CN116474766A - Cerium oxide loaded manganese-zinc oxide catalyst, preparation method and method for preparing malonate derivative by using cerium oxide loaded manganese-zinc oxide catalyst - Google Patents

Cerium oxide loaded manganese-zinc oxide catalyst, preparation method and method for preparing malonate derivative by using cerium oxide loaded manganese-zinc oxide catalyst Download PDF

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CN116474766A
CN116474766A CN202310267151.2A CN202310267151A CN116474766A CN 116474766 A CN116474766 A CN 116474766A CN 202310267151 A CN202310267151 A CN 202310267151A CN 116474766 A CN116474766 A CN 116474766A
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manganese
cerium oxide
catalyst
cerium
zinc oxide
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黄文学
严成岳
庞海洋
冉建锋
王欢
沈稳
谢硕
张永振
黎源
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Wanhua Chemical Group Co Ltd
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0213—Preparation of the impregnating solution
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
    • C07C67/40—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester by oxidation of primary alcohols
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Abstract

The invention provides a cerium oxide-supported manganese-zinc oxide catalyst, a preparation method and application thereof in preparing malonate derivatives by oxidizing and esterifying 3-hydroxy propionate. The cerium oxide loaded manganese-zinc oxide catalyst has novel structure, simple preparation method, high-efficiency catalytic oxidation esterification reaction and good application value; the malonate derivative is novel in synthetic route, is prepared from the simple and easily available 3-hydroxy propionate serving as a raw material through one-step oxidation and esterification reaction, has high yield and less three wastes, and has better advantages compared with the current mainstream technology.

Description

Cerium oxide loaded manganese-zinc oxide catalyst, preparation method and method for preparing malonate derivative by using cerium oxide loaded manganese-zinc oxide catalyst
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a cerium oxide loaded manganese-zinc oxide catalyst, a preparation method and application thereof in preparation of malonate through oxidative esterification of 3-hydroxy propionate.
Background
Malonic acid and its ester derivatives are widely used in the fields of pharmacy, spice, food additive, polyester and the like, and are important fine chemical raw materials and intermediates; typical malonate products are dimethyl malonate, diethyl malonate, dipropyl malonate, and the like. Dimethyl malonate is an important raw material for producing medical pipecolic acid, which is representative of a second-generation quinolone antibacterial drug, has a broader antibacterial spectrum compared with nalidixic acid, and can be used for urinary tract infection and otorhinolaryngological infection; the pipecolic acid is produced from dimethyl malonate, orthoformate, urea, etc. The diethyl malonate can be used for synthesizing pharmaceutical and chemical products such as barbituric acid, amino acid, vitamin (B1, B2 and B6) phenyl phenylbutazone and the like.
The main production methods of malonate at present are a cyanidation esterification method and a catalytic carbonylation method, and the cyanidation esterification method is commonly adopted at home at present. The cyanidation esterification method uses chloroacetic acid as a raw material, firstly, the chloroacetic acid is neutralized with sodium carbonate to obtain corresponding chloroacetic acid sodium salt, then the corresponding chloroacetic acid sodium salt is reacted with sodium cyanide, the cyanoacetic acid is obtained after neutralization, and finally, the malonic ester is obtained through esterification under the catalysis of concentrated sulfuric acid. Although the method has been produced in large scale, the disadvantages are very obvious, and firstly, a great amount of virulent sodium cyanide raw materials are used in the reaction process, so that the safety risk is high; secondly, the reaction process involves multiple times of acid-base neutralization to generate a large amount of waste salt and wastewater, and if the treatment is not good, serious pollution to the ecological environment can be generated; finally, the process adopts a large amount of hydrochloric acid and sulfuric acid, which also has serious corrosion to equipment.
In recent years, there are some foreign documents and patents on the synthesis of malonate compounds, which report a catalytic carbonylation method, and the method also uses chloroacetic acid as a starting material. Firstly, esterifying chloroacetic acid to obtain corresponding chloroacetate, and then esterifying and carbonylating the chloroacetate with carbon monoxide and alcohol under the action of a homogeneous cobalt catalyst to obtain the corresponding malonate compound. To facilitate the forward progress of the reaction, the system generally requires the addition of an equivalent amount of base to neutralize the hydrochloric acid produced by the reaction. The catalytic carbonylation method has short reaction flow and relatively less three wastes, and is an advanced malonate preparation process at present; however, the key carbonylation reaction needs to be carried out under high pressure, the reaction conditions are harsh, the catalytic activity of the cobalt catalyst is low, the deactivation is rapid, and the cost of the catalyst is relatively high, so that the catalytic carbonylation method is not adopted by manufacturers at present in China.
