular to a molybdenum-based catalyst and a preparation method and application thereof.
背景技术Background technique
钼基催化剂在丙烯氧化以及氨氧化反应中是一种典型的催化剂，此外还应用于一些烃类的氧化脱氢反应。由于氧化反应多数放热明显，导致反应过程中催化剂床层热点温度过高，易造成活性中心的团聚和流失，最终导致催化剂逐渐失活且再生困难。Molybdenum-based catalysts are a typical catalyst in propylene oxidation and ammoxidation reactions, and are also used in oxidative dehydrogenation reactions of some hydrocarbons. Since most of the oxidation reactions are exothermic, the hot spot temperature of the catalyst bed during the reaction is too high, which is easy to cause the agglomeration and loss of active centers, and eventually the catalyst is gradually deactivated and regeneration is difficult.
钼基催化剂分为非负载型和负载型催化剂，非负载型催化剂活性成分容易团聚，稳定性差，所以目前的钼基催化剂多为负载型催化剂。传统的负载型催化剂的制备方法包括浸渍法、混捏法、共沉淀法、离子交换法等，目前工业上使用较多的是浸渍法和混捏法。其中，混捏法是早期的催化剂制备方法，该方法是将金属及助剂组分化合物、载体粉末与黏结剂混合在一起，然后经捏合、成型、烘干和焙烧制得催化剂。该方法优点是制备过程简单，但缺点是活性金属组分分散性差。浸渍法是目前制备负载型催化剂最常用的方法，该方法先制备载体，然后将含有活性组分的溶液浸渍负载在载体上，最后经干燥、焙烧等 步骤制得催化剂。该方法所制备的催化剂中金属分散性相对较好，但活性金属组分与载体间相互作用较弱，仍然存在活性组分高温易聚集烧结等缺点。Molybdenum-based catalysts are divided into unsupported and supported catalysts. The active components of unsupported catalysts are easy to agglomerate and have poor stability. Therefore, most of the current molybdenum-based catalysts are supported catalysts. The traditional preparation methods of supported catalysts include impregnation method, kneading method, co-precipitation method, ion exchange method, etc. At present, impregnation method and kneading method are mostly used in industry. Among them, the kneading method is an early catalyst preparation method. The method is to mix the metal and auxiliary component compounds, the carrier powder and the binder together, and then knead, shape, dry and roast to prepare the catalyst. The advantage of this method is that the preparation process is simple, but the disadvantage is that the active metal component is poorly dispersed. The impregnation method is currently the most commonly used method for preparing supported catalysts. This method first prepares the support, then impregnates the solution containing the active components on the support, and finally prepares the catalyst through steps such as drying and roasting. The catalyst prepared by this method has relatively good metal dispersibility, but the interaction between the active metal component and the carrier is weak, and there are still disadvantages such as the active component being easy to aggregate and sinter at high temperature.
发明内容Summary of the invention
根据本申请的各种实施例，提供一种钼基催化剂及其制备方法和应用。According to various embodiments of the present application, a molybdenum-based catalyst and a preparation method and application thereof are provided.
所述钼基催化剂包括活性组分钼和载体，所述活性组分钼以单质Mo和MoO x的形式存在，其中0<x≤3，所述载体为金属氧化物，表面具有氧空位，所述活性组分钼中的单质Mo与所述氧空位结合，形成Mo-[O]-M结构，其中[O]代表所述氧空位，M为所述载体中的金属元素，所述活性组分钼呈纳米颗粒状分布于所述载体表面。 The molybdenum-based catalyst includes an active component molybdenum and a carrier. The active component molybdenum exists in the form of elemental Mo and MoO x , where 0<x≤3, the carrier is a metal oxide, and the surface has oxygen vacancies. The elemental Mo in the active component molybdenum combines with the oxygen vacancy to form a Mo-[O]-M structure, where [O] represents the oxygen vacancy, M is the metal element in the carrier, and the active group Molybdenum is distributed on the surface of the carrier in the form of nanoparticles.
上述钼基催化剂中，采用具有氧空位的载体负载活性组分钼，活性组分钼以单质Mo和MoO x(0<x≤3)的形式存在的，单质Mo与氧空位之间具有强的界面作用，可使活性组分钼与载体表面结合更牢固，同时使得该钼基催化剂具有优异的催化活性。 In the above-mentioned molybdenum-based catalyst, a carrier with oxygen vacancies is used to support the active component molybdenum. The active component molybdenum exists in the form of elemental Mo and MoO x (0<x≤3). There is a strong relationship between elemental Mo and oxygen vacancies. The interface effect can make the active component molybdenum and the surface of the carrier bond more firmly, and at the same time make the molybdenum-based catalyst have excellent catalytic activity.
并且，由于活性组分钼中的单质Mo和与载体表面氧空位之间强的相互作用，该钼基催化剂中活性组分钼能够呈高分散的纳米颗粒状分布于载体表面，其粒径尺寸能够达到5nm，甚至1nm以下，这样高分散状态的催化剂活性位点暴露率极高，具有优异的催化活性和选择性。Moreover, due to the strong interaction between the elemental Mo in the active component molybdenum and the oxygen vacancies on the carrier surface, the active component molybdenum in the molybdenum-based catalyst can be distributed on the surface of the carrier in the form of highly dispersed nanoparticles, and its particle size It can reach 5nm or even below 1nm, so the highly dispersed state of the catalyst active site exposure rate is extremely high, with excellent catalytic activity and selectivity.
另外，由于活性组分钼与载体表面氧空位之间强的界面作用，能够有效稳定该超细纳米颗粒，防止其团聚和流失。In addition, due to the strong interfacial action between the active component molybdenum and the oxygen vacancies on the surface of the carrier, the ultrafine nanoparticles can be effectively stabilized to prevent their agglomeration and loss.
在其中一个实施例中，所述活性组分钼的粒径小于等于5nm。In one of the embodiments, the particle size of the active component molybdenum is less than or equal to 5 nm.
在其中一个实施例中，所述活性组分钼的存在形式中单质Mo的摩尔含量为60％至100％。In one of the embodiments, the molar content of the elemental Mo in the existence form of the active component molybdenum is 60% to 100%.
在其中一个实施例中，所述载体包括第一载体，所述第一载体选自Ti、Zr、Ce、V、Cr、Mn、Fe、Zn、Ga、Ge、Sn、Bi、Y、Nb、La、Re中的一种元素或多种元素的氧化物。In one of the embodiments, the carrier includes a first carrier selected from Ti, Zr, Ce, V, Cr, Mn, Fe, Zn, Ga, Ge, Sn, Bi, Y, Nb, Oxides of one element or multiple elements in La and Re.
在其中一个实施例中，所述载体还包括第二载体，所述第二载体具有的氧空位浓度低于所述第一载体具有的氧空位浓度。In one of the embodiments, the carrier further includes a second carrier, and the second carrier has an oxygen vacancy concentration lower than the oxygen vacancy concentration of the first carrier.
在其中一个实施例中，所述第二载体选自Al、Mg、Ca中的一种元素或多种元素的氧化物。In one of the embodiments, the second carrier is selected from one element or oxides of multiple elements among Al, Mg, and Ca.
在其中一个实施例中，所述第二载体占载体质量的0.5％至30％。In one of the embodiments, the second carrier accounts for 0.5% to 30% of the mass of the carrier.
在其中一个实施例中，所述活性组分钼的负载量按质量百分数记为0.1％至50％。In one of the embodiments, the loading amount of the active component molybdenum is recorded as 0.1% to 50% by mass percentage.
