CN113019436B - Catalyst for one-step preparation of 1, 3-butanediol from propylene and methanol, and preparation and application thereof - Google Patents

Catalyst for one-step preparation of 1, 3-butanediol from propylene and methanol, and preparation and application thereof Download PDF

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CN113019436B
CN113019436B CN201911250094.7A CN201911250094A CN113019436B CN 113019436 B CN113019436 B CN 113019436B CN 201911250094 A CN201911250094 A CN 201911250094A CN 113019436 B CN113019436 B CN 113019436B
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molybdenum
catalyst
iron
zsm
methanol
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CN113019436A (en
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王峰
李书双
张志鑫
张健
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Dalian Institute of Chemical Physics of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

The invention discloses a preparation method of a catalyst for preparing 1, 3-butanediol by one-step reaction of propylene and methanol. The material is characterized in that a macromolecule self-assembly strategy is adopted, and a layer of Mo and Fe self-assembly structure is wrapped on the surface of a ZSM-5 molecular sieve, so that the material simultaneously has an oxidation active site and an acid condensation active site for oxidizing methanol into formaldehyde. After being oxidized into formaldehyde on the surface of the iron-molybdenum active site, the methanol is subjected to condensation reaction with propylene and water generated in the previous oxidation process under the action of an acidic condensation active site, so that the propylene and the methanol are reacted in one step to generate the 1, 3-butanediol. The preparation method is easy to amplify and has good industrial application prospect.

Description

Catalyst for one-step preparation of 1, 3-butanediol from propylene and methanol, and preparation and application thereof
Technical Field
The invention relates to a preparation method of a catalyst for preparing 1, 3-butanediol by one-step reaction of propylene and methanol, belonging to the catalyst preparation technology in the field of industrial catalysis.
Background
In recent years, with the rapid development of the domestic polyester industry, the demand for glycols represented by ethylene glycol and butanediol has also rapidly increased. Wherein, the 1, 3-butanediol is the main raw material for producing polyester resin, alkyd resin, plasticizer and polyurethane coating, and has very wide application field.
At present, the disclosed preparation processes of 1, 3-butanediol mainly comprise: (1) acetaldehyde is used as a raw material, self-condensation is carried out in an alkaline solution to generate 3-hydroxybutyraldehyde, and then hydrogenation is carried out to generate 1, 3-butanediol. Chinese patent CN108383684A discloses a process for producing 1, 3-butanediol from acetaldehyde via a route of 2, 6-dimethyl-1, 3-dioxan-4-ol, which improves the stability of the intermediate product and also improves the selectivity of 1, 3-butanediol. (2) Preparing 1, 3-butanediol by a biological fermentation method. CN 107002101A, CN 102625846B disclose a method of biochemically preparing 1, 3-butanediol, and enzymatically converting 3-oxo-5-hydroxypentanoyl-CoA into 1, 3-butanediol using a polypeptide having ketothiolase activity. (3) Condensing propylene and formaldehyde to prepare 1, 3-butanediol. CN 108017513 a, CN 103102229 a disclose a method for preparing 1, 3-butanediol (3-methyl-1, 3-butanediol) from formaldehyde and propylene (isobutylene). The above methods have advantages and disadvantages, and acetaldehyde condensation hydrogenation is the most important production route at present, however, the above techniques are mainly monopolized by western countries such as Japan and USA. The biological fermentation method and the propylene and formaldehyde condensation method have many reaction steps because the preparation of the catalyst is immature, and the large-scale production cannot be realized.
Aiming at the problems, the invention discloses a method for preparing a 1, 3-butanediol catalyst by propylene and formaldehyde in one step, which is to coat a layer of ferromolybdenum composite oxide on the surface of ZSM-5 to prepare a specific MoO with multilevel pore channels 3 -Fe 2 (MoO 4 ) 3 a/ZSM-5 catalyst. Methanol is firstly oxidized on the surface of the catalyst to generate formaldehyde, and then is diffused to the internal ZSM-5 acidic condensation active site through a channel to react with propylene and water generated in the methanol oxidation process to generate 1, 3-butanediol.
Compared with the formaldehyde and propylene routes reported before, the method integrates the steps of methanol oxidation and formaldehyde condensation, thereby simplifying the reaction process and avoiding the problems of storage and transportation of formaldehyde.
