CN116984027A - Transition metal doped molecular sieve@organic amine catalyst and preparation method and application thereof - Google Patents

Transition metal doped molecular sieve@organic amine catalyst and preparation method and application thereof Download PDF

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CN116984027A
CN116984027A CN202310966086.2A CN202310966086A CN116984027A CN 116984027 A CN116984027 A CN 116984027A CN 202310966086 A CN202310966086 A CN 202310966086A CN 116984027 A CN116984027 A CN 116984027A
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molecular sieve
organic amine
transition metal
metal doped
catalyst
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CN116984027B (en
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孟宪锋
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Jiangsu Noon Crop Science Co ltd
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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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0237—Amines
    • B01J31/0238—Amines with a primary amino group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains three hetero rings
    • C07D471/14—Ortho-condensed systems
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
    • B01J2231/4283—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using N nucleophiles, e.g. Buchwald-Hartwig amination
    • 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
    • Y02P20/584—Recycling of catalysts

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The invention relates to a transition metal doped molecular sieve@organic amine catalyst, which comprises the following components: a carrier and a chain-like organic amine supported on the carrier; wherein the loading of the chain organic amine is 10-45%; the carrier is a transition metal doped molecular sieve with ordered macropores and mesoporous structures, and the transition metal is cobalt or zinc; the pore diameter of the ordered macropores is 100-900nm. The novel catalyst can improve the specific surface area of the carrier and the catalytic efficiency of the catalyst, can stably improve the product yield at a lower reaction temperature, and reduces the difficulty of subsequent separation and purification. The invention also relates to a preparation method of the catalyst and application of the catalyst in a process for catalyzing 2,2' -bipyridine and dichloroethane to directly synthesize diquat dichloride.

Description

Transition metal doped molecular sieve@organic amine catalyst and preparation method and application thereof
Technical Field
The invention belongs to the field of green chemical manufacturing, and relates to a transition metal doped molecular sieve@organic amine catalyst, and a preparation method and application thereof.
Background
Diquat (diquat) has a chemical name of 1,1 '-ethylene-2, 2' -bipyridinium salt, which is developed by the company of Dada, switzerland, is an excellent contact desiccant and pyridine herbicide with systemic property, and is one of the most widely used biocidal herbicide products worldwide at present. The main preparation method of diquat is that 2,2' -dipyridine and 1, 2-dibromoethane are cyclized (US 2823987), and meanwhile, the change of anions of diquat does not destroy the weeding activity, so the prior art proposes to adopt 1, 2-dichloroethane to replace 1, 2-dibromoethane, so as to generate diquat dichloride (1, 1' -ethylene-2, 2' -dipyridyl dichloride). The preparation method of the diquat dichloride comprises an ion exchange method, a glycol method, a catalytic method and the like; the catalytic method is to make the 2,2' -dipyridine and 1, 2-dichloroethane cyclize to react in a high-pressure reaction kettle under the protection of nitrogen atmosphere in the presence of a catalyst to obtain the product. The product yield of the catalytic process is directly related to the catalyst and also related to the difficulty of product separation.
Some catalyst patent schemes are also proposed in the industry, such as an organic amine catalyst disclosed in China CN115672399A, which comprises a carrier and chain organic amine supported on the carrier, wherein the product yield of the catalyst is 81.3-88.3%, and in each embodiment, the reaction pressure is 2.5MPa, the reaction temperature is 200-250 ℃ and the reaction time is more than 6 hours. In addition, chinese CN115894492a discloses that the palladium-phosphine complex is used as a catalyst, which can significantly reduce the reaction temperature and accelerate the reaction rate, and obtain a higher yield of diquat dichloride under mild reaction conditions, so as to avoid serious equipment corrosion under high temperature conditions. However, the process has strong temperature and catalyst consumption dependence, for example, the product yield can reach 91.1% when the reaction is carried out for 6 hours at 180 ℃, but the diquat dichloride yield is only 57.7% when the temperature is 140 ℃; also, as the catalyst amount decreases, the product yield decreases extremely rapidly. Under the conditions that the conversion rate of the two catalysts is reduced and unstable, the porous carbon-loaded organic amine has a mesoporous structure, so that the organic amine in the mesoporous cannot be fully contacted with the reactant, and the conversion rate of the reactant is difficult to increase; the palladium-phosphine complex is soluble in a solvent in a reaction system, which is unfavorable for separation and recycling of the catalyst.