In view of the importance of malonate compounds and the shortcomings of the two synthesis methods in the prior art, in order to make the intermediates more economical and efficient and prepare the intermediates, development of novel catalysts and synthesis routes capable of preparing malonate compounds under mild conditions, low cost and environment friendliness is needed.
Disclosure of Invention
The invention aims to provide a cerium oxide supported manganese-zinc oxide catalyst which has novel structure, mild preparation conditions and simple and convenient operation, and can efficiently catalyze the oxidative esterification reaction of 3-hydroxy propionate to obtain the corresponding malonate derivative with high yield.
Another object of the present invention is to provide a method for preparing such a cerium oxide-supported manganese-zinc oxide catalyst.
It is a further object of the present invention to provide a process for preparing malonate derivatives by oxidative esterification of 3-hydroxypropionate esters using the catalyst.
In order to achieve the above purposes and achieve the above technical effects, the present invention adopts the following technical scheme:
a cerium oxide loaded manganese-zinc oxide catalyst takes cerium oxide as a carrier, manganese as an active component, zinc oxide and optional alkali metal oxide as auxiliary active components, wherein the loading of the manganese is 0.5-2.0wt% and the loading of the zinc oxide and the alkali metal oxide is 0.5-1.0wt% based on the mass of the cerium oxide carrier.
On the other hand, the preparation method of the cerium oxide supported manganese-zinc oxide catalyst comprises the following steps:
(1) Preparing a manganese solution: taking a certain amount of aqueous solution of manganese salt, then adding water-soluble zinc salt, optional alkali metal salt and auxiliary agent, and fully stirring to obtain a clear solution;
(2) Dissolving cerium salt in deionized water, adding solid alkali under stirring, reacting to obtain cerium oxide suspension, stopping stirring, standing, removing supernatant, and washing precipitate with deionized water to obtain cerium oxide powder;
(3) Adding the cerium oxide powder obtained in the step (2) into the solution obtained in the step (1) at one time, stirring and soaking, evaporating the solvent, and sequentially carrying out high-temperature roasting and reduction roasting treatment on the obtained solid to obtain the cerium oxide loaded manganese-zinc oxide catalyst.
In a specific embodiment, the manganese salt is at least one selected from manganese chloride, manganese bromide, manganese sulfamate, manganese sulfate, manganese nitrate, manganese acetate, manganese acetylacetonate, manganese perchlorate and manganese phosphate; the solid alkali is at least any one of sodium hydroxide, potassium hydroxide and lithium hydroxide; the cerium salt is at least one of cerium nitrate and cerium chloride.
In a specific embodiment, the high temperature firing temperature is 400-600 ℃ and the firing time is 2-4 hours, the atmosphere is an inert atmosphere.
In a specific embodiment, the reducing roasting temperature is 100-200 ℃, the roasting time is 2-4 hours, the reducing gas is a mixture of hydrogen and inert gas, and the volume fraction of the hydrogen is 5-20vol%.
In a specific embodiment, the cerium oxide-supported manganese-zinc oxide catalyst as described above or prepared by the above-described preparation method is used as a catalyst for the oxidative esterification reaction.
In a specific embodiment, the method comprises the step of taking 3-hydroxy propionate as a raw material and carrying out oxidation esterification reaction to generate malonate derivative in the presence of alcohol, oxidant and catalyst.
In a specific embodiment, the alcohol is at least any one of a primary alcohol, a secondary alcohol, a tertiary alcohol; preferably, at least one of methanol, ethanol, propanol, n-butanol, n-pentanol, n-hexanol, isopropanol, isobutanol, tert-butanol, tert-pentanol, cyclohexanol, benzyl alcohol; more preferably, the alcohol is added in an amount of 8 to 12 times the molar amount of 3-hydroxypropionate; the addition amount of the catalyst is 0.5-1.0wt% of the mass of the 3-hydroxy propionate.
In a specific embodiment, the oxidizing agent is selected from at least any one of air, oxygen-depleted air, preferably air or oxygen; preferably, the coagent is a catalytic amount of peroxide; more preferably, the peroxide is at least any one selected from tert-butyl hydroperoxide, phenethyl hydroperoxide, cumene hydroperoxide, pinane hydroperoxide; more preferably, the peroxide is added in an amount of 0.5 to 5.0mol% based on the molar amount of 3-hydroxypropionate.
In a specific embodiment, the oxidative esterification reaction is carried out at a reaction temperature of 60 to 150 ℃ for a reaction time of 5 to 10 hours and at a reaction pressure of from atmospheric pressure to 5.0mpa g.
Compared with the prior art, the invention has the following beneficial effects:
1) The catalyst disclosed by the invention is novel in structure and simple in preparation process; unlike known literature reports, the preparation system of the malonate derivative realizes the oxidative esterification of 3-hydroxy propionate without adding extra alkali, and malonate products are obtained in high yield.