Disclosure of Invention
The invention aims to provide a preparation method of a catalyst for preparing 1, 3-butanediol from propylene and methanol in one step, which prepares a ZSM-5 catalyst coated by iron and molybdenum oxides and integrates an iron and molybdenum oxidation active site and an acid condensation active site into the same catalyst.
The invention provides a preparation method of a catalyst for preparing 1, 3-butanediol from propylene and methanol in one step, which is characterized by comprising the following steps: firstly, dissolving tetrapropylammonium hydroxide into water, adding ammonia water with the mass concentration of 25-28% to adjust the pH value to 8-10, respectively adding tetraethoxysilane and amphiphilic organic silicon under the stirring condition, stirring for 10-30 minutes at the temperature of 20-40 ℃, adding aluminum nitrate according to the Si/Al ratio of 30-200, transferring into a crystallization kettle, crystallizing for 24-120 hours at the temperature of 80-250 ℃, performing suction filtration, and drying to obtain a ZSM-5 carrier; dispersing the carrier into a solvent, adding a molybdenum organic heterocyclic compound and an iron organic heterocyclic compound according to the required molybdenum-iron atomic ratio, and then evaporating the solvent to dryness at the temperature of 20-250 ℃ (preferably 80-150 ℃) and under the humidity condition of 10-95% (preferably 40-80%); by utilizing ZSM-5 itself havingThe template agent enables molybdenum and iron organic heterocyclic rings to self-assemble into a structure with the size of 10-200 nm; then roasting at 250-550 deg.C (preferably 350-450 deg.C), coating a layer of MoO on the surface of ZSM-5 carrier 3 -Fe 2 (MoO 4 ) 3 Component (A) to obtain a composition coated with MoO on the surface 3 -Fe 2 (MoO 4 ) 3 SM-5 catalyst (c).
The invention provides a preparation method of a catalyst for preparing 1, 3-butanediol from propylene and methanol in one step, which is characterized by comprising the following steps: in the catalyst, the mass loading of molybdenum oxide is 5-30%, and the mass loading of iron molybdate is 5-20%.
The invention provides a preparation method of a catalyst for preparing 1, 3-butanediol from propylene and methanol in one step, which is characterized by comprising the following steps: the molar ratio of molybdenum atoms to iron atoms is controlled between 1.6 and 4.0.
The invention provides a preparation method of a catalyst for preparing 1, 3-butanediol from propylene and methanol in one step, which is characterized by comprising the following steps: amphiphilic silicones include in particular: twelve carbon long organosilane quaternary ammonium salt ((CH) 3 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 12 H 25 Cl), fourteen-carbon long organosilane quaternary ammonium salt ((CH) 3 CH 2 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 14 H 29 Cl), sixteen carbon long organosilane quaternary ammonium salt ((CH) 3 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 16 H 33 Cl), octadecyl long organosilane quaternary ammonium salt ((CH) 3 CH 2 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 18 H 37 Br) or the like, and one or more of the above components.
The invention provides a preparation method of a catalyst for preparing 1, 3-butanediol from propylene and methanol in one step, which is characterized by comprising the following steps: the molybdenum organic heterocyclic compound specifically includes: molybdenum porphyrin, molybdenum phthalocyanine, molybdenum naphthalocyanine or molybdenum spiro cyanine or a mixture of one or more of the components;
the iron organic heterocyclic compound specifically includes: ferriporphyrin, iron phthalocyanine, iron naphthalocyanine, iron spiro cyanine, ferrocene, cyclopentadienyl carbonyl iron, or a mixture of one or more of the above components.
The invention provides a preparation method of a catalyst for preparing 1, 3-butanediol from propylene and methanol in one step, which is characterized by comprising the following steps: the solvent comprises one or more of water, chloroform, ethanol, cyclohexane, toluene, dichloroethane, methanol, ethylene glycol and glycerol, and the mass concentration of the carrier in the solvent is 10-80%.
The invention provides a preparation method of a catalyst for preparing 1, 3-butanediol from propylene and methanol in one step, which is characterized by comprising the following steps: the roasting treatment atmosphere is one of air, nitrogen, argon or oxygen.