Disclosure of Invention
First, the technical problem to be solved
In view of the above-mentioned shortcomings and disadvantages of the prior art, the present invention provides a transition metal doped molecular sieve @ organic amine catalyst, which uses a zinc/cobalt doped macroporous-mesoporous molecular sieve as a carrier, thereby improving the specific surface area of the carrier and the catalytic efficiency of the catalyst, stably improving the product yield at a lower reaction temperature, and reducing the difficulty of subsequent separation and purification. The invention also relates to a preparation method of the catalyst and application of the catalyst in a process for catalyzing 2,2' -bipyridine and dichloroethane to directly synthesize diquat dichloride.
(II) technical scheme
In a first aspect, the present invention provides a transition metal doped molecular sieve @ organic amine catalyst comprising: a carrier and a chain-like organic amine supported on the carrier; wherein the loading of the chain organic amine is 10-45%; the carrier is a transition metal doped molecular sieve with ordered macropores and mesoporous structures, and the transition metal is cobalt or zinc; the pore diameter of the ordered macropores is 100-900nm. Preferably, the loading of the chain organic amine is 10-30%.
According to a preferred embodiment of the present invention, the chain organic amine is one or more of linear polyethylenimine, triethylenediamine, hexamethyleneimine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine.
According to the preferred embodiment of the invention, in the transition metal doped molecular sieve, the doping total amount of the transition metal is 5-20%; preferably, the transition metal is a combination of cobalt and zinc.
In a second aspect, the present invention provides a method for preparing a transition metal doped molecular sieve @ organic amine catalyst comprising:
s1, preparing a carrier
Adding an ionic surfactant, an inorganic silicon source, a molecular sieve structure directing agent, polymer microspheres, a complexing agent, a transition metal ion salt, an aluminum source and alkali into water, stirring and assisting in ultrasonic treatment for 4-10h, evaporating to remove part of solvent, and then transferring into a reaction kettle for crystallization at 130-160 ℃ for 5-10 days; crushing the crystallized product to 100-400 meshes, and removing the polymer microsphere and the molecular sieve structure directing agent by a calcination method to obtain the molecular sieve with ordered macropores and mesopores;
the transition metal ion salt is cobalt salt and/or zinc salt, the particle size of the polymer microsphere is 100-900nm, and the specific gravity of the polymer microsphere is 1.05-1.18 times of that of water;
s2, load chain organic amine
And dissolving chain organic amine in an organic solvent, adding a carrier under the condition of stirring, continuing stirring until a suspension is obtained, and then evaporating the organic solvent of the suspension to obtain the transition metal doped molecular sieve@organic amine catalyst.
According to the preferred embodiment of the invention, in S1, the ionic surfactant is stearic acid or sodium dodecyl sulfonate, and the addition amount of the ionic surfactant in a reaction system is 0.02-0.3wt%; the inorganic silicon source is silicon tetrachloride or water glass; the molecular sieve structure directing agent is tetrapropylammonium hydroxide; the polymer microsphere is polymethyl methacrylate microsphere; the complexing agent is ammonia water or hydrazine hydrate; the aluminum source is one of sodium metaaluminate, aluminum sulfate, aluminum nitrate or aluminum isopropoxide; the base is sodium hydroxide, which adjusts the pH to 11-14. The transition metal is introduced in the form of a metal nitrate solution.