2) The catalyst has unique structure, manganese is used as an active metal, after alcohol hydroxyl is oxidized to obtain aldehyde, the metal of the auxiliary active component catalyzes alcohol and aldehyde to condense to obtain acetal, and the acetal is further oxidized to obtain malonate derivative ester.
3) In the preparation method of the malonate derivative, the oxidation and esterification reaction can directly adopt air or oxygen as an oxidant, so that the cost is low, and the byproduct is water, thereby being environment-friendly; the oxidation reaction is preferably carried out by adding a catalytic amount of peroxide effective to promote the reaction.
4) The preparation method of the malonate derivative has novel synthetic route, and the 3-hydroxy propionate can be obtained by ring-opening reaction of cheap and easily available-propiolactone and alcohol; the product is rich in variety, and can be used for synthesizing a series of malonate derivatives such as methyl malonate, ethyl malonate and the like.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The invention discloses a cerium oxide loaded manganese-zinc oxide catalyst prepared by an impregnation method, in particular to a preparation method of the cerium oxide loaded manganese-zinc oxide catalyst, which comprises the following steps:
(1) Preparing a manganese solution: taking a certain amount of manganese salt aqueous solution, then adding water-soluble zinc salt, optional alkali metal salt and polyvinylpyrrolidone, and fully stirring to obtain a clear solution; wherein polyvinylpyrrolidone acts as an aid similar to a dispersant, it will be appreciated by those skilled in the art that other aids with similar dispersion, such as cellulose, cellulose ether, cellulose acetate, etc., may also be used, which are removed by calcination during subsequent calcination.
(2) Dissolving cerium salt in deionized water, adding solid alkali at one time under rapid stirring, reacting at 20-50 ℃ to obtain cerium oxide suspension, stopping stirring, standing, removing supernatant, and washing precipitate with deionized water for 4-5 times to obtain cerium oxide powder.
(3) Adding the obtained cerium oxide powder into the manganese salt aqueous solution obtained in the step (1) at one time, stirring and impregnating for 4-6 hours, evaporating the solvent, and sequentially carrying out high-temperature roasting and reduction roasting treatment on the obtained solid to obtain the target catalyst.
In the invention, the manganese salt is at least any one of manganese chloride, manganese bromide, manganese sulfamate, manganese sulfate, manganese nitrate, manganese acetate, manganese acetylacetonate, manganese perchlorate, manganese phosphate and the like; the solid alkali is at least any one of sodium hydroxide, potassium hydroxide, lithium hydroxide and the like; the cerium salt is at least any one of cerium nitrate, cerium chloride and the like.
In the invention, the high-temperature roasting atmosphere is inert atmosphere, such as nitrogen, and the roasting temperature is 400-600 ℃ for 2-4 hours; the reducing roasting temperature is 100-200 ℃ for 2-4 hours, the reducing gas is a mixture of hydrogen and inert gas, and the volume fraction of the hydrogen is 5-20vol%, such as 5%, 10%, 15% and 20%. In this step, manganese oxide is reduced to a form of elemental manganese by reduction roasting to enhance the activity of the catalyst.
In the present invention, the manganese is supported in an amount of 0.5 to 2.0wt% based on the mass of the cerium oxide support, including, for example, but not limited to, 0.5%, 1.0%, 1.5%, 2.0%, and the zinc oxide and alkali metal oxide are supported in an amount of 0.5 to 1.0wt%, including, for example, but not limited to, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%. Wherein, when the content of the alkali metal oxide is 0, the loading of the zinc oxide is 0.5 to 1.0 weight percent; it is preferred to add a portion of the alkali metal oxide, e.g., the alkali metal oxide, at the same loading as the zinc oxide, or slightly more than the zinc oxide, preferably less than the zinc oxide loading, e.g., no more than half the zinc oxide loading.
On the other hand, the catalyst is used for catalyzing the oxidation and esterification reaction of 3-hydroxy propionate to prepare malonate derivatives, alcohol substrate is used as solvent, air or oxygen is used as oxidant, and a series of malonate derivatives are obtained through high-yield oxidation and esterification.
The reaction scheme is shown below:
in the present invention, R is selected from, for example, alkyl, benzyl, phenyl, etc., and specifically, the 3-hydroxypropionate may be methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, n-butyl 3-hydroxypropionate, n-propyl 3-hydroxypropionate, isobutyl 3-hydroxypropionate, benzyl 3-hydroxypropionate, etc., and the malonate derivative produced is dimethyl malonate, diethyl n-butyl malonate, di-n-propyl malonate, diisobutyl malonate, dibenzyl malonate, etc., respectively.