所述钼基催化剂的制备方法，包括以下步骤：The preparation method of the molybdenum-based catalyst includes the following steps:
将钼的前驱体负载在载体上并进行干燥，得到第一固体，所述载体为氧化物；Loading the precursor of molybdenum on a carrier and drying to obtain a first solid, and the carrier is an oxide;
将所述第一固体置于空气或惰性气体中进行第一次煅烧，得到第二固体；Placing the first solid in air or inert gas for the first calcination to obtain a second solid;
将所述第二固体置于还原性气体中进行第二次煅烧，得到钼基催化剂。The second solid is placed in a reducing gas for a second calcination to obtain a molybdenum-based catalyst.
上述钼基催化剂的制备方法中，采用可形成氧空位的载体负载活性组分钼，通过两次煅烧制备得到高分散度的钼基催化剂，第一次煅烧在空气或惰性气体中，第二次煅烧在还原性气体中，经过两次煅烧得到以单质Mo为主要活性组分的钼基催化剂。并且，该制备方法使得载体表面形成大量氧空位，活性组分钼中的单质Mo与载体表面的氧空位形成Mo-[O]-M结构，使活性组分钼与载体之间形成强的界面作用，从而使得活性组分钼能够呈纳米颗粒状分布于所述载体表面，其颗粒粒径能够达到5nm，甚至1nm以下，同时使得该催化剂的活性组分不易团聚和流失，具有优异的催化活性。In the preparation method of the molybdenum-based catalyst, a carrier capable of forming oxygen vacancies is used to support the active component molybdenum, and a highly dispersed molybdenum-based catalyst is prepared by two calcinations. The first time is calcined in air or inert gas, and the second time Calcined in reducing gas, after two calcinations, a molybdenum-based catalyst with elemental Mo as the main active component is obtained. In addition, the preparation method makes a large number of oxygen vacancies formed on the surface of the carrier, the elemental Mo in the active component molybdenum and the oxygen vacancies on the surface of the carrier form a Mo-[O]-M structure, so that a strong interface between the active component molybdenum and the carrier is formed As a result, the active component molybdenum can be distributed on the surface of the carrier in the form of nanoparticles, and its particle size can reach 5nm or even below 1nm. At the same time, the active component of the catalyst is not easy to agglomerate and lose, and it has excellent catalytic activity. .
在其中一个实施例中，所述第一次煅烧的步骤中，煅烧温度为600℃至1000℃，煅烧时间为0.1小时至12小时。In one of the embodiments, in the first calcination step, the calcination temperature is 600° C. to 1000° C., and the calcination time is 0.1 hour to 12 hours.
在其中一个实施例中，所述第二次煅烧的步骤中，煅烧温度为300℃至800℃，煅烧时间为0.1小时至24小时。In one of the embodiments, in the second calcination step, the calcination temperature is 300° C. to 800° C., and the calcination time is 0.1 hour to 24 hours.
在其中一个实施例中，所述载体含有本征氧空位。In one of the embodiments, the carrier contains intrinsic oxygen vacancies.
在其中一个实施例中，所述钼的前躯体为钼酸或可溶性钼酸盐。In one of the embodiments, the precursor of molybdenum is molybdic acid or soluble molybdate.
在其中一个实施例中，所述钼的前躯体选自(NH 4) 2Mo 2O 7、(NH 4) 2Mo 4O 13·2H 2O、H 2MoO 4、K 2MoO 4、(NH 4) 6Mo 7O 24·4H 2O、Na 2MoO 4·2H 2O中的一种或多种。 In one of the embodiments, the precursor of molybdenum is selected from (NH 4 ) 2 Mo 2 O 7 , (NH 4 ) 2 Mo 4 O 13. 2H 2 O, H 2 MoO 4 , K 2 MoO 4 , ( One or more of NH 4 ) 6 Mo 7 O 24 ·4H 2 O and Na 2 MoO 4 ·2H 2 O.
在其中一个实施例中，所述钼的前躯体与所述载体的质量比为1至30。In one of the embodiments, the mass ratio of the precursor of the molybdenum to the carrier is 1-30.
在其中一个实施例中，所述还原性气体包括氢气、甲烷、乙烷、乙烯、乙炔、丙烷、丙烯、丙炔、丙二烯、正丁烷、异丁烷、1-丁烯、2-丁烯、异丁烯、1,3-丁二烯、一氧化碳中的一种或多种。In one of the embodiments, the reducing gas includes hydrogen, methane, ethane, ethylene, acetylene, propane, propylene, propyne, propadiene, n-butane, isobutane, 1-butene, 2- One or more of butene, isobutene, 1,3-butadiene, and carbon monoxide.
所述的钼基催化剂或所述的制备方法得到的钼基催化剂在醇和烃类物质的氧化反应中的应用。The application of the molybdenum-based catalyst or the molybdenum-based catalyst obtained by the preparation method in the oxidation reaction of alcohols and hydrocarbons.
在其中一个实施例中，所述氧化反应包括甲醇氨氧化制备氢氰酸、丙烯氨氧化制备丙烯腈、丙烯氧化制备丙烯醛、丁烷氧化制备马来酸酐、环己烷氧化制备环己酮和环己醇、邻二甲苯氧化制备苯酐、对二甲苯氧化制备对苯二甲酸、羟甲基糠醛氧化制备呋喃二甲酸、维生素E生产中制备三甲基苯醌中的一种或多种。In one of the embodiments, the oxidation reaction includes ammoxidation of methanol to prepare hydrocyanic acid, ammoxidation of propylene to prepare acrylonitrile, oxidation of propylene to prepare acrolein, oxidation of butane to prepare maleic anhydride, oxidation of cyclohexane to prepare cyclohexanone, and One or more of cyclohexanol and o-xylene are oxidized to prepare phthalic anhydride, p-xylene is oxidized to prepare terephthalic acid, hydroxymethyl furfural is oxidized to prepare furandicarboxylic acid, and trimethylbenzoquinone is prepared in the production of vitamin E.
附图说明Description of the drawings
为了更好地描述和说明这里公开的那些发明的实施例和/或示例，可以参 考一幅或多幅附图。用于描述附图的附加细节或示例不应当被认为是对所公开的发明、目前描述的实施例和/或示例以及目前理解的这些发明的最佳模式中的热河一者的范围的限制。In order to better describe and illustrate the embodiments and/or examples of those inventions disclosed herein, one or more drawings may be referred to. The additional details or examples used to describe the drawings should not be considered as limitations on the scope of the disclosed invention, the currently described embodiments and/or examples, and the best mode of these inventions currently understood .
图1为本发明实施例5制备的钼基催化剂透射电镜扫描照片；Figure 1 is a scanning electron microscope photograph of the molybdenum-based catalyst prepared in Example 5 of the present invention;
图2为本发明对比例1制备的钼基催化剂透射电镜扫描照片。Figure 2 is a scanning electron microscope photograph of the molybdenum-based catalyst prepared in Comparative Example 1 of the present invention.
具体实施方式Detailed ways
为了使本发明的目的、技术方案及优点更加清楚明白，以下通过实施例，并结合附图，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本发明，并不用于限定本发明。In order to make the objectives, technical solutions, and advantages of the present invention clearer, the following further describes the present invention in detail through embodiments and in conjunction with the accompanying drawings. It should be understood that the specific embodiments described here are only used to explain the present invention, but not to limit the present invention.