The invention provides a preparation method of a catalyst for preparing 1, 3-butanediol from propylene and methanol in one step, which is characterized by comprising the following steps: dissolving tetrapropylammonium hydroxide into water to form a solution with the mass concentration of 1-30%, wherein the mass concentration of tetrapropylammonium hydroxide is as follows: ethyl orthosilicate: the molar ratio of the amphiphilic organic silicon is 0.05-0.5:1: 0.01-0.1.
The invention provides a preparation method of a catalyst for preparing 1, 3-butanediol by propylene and methanol in one step, and the catalyst can be applied to the preparation of 1, 3-butanediol by propylene and methanol in one step.
Detailed Description
Example 1:
to 91mL0.5mol/L of tetrapropylammonium hydroxide aqueous solution was added 17% aqueous ammonia to adjust the pH to 9.0, followed by 50.7mL of ethyl orthosilicate and 2.5mL of hexadecane long organosilane quaternary ammonium salt ((CH) 3 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 16 H 33 Cl), stirring and hydrolyzing at 35 ℃ for 2h, adding aluminum nitrate according to Si/Al (equal to 50), stirring for 30 min, then transferring into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, crystallizing at 250 ℃ for 72h, and performing suction filtration and drying to obtain the ZSM-5 carrier with the hierarchical pore channel. Dispersing 50g of ZSM-5 carrier into 100mL of ethanol, adding ferriporphyrin according to the mass loading of 10% of iron molybdate, adding molybdenum phthalocyanine according to the mass loading of 20% of molybdenum trioxide, stirring for 1h, and heating at 80 DEG CEvaporating ethanol to dryness under the condition that the humidity is 60%, and then carrying out roasting treatment for 1h under the air atmosphere of 400 ℃ to obtain MoO with specific loading capacity 3 -Fe 2 (MoO 4 ) 3 A/ZSM-5 catalyst.
Comparative example 1: (No addition of Long-chain organosilicon reagent)
Adding 17% ammonia water into 91mL0.5mol/L tetrapropylammonium hydroxide aqueous solution to adjust the pH value to 9.0, then adding 50.7mL ethyl orthosilicate, stirring and hydrolyzing at 35 ℃ for 2h, then adding aluminum nitrate according to Si/Al value of 50, stirring for 30 min, then transferring into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, crystallizing at 250 ℃ for 72h, and obtaining the ZSM-5 carrier with the multistage pore channel through suction filtration and drying. Dispersing 50g of ZSM-5 carrier into 100mL of ethanol, adding ferriporphyrin according to the mass loading of 10% of iron molybdate, adding molybdenum phthalocyanine according to the mass loading of 20% of molybdenum trioxide, stirring for 1h, evaporating ethanol to dryness under the conditions that the temperature is 80 ℃ and the humidity is 60%, and then roasting for 1h under the air atmosphere of 400 ℃ to obtain MoO with specific loading 3 -Fe 2 (MoO 4 ) 3 a/ZSM-5 catalyst.
Example 2: molybdenum iron atomic ratio of 1.6
To 91mL0.5mol/L of tetrapropylammonium hydroxide aqueous solution was added 17% aqueous ammonia to adjust the pH to 9.0, followed by 50.7mL of ethyl orthosilicate and 2.5mL of hexadecane long organosilane quaternary ammonium salt ((CH) 3 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 16 H 33 Cl), stirring and hydrolyzing at 35 ℃ for 2h, adding aluminum nitrate according to Si/Al (50), stirring for 30 min, transferring into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, crystallizing at 250 ℃ for 72h, filtering, and drying to obtain the ZSM-5 carrier with the multistage pore canal. Dispersing 50g of ZSM-5 carrier into 100mL of ethanol, adding ferriporphyrin according to the mass loading of 10% of iron molybdate, adding molybdenum phthalocyanine according to the molybdenum-iron atomic ratio of 1.6, stirring for 1h, evaporating ethanol under the conditions that the temperature is 80 ℃ and the humidity is 60%, and then roasting for 1h at 400 ℃ in air atmosphere to obtain MoO with specific loading 3 -Fe 2 (MoO 4 ) 3 A/ZSM-5 catalyst.