In the present invention, in the oxidative esterification reaction, the alcohol is a reaction substrate and a reaction solvent, and the alcohol may be a primary alcohol, a secondary alcohol, a tertiary alcohol, or the like, for example, any one of methanol, ethanol, propanol, n-butanol, n-pentanol, n-hexanol, isopropanol, isobutanol, t-butanol, t-pentanol, cyclohexanol, benzyl alcohol, or the like. The addition amount of the alcohol is 8-12 times of the molar amount of the 3-hydroxy propionate; for example, including but not limited to 8-fold, 9-fold, 10-fold, etc.
In the invention, the catalyst is the cerium oxide loaded manganese-zinc oxide catalyst, and the addition amount of the catalyst is 0.5-1.0wt% of the mass of the 3-hydroxy propionate; for example, including but not limited to 0.5wt%, 0.6wt%, 1.0wt%, etc.
In the oxidation reaction, the oxidant can be air, oxygen-deficient air and the like, and air, oxygen and the like are preferably used as the oxidant; during the reaction, the reaction pressure was maintained by continuously introducing air or oxygen, and the oxidant was substantially in excess. The oxidation reaction is preferably further promoted by the addition of a catalytic amount of peroxide, which may be t-butyl hydroperoxide, phenethyl hydroperoxide, cumene hydroperoxide, pinane hydroperoxide, etc., for example, 0.5 to 5.0 mole% of the molar amount of 3-hydroxypropionate, including, for example, but not limited to, 0.5 mole%, 1.0 mole%, 1.5 mole%, 2.0 mole%, 2.5 mole%, 3.0 mole%, 3.5 mole%, 4.0 mole%, 4.5 mole%, 5.0 mole%.
In the present invention, the reaction temperature in the oxidative esterification reaction is 60 to 150 ℃, for example 60 ℃,70 ℃,80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, etc., and the reaction pressure is from normal pressure to 5.0MPa, for example 2.0MPa, 2.5MPa, 3.0MPa, 3.5MPa, 4.0MPa, 4.5MPa, 5.0MPa, etc.
In the present invention, the pressures are gauge pressures unless otherwise indicated.
The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.
The main raw material information is as follows:
methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, AR, aara Ding Shiji;
methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, n-propyl 3-hydroxypropionate, n-butyl 3-hydroxypropionate, and a carbofuran reagent with a purity of 98-99%; benzyl 3-hydroxy propionate, isobutyl 3-hydroxy propionate, macllin, 98%. O-xylene, chromatographically pure, carbofuran.
Zinc nitrate, lithium nitrate, manganese acetate, sodium hydroxide, potassium hydroxide, 99%, enokay reagent;
potassium nitrate, manganese acetylacetonate, a ridge reagent, AR;
polyvinylpyrrolidone K15, a new source of love; cerium nitrate, 99% and Chinese medicine reagent.
Ortho-xylene, tertiary butyl hydroperoxide, phenethyl hydroperoxide, cumene hydroperoxide, pinane hydroperoxide, and alar Ding Shiji.
The gas chromatography test conditions of the present invention are as follows:
instrument model: agilent 7890B; chromatographic column: capillary column HP-DB-5 (60 m 0.30mm 0.25 μm); the initial temperature is 40 ℃, and the temperature is increased to 115 ℃ at the speed of 5 ℃/min; then the temperature is raised to 240 ℃ at the speed of 10 ℃/min and the temperature is kept for 5min. The carrier gas is high-purity nitrogen, the split ratio is 40:1, and the split flow is 45mL/min. Carrier gas saving: 20mL/min, and a wait time of 2min was started. The sample injection temperature is 280 ℃, the detector is FID, the detector temperature is 280 ℃, the air flow rate is 350mL/min, the hydrogen flow rate is 35mL/min, the tail blowing flow rate is 30mL/min, and the sample injection amount is 0.2 mu L.