本发明实施例提供一种钼基催化剂，包括活性组分钼和载体，所述活性组分钼以单质Mo和MoO x的形式存在，其中0<x≤3，所述载体为金属氧化物，表面具有氧空位，所述活性组分钼中的单质Mo与所述氧空位结合，形成Mo-[O]-M结构，其中[O]代表所述氧空位，M为所述氧化物载体中的金属元素，所述活性组分钼呈纳米颗粒状分布与所述载体表面。 The embodiment of the present invention provides a molybdenum-based catalyst, comprising an active component molybdenum and a carrier, the active component molybdenum exists in the form of elemental Mo and MoO x , where 0<x≤3, and the carrier is a metal oxide, The surface has oxygen vacancies. The elemental Mo in the active component molybdenum combines with the oxygen vacancies to form a Mo-[O]-M structure, where [O] represents the oxygen vacancies, and M is the oxide carrier The active component molybdenum is distributed on the surface of the carrier in the form of nanoparticles.
本发明实施例提供的钼基催化剂，采用具有氧空位的载体负载活性组分钼，活性组分钼以单质Mo和MoO x(0<x≤3)的形式存在的，单质Mo与氧空位之间具有强的界面作用，可使活性组分钼与载体表面结合更牢固，同时使得该钼基催化剂具有优异的催化活性。 The molybdenum-based catalyst provided by the embodiment of the present invention adopts a carrier with oxygen vacancies to support the active component molybdenum. The active component molybdenum exists in the form of elemental Mo and MoO x (0<x≤3). There is a strong interface effect between the active component molybdenum and the surface of the carrier more firmly, and at the same time, the molybdenum-based catalyst has excellent catalytic activity.
并且，由于活性组分钼中的单质Mo和与载体表面氧空位之间强的相互作用，该钼基催化剂中活性组分钼能够呈高分散的纳米颗粒状分布于载体表面，这样高分散状态的催化剂活性位点暴露率极高，具有优异的催化活性和选择性。Moreover, due to the strong interaction between the elemental Mo in the active component molybdenum and the oxygen vacancies on the surface of the carrier, the active component molybdenum in the molybdenum-based catalyst can be distributed on the surface of the carrier in the form of highly dispersed nanoparticles, such a highly dispersed state The catalyst has a very high exposure rate of active sites and has excellent catalytic activity and selectivity.
另外，由于活性组分钼与载体表面氧空位之间强的界面作用，能够有效 稳定该超细纳米颗粒，防止其团聚和流失。In addition, due to the strong interfacial action between the active component molybdenum and the oxygen vacancies on the surface of the carrier, the ultrafine nanoparticles can be effectively stabilized and prevented from agglomeration and loss.
在一个或多个实施例中，所述活性组分钼的粒径小于等于5nm，优选小于等于1nm。所述活性组分钼的粒径越小，表面暴露的原子数越多，活性位点越多，催化剂活性越高。In one or more embodiments, the particle size of the active component molybdenum is less than or equal to 5 nm, preferably less than or equal to 1 nm. The smaller the particle size of the active component molybdenum, the more the number of atoms exposed on the surface, the more active sites, and the higher the catalyst activity.
在一个或多个实施例中，所述活性组分钼中MoO x包括MoO、MoO 2、MoO 3中的一种或多种。 In one or more embodiments, the MoO x in the active component molybdenum includes one or more of MoO, MoO 2 , and MoO 3 .
所述活性组分钼以单质Mo和MoO x的形式存在，其中，单质Mo与所述载体表面氧空位的具有强的界面作用，可形成Mo-[O]-M结构，提高所述活性组分钼的分散度。在一个或多个实施例中，所述单质Mo的摩尔含量为60％至100％。 The active component molybdenum exists in the form of elemental Mo and MoO x . Among them, elemental Mo has a strong interfacial effect with the oxygen vacancies on the surface of the carrier, and can form a Mo-[O]-M structure to improve the active composition. The degree of dispersion of molybdenum. In one or more embodiments, the molar content of the elemental Mo is 60% to 100%.
为了保证所述钼基催化剂中活性组分钼的高分散度以及防止活性组分钼的团聚和流失，所述载体表面具有大量的氧空位。In order to ensure the high dispersion of the active component molybdenum in the molybdenum-based catalyst and prevent the agglomeration and loss of the active component molybdenum, the surface of the carrier has a large number of oxygen vacancies.
在一个或多个实施例中，所述载体包括第一载体，所述第一载体为金属氧化物，可选自Ti、Zr、Ce、V、Cr、Mn、Fe、Zn、Ga、Ge、Sn、Bi、Y、Nb、La、Re中的一种元素或多种元素的氧化物。In one or more embodiments, the carrier includes a first carrier, and the first carrier is a metal oxide, which may be selected from Ti, Zr, Ce, V, Cr, Mn, Fe, Zn, Ga, Ge, One element or oxides of multiple elements among Sn, Bi, Y, Nb, La, and Re.
考虑到Ti、Zr、Ce、Mn、Fe、Zn、Ga、Sn、Bi、La、Re中的一种或多种元素的氧化物表面可包含更高浓度的氧空位，与所述单质Mo之间存在更强的界面作用，其结合更牢固、稳定，可使所述活性组分钼的分散度更高。在一个或多个实施例中，所述金属氧化物选自Ti、Zr、Ce、Mn、Fe、Zn、Ga、Sn、Bi、La、Re中的一种或多种元素的氧化物。Considering that the oxide surface of one or more elements of Ti, Zr, Ce, Mn, Fe, Zn, Ga, Sn, Bi, La, and Re may contain a higher concentration of oxygen vacancies, which is different from the elemental Mo There is a stronger interfacial effect between them, and the combination is firmer and stable, and the dispersion of the active component molybdenum can be higher. In one or more embodiments, the metal oxide is selected from oxides of one or more elements of Ti, Zr, Ce, Mn, Fe, Zn, Ga, Sn, Bi, La, and Re.
在一个或多个实施例中，所述载体还包括与第一载体混合的第二载体，所述第二载体的表面可包含的氧空位浓度较低，与所述单质Mo之间的界面作用较弱，所述第一载体与所述第二载体的配合可使所述载体具有更好的氧空位浓 度和更好的负载作用，其中，所述第二载体占载体质量的0.5％至30％。In one or more embodiments, the carrier further includes a second carrier mixed with the first carrier, and the surface of the second carrier may contain a lower concentration of oxygen vacancies, and the interface between the carrier and the elemental Mo Weaker, the cooperation of the first carrier and the second carrier can make the carrier have a better oxygen vacancy concentration and better loading effect, wherein the second carrier accounts for 0.5% to 30% of the carrier mass %.
在一个或多个实施例中，所述第二载体可选自Al、Mg、Ca中的一种元素或多种元素的氧化物。In one or more embodiments, the second carrier may be selected from one element or oxides of multiple elements among Al, Mg, and Ca.
所述催化剂的粒径和比表面积无特别限制，在更利于所述活性组分钼的负载和分散的情况下，在一个或多个实施例中，所述催化剂的粒径可优选为0.03μm至0.5μm，比表面积可选优为20m 2/g至230m 2/g。 The particle size and specific surface area of the catalyst are not particularly limited. In the case of more favorable loading and dispersion of the active component molybdenum, in one or more embodiments, the particle size of the catalyst may preferably be 0.03 μm To 0.5μm, the specific surface area is preferably 20m 2 /g to 230m 2 /g.
在一个或多个实施例中，所述活性组分钼的负载量按质量百分数记为0.1％至50％。In one or more embodiments, the loading amount of the active component molybdenum is recorded as 0.1% to 50% by mass percentage.