Example 3: molybdenum iron atomic ratio of 4.0
To 91mL of a 0.5mol/L aqueous tetrapropylammonium hydroxide solution, 17% aqueous ammonia was added to adjust the pH to 9.0, followed by 50.7mL of ethyl orthosilicate and 2.5mL of a hexadecane long organosilane quaternary ammonium salt ((CH) 3 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 16 H 33 Cl), stirring and hydrolyzing at 35 ℃ for 2h, adding aluminum nitrate according to Si/Al (equal to 50), stirring for 30 min, then transferring into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, crystallizing at 250 ℃ for 72h, and performing suction filtration and drying to obtain the ZSM-5 carrier with the hierarchical pore channel. Dispersing 50g of ZSM-5 carrier into 100mL of ethanol, adding iron porphyrin according to the mass loading of 15% of iron molybdate, adding molybdenum porphyrin according to the mass loading of 4.0 iron molybdate atoms, stirring for 1h, evaporating ethanol to dryness at the temperature of 80 ℃ and the temperature of 60%, and then roasting at the temperature of 400 ℃ for 6h to obtain MoO with specific loading 3 -Fe 2 (MoO 4 ) 3 a/ZSM-5 catalyst.
Example 4: long chain organosilicon species
After adjusting the pH to 9.0 by adding 17% aqueous ammonia to 91mL0.5mol/L aqueous tetrapropylammonium hydroxide solution, 50.7mL of ethyl orthosilicate and 2.5mL of dodecacarbon long organosilane quaternary ammonium salt ((CH) 3 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 16 H 33 Cl), stirring and hydrolyzing at 35 ℃ for 2h, adding aluminum nitrate according to Si/Al (equal to 50), stirring for 30 min, then transferring into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, crystallizing at 250 ℃ for 72h, and performing suction filtration and drying to obtain the ZSM-5 carrier with the hierarchical pore channel. Dispersing 50g of ZSM-5 carrier into 100mL of ethanol, adding ferriporphyrin according to the mass loading of 10% of iron molybdate, adding molybdenum phthalocyanine according to the mass loading of 20% of molybdenum trioxide, stirring for 1h, evaporating ethanol to dryness under the conditions that the temperature is 80 ℃ and the humidity is 60%, and then roasting for 8h under the air atmosphere of 400 ℃ to obtain MoO with specific loading 3 -Fe 2 (MoO 4 ) 3 a/ZSM-5 catalyst.
Example 5: long chain organosilicon species
To 91mL0.5mol/L of tetrapropylammonium hydroxide aqueous solution was added 17% aqueous ammonia to adjust the pH to 9.0, followed by 50.7mL of ethyl orthosilicate and 2.5mL of octadecylsilyl quaternary ammonium salt ((CH) 3 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 16 H 33 Cl), stirring and hydrolyzing at 35 ℃ for 2h, adding aluminum nitrate according to Si/Al (equal to 50), stirring for 30 min, then transferring into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, crystallizing at 250 ℃ for 72h, and performing suction filtration and drying to obtain the ZSM-5 carrier with the hierarchical pore channel. Dispersing 50g of ZSM-5 carrier into 100mL of ethanol, adding ferriporphyrin according to the mass loading of 10% of iron molybdate, adding molybdenum phthalocyanine according to the mass loading of 20% of molybdenum trioxide, stirring for 1h, evaporating ethanol under the conditions that the temperature is 80 ℃ and the humidity is 60%, and then roasting at 400 ℃ for 12h in an air atmosphere to obtain MoO with a specific loading 3 -Fe 2 (MoO 4 ) 3 a/ZSM-5 catalyst.
Example 6: class of molybdenum organic heterocyclic compounds
To 91mL0.5mol/L of tetrapropylammonium hydroxide aqueous solution was added 17% aqueous ammonia to adjust the pH to 9.0, followed by 50.7mL of ethyl orthosilicate and 2.5mL of hexadecane long organosilane quaternary ammonium salt ((CH) 3 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 16 H 33 Cl), stirring and hydrolyzing at 35 ℃ for 2h, adding aluminum nitrate according to Si/Al (100), stirring for 30 min, transferring into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, crystallizing at 250 ℃ for 72h, filtering, and drying to obtain the ZSM-5 carrier with the multistage pore canal. Dispersing 50g of ZSM-5 carrier into 100mL of ethanol, adding ferriporphyrin according to the loading of 10 mass percent of iron molybdate, adding molybdophosphorus according to the loading of 30 mass percent of molybdenum trioxide, stirring for 1h, evaporating ethanol to dryness under the conditions that the temperature is 80 ℃ and the humidity is 60 percent, and then roasting for 12h under the air atmosphere of 400 ℃ to obtain MoO with specific loading 3 -Fe 2 (MoO 4 ) 3 a/ZSM-5 catalyst.