The molecular sieve structure directing agent may be selected according to the type of molecular sieve to be synthesized, such as tetrapropylammonium bromide, and the like. The polymer microsphere must be made of material with proper specific gravity, which can be calcined and removed, and the polymer microsphere cannot be too light or too heavy, and the too light microsphere floats on the water surface and cannot be distributed in the molecular sieve product, and the too heavy microsphere can concentrate to sink. The polymer microsphere with specific gravity of 1.05-1.18 has larger specific gravity than water, and can be uniformly embedded into the molecular sieve after the polymer microsphere is subjected to evaporation to remove partial solvent and crystallization reaction.
According to the preferred embodiment of the invention, in S1, the silicon-aluminum molar ratio of the obtained molecular sieve is controlled by adjusting the dosage ratio of the inorganic silicon source and the aluminum source; the doping amount of zinc or cobalt in the obtained molecular sieve is controlled by adjusting the addition amount of the transition metal ion salt.
According to the preferred embodiment of the invention, in S1, the ratio of the total molar concentration of the complexing agent to the transition metal ions in the reaction system is 1:1.
In accordance with a preferred embodiment of the present invention, in S1, the method for removing polymeric microspheres and molecular sieve structure directing agent by calcination comprises: heating to 180-250 ℃ in an air atmosphere, and calcining for 1-3h; heating to 400-600 ℃ and calcining for 1-4h. In the calcination process, organic components such as complexing agents, surfactants, molecular sieve structure directing agents and the like are also removed by calcination, and tiny pores are left in situ to form micropores.
According to a preferred embodiment of the present invention, in S2, the organic solvent is selected from one or more of methanol, ethanol, propanol, acetone, isopropanol; the mass ratio of the chain organic amine to the organic solvent is 1:2-10.
In a third aspect, the invention also relates to application of the transition metal doped molecular sieve@organic amine catalyst in a process for directly catalyzing and synthesizing diquat dichloride by taking 2,2' -bipyridine and 1, 2-dichloroethane as raw materials.
Preferably, the preparation method of the diquat dichloride comprises the following steps: placing a transition metal doped molecular sieve@organic amine catalyst into a high-pressure reaction kettle, and adding the catalyst into the high-pressure reaction kettle in a molar ratio of 1:1, charging nitrogen as protective gas, maintaining the reaction pressure of 0.5-2.0MPa and the reaction temperature of 130-148 ℃, stopping heating after reacting for 1.5-5h, adding deionized water after the reaction kettle is cooled to room temperature, stirring and filtering, and separating out water phase from the filtrate to obtain diquat dichloride solution. The catalyst recovered by filtration can be recycled.
When the dosage of the transition metal doped molecular sieve@organic amine catalyst is 7-10%, the reaction time is more than 2 hours, and the product yield is stable to be more than 94.4%.
(III) beneficial effects
The transition metal doped molecular sieve@organic amine catalyst is mainly characterized in that a carrier is improved, and the carrier is replaced by activated carbon, diatomite and the like in the prior art, so that the specific surface area of the carrier can be greatly increased, more chain-shaped organic amine active sites are exposed, the catalytic active sites can be fully contacted with raw materials, and the catalytic efficiency of the catalyst is improved. In addition, the transition metal zinc or cobalt doped molecular sieve is also favorable for crystallization of the molecular sieve, and the surface of the molecular sieve is enabled to generate worm hole defects, so that the specific surface area of the molecular sieve is further increased, the mesoporous structure is improved, and meanwhile, the molecular sieve doped with zinc or cobalt (particularly doped with cobalt) has certain catalytic capability, so that the catalytic efficiency of the catalyst is further increased, the service life is prolonged, the product yield is increased, and the stability of the product yield is ensured.
Drawings
FIG. 1 is an SEM image of a first step product molecular sieve of the present invention for preparing a transition metal doped molecular sieve @ organic amine catalyst.
Detailed Description
The invention will be better explained by the following detailed description of the embodiments with reference to the drawings. The loading in the invention is the mass percent of the chain organic amine to occupy the organic amine catalyst (the total mass of the carrier and the chain organic amine).