Example 1
1wt％Mn-0.5wt％ZnO-CeO 2 Catalyst preparation
An aqueous solution (23.6 mL) of manganese acetate having a concentration of 0.2wt% was weighed at room temperature, and zinc nitrate (17 mg) and polyvinylpyrrolidone K15 (0.1 g) were sequentially added thereto, followed by stirring at room temperature for 0.5h to obtain a clear solution for use. Dissolving cerium nitrate (3.38 g) in deionized water (40 mL), adding sodium hydroxide (4.8 g) particles at one time under rapid stirring, placing the obtained solution in a water bath at 50deg.C, stirring for 30min to obtain cerium oxide suspension, stopping stirring, standing, removing supernatant, washing precipitate with deionized water for 4-5 times, and washing the pH of the water washing solution<And 9, judging that the product is qualified. Adding the obtained cerium oxide precipitate into manganese acetate solution (23.6 mL) prepared in advance to obtain suspension, stirring at room temperature for 6 hr, evaporating solvent, calcining the obtained solid powder at 500deg.C for 2 hr, and mixing with hydrogen and nitrogen (10% H) 2 +90％N 2 ) Reducing and roasting for 2 hours at 140 ℃ in the gas atmosphere to obtain 1.52g of target cerium oxide-supported manganese-zinc oxide catalyst named 1wt% Mn-0.5wt% ZnO-CeO 2 。
Example 2
2wt％Mn-1wt％ZnO-CeO 2 Catalyst preparation
An aqueous solution (25.2 mL) of manganese acetate having a concentration of 0.4wt% was weighed at room temperature, and zinc nitrate (37 mg) and polyvinylpyrrolidone K15 (0.15 g) were sequentially added thereto, followed by stirring at room temperature for 0.5h to obtain a clear solution for use. Dissolving cerium nitrate (3.61 g) in deionized water (40 mL), adding sodium hydroxide (4.8 g) particles at one time under rapid stirring, placing the obtained solution in a water bath at 40 ℃ for continuous stirring for 30min to obtain cerium oxide suspension, stopping stirring, standing, removing supernatant, washing precipitate with deionized water for 4-5 times, and washing the pH of the washing solution<And 9, judging that the product is qualified. Adding the obtained cerium oxide precipitate into pre-prepared manganese acetylacetonate solution (25.2 mL) to obtain suspension, stirring at room temperature for 6 hr, evaporating to dry the solvent, calcining the obtained solid powder at 400deg.C for 2 hr, and mixing with hydrogen and nitrogen (15% H) 2 +85％N 2 ) Reducing and baking at 140 deg.C in atmosphereThe mixture is burned for 2 hours to obtain 1.65g of target cerium oxide supported manganese-zinc oxide catalyst which is named as 2wt percent Mn-1wt percent ZnO-CeO 2 。
Example 3
1wt％Mn-0.5wt％ZnOLi 2 O-CeO 2 Catalyst preparation
An aqueous solution (34.2 mL) of manganese acetate having a concentration of 0.2wt% was weighed at room temperature, and zinc nitrate (35 mg), lithium nitrate (24 mg) and polyvinylpyrrolidone K15 (0.1 g) were sequentially added thereto, followed by stirring at room temperature for 0.5h to obtain a clear solution for use. Dissolving cerium nitrate (4.74 g) in deionized water (50 mL), adding sodium hydroxide (6.0 g) particles at one time under rapid stirring, placing the obtained solution in a water bath at 50 ℃ and stirring for 1h to obtain cerium oxide suspension, stopping stirring, standing, removing supernatant, washing precipitate with deionized water for 4-5 times, and washing the pH of the washing solution<And 9, judging that the product is qualified. Adding the obtained cerium oxide precipitate into manganese acetate solution (34.2 mL) prepared in advance to obtain suspension, stirring at room temperature for 6 hr, evaporating solvent, calcining the obtained solid powder at 600deg.C for 2 hr, and mixing with hydrogen and nitrogen (10% H) 2 +90％N 2 ) Reducing and roasting for 1h in 100 ℃ atmosphere to obtain 2.14g of target cerium oxide-supported manganese-zinc oxide catalyst named 1wt% Mn-0.5wt% ZnOLi 2 O-CeO 2 。
Example 4
1wt％Mn-1wt％ZnOK 2 O-CeO 2 Catalyst preparation
An aqueous solution (45.6 mL) of manganese nitrate having a concentration of 0.1wt% was weighed at room temperature, and zinc nitrate (24 mg), potassium nitrate (8 mg) and polyvinylpyrrolidone K15 (0.1 g) were sequentially added thereto, followed by stirring at room temperature for 0.5h to obtain a clear solution for use. Dissolving cerium nitrate (3.16 g) in deionized water (40 mL), adding sodium hydroxide (4.8 g) particles at one time under rapid stirring, placing the obtained solution in a water bath at 50deg.C, stirring for 30min to obtain cerium oxide suspension, stopping stirring, standing, removing supernatant, washing precipitate with deionized water for 4-5 times, and washing the pH of the water washing solution<And 9, judging that the product is qualified. The obtained cerium oxide precipitate was added to a manganese nitrate solution (29.4 mL) prepared in advance to obtain a suspension, stirring was continued at room temperature for 6 hours, then the solvent was evaporated,the solid powder obtained was calcined at 500℃for 2h and then mixed with hydrogen and nitrogen (20% H) 2 +80％N 2 ) Reducing and roasting for 2 hours at 180 ℃ in the gas atmosphere to obtain 1.43g of target cerium oxide-supported manganese-zinc oxide catalyst named 1wt percent Mn-1wt percent ZnOK 2 O-CeO 2 。