Example 7: class of molybdenum organic heterocyclic compounds
Adding 91mL0.5mol/L tetrapropylammonium hydroxide aqueous solutionAdding 17% ammonia water to adjust the pH value to 9.0, then adding 50.7mL of ethyl orthosilicate and 2.5mL of tetradecane long organosilane quaternary ammonium salt ((CH3O)3SiC3H6N (CH3)2C16H33Cl), stirring and hydrolyzing at 35 ℃ for 2H, then adding aluminum nitrate according to Si/Al (50), stirring for 30 min, then transferring into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, crystallizing at 250 ℃ for 72H, filtering by suction, and drying to obtain the ZSM-5 carrier with the multistage pore channels. Dispersing 50g of ZSM-5 carrier into 100mL of ethanol, adding ferriporphyrin according to the mass loading of 5% of iron molybdate, adding molybdenum naphthalocyanine according to the mass loading of 5% of molybdenum trioxide, stirring for 1h, evaporating ethanol to dryness under the conditions that the temperature is 80 ℃ and the humidity is 60%, and then roasting for 6h under the air atmosphere of 400 ℃ to obtain MoO with specific loading 3 -Fe 2 (MoO 4 ) 3 A/ZSM-5 catalyst.
Example 8: class of iron organic heterocyclic compounds
To 91mL0.5mol/L of tetrapropylammonium hydroxide aqueous solution was added 17% aqueous ammonia to adjust the pH to 9.0, followed by 50.7mL of ethyl orthosilicate and 2.5mL of hexadecane long organosilane quaternary ammonium salt ((CH) 3 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 16 H 33 Cl), stirring and hydrolyzing at 35 ℃ for 2h, adding aluminum nitrate according to Si/Al (equal to 50), stirring for 30 min, then transferring into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, crystallizing at 250 ℃ for 72h, and performing suction filtration and drying to obtain the ZSM-5 carrier with the hierarchical pore channel. Dispersing 50g of ZSM-5 carrier into 100mL of ethanol, adding iron phthalocyanine according to the mass loading of 5% of iron molybdate, adding molybdenum phthalocyanine according to the mass loading of 20% of molybdenum trioxide, stirring for 1h, evaporating ethanol to dryness under the conditions that the temperature is 80 ℃ and the humidity is 60%, and then roasting at 400 ℃ for 12h in an air atmosphere to obtain MoO with specific loading 3 -Fe 2 (MoO 4 ) 3 a/ZSM-5 catalyst.
Example 9: class of iron organic heterocyclic compounds
To 91mL of a 0.5mol/L aqueous tetrapropylammonium hydroxide solution, 17% aqueous ammonia was added to adjust the pH to 9.0, followed by 50.7mL of ethyl orthosilicate and 2.5mL of a hexadecane long organosilane quaternary ammonium salt ((CH) 3 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 16 H 33 Cl), stirring and hydrolyzing at 35 ℃ for 2h, adding aluminum nitrate according to Si/Al (equal to 50), stirring for 30 min, then transferring into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, crystallizing at 250 ℃ for 72h, and performing suction filtration and drying to obtain the ZSM-5 carrier with the hierarchical pore channel. Dispersing 50g of ZSM-5 carrier into 100mL of ethanol, adding ferric spiro cyanine according to the mass loading of 20% of iron molybdate, adding molybdenum phthalocyanine according to the mass loading of 20% of molybdenum trioxide, stirring for 1h, evaporating ethanol to dryness under the conditions that the temperature is 80 ℃ and the humidity is 60%, and then roasting for 6h under the air atmosphere of 400 ℃ to obtain MoO with specific loading 3 -Fe 2 (MoO 4 ) 3 a/ZSM-5 catalyst.
