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WO2021004424A1 - Catalyseur à base de molybdène, un procédé de préparation de celui-ci et son utilisation - Google Patents

Catalyseur à base de molybdène, un procédé de préparation de celui-ci et son utilisation Download PDF

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Publication number
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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Prior art keywords
molybdenum
carrier
based catalyst
active component
catalyst according
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Chinese (zh)
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WO2021004424A9 (fr
Inventor
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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Shandong Nhu Amino Acid Co Ltd
SHANDONG NHU PHARMACEUTICAL CO Ltd
Shandong Nhu Vitamin Co Ltd
Zhejiang University ZJU
Zhejiang NHU Co Ltd
Shangyu NHU Biological Chemical Co Ltd
Original Assignee
Shandong Nhu Amino Acid Co Ltd
SHANDONG NHU PHARMACEUTICAL CO Ltd
Shandong Nhu Vitamin Co Ltd
Zhejiang University ZJU
Zhejiang NHU Co Ltd
Shangyu NHU Biological Chemical Co Ltd
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Application filed by Shandong Nhu Amino Acid Co Ltd, SHANDONG NHU PHARMACEUTICAL CO Ltd, Shandong Nhu Vitamin Co Ltd, Zhejiang University ZJU, Zhejiang NHU Co Ltd, Shangyu NHU Biological Chemical Co Ltd filed Critical Shandong Nhu Amino Acid Co Ltd
Priority to DE112020000197.0T priority Critical patent/DE112020000197T5/de
Publication of WO2021004424A1 publication Critical patent/WO2021004424A1/fr
Publication of WO2021004424A9 publication Critical patent/WO2021004424A9/fr
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    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—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
    • 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
    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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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
    • B01J23/24—Chromium, molybdenum or tungsten
    • 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
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
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    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
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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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    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
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    • C01C3/02—Preparation, separation or purification of hydrogen cyanide
    • C01C3/0208—Preparation in gaseous phase
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    • C07C253/26—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing carbon-to-carbon multiple bonds, e.g. unsaturated aldehydes
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—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
    • C07C45/33—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
    • 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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    • C07C46/00—Preparation of quinones
    • C07C46/02—Preparation of quinones by oxidation giving rise to quinoid structures
    • 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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    • C07C67/00—Preparation of carboxylic acid esters
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    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • 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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    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
    • 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
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    • 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 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.

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Abstract

L'invention concerne un catalyseur à base de molybdène, un procédé de préparation de celui-ci et son utilisation. Le catalyseur à base de molybdène comprend un composant actif molybdène et un support, le composant actif molybdène étant présent sous la forme de Mo élémentaire et MoOx, où 0 < x ≤ 3, et le support est un oxyde métallique ayant une lacune d'oxygène sur la surface de celui-ci; le Mo élémentaire dans le composant actif molybdène est combiné avec la lacune d'oxygène pour former une structure Mo-[O]-M, dans laquelle [O] représente la lacune d'oxygène, et M est un élément métallique dans le support, et le composant actif molybdène est distribué sur la surface du support sous la forme de nanoparticules.
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