Example 1 (cobalt doped molecular sieve @ organoamine catalyst with 17% organoamine loading)
The transition metal doped molecular sieve@organic amine catalyst of the embodiment consists of a carrier and chain organic amine supported on the carrier. Wherein, the chain organic amine is linear polyethylenimine with 17 percent of loading. The carrier is cobalt doped ordered macroporous-mesoporous molecular sieve.
The preparation method of the transition metal doped molecular sieve@organic amine catalyst comprises the following steps:
(1) Adding 0.5g of ionic surfactant, 6.1g of sodium silicate, 40mL of molecular sieve structure directing agent (tetrapropylammonium hydroxide), 18g of polymethyl methacrylate microsphere (particle size=500 nm), 3.5g of ammonia water, 3.3g of cobalt nitrate, 0.084g of sodium metaaluminate and sodium hydroxide alkali (pH is regulated=12.5) into 400g of water, carrying out stirring auxiliary ultrasonic treatment for 5h, evaporating to remove 1/2 of solvent, and transferring into a reaction kettle to crystallize for 5 days at 150 ℃; crushing the crystallized product to 300 meshes; calcining at 200deg.C for 2.5h in air atmosphere, calcining at 500deg.C for 3h, removing polymer microsphere and molecular sieve structure guiding agent to obtain molecular sieve (SEM diagram shown in figure 1) with ordered macropores and mesopores, wherein the macropore pore diameter is equivalent to polymethyl methacrylate microsphere, the mesopore morphology is determined by molecular sieve structure guiding agent, and the pores left after calcining some organic matters form micropores.
(2) Dissolving 0.6g of linear polyethylenimine in 5.4g of ethanol, heating to 50 ℃, adding the molecular sieve obtained in the step (1) under stirring, and continuing stirring to obtain a suspension; and (3) raising the temperature to 80 ℃, continuously stirring and steaming to remove ethanol in the suspension, and obtaining the transition metal doped molecular sieve@organic amine catalyst after the ethanol is completely volatilized, wherein the cobalt doping amount of the product is 18% as determined by ICP-MS.
Example 2 (cobalt doped molecular sieve @ organoamine catalyst with 20% organoamine loading)
The transition metal doped molecular sieve@organic amine catalyst of the embodiment consists of a carrier and chain organic amine supported on the carrier. Wherein, the chain organic amine is linear polyethylenimine with a loading of 20%. The carrier is cobalt doped ordered macroporous-mesoporous molecular sieve.
The preparation method of the transition metal doped molecular sieve@organic amine catalyst is described in example 1, except that the step (2) increases the amount of linear polyethylenimine, and comprises:
dissolving 0.9g of linear polyethylenimine in 8g of ethanol, heating to 50 ℃, adding the molecular sieve obtained in the step (1) under stirring, and continuing stirring to obtain a suspension; and (3) raising the temperature to 80 ℃, continuously stirring and steaming to remove ethanol in the suspension, and obtaining the transition metal doped molecular sieve@organic amine catalyst after the ethanol is completely volatilized, wherein the cobalt doping amount of the product is 17% as determined by ICP-MS.
Example 3 (Zinc doped molecular Screen @ organic amine catalyst with organic amine Supported 20%)
The transition metal doped molecular sieve@organic amine catalyst of the embodiment consists of a carrier and chain organic amine supported on the carrier. Wherein, the chain organic amine is linear polyethylenimine with a loading of 20%. The carrier is a zinc doped ordered macroporous-mesoporous molecular sieve.
The preparation method of the transition metal doped molecular sieve@organic amine catalyst comprises the following steps:
(1) Adding 0.5g of ionic surfactant, 6.1g of sodium silicate, 40mL of molecular sieve structure directing agent (tetrapropylammonium hydroxide), 18g of polymethyl methacrylate microsphere (particle size=500 nm), 3.5g of ammonia water, 3.42g of zinc nitrate, 0.084g of sodium metaaluminate and sodium hydroxide alkali (pH is regulated=12.5) into 400g of water, carrying out stirring auxiliary ultrasonic treatment for 5h, evaporating to remove 1/2 of solvent, and transferring into a reaction kettle to crystallize for 5 days at 150 ℃; crushing the crystallized product to 300 meshes; calcining for 2.5h at 200 ℃ in air atmosphere, calcining for 3h at 500 ℃ and removing the polymer microspheres and the molecular sieve structure directing agent to obtain the molecular sieve with ordered macropores and mesopores.