Example 10: kind of solvent
To 91mL0.5mol/L of tetrapropylammonium hydroxide aqueous solution was added 17% aqueous ammonia to adjust the pH to 9.0, followed by 50.7mL of ethyl orthosilicate and 2.5mL of hexadecane long organosilane quaternary ammonium salt ((CH) 3 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 16 H 33 Cl), stirring and hydrolyzing at 35 ℃ for 2h, adding aluminum nitrate according to Si/Al (50), stirring for 30 min, transferring into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, crystallizing at 250 ℃ for 72h, filtering, and drying to obtain the ZSM-5 carrier with the multistage pore canal. Dispersing 50g of ZSM-5 carrier into 100mL of cyclohexane, adding ferriporphyrin according to the mass loading of 10% of iron molybdate, adding molybdenum phthalocyanine according to the mass loading of 20% of molybdenum trioxide, stirring for 1h, evaporating ethanol under the conditions that the temperature is 80 ℃ and the humidity is 60%, and then roasting at 400 ℃ for 12h in an air atmosphere to obtain MoO with specific loading 3 -Fe 2 (MoO 4 ) 3 a/ZSM-5 catalyst.
Example 11: kind of solvent
To 91mL0.5mol/L of tetrapropylammonium hydroxide aqueous solution was added 17% aqueous ammonia to adjust the pH to 9.0, followed by 50.7mL of ethyl orthosilicate and 2.5mL of hexadecane long organosilane quaternary ammonium salt ((CH) 3 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 16 H 33 Cl) inStirring and hydrolyzing for 2h at 35 ℃, adding aluminum nitrate according to Si/Al which is 50, stirring for 30 min, then transferring into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, crystallizing for 72h at 250 ℃, and performing suction filtration and drying to obtain the ZSM-5 carrier with the multistage pore channels. Dispersing 50g of ZSM-5 carrier into 100mL of water, adding ferriporphyrin according to the mass loading of 10% of iron molybdate, adding molybdenum phthalocyanine according to the mass loading of 20% of molybdenum trioxide, stirring for 1h, evaporating ethanol under the conditions that the temperature is 80 ℃ and the humidity is 60%, and then roasting for 6h under the air atmosphere at 400 ℃ to obtain MoO with specific loading 3 -Fe 2 (MoO 4 ) 3 a/ZSM-5 catalyst.
Example 12: roasting atmosphere
To 91mL of a 0.5mol/L aqueous tetrapropylammonium hydroxide solution, 17% aqueous ammonia was added to adjust the pH to 9.0, followed by 50.7mL of ethyl orthosilicate and 2.5mL of a hexadecane long organosilane quaternary ammonium salt ((CH) 3 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 16 H 33 Cl), stirring and hydrolyzing at 35 ℃ for 2h, adding aluminum nitrate according to Si/Al (equal to 50), stirring for 30 min, then transferring into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, crystallizing at 250 ℃ for 72h, and performing suction filtration and drying to obtain the ZSM-5 carrier with the hierarchical pore channel. Dispersing 50g of ZSM-5 carrier into 100mL of ethanol, adding ferriporphyrin according to the mass loading of 10% of iron molybdate, adding molybdenum phthalocyanine according to the mass loading of 20% of molybdenum trioxide, stirring for 1h, evaporating ethanol under the conditions that the temperature is 80 ℃ and the humidity is 60%, and then roasting for 6h under the nitrogen atmosphere at 400 ℃ to obtain MoO with specific loading 3 -Fe 2 (MoO 4 ) 3 a/ZSM-5 catalyst.
Example 13: roasting atmosphere
To 91mL0.5mol/L of tetrapropylammonium hydroxide aqueous solution was added 17% aqueous ammonia to adjust the pH to 9.0, followed by 50.7mL of ethyl orthosilicate and 2.5mL of hexadecane long organosilane quaternary ammonium salt ((CH) 3 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 16 H 33 Cl), hydrolyzing at 35 ℃ for 2h with stirring, adding aluminum nitrate according to Si/Al value of 50, stirring for 30 min, and transferring to a polymerization zoneCrystallizing at 250 deg.c for 72 hr in stainless steel crystallizing kettle with tetrafluoroethylene lining, suction filtering and drying to obtain ZSM-5 carrier with multistage pore canal. Dispersing 50g of ZSM-5 carrier into 100mL of ethanol, adding ferriporphyrin according to the mass loading of 10% of iron molybdate, adding molybdenum phthalocyanine according to the mass loading of 20% of molybdenum trioxide, stirring for 1h, evaporating ethanol to dryness under the conditions that the temperature is 80 ℃ and the humidity is 60%, and then roasting for 6h under the oxygen atmosphere at 400 ℃ to obtain MoO with specific loading 3 -Fe 2 (MoO 4 ) 3 ZSM-5 catalyst
The BET characterization results show that the pore channel distribution of comparative example 1 is mainly in the micropore range of 0.4 to 0.8nm, while examples 1,3, 5, 7, 8, 11, 12, etc. in which the silicone is introduced have a certain amount of mesopores in the range of 4 to 10nm in addition to the above micropore range.