本发明实施例还提供一种钼基催化剂的制备方法，包括以下步骤：The embodiment of the present invention also provides a method for preparing a molybdenum-based catalyst, which includes the following steps:
S10，将钼的前躯体负载在载体上并进行干燥，得到第一固体，所述载体为氧化物；S10, loading the precursor of molybdenum on a carrier and drying to obtain a first solid, and the carrier is an oxide;
S20，将第一固体置于空气或惰性气体中进行第一次煅烧，得到第二固体；S20, placing the first solid in air or inert gas for the first calcination to obtain a second solid;
S30，将第二固体置于还原性气体中进行第二次煅烧，得到钼基催化剂。S30, placing the second solid in a reducing gas for a second calcination to obtain a molybdenum-based catalyst.
本发明实施例提供的钼基催化剂的制备方法，采用可形成氧空位的载体负载活性组分钼，通过两次煅烧制备得到高分散度的钼基催化剂，第一次煅烧在空气或惰性气体中，第二次煅烧在还原性气体中，经过两次煅烧得到以单质Mo为主要活性组分的钼基催化剂，并且该制备方法使得载体表面形成大量氧空位，活性组分中的单质Mo与载体表面的氧空位形成Mo-[O]-M结构，使活性组分与载体之间形成强的界面作用，从而使得活性组分能够呈纳米颗粒状分布于所述载体表面，其颗粒粒径能够达到5nm，甚至1nm以下，同时使得该催化剂的活性组分不易团聚和流失，具有优异的催化活性。The preparation method of the molybdenum-based catalyst provided by the embodiment of the present invention adopts a carrier capable of forming oxygen vacancies to support the active component molybdenum, and prepares a highly dispersed molybdenum-based catalyst through two calcinations, and the first calcination is in air or inert gas , The second calcination in reducing gas, after two calcinations to obtain a molybdenum-based catalyst with elemental Mo as the main active component, and the preparation method makes a large number of oxygen vacancies formed on the surface of the carrier, the elemental Mo in the active component and the carrier The oxygen vacancies on the surface form a Mo-[O]-M structure, which makes the active component and the carrier form a strong interface, so that the active component can be distributed on the surface of the carrier in the form of nanoparticles, and the particle size can be Reaching 5nm, even below 1nm, at the same time makes the active components of the catalyst difficult to agglomerate and lose, and has excellent catalytic activity.
步骤S10中，所述载体可包含本征氧空位，也可不含本征氧空位，在之后的所述第一次煅烧或所述第二次煅烧过程中形成氧空位。In step S10, the carrier may contain intrinsic oxygen vacancies or may not contain intrinsic oxygen vacancies, and oxygen vacancies will be formed during the subsequent first calcination or the second calcination.
在一个或多个实施例中，将钼的前躯体负载在载体上并进行干燥的方法为浸渍法，包括将所述载体分散并浸渍在所述钼的前躯体溶液中，使所述钼的前躯体负载在所述载体上。In one or more embodiments, the method of loading the precursor of molybdenum on the carrier and drying is an immersion method, which includes dispersing and immersing the carrier in the solution of the precursor of molybdenum to make the molybdenum The forebody is loaded on the carrier.
浸渍可以采用过量浸渍法，将所述载体浸泡在过量的所述钼的前躯体溶液中进行搅拌，然后将多余的溶剂蒸干，对蒸干溶剂时的温度没有特别的限定，但是进一步考虑到时间成本和浸渍效率，在一个或多个实施例中，所述蒸干溶剂时的温度为60℃至80℃。该步骤中采用过量浸渍法可使所述钼的前躯体更均匀的分散在所述载体的表面。The impregnation can adopt the excessive impregnation method. The carrier is immersed in an excessive amount of the precursor solution of molybdenum and stirred, and then the excess solvent is evaporated to dryness. The temperature when the solvent is evaporated is not particularly limited, but it is further considered Time cost and impregnation efficiency. In one or more embodiments, the temperature when the solvent is evaporated to dryness is 60°C to 80°C. In this step, the excessive impregnation method can make the molybdenum precursor more uniformly dispersed on the surface of the carrier.
根据本发明实施例的催化剂的制备方法，对钼的前躯体的种类无特别限制，可以为常规选择。所述钼的前躯体可以为各种在25℃下可溶于水，能够提供离子形式的Mo的物质，例如，可以为钼酸或可溶性钼酸盐。According to the preparation method of the catalyst of the embodiment of the present invention, the type of the precursor of molybdenum is not particularly limited, and can be conventionally selected. The precursor of molybdenum may be various substances that are soluble in water at 25° C. and can provide Mo in ionic form, for example, may be molybdic acid or soluble molybdate.
在一个或多个实施例中，所述钼的前躯体可选自(NH 4) 2Mo 2O 7、(NH 4) 2Mo 4O 13·2H 2O、H 2MoO 4、K 2MoO 4、(NH 4) 6Mo 7O 24·4H 2O、Na 2MoO 4·2H 2O中的一种或多种。 In one or more embodiments, the precursor of molybdenum may be selected from (NH 4 ) 2 Mo 2 O 7 , (NH 4 ) 2 Mo 4 O 13. 2H 2 O, H 2 MoO 4 , K 2 MoO 4. One or more of (NH 4 ) 6 Mo 7 O 24 ·4H 2 O and Na 2 MoO 4 ·2H 2 O.
本发明实施例提供的催化剂的制备方法中，所述载体可包括第一载体或者包括第一载体和第二载体，所述第一载体选自Ti、Zr、Ce、V、Cr、Mn、Fe、Zn、Ga、Ge、Sn、Bi、Y、Nb、La、Re中的一种元素或多种元素的氧化物，优选为Ti、Zr、Ce、Mn、Fe、Zn、Ga、Sn、Bi、La、Re中的一种或多种元素的氧化物，所述第二载体选自Al、Mg、Ca中的一种元素或多种元素的氧化物。In the preparation method of the catalyst provided by the embodiment of the present invention, the support may include a first support or a first support and a second support, and the first support may be selected from Ti, Zr, Ce, V, Cr, Mn, Fe Oxides of one element or multiple elements among Zn, Ga, Ge, Sn, Bi, Y, Nb, La, Re, preferably Ti, Zr, Ce, Mn, Fe, Zn, Ga, Sn, Bi An oxide of one or more elements of La, La and Re, and the second support is selected from an oxide of one or more elements of Al, Mg, and Ca.
在一个或多个实施例中，所述钼的前躯体与所述载体的质量比为1至30。In one or more embodiments, the mass ratio of the precursor of the molybdenum to the carrier is 1-30.
步骤S20中，将所述第一固体置于空气或惰性气体中进行第一次煅烧，一方面可使所述钼的前驱体煅烧为氧化物，另一方面可使所述载体表面形成氧空位。所述第一次煅烧的煅烧温度为600℃至1000℃，煅烧时间为0.1小时至 12小时。所述惰性气体可包括氮气、氩气、氦气、氖气、氪气、氙气中的一种或多种。In step S20, the first solid is placed in air or inert gas for the first calcination. On the one hand, the molybdenum precursor can be calcined into oxides, and on the other hand, oxygen vacancies can be formed on the surface of the carrier. . The calcination temperature of the first calcination is 600°C to 1000°C, and the calcination time is 0.1 hour to 12 hours. The inert gas may include one or more of nitrogen, argon, helium, neon, krypton, and xenon.