(2) Dissolving 0.9g of linear polyethylenimine in 8g of ethanol, heating to 50 ℃, adding the molecular sieve obtained in the step (1) under stirring, and continuing stirring to obtain a suspension; and (3) raising the temperature to 80 ℃, continuously stirring and steaming to remove ethanol in the suspension, and obtaining the transition metal doped molecular sieve@organic amine catalyst after the ethanol is completely volatilized, wherein the zinc doping amount of the product is 20% as determined by ICP-MS.
Example 4 (Zinc doped molecular Screen @ organic amine catalyst with 30% organic amine loading)
The transition metal doped molecular sieve@organic amine catalyst of the embodiment consists of a carrier and chain organic amine supported on the carrier. Wherein, the chain organic amine is linear polyethylenimine with a loading of 30%. The carrier is a zinc doped ordered macroporous-mesoporous molecular sieve.
The preparation method of the transition metal doped molecular sieve@organic amine catalyst is described in example 3, except that the step (2) increases the amount of linear polyethylenimine, and comprises: dissolving 1.3g of linear polyethylenimine in 10.5g of ethanol, heating to 50 ℃, adding the molecular sieve obtained in the step (1) under stirring, and continuing stirring to obtain a suspension; and (3) raising the temperature to 80 ℃, continuously stirring and steaming to remove ethanol in the suspension, and obtaining the transition metal doped molecular sieve@organic amine catalyst after the ethanol is completely volatilized, wherein the zinc doping amount of the product is 19% as determined by ICP-MS.
Example 5 (Zinc doped molecular Screen @ organic amine catalyst with an organic amine load of 10%)
The transition metal doped molecular sieve@organic amine catalyst of the embodiment consists of a carrier and chain organic amine supported on the carrier. Wherein the chain organic amine is tetraethylenepentamine, and the loading amount is 10%. The carrier is a zinc doped ordered macroporous-mesoporous molecular sieve.
The preparation method of the transition metal doped molecular sieve@organic amine catalyst is described in example 3, except that the amine dosage is reduced in step (2), and the preparation method comprises the following steps: dissolving 0.45g of tetraethylenepentamine in 5g of ethanol, heating to 50 ℃, adding the molecular sieve obtained in the step (1) under stirring, and continuing stirring to obtain a suspension; and (3) raising the temperature to 80 ℃, continuously stirring and steaming to remove ethanol in the suspension, and obtaining the transition metal doped molecular sieve@organic amine catalyst after the ethanol is completely volatilized, wherein the zinc doping amount of the product is 22% as determined by ICP-MS.
Example 6 (Zinc doped molecular Screen @ organic amine catalyst with organic amine Supported 40%)
The transition metal doped molecular sieve@organic amine catalyst of the embodiment consists of a carrier and chain organic amine supported on the carrier. Wherein, the chain organic amine is supported by 20%. The carrier is a zinc doped ordered macroporous-mesoporous molecular sieve.
The preparation method of the transition metal doped molecular sieve@organic amine catalyst is described in example 3, except that in step (2), the linear polyethylenimine is replaced by diethylenetriamine, and the preparation method comprises the following steps: dissolving 1.8g of diethylenetriamine in 15.0g of ethanol, heating to 50 ℃, adding the molecular sieve obtained in the step (1) under stirring, and continuing stirring to obtain a suspension; and (3) raising the temperature to 80 ℃, continuously stirring and steaming to remove ethanol in the suspension, and obtaining the transition metal doped molecular sieve@organic amine catalyst after the ethanol is completely volatilized, wherein the zinc doping amount of the product is 16% as determined by ICP-MS.