Comparative example 1
As compared with example 4, except that zinc nitrate and potassium nitrate were not added, the other conditions were exactly the same, and a cerium oxide-supported manganese catalyst was obtained, designated as 1wt% Mn-CeO 2 。
Comparative example 2
As compared with example 4, except that the aqueous solution of manganese nitrate was not added, the conditions were exactly the same, and a cerium oxide-supported zinc oxide catalyst was obtained, which was named as 1wt% ZnOK 2 O-CeO 2 。
Comparative example 3
As compared with example 4, except that only the aqueous solution of manganese nitrate, zinc nitrate and potassium nitrate were not added, the other conditions were exactly the same, and a cerium oxide catalyst was obtained, which was named CeO 2 。
Example 5
Synthesis of dimethyl malonate by catalyzing methyl 3-hydroxypropionate through cerium oxide loaded manganese
A magnetic stirrer was first added to a 200mL autoclave at room temperature, then methyl 3-hydroxypropionate (9.37 g,0.09 mol) and methanol (34.61 g,1.08 mol), a catalyst (0.5 wt% relative to the hydroxypropionate), cumene hydroperoxide (86 mg,0.45mmol,80% purity) and an internal standard o-xylene (0.48 g,4.5 mmol) were sequentially added, and the autoclave was sealed, and 2.5MPa of air was charged with an oxygen partial pressure of 0.5MPa. Placing the autoclave into an oil bath, stirring, raising the temperature to a certain reaction temperature of 90 ℃, preserving heat and pressure, reacting for 6 hours, cooling, filtering and separating the catalyst, sampling and analyzing. The qualitative analysis of the obtained sample adopts a gas chromatography-mass spectrometry combined technology, and the quantitative analysis is realized by gas chromatography.
The catalysts of the above examples and comparative examples were prepared in the same manner as in example 5, and the conversion of methyl 3-hydroxypropionate as the raw material and the selectivity of dimethyl malonate as the target product were shown in the following table.
Example 6
1wt％Mn-1wt％ZnOK 2 O-CeO 2 Catalytic synthesis of diethyl malonate from ethyl 3-hydroxy propionate
At room temperature, a magnetic stirrer was first added to a 200mL autoclave, followed by the sequential addition of ethyl 3-hydroxypropionate (9.45 g,0.08 mol) and ethanol (44.23 g,0.96 mol), a catalyst cerium oxide supported manganese catalyst 1wt% Mn-1wt% ZnOK 2 O-CeO 2 (0.6 wt%, relative to the hydroxypropionate), cumene hydroperoxide (76 mg,0.4mmol,80% purity) and the internal standard o-xylene (0.42 g,4.2 mmol) were sealed and the autoclave was charged with 5.0MPa air with an oxygen partial pressure of 1.0MPa. Placing the autoclave into an oil bath, stirring, raising the temperature to a certain reaction temperature of 90 ℃, preserving heat and pressure, reacting for 8 hours, cooling, filtering and separating the catalyst, sampling and analyzing. The qualitative analysis of the obtained sample adopts a gas chromatography-mass spectrometry combined technology, and the quantitative analysis is realized by gas chromatography. The conversion rate of the raw material 3-hydroxy ethyl propionate is 99%, and the selectivity of the target product diethyl malonate is 98%.
Example 7
1wt％Mn-1wt％ZnOK 2 O-CeO 2 Synthesis of diethyl n-butyl malonate by catalyzing n-butyl 3-hydroxy propionate
At room temperature, a magnetic stirrer was first added to a 200mL autoclave, followed by the sequential addition of the raw materials n-butyl 3-hydroxypropionate (11.69 g,0.08 mol) and n-butanol (59.30 g,0.8 mol), the catalyst cerium oxide supported manganese catalyst 1wt% Mn-1wt% ZnOK 2 O-CeO 2 (0.5 wt%, relative to the hydroxypropionate), cumene hydroperoxide (76 mg,0.4mmol,80% purity) and the internal standard o-xylene (0.42 g,4.2 mmol) were sealed and the autoclave was charged with 5.0MPa air with an oxygen partial pressure of 1.0MPa.Placing the autoclave into an oil bath, stirring, raising the temperature to a certain reaction temperature of 120 ℃, preserving heat and pressure, reacting for 5 hours, cooling, filtering and separating the catalyst, sampling and analyzing. The qualitative analysis of the obtained sample adopts a gas chromatography-mass spectrometry combined technology, and the quantitative analysis is realized by gas chromatography. The conversion rate of the raw material 3-hydroxy propionic acid n-butyl ester is 99%, and the selectivity of the target product malonic acid di-n-butyl ester is 98%.