步骤S30中，将所述第二固体置于还原性气体中进行第二次煅烧，一方面可继续在所述载体的表面产生氧空位，进一步提高载体表面氧空位的浓度，另一方面在还原性气体作用下，经过所述第一次煅烧后形成的所述氧化物可被还原为单质Mo及各种氧化态的氧化物，而所述单质Mo可与所述载体表面的氧空位结合，形成Mo-[O]-M，使所述载体的晶型发生变化，诱导所述活性组分钼颗粒在载体表面分散，进一步提高所述活性组分钼的分散度，使所述活性组分钼呈纳米颗粒状分布于所述载体表面。In step S30, the second solid is placed in a reducing gas for a second calcination. On the one hand, oxygen vacancies can continue to be generated on the surface of the carrier to further increase the concentration of oxygen vacancies on the surface of the carrier. Under the action of the natural gas, the oxide formed after the first calcination can be reduced to elemental Mo and oxides of various oxidation states, and the elemental Mo can bind to the oxygen vacancies on the surface of the carrier, The formation of Mo-[O]-M changes the crystal form of the carrier, induces the molybdenum particles of the active component to disperse on the surface of the carrier, further improves the dispersion of the active component molybdenum, and makes the active component Molybdenum is distributed on the surface of the carrier in the form of nanoparticles.
在一个或多个实施例中，该制备方法制备的所述钼基催化剂中活性组分钼的颗粒粒径小于等于5nm，进一步小于等于1nm。In one or more embodiments, the particle diameter of the active component molybdenum in the molybdenum-based catalyst prepared by the preparation method is less than or equal to 5 nm, and further less than or equal to 1 nm.
所述还原性气体可包括氢气、甲烷、乙烷、乙烯、乙炔、丙烷、丙烯、丙炔、丙二烯、正丁烷、异丁烷、1-丁烯、2-丁烯、异丁烯、1,3-丁二烯、一氧化碳中的一种或多种。The reducing gas may include hydrogen, methane, ethane, ethylene, acetylene, propane, propylene, propyne, propadiene, n-butane, isobutane, 1-butene, 2-butene, isobutene, 1 , One or more of 3-butadiene and carbon monoxide.
本发明实施例提供的钼基催化剂的制备方法，原料价格低廉，制备方法简单，易于规模化生产，并且所制备的钼基催化剂中活性组分钼的分散度高，可以使活性组分钼的粒径达到5nm甚至1nm以下，并且活性组分钼中包含单质钼，具有优异的催化活性和选择性，同时活性组分钼与载体之间的结合作用强，活性组分钼不易团聚和流失，催化剂的稳定性更好。The preparation method of the molybdenum-based catalyst provided by the embodiments of the present invention has low raw material price, simple preparation method, and easy large-scale production. In addition, the molybdenum-based catalyst prepared has a high degree of dispersion of the active component molybdenum, which can make the active component molybdenum The particle size reaches 5nm or even below 1nm, and the active component molybdenum contains elemental molybdenum, which has excellent catalytic activity and selectivity. At the same time, the active component molybdenum has a strong binding effect with the carrier, and the active component molybdenum is not easy to agglomerate and lose. The stability of the catalyst is better.
本发明实施例进一步提供所述的钼基催化剂或所述的制备方法得到的钼基催化剂在醇和烃类物质的氧化反应中的应用。The embodiment of the present invention further provides the application of the molybdenum-based catalyst or the molybdenum-based catalyst obtained by the preparation method in the oxidation reaction of alcohols and hydrocarbons.
所述氧化反应可包括甲醇氨氧化制备氢氰酸、丙烯氨氧化制备丙烯腈、丙烯氧化制备丙烯醛、丁烷氧化制备马来酸酐、环己烷氧化制备环己酮和环己 醇、邻二甲苯氧化制备苯酐、对二甲苯氧化制备对苯二甲酸、羟甲基糠醛氧化制备呋喃二甲酸、维生素E生产中制备三甲基苯醌中的一种或多种。The oxidation reaction may include the ammoxidation of methanol to prepare hydrocyanic acid, the ammoxidation of propylene to prepare acrylonitrile, the oxidation of propylene to prepare acrolein, the oxidation of butane to prepare maleic anhydride, the oxidation of cyclohexane to prepare cyclohexanone and cyclohexanol, and two One or more of phthalic anhydride prepared by oxidation of toluene, terephthalic acid prepared by oxidation of p-xylene, furandicarboxylic acid prepared by oxidation of hydroxymethyl furfural, and trimethylbenzoquinone prepared in the production of vitamin E.
实施例1Example 1
S10，称取1g四水合钼酸铵溶于30mL水中，加入5g氧化锆，80℃下搅拌直至溶剂被蒸干，得到第一固体；S10: Weigh 1g of ammonium molybdate tetrahydrate and dissolve in 30mL of water, add 5g of zirconia, and stir at 80°C until the solvent is evaporated to dryness to obtain the first solid;
S20，将得到的第一固体置于氮气气氛下煅烧1小时，升温速率为3℃/min，维持温度为800℃，得到第二固体；S20, calcining the obtained first solid in a nitrogen atmosphere for 1 hour at a heating rate of 3°C/min and maintaining the temperature at 800°C to obtain a second solid;
S30，将第二固体置于氢气气氛下还原8小时，温度为500℃，升温速率为3℃/min，自然冷却至室温即可得到钼基催化剂，经X射线光电子能谱测定，活性组分钼的存在形式中单质Mo的摩尔含量为62.3％。S30, the second solid is reduced under a hydrogen atmosphere for 8 hours at a temperature of 500°C, a heating rate of 3°C/min, and naturally cooled to room temperature to obtain a molybdenum-based catalyst. The active component is determined by X-ray photoelectron spectroscopy. The molar content of elemental Mo in the existing form of molybdenum is 62.3%.
实施例2Example 2
与实施例1的制备方法基本相同，不同之处在于，载体为氧化铈。The preparation method is basically the same as in Example 1, except that the carrier is cerium oxide.
实施例3Example 3
与实施例1的制备方法基本相同，不同之处在于，载体为氧化钛。The preparation method is basically the same as that of Example 1, except that the support is titanium oxide.
实施例4Example 4
与实施例1的制备方法基本相同，不同之处在于，载体为氧化铌。The preparation method is basically the same as that of Example 1, except that the carrier is niobium oxide.
实施例5Example 5
与实施例1的制备方法基本相同，不同之处在于，载体为氧化铁、氧化铝、氧化锰和氧化锆的混合氧化物。The preparation method is basically the same as in Example 1, except that the carrier is a mixed oxide of iron oxide, aluminum oxide, manganese oxide, and zirconium oxide.
实施例6Example 6
与实施例1的制备方法基本相同，不同之处在于，载体为氧化钛和氧化硅的混合氧化物。The preparation method is basically the same as that of Example 1, except that the carrier is a mixed oxide of titanium oxide and silicon oxide.
实施例7Example 7
与实施例1的制备方法基本相同，不同之处在于，载体为氧化铋、五氧化二钒和氧化铝的混合氧化物。The preparation method is basically the same as that of Example 1, except that the carrier is a mixed oxide of bismuth oxide, vanadium pentoxide and aluminum oxide.
对比例1Comparative example 1
与实施例1的制备方法不同之处在于，步骤S30中，第二固体不在还原性气体中煅烧，仍在氮气气氛下煅烧相同的时间，温度也同样为500℃，升温速率也为3℃/min，自然冷却至室温即可得到钼基催化剂。The difference from the preparation method of Example 1 is that in step S30, the second solid is not calcined in a reducing gas, but is still calcined in a nitrogen atmosphere for the same time, the temperature is also 500°C, and the heating rate is also 3°C/ Min, the molybdenum-based catalyst can be obtained by natural cooling to room temperature.