Example 7 (Zinc cobalt doped molecular sieve @ organic amine catalyst with organic amine Supports of 20%)
The transition metal doped molecular sieve@organic amine catalyst of the embodiment consists of a carrier and chain organic amine supported on the carrier. Wherein, the chain organic amine is linear polyethylenimine with a loading of 20%. The carrier is an ordered macroporous-mesoporous molecular sieve doped with zinc and cobalt according to a molar ratio of 1:1. The preparation method comprises the following steps:
(1) Adding 0.6g of ionic surfactant, 6.1g of sodium silicate, 40mL of molecular sieve structure directing agent (tetrapropylammonium hydroxide), 18g of polymethyl methacrylate microsphere (particle size=500 nm), 3.5g of ammonia water, 1.7g of zinc nitrate, 1.65g of cobalt nitrate, 0.207g of aluminum isopropoxide and sodium hydroxide alkali (pH value is regulated=11.5) into 400g of water, carrying out stirring auxiliary ultrasonic treatment for 4h, evaporating to remove 1/2 of solvent, and then transferring into a reaction kettle to crystallize for 5 days at 145 ℃; crushing the crystallized product to 300 meshes; and heating to 200 ℃ in an air atmosphere, calcining for 2.5 hours, heating to 500 ℃ and calcining for 2.5 hours, and removing the polymer microspheres and the molecular sieve structure directing agent to obtain the molecular sieve with ordered macropores and mesopores.
(2) Dissolving 0.90g of linear polyethylenimine in 8g of ethanol, heating to 50 ℃, adding the molecular sieve obtained in the step (1) under stirring, and continuing stirring to obtain a suspension; and (3) raising the temperature to 80 ℃, continuously stirring and steaming to remove ethanol in the suspension, and obtaining the transition metal doped molecular sieve@organic amine catalyst after the ethanol is completely volatilized, wherein the zinc doping amount is 10.4% and the cobalt doping amount is 9.3% as determined by ICP-MS.
Examples 8 to 14
Examples 8-14 diquat dichloride was prepared as follows:
2.0g of the transition metal doped molecular sieve@organic amine catalyst prepared in examples 1-7 is weighed in sequence, placed into a high-pressure reaction kettle, then 15.62g of 2,2' -bipyridine and 9.9g of dichloroethane are added, nitrogen is filled as protective gas, the reaction pressure is maintained to be 2.0MPa, the reaction temperature is 145 ℃, the heating is stopped after the reaction is carried out for 4 hours under the condition, deionized water is added after the reaction kettle is cooled to room temperature, stirring and filtering are carried out, and the filtrate is separated from the water phase to obtain the diquat dichloride solution. The catalyst recovered by filtration can be recycled. The yields of diquat dichloride from examples 8-14 were calculated and shown in Table 1.
Table 1: examples 8-14 the yields of diquat dichloride and bipyridine conversion were as follows:
group of Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14
Yield% 97.56％ 98.74％ 96.24％ 96.79％ 95.4％ 96.87％ 97.15％
Conversion% 98.45％ 99.65％ 97.22％ 97.88％ 97.18％ 97.95％ 98.37％
According to the experimental results, the transition metal doped molecular sieve@organic amine catalyst has high-efficiency catalytic efficiency for catalyzing 2,2' -bipyridine and dichloroethane to synthesize diquat dichloride, and the yield of the diquat dichloride is always kept above 95.4% at a lower reaction temperature and a lower reaction kettle pressure. Of these, the higher the loading of the chain organic amine, the higher the catalytic efficiency, but at more than 30%, the catalytic effect almost reaches a steady state. The catalyst used in example 13 had a chain organic amine loading of 40% and example 11 had a catalyst loading of 30% with substantially equal final product yields. The catalysts prepared from examples 8-9 had the highest catalytic efficiency when the doped transition metal was cobalt compared to the other examples compared to the case of doping with zinc.