Example 8
1wt％Mn-1wt％ZnOK 2 O-CeO 2 Synthesis of di-n-propyl malonate by catalyzing n-propyl 3-hydroxy propionate
At room temperature, a magnetic stirrer was first added to a 200mL autoclave, followed by the sequential addition of the raw materials n-propyl 3-hydroxypropionate (11.89 g,0.09 mol) and n-propanol (59.49 g,0.99 mol), the catalyst cerium oxide supported manganese catalyst 1wt% Mn-1wt% ZnOK 2 O-CeO 2 (1.0 wt%, relative to the hydroxypropionate), t-butyl hydroperoxide (116 mg,0.9mmol,70% in water) and the internal standard o-xylene (0.48 g,4.5 mmol) were added and the autoclave was sealed and filled with 4.0MPa air, oxygen partial pressure 0.8MPa. Placing the autoclave into an oil bath, stirring, raising the temperature to a certain reaction temperature of 120 ℃, preserving heat and pressure, reacting for 6 hours, cooling, filtering and separating the catalyst, sampling and analyzing. The qualitative analysis of the obtained sample adopts a gas chromatography-mass spectrometry combined technology, and the quantitative analysis is realized by gas chromatography. The conversion rate of the raw material 3-hydroxy propyl propionate is 99%, and the selectivity of the target product di-n-propyl malonate is 98%.
Example 9
1wt％Mn-1wt％ZnOK 2 O-CeO 2 Catalytic synthesis of diisobutyl malonate from isobutyl 3-hydroxy propionate
At room temperature, a magnetic stirrer was first added to a 200mL autoclave, followed by sequential addition of the starting materials isobutyl 3-hydroxypropionate (10.23 g,0.07 mol) and isobutanol (57.07 g,0.77 mol), the catalyst cerium oxide supported manganese catalyst 1wt% Mn-1wt% ZnOK 2 O-CeO 2 (1.0 wt%, relative to the hydroxy propionate), styrene hydroperoxide (322 mg,1.4mmol,60% solution) and the internal standard o-xylene (0.37 g,3.5 mmol), the autoclave was sealed and charged with 5.0MPa airThe partial pressure of oxygen was 0.5MPa. Placing the autoclave into an oil bath, stirring, raising the temperature to a certain reaction temperature of 150 ℃, preserving heat and pressure, reacting for 10 hours, cooling, filtering and separating the catalyst, sampling and analyzing. The qualitative analysis of the obtained sample adopts a gas chromatography-mass spectrometry combined technology, and the quantitative analysis is realized by gas chromatography. The conversion rate of the raw material isobutyl 3-hydroxypropionate is>99%, and the selectivity of the target product diisobutyl malonate is 99%.
Example 10
1wt％Mn-0.5wt％ZnOLi 2 O-CeO 2 Catalytic synthesis of dibenzyl malonate from benzyl 3-hydroxy propionate
At room temperature, a magnetic stirrer was first added to a 200mL autoclave, followed by sequential addition of benzyl 3-hydroxypropionate (9.01 g,0.05 mol) and benzyl alcohol (43.26 g,0.40 mol), a catalyst cerium oxide-supported manganese catalyst 1wt% Mn-0.5wt% ZnOLi 2 O-CeO 2 (0.5 wt%, relative to the hydroxypropionate), pinane hydroperoxide (52 mg,0.3 mmol) and the internal standard o-xylene (0.27 g,2.5 mmol), the autoclave was sealed and charged with 1.0MPa air, oxygen partial pressure 0.2MPa. Placing the autoclave into an oil bath, stirring, raising the temperature to a certain reaction temperature of 60 ℃, preserving heat and pressure, reacting for 7 hours, cooling, filtering and separating the catalyst, sampling and analyzing. The qualitative analysis of the obtained sample adopts a gas chromatography-mass spectrometry combined technology, and the quantitative analysis is realized by gas chromatography. The conversion rate of the raw material 3-hydroxy propionic acid benzyl ester is 99%, and the selectivity of the target product dibenzyl malonate is 98%.
Example 11
1wt％Mn-0.5wt％ZnOLi 2 O-CeO 2 Catalytic synthesis of dibenzyl malonate from benzyl 3-hydroxy propionate without addition of auxiliary agent
At room temperature, a magnetic stirrer was first added to a 200mL autoclave, followed by sequential addition of benzyl 3-hydroxypropionate (9.01 g,0.05 mol) and benzyl alcohol (43.26 g,0.40 mol), a catalyst cerium oxide-supported manganese catalyst 1wt% Mn-0.5wt% ZnOLi 2 O-CeO 2 (0.5 wt% relative to the hydroxypropionate) and internal standard o-xylene (0.27 g,2.5 mmol), the autoclave was sealed, filled with 1.0MPa air and the partial pressure of oxygen was 0.2MPa. Placing the autoclavePlacing the mixture into an oil bath, stirring, raising the temperature to a certain reaction temperature of 60 ℃, preserving heat and pressure, reacting for 7 hours, cooling, filtering and separating the catalyst, and sampling and analyzing. The qualitative analysis of the obtained sample adopts a gas chromatography-mass spectrometry combined technology, and the quantitative analysis is realized by gas chromatography. The conversion rate of the raw material 3-hydroxy propionic acid benzyl ester is 78%, and the selectivity of the target product dibenzyl malonate is 91%.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and additions may be made to those skilled in the art without departing from the method of the present invention, which modifications and additions are also to be considered as within the scope of the present invention.