用透射电镜观察实施例1-7以及对比例1制备的钼基催化剂，并利用图像处理软件测量、统计、平均化处理，得到实施例1-7以及对比例1制备的钼基催化剂中活性组分钼颗粒的平均粒径，结果如表A所示，其中图1为实施例5所制备的钼基催化剂的透射电镜照片，图2为对比例1制备的钼基催化剂的透射电镜照片。The molybdenum-based catalysts prepared in Examples 1-7 and Comparative Example 1 were observed with a transmission electron microscope, and image processing software was used for measurement, statistics, and averaging to obtain active groups in the molybdenum-based catalysts prepared in Examples 1-7 and Comparative Example 1. The average particle size of the molybdenum particles is divided, and the results are shown in Table A. Figure 1 is a transmission electron microscope photo of the molybdenum-based catalyst prepared in Example 5, and Figure 2 is a transmission electron microscope photo of the molybdenum-based catalyst prepared in Comparative Example 1.
表ATable A
Figure PCTCN2020100410-appb-000001
Figure PCTCN2020100410-appb-000001
应用例1Application example 1
采用实施例5及对比例1中制备的钼基催化剂催化甲醇氨氧化制备氢氰酸，反应方程式如下：The molybdenum-based catalysts prepared in Example 5 and Comparative Example 1 were used to catalyze methanol ammoxidation to prepare hydrocyanic acid. The reaction equation is as follows:
Figure PCTCN2020100410-appb-000002
Figure PCTCN2020100410-appb-000002
具体反应条件为：采用固定床反应器，装填80g催化剂，质量空速为0.34h -1，氨气与甲醇的摩尔比为1.03:1，空气与甲醇的摩尔比为290:1，反应温度设定为390℃。 The specific reaction conditions are: a fixed bed reactor is used, 80g of catalyst is loaded, the mass space velocity is 0.34h -1 , the molar ratio of ammonia to methanol is 1.03:1, the molar ratio of air to methanol is 290:1, and the reaction temperature is set Set at 390°C.
经过气相色谱分析，实施例5以及对比例1得到的钼基催化剂的性能如表1所示。After gas chromatography analysis, the properties of the molybdenum-based catalysts obtained in Example 5 and Comparative Example 1 are shown in Table 1.
表1Table 1
Figure PCTCN2020100410-appb-000003
Figure PCTCN2020100410-appb-000003
应用例2Application example 2
采用实施例5及对比例1中制备的钼基催化剂催化丙烯氧化制备丙烯醛，反应方程式如下：The molybdenum-based catalyst prepared in Example 5 and Comparative Example 1 was used to catalyze the oxidation of propylene to produce acrolein. The reaction equation is as follows:
Figure PCTCN2020100410-appb-000004
Figure PCTCN2020100410-appb-000004
具体反应条件为：采用固定床反应器，装填50g催化剂，反应原料为含15vol.％(体积比)丙烯、85vol.％(体积比)空气的混合气体，质量空速为1500h -1，反应温度设定为320℃。 The specific reaction conditions are: a fixed bed reactor is used, 50g of catalyst is filled, the reaction raw material is a mixed gas containing 15vol.% (volume ratio) propylene and 85vol.% (volume ratio) air, the mass space velocity is 1500h -1 , the reaction temperature Set to 320°C.
经过气相色谱分析，实施例5以及对比例1得到的钼基催化剂的性能如表2所示。After gas chromatography analysis, the properties of the molybdenum-based catalysts obtained in Example 5 and Comparative Example 1 are shown in Table 2.
表2Table 2
Figure PCTCN2020100410-appb-000005
Figure PCTCN2020100410-appb-000005
Figure PCTCN2020100410-appb-000006
Figure PCTCN2020100410-appb-000006
应用例3Application example 3
采用实施例7及对比例1中制备的钼基催化剂催化丙烯氨氧化制备丙烯腈，反应方程式如下：The molybdenum-based catalyst prepared in Example 7 and Comparative Example 1 was used to catalyze the ammoxidation of propylene to produce acrylonitrile. The reaction equation is as follows:
Figure PCTCN2020100410-appb-000007
Figure PCTCN2020100410-appb-000007
具体反应条件为：采用40mL流化床反应器，丙烯以0.07h -1的空速进料，氨气与丙烯的摩尔比为1.04，空气与丙烯的摩尔比为10，反应温度设定为430℃。 The specific reaction conditions are: a 40mL fluidized bed reactor is used, propylene is fed at a space velocity of 0.07h -1 , the molar ratio of ammonia to propylene is 1.04, the molar ratio of air to propylene is 10, and the reaction temperature is set to 430 ℃.
经过气相色谱分析，实施例7以及对比例1得到的钼基催化剂的性能如表3所示。After gas chromatography analysis, the properties of the molybdenum-based catalysts obtained in Example 7 and Comparative Example 1 are shown in Table 3.
表3table 3
Figure PCTCN2020100410-appb-000008
Figure PCTCN2020100410-appb-000008
应用例4Application example 4
采用实施例7及对比例1中制备的钼基催化剂催化正丁烷氧化制备马来 酸酐，反应方程式如下：The molybdenum-based catalyst prepared in Example 7 and Comparative Example 1 was used to catalyze the oxidation of n-butane to prepare maleic anhydride. The reaction equation is as follows:
Figure PCTCN2020100410-appb-000009
Figure PCTCN2020100410-appb-000009
具体反应条件为：采用固定床反应器，装填50g催化剂，反应原料为含1.7vol.％(体积比)正丁烷、98.3vol.％(体积比)空气的混合气体，质量空速为1500h -1，反应温度设定为400℃。 Specific reaction conditions were: a fixed-bed reactor, the catalyst packed 50g, reaction feed containing 1.7vol% (by volume) n-butane, a mixed gas 98.3vol% (by volume) of air, WHSV is 1500h -.. 1. Set the reaction temperature to 400°C.
经过气相色谱分析，实施例7以及对比例1得到的钼基催化剂的性能如表4所示。After gas chromatography analysis, the properties of the molybdenum-based catalysts obtained in Example 7 and Comparative Example 1 are shown in Table 4.
表4Table 4
Figure PCTCN2020100410-appb-000010
Figure PCTCN2020100410-appb-000010
应用例5Application example 5
采用实施例7及对比例1中制备的钼基催化剂催化邻二甲苯氧化制备苯酐，反应方程式如下：The molybdenum-based catalyst prepared in Example 7 and Comparative Example 1 was used to catalyze the oxidation of o-xylene to prepare phthalic anhydride. The reaction equation is as follows:
Figure PCTCN2020100410-appb-000011
Figure PCTCN2020100410-appb-000011
具体反应条件为：采用固定床反应器，装填50g催化剂，反应原料为含 3.3vol.％(体积比)正丁烷、96.7vol.％(体积比)空气的混合气体，质量空速为1500h -1，反应温度设定为360℃。 Specific reaction conditions were: a fixed-bed reactor, the catalyst packed 50g, reaction feed containing 3.3vol% (by volume) n-butane, a mixed gas 96.7vol% (by volume) of air, WHSV is 1500h -.. 1. The reaction temperature is set to 360°C.
经过气相色谱分析，实施例7以及对比例1得到的钼基催化剂性能如表5所示。After gas chromatography analysis, the performance of the molybdenum-based catalyst obtained in Example 7 and Comparative Example 1 is shown in Table 5.