Examples 15 to 21
Examples 15-21 diquat dichloride was prepared as follows:
2.1g of the transition metal doped molecular sieve@organic amine catalyst prepared in examples 1-7 is weighed in sequence, placed into a high-pressure reaction kettle, then 15.62g of 2,2' -bipyridine and 9.9g of dichloroethane are added, nitrogen is filled as protective gas, the reaction pressure is maintained to be 1.5MPa, the reaction temperature is 135 ℃, the heating is stopped after the reaction is carried out for 5 hours under the condition, deionized water is added after the reaction kettle is cooled to room temperature, stirring and filtering are carried out, and the filtrate is separated from the water phase to obtain the diquat dichloride solution. The catalyst recovered by filtration can be recycled. The yields of diquat dichloride from examples 15-21 were calculated and shown in Table 2.
Table 2: examples 15-21 the yields and bipyridylium conversion of diquat dichloride were as follows:
group of Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 Example 21
Yield% 96.45％ 97.33％ 95.13％ 95.64％ 94.40％ 95.73％ 96.03％
Conversion% 97.67％ 98.85％ 96.35％ 96.86％ 95.62％ 96.97％ 97.16％
As can be seen from the above examples, when the reaction conditions in the reaction vessel are controlled to milder conditions, such as lowering the reaction temperature and the reaction vessel pressure, the reaction time is only slightly increased and the product yield, the raw material conversion, etc. are not significantly lowered. The experimental results show that the catalyst provided by the invention has good catalytic stability, reduces the strict dependence of the technological process on temperature and pressure conditions, and simplifies the control requirements of the technological conditions.
Comparative example 1
The catalyst prepared in this comparative example did not contain transition metal doping, and specifically, cobalt nitrate was not added in step (1) of the preparation method of the organic amine catalyst of example 1. The catalyst prepared by the foregoing method was used to prepare diquat dichloride by the method and conditions of example 8.
Comparative example 2
This comparative example is a molecular sieve prepared in step (1) of the method for preparing an organic amine catalyst of example 1, which is not impregnated with an ethanol solution of linear polyethylenimine. The molecular sieve prepared by the foregoing method was used to prepare diquat dichloride according to the method and conditions of example 8.
Comparative example 3
The preparation method of the organic amine catalyst of the comparative example is as follows:
1.5g of linear polyethylenimine is dissolved in 10.5g of ethanol, the temperature is raised to 50 ℃, 3.5g of active carbon is added under the condition of stirring, and the heat preservation and stirring are continued for 3 hours to obtain a suspension; and (3) raising the temperature to 85 ℃, continuously stirring and steaming to remove the ethanol in the suspension, and obtaining the activated carbon-loaded organic amine catalyst after the ethanol is completely volatilized, wherein the loading capacity is 30%. The catalyst prepared by the foregoing method was used to prepare diquat dichloride by the method and conditions of example 8. The yields of diquat dichloride in the processes of comparative example 8, comparative examples 1-3 are shown in Table 3.
Table 3: the yields and bipyridylium conversion of the dichlofenac salts of example 8, comparative examples 1-3 are as follows:
group of Example 8 Comparative example 1 Comparative example 2 Comparative example 3
Yield% 97.56％ 85.02％ 34.27％ 86.26％
Conversion% 98.45％ 89.65％ 40.36％ 90.17％
As can be seen from the above experimental results, in comparative example 1, the molecular sieve was not doped with cobalt transition metal, and although the molecular sieve also had a multi-stage pore structure such as ordered macropores and mesopores, the catalytic efficiency was still lower than that of example 8. The molecular sieve of comparative example 2 also has some catalytic capacity without loading and impregnating the chain organic amine. If the molecular sieve is not added, the conversion rate of the 2,2' -bipyridine and 9.9g of dichloroethane to the dichlormid is only about 20%. The organic amine catalyst in comparative example 3, although the catalyst had a 30% loading of the catalytically active component, had a lower catalytic efficiency than that of example 8 of the present invention (17% loading of the organic amine). This indicates that the catalyst of the present invention has higher catalytic efficiency when the amounts of the catalytically active materials are equal.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.