Claims (10)

1. The cerium oxide loaded manganese-zinc oxide catalyst is characterized in that cerium oxide is used as a carrier, manganese is used as an active component, zinc oxide and optional alkali metal oxide are used as auxiliary active components, wherein the loading of manganese is 0.5-2.0wt% and the loading of zinc oxide and alkali metal oxide is 0.5-1.0wt% based on the mass of the cerium oxide carrier.
2. The method for preparing the cerium oxide-supported manganese-zinc oxide catalyst according to claim 1, comprising the steps of:
(1) Preparing a manganese solution: taking a certain amount of aqueous solution of manganese salt, then adding water-soluble zinc salt, optional alkali metal salt and auxiliary agent, and fully stirring to obtain a clear solution;
(2) Dissolving cerium salt in deionized water, adding solid alkali under stirring, reacting to obtain cerium oxide suspension, stopping stirring, standing, removing supernatant, and washing precipitate with deionized water to obtain cerium oxide powder;
(3) Adding the cerium oxide powder obtained in the step (2) into the solution obtained in the step (1) at one time, stirring and soaking, evaporating the solvent, and sequentially carrying out high-temperature roasting and reduction roasting treatment on the obtained solid to obtain the cerium oxide loaded manganese-zinc oxide catalyst.
3. The preparation method according to claim 2, wherein the manganese salt is at least one selected from the group consisting of manganese chloride, manganese bromide, manganese sulfamate, manganese sulfate, manganese nitrate, manganese acetate, manganese acetylacetonate, manganese perchlorate and manganese phosphate; the solid alkali is at least any one of sodium hydroxide, potassium hydroxide and lithium hydroxide; the cerium salt is at least one of cerium nitrate and cerium chloride.
4. A method according to any one of claims 1 to 3, wherein the high temperature calcination temperature is 400 to 600 ℃, the calcination time is 2 to 4 hours, and the atmosphere is an inert atmosphere.
5. The method according to claim 4, wherein the reducing roasting temperature is 100-200 ℃, the roasting time is 2-4 hours, the reducing gas is a mixture of hydrogen and inert gas, and the volume fraction of the hydrogen is 5-20vol%.
6. A method for preparing malonate derivative by oxidative esterification of 3-hydroxy propionate, characterized in that cerium oxide-supported manganese-zinc oxide catalyst according to claim 1 or prepared by the preparation method according to any one of claims 2 to 5 is used as catalyst for oxidative esterification.
7. The method of claim 6, comprising the step of producing malonate derivatives by oxidative esterification of 3-hydroxypropionate in the presence of an alcohol, an oxidizing agent, a catalyst, and optionally an auxiliary agent.
8. The method of claim 7, wherein the alcohol is at least any one of a primary alcohol, a secondary alcohol, a tertiary alcohol; preferably, at least one of methanol, ethanol, propanol, n-butanol, n-pentanol, n-hexanol, isopropanol, isobutanol, tert-butanol, tert-pentanol, cyclohexanol, benzyl alcohol; more preferably, the alcohol is added in an amount of 8 to 12 times the molar amount of 3-hydroxypropionate; the addition amount of the catalyst is 0.5-1.0wt% of the mass of the 3-hydroxy propionate.
9. The method according to claim 7, wherein the oxidant is selected from at least any one of air, oxygen-depleted air, preferably air or oxygen; preferably, the coagent is a catalytic amount of peroxide; more preferably, the peroxide is at least any one selected from tert-butyl hydroperoxide, phenethyl hydroperoxide, cumene hydroperoxide, pinane hydroperoxide; more preferably, the peroxide is added in an amount of 0.5 to 5.0mol% based on the molar amount of 3-hydroxypropionate.
10. The method according to claim 7, wherein the reaction temperature of the oxidative esterification reaction is 60 to 150 ℃, the reaction time is 5 to 10 hours, and the reaction pressure is normal pressure to 5.0MPaG.
CN202310267151.2A 2023-03-20 2023-03-20 Cerium oxide loaded manganese-zinc oxide catalyst, preparation method and method for preparing malonate derivative by using cerium oxide loaded manganese-zinc oxide catalyst Pending CN116474766A (en)

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