表5table 5
Figure PCTCN2020100410-appb-000012
Figure PCTCN2020100410-appb-000012
应用例6Application example 6
采用实施例1-2及对比例1中制备的钼基催化剂催化羟甲基糠醛氧化制备呋喃二甲酸及其酯，反应方程式如下：The molybdenum-based catalysts prepared in Examples 1-2 and Comparative Example 1 were used to catalyze the oxidation of hydroxymethyl furfural to prepare furandicarboxylic acid and its esters. The reaction equation is as follows:
Figure PCTCN2020100410-appb-000013
Figure PCTCN2020100410-appb-000013
具体反应条件为：采用不锈钢高压反应釜，加入100mg催化剂、100mg羟甲基糠醛、5mL甲醇，随后充入3MPa标准空气(79vol％N 2和21vol％O 2的混合气体，vol为体积比)，于800rpm搅拌速度下加热至120℃，反应时间5小时。 Specific reaction conditions were: stainless steel autoclave, the catalyst was added 100mg, 100mg hydroxymethyl furfural, 5 mL methanol, and then charged into 3MPa standard air (mixed gas of 79vol% N 2 and 21vol% O 2 of, vol volume ratio), It was heated to 120°C under a stirring speed of 800 rpm, and the reaction time was 5 hours.
经过气相色谱分析，实施例1-2以及对比例1得到的钼基催化剂的性能如表6所示。After gas chromatography analysis, the properties of the molybdenum-based catalysts obtained in Examples 1-2 and Comparative Example 1 are shown in Table 6.
表6Table 6
催化剂种类Catalyst type 呋喃二甲酸二甲酯的摩尔收率(％)The molar yield of dimethyl furandicarboxylate (%)
实施例1所制钼基催化剂The molybdenum-based catalyst prepared in Example 1 86.686.6
实施例2所制钼基催化剂Molybdenum-based catalyst prepared in Example 2 84.784.7
对比例1所制钼基催化剂Molybdenum-based catalyst prepared in Comparative Example 1 43.6％43.6%
应用例7Application example 7
采用实施例1-2及对比例1中制备的钼基催化剂催化对二甲苯氧化制备对苯二甲酸及其酯，反应方程式如下：The molybdenum-based catalyst prepared in Example 1-2 and Comparative Example 1 was used to catalyze the oxidation of p-xylene to prepare terephthalic acid and its esters. The reaction equation is as follows:
Figure PCTCN2020100410-appb-000014
Figure PCTCN2020100410-appb-000014
具体反应条件为：采用不锈钢高压反应釜，加入100mg催化剂、100mg对二甲苯、5mL甲醇，随后充入3MPa标准空气(79vol％N 2和21vol％O 2的混合气体，vol为体积比)，于800rpm搅拌速度下加热至120℃，反应时间5小时。 The specific reaction conditions are: using a stainless steel autoclave, adding 100mg catalyst, 100mg p-xylene, 5mL methanol, and then filling 3MPa standard air (79vol% N 2 and 21vol% O 2 mixed gas, vol is the volume ratio), Heat to 120°C under 800rpm stirring speed, reaction time 5 hours.
经过气相色谱分析，实施例1-2以及对比例1得到的钼基催化剂的性能如表7所示。After gas chromatography analysis, the properties of the molybdenum-based catalysts obtained in Examples 1-2 and Comparative Example 1 are shown in Table 7.
表7Table 7
催化剂种类Catalyst type 对苯二甲酸二甲酯的摩尔收率(％)The molar yield of dimethyl terephthalate (%)
实施例1所制钼基催化剂The molybdenum-based catalyst prepared in Example 1 89.489.4
实施例2所制钼基催化剂Molybdenum-based catalyst prepared in Example 2 88.688.6
对比例1所制钼基催化剂Molybdenum-based catalyst prepared in Comparative Example 1 60.3％60.3%
应用例8Application example 8
采用实施例1-7以及对比例1中制备的钼基催化剂催化2,5,6-三甲基苯酚氧化制备三甲基苯醌，反应方程式如下：The molybdenum-based catalysts prepared in Examples 1-7 and Comparative Example 1 were used to catalyze the oxidation of 2,5,6-trimethylphenol to prepare trimethylbenzoquinone. The reaction equation is as follows:
Figure PCTCN2020100410-appb-000015
Figure PCTCN2020100410-appb-000015
具体反应条件为：采用25mL三口烧瓶，加入50mg催化剂、200mg 2,5,6-三甲基苯酚、5mL乙醇、2mL双氧水(30wt％H 2O 2)，于800rpm搅拌速度下加热至30℃，反应时间3小时。 The specific reaction conditions are: using a 25mL three-necked flask, adding 50mg of catalyst, 200mg of 2,5,6-trimethylphenol, 5mL of ethanol, 2mL of hydrogen peroxide (30wt% H 2 O 2 ), heating to 30°C at a stirring speed of 800 rpm, The reaction time is 3 hours.
经过气相色谱分析，实施例1-7及对比例1得到的钼基催化剂的性能如表8所示。After gas chromatography analysis, the properties of the molybdenum-based catalysts obtained in Examples 1-7 and Comparative Example 1 are shown in Table 8.
表8Table 8
Figure PCTCN2020100410-appb-000016
Figure PCTCN2020100410-appb-000016
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。The technical features of the above-mentioned embodiments can be combined arbitrarily. In order to make the description concise, all possible combinations of the technical features in the above-mentioned embodiments are not described. However, as long as there is no contradiction in the combination of these technical features, All should be considered as the scope of this specification.
以上所述实施例仅表达了本申请的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对申请专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本申请构思的前提下，还可以做出若干变形和改进，这些都属于本申请的保护范围。因此，本申请专利的保护范围应以所附权利要求为准。The above-mentioned embodiments only express a few implementation modes of the present application, and their description is relatively specific and detailed, but they should not be understood as a limitation on the scope of the patent application. It should be pointed out that for those of ordinary skill in the art, without departing from the concept of this application, several modifications and improvements can be made, and these all fall within the protection scope of this application. Therefore, the scope of protection of the patent of this application shall be subject to the appended claims.

Claims (19)

  1. 一种钼基催化剂，其特征在于，包括活性组分钼和载体，所述活性组分钼以单质Mo和MoO x的形式存在，其中0<x≤3，所述载体为金属氧化物，表面具有氧空位，所述活性组分钼中的单质Mo与所述氧空位结合，形成Mo-[O]-M结构，其中[O]代表所述氧空位，M为所述载体中的金属元素，所述活性组分钼呈纳米颗粒状分布于所述载体表面。 A molybdenum-based catalyst is characterized in that it comprises an active component molybdenum and a carrier. The active component molybdenum exists in the form of elemental Mo and MoO x , where 0<x≤3, and the carrier is a metal oxide. With oxygen vacancies, the elemental Mo in the active component molybdenum combines with the oxygen vacancies to form a Mo-[O]-M structure, where [O] represents the oxygen vacancies, and M is the metal element in the carrier The active component molybdenum is distributed on the surface of the carrier in the form of nanoparticles.
  2. 根据权利要求1所述的钼基催化剂，其特征在于，所述活性组分钼的粒径小于等于5nm。The molybdenum-based catalyst according to claim 1, wherein the particle size of the active component molybdenum is less than or equal to 5 nm.
  3. 根据权利要求1所述的钼基催化剂，其特征在于，所述活性组分钼的存在形式中单质Mo的摩尔含量为60％至100％。The molybdenum-based catalyst according to claim 1, wherein the molar content of the elemental Mo in the existence form of the active component molybdenum is 60% to 100%.