Claims (10)

1. A transition metal doped molecular sieve @ organic amine catalyst comprising: a carrier and a chain-like organic amine supported on the carrier; wherein the loading of the chain organic amine is 10-45%; the carrier is a transition metal doped molecular sieve with ordered macropores and mesoporous structures, and the transition metal is cobalt or zinc; the pore diameter of the ordered macropores is 100-900nm.
2. The transition metal doped molecular sieve @ organic amine catalyst of claim 1, wherein the chain organic amine is one or more of a linear polyethylenimine, triethylenediamine, hexamethyleneimine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine.
3. The transition metal doped molecular sieve @ organic amine catalyst of claim 1 wherein the total amount of transition metal doping in the transition metal doped molecular sieve is from 5 to 20%.
4. A transition metal doped molecular sieve @ organic amine catalyst according to claim 1 or 3 wherein the transition metal is a combination of cobalt and zinc.
5. The preparation method of the transition metal doped molecular sieve@organic amine catalyst is characterized by comprising the following steps of:
s1, preparing a carrier
Adding an ionic surfactant, an inorganic silicon source, a molecular sieve structure directing agent, polymer microspheres, transition metal ion salt, an aluminum source and alkali into water, stirring and assisting in ultrasonic treatment for 4-10h, evaporating to remove part of solvent, and then transferring into a reaction kettle for crystallization for 5-10 days at 130-160 ℃; crushing the crystallized product to 100-400 meshes, and removing the polymer microsphere and the molecular sieve structure directing agent by a calcination method to obtain the molecular sieve with ordered macropores and mesopores;
the transition metal ion salt is cobalt salt and/or zinc salt, the particle size of the polymer microsphere is 100-900nm, and the specific gravity of the polymer microsphere is 1.05-1.18 times of that of water;
s2, load chain organic amine
And dissolving chain organic amine in an organic solvent, adding a carrier under the condition of stirring, continuing stirring until a suspension is obtained, and then evaporating the organic solvent of the suspension to obtain the transition metal doped molecular sieve@organic amine catalyst.
6. The preparation method according to claim 5, wherein in S1, the ionic surfactant is stearic acid or sodium dodecyl sulfate, and the addition amount of the ionic surfactant in the reaction system is 0.02-0.3wt%; the inorganic silicon source is silicon tetrachloride or water glass; the molecular sieve structure directing agent is tetrapropylammonium hydroxide; the polymer microsphere is polymethyl methacrylate microsphere; the complexing agent is ammonia water or hydrazine hydrate; the aluminum source is one of sodium metaaluminate, aluminum sulfate, aluminum nitrate or aluminum isopropoxide; the alkali is sodium hydroxide, which adjusts the pH of the reaction system of S1 to 11-14.
7. The method according to claim 6, wherein in S1, the ratio of the total molar concentration of the complexing agent to the total molar concentration of the transition metal ions in the reaction system is 1:1.
8. The transition metal doped molecular sieve @ organic amine catalyst of claim 1, wherein in S1, the method of calcining to remove the polymeric microspheres and molecular sieve structure directing agent comprises: heating to 180-250 ℃ in an air atmosphere, and calcining for 1-3h; heating to 400-600 ℃ and calcining for 1-4h.
9. The transition metal doped molecular sieve @ organic amine catalyst of claim 1 wherein in S2, said organic solvent is selected from one or more of methanol, ethanol, propanol, acetone, isopropanol; the mass ratio of the chain organic amine to the organic solvent is 1:2-10.
10. Use of the transition metal doped molecular sieve @ organic amine catalyst of any one of claims 1-4 or prepared by the preparation method of any one of claims 5-9 in a process for directly catalyzing and synthesizing diquat dichloride by using 2,2' -bipyridine and 1, 2-dichloroethane as raw materials.
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HONGJIAN WEN ETAL.: "Synthesis of ZnO nanoparticles supported on mesoporous SBA-15 with coordination effect -assist for anti-bacterial assessment", 《COLLOIDS AND SURFACES B: BIOINTERFACES》, vol. 181, pages 285 - 294 *

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