The catalysts obtained in examples 1,3, 5, 7, 8, 11 and 12 and comparative example 1 were applied to a reaction for preparing 1, 3-butanediol from propylene and methanol. The reaction results are shown in the following table, wherein the propylene content by volume is 6%, the methanol content by volume is 13%, the oxygen content by volume is 9%, and the balance is nitrogen.
The following table shows the corresponding reaction results of a part of the catalysts prepared by the process of the invention
Figure BDA0002308777410000071

Claims (7)

1. The application of the catalyst prepared by the preparation method for preparing the 1, 3-butanediol catalyst by one step from propylene and methanol in the preparation of the 1, 3-butanediol by one step from the propylene and the methanol is characterized in that: firstly, dissolving tetrapropylammonium hydroxide into water, adding ammonia water with the mass concentration of 15-28% to adjust the pH value to 8-10, respectively adding tetraethoxysilane and amphiphilic organic silicon under the stirring condition, stirring for 10-30 minutes at 20-40 ℃, adding aluminum nitrate according to the molar ratio Si/Al =30-200, transferring into a crystallization kettle, crystallizing for 24-120 hours at 80-250 ℃, performing suction filtration, and drying to obtain a ZSM-5 carrier; dispersing the carrier into solvent, adding Mo organic material according to the required Mo-Fe atomic ratioMixing the heterocyclic compound with ferric organic compound, and evaporating the solvent to dryness at 20-250 deg.C and 10-95% humidity; utilizing a template agent of ZSM-5 to enable molybdenum and an iron organic heterocyclic compound to be self-assembled into a structure with the size of 10-200 nm; then roasting at 250-550 ℃, and coating a layer of MoO on the surface of the ZSM-5 carrier 3 -Fe 2 (MoO 4 ) 3 Component (A) to obtain a composition coated with MoO on the surface 3 -Fe 2 (MoO 4 ) 3 The ZSM-5 catalyst of (1); amphiphilic silicones include in particular: (CH) 3 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 12 H 25 Cl、 (CH 3 CH 2 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 14 H 29 Cl、 (CH 3 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 16 H 33 One or more of Cl is used in combination.
2. Use of a catalyst according to claim 1, characterized in that: in the catalyst, the mass loading of molybdenum oxide is 5-30%, and the mass loading of iron molybdate is 5-20%.
3. The use of the catalyst according to claim 2, wherein the molar ratio of molybdenum atoms to iron atoms is controlled to be in the range of 1.6 to 4.0.
4. Use of a catalyst according to claim 1, characterized in that: the molybdenum organic heterocyclic compound specifically includes: molybdenum porphyrin, molybdenum phthalocyanine, molybdenum naphthalocyanine or molybdenum spiro cyanine or one or more of the components are mixed for use;
the iron organic heterocyclic compound specifically includes: ferriporphyrin, iron phthalocyanine, iron naphthalocyanine, iron spiro cyanine, ferrocene, cyclopentadienyl carbonyl iron, or a mixture of one or more of the above components.
5. Use of a catalyst according to claim 1, characterized in that: the solvent comprises one or more of water, chloroform, ethanol, cyclohexane, toluene, dichloroethane, methanol, ethylene glycol and glycerol, and the mass concentration of the carrier in the solvent is 10-80%.
6. Use of a catalyst according to claim 1, characterized in that: the roasting atmosphere is one or more than two of air, nitrogen, argon or oxygen.
7. Use of a catalyst according to claim 1, characterized in that: dissolving tetrapropylammonium hydroxide into water to form a solution with the mass concentration of 1-30%, wherein the mass concentration of tetrapropylammonium hydroxide: ethyl orthosilicate: the molar ratio of the amphiphilic organic silicon is 0.05-0.5:1: 0.01-0.1.
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