  4. 根据权利要求1所述的钼基催化剂，其特征在于，所述载体包括第一载体，所述第一载体选自Ti、Zr、Ce、V、Cr、Mn、Fe、Zn、Ga、Ge、Sn、Bi、Y、Nb、La、Re中的一种元素或多种元素的氧化物。The molybdenum-based catalyst according to claim 1, wherein the carrier comprises a first carrier, and the first carrier is selected from Ti, Zr, Ce, V, Cr, Mn, Fe, Zn, Ga, Ge, One element among Sn, Bi, Y, Nb, La, and Re or oxides of multiple elements.
  5. 根据权利要求4所述的钼基催化剂，其特征在于，所述载体还包括第二载体，所述第二载体具有的氧空位浓度低于所述第一载体具有的氧空位浓度。The molybdenum-based catalyst according to claim 4, wherein the carrier further comprises a second carrier, and the second carrier has an oxygen vacancy concentration lower than that of the first carrier.
  6. 根据权利要求5所述的钼基催化剂，其特征在于，所述第二载体选自Al、Mg、Ca中的一种元素或多种元素的氧化物。The molybdenum-based catalyst according to claim 5, wherein the second support is selected from one element or oxides of multiple elements selected from Al, Mg, and Ca.
  7. 根据权利要求1所述的钼基催化剂，其特征在于，所述活性组分钼的负载量按质量百分数记为0.1％至50％。The molybdenum-based catalyst according to claim 1, wherein the loading amount of the active component molybdenum is recorded as 0.1% to 50% by mass percentage.
  8. 一种钼基催化剂的制备方法，其特征在于，包括以下步骤：A preparation method of a molybdenum-based catalyst is characterized in that it comprises the following steps:
    将钼的前驱体负载在载体上并进行干燥，得到第一固体，所述载体为氧化物；Loading the precursor of molybdenum on a carrier and drying to obtain a first solid, and the carrier is an oxide;
    将所述第一固体置于空气或惰性气体中进行第一次煅烧，得到第二固体；Placing the first solid in air or inert gas for the first calcination to obtain a second solid;
    将所述第二固体置于还原性气体中进行第二次煅烧，得到钼基催化剂。The second solid is placed in a reducing gas for a second calcination to obtain a molybdenum-based catalyst.
  9. 根据权利要求8所述的钼基催化剂的制备方法，其特征在于，所述第一次煅烧的步骤中，煅烧温度为600℃至1000℃，煅烧时间为0.1小时至12小时。The method for preparing a molybdenum-based catalyst according to claim 8, wherein in the first calcination step, the calcination temperature is 600°C to 1000°C, and the calcination time is 0.1 hour to 12 hours.
  10. 根据权利要求8所述的钼基催化剂的制备方法，其特征在于，所述第 二次煅烧的步骤中，煅烧温度为300℃至800℃，煅烧时间为0.1小时至24小时。The method for preparing a molybdenum-based catalyst according to claim 8, wherein in the second calcination step, the calcination temperature is 300°C to 800°C, and the calcination time is 0.1 hour to 24 hours.
  11. 根据权利要求8所述的钼基催化剂的制备方法，其特征在于，所述载体含有本征氧空位。The method for preparing a molybdenum-based catalyst according to claim 8, wherein the carrier contains intrinsic oxygen vacancies.
  12. 根据权利要求8所述的钼基催化剂的制备方法，其特征在于，所述载体包括第一载体，所述第一载体选自Ti、Zr、Ce、V、Cr、Mn、Fe、Zn、Ga、Ge、Sn、Bi、Y、Nb、La、Re中的一种元素或多种元素的氧化物。The method for preparing a molybdenum-based catalyst according to claim 8, wherein the support comprises a first support, and the first support is selected from Ti, Zr, Ce, V, Cr, Mn, Fe, Zn, Ga , Ge, Sn, Bi, Y, Nb, La, Re, or oxides of multiple elements.
  13. 根据权利要求12所述的钼基催化剂的制备方法，其特征在于，所述载体还包括第二载体，所述第二载体选自Al、Mg、Ca中的一种元素或多种元素的氧化物。The method for preparing a molybdenum-based catalyst according to claim 12, wherein the carrier further comprises a second carrier, and the second carrier is selected from the oxidation of one element or multiple elements in Al, Mg, and Ca. Things.
  14. 根据权利要求8所述的钼基催化剂的制备方法，其特征在于，所述钼的前躯体为钼酸或可溶性钼酸盐。The method for preparing a molybdenum-based catalyst according to claim 8, wherein the precursor of the molybdenum is molybdic acid or soluble molybdate.
  15. 根据权利要求12所述的钼基催化剂的制备方法，其特征在于，所述钼的前躯体选自(NH 4) 2Mo 2O 7、(NH 4) 2Mo 4O 13·2H 2O、H 2MoO 4、K 2MoO 4、(NH 4) 6Mo 7O 24·4H 2O、Na 2MoO 4·2H 2O中的一种或多种。 The method for preparing a molybdenum-based catalyst according to claim 12, wherein the precursor of the molybdenum is selected from (NH 4 ) 2 Mo 2 O 7 , (NH 4 ) 2 Mo 4 O 13 ·2H 2 O, One or more of H 2 MoO 4 , K 2 MoO 4 , (NH 4 ) 6 Mo 7 O 24 ·4H 2 O, and Na 2 MoO 4 ·2H 2 O.
  16. 根据权利要求8所述的钼基催化剂的制备方法，其特征在于，所述钼的前躯体与所述载体的质量比为1至30。The method for preparing a molybdenum-based catalyst according to claim 8, wherein the mass ratio of the precursor of the molybdenum to the carrier is 1-30.
  17. 根据权利要求8所述的钼基催化剂的制备方法，其特征在于，所述还原性气体包括氢气、甲烷、乙烷、乙烯、乙炔、丙烷、丙烯、丙炔、丙二烯、正丁烷、异丁烷、1-丁烯、2-丁烯、异丁烯、1,3-丁二烯、一氧化碳中的一种或多种。The method for preparing a molybdenum-based catalyst according to claim 8, wherein the reducing gas includes hydrogen, methane, ethane, ethylene, acetylene, propane, propylene, propyne, propadiene, n-butane, One or more of isobutane, 1-butene, 2-butene, isobutene, 1,3-butadiene, and carbon monoxide.
  18. 如权利要求1-7任一项所述的钼基催化剂或权利要求8-17任一项所述的制备方法得到的钼基催化剂在醇和烃类物质的氧化反应中的应用。The application of the molybdenum-based catalyst according to any one of claims 1-7 or the molybdenum-based catalyst obtained by the preparation method according to any one of claims 8-17 in the oxidation reaction of alcohols and hydrocarbons.
  19. 根据权利要求18所述的应用，其特征在于，所述氧化反应包括甲醇氨氧化制备氢氰酸、丙烯氨氧化制备丙烯腈、丙烯氧化制备丙烯醛、丁烷氧化制备马来酸酐、环己烷氧化制备环己酮和环己醇、邻二甲苯氧化制备苯酐、对二甲苯氧化制备对苯二甲酸、羟甲基糠醛氧化制备呋喃二甲酸、维生素E生产中制备三甲基苯醌中的一种或多种。The application according to claim 18, wherein the oxidation reaction comprises ammoxidation of methanol to prepare hydrocyanic acid, ammoxidation of propylene to prepare acrylonitrile, oxidation of propylene to prepare acrolein, and oxidation of butane to prepare maleic anhydride and cyclohexane Oxidation to produce cyclohexanone and cyclohexanol, o-xylene oxidation to produce phthalic anhydride, p-xylene oxidation to produce terephthalic acid, hydroxymethyl furfural to produce furandicarboxylic acid, one of the trimethyl benzoquinone produced in the production of vitamin E Kind or more.
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