CN108440262B - Method for preparing 4-oxoisophorone by catalytic oxidation of beta-isophorone with solid-liquid two-phase - Google Patents
Method for preparing 4-oxoisophorone by catalytic oxidation of beta-isophorone with solid-liquid two-phase Download PDFInfo
- Publication number
- CN108440262B CN108440262B CN201810322296.7A CN201810322296A CN108440262B CN 108440262 B CN108440262 B CN 108440262B CN 201810322296 A CN201810322296 A CN 201810322296A CN 108440262 B CN108440262 B CN 108440262B
- Authority
- CN
- China
- Prior art keywords
- isophorone
- catalyst
- beta
- mass
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing 4-oxo-isophorone by catalytic oxidation of beta-isophorone with solid-liquid two-phase. The method adopts gamma-aluminum oxide loaded metal composite oxide (CuO-Co)2O3‑Fe2O3‑MgO/Al2O3) As a catalyst. The method comprises the following steps: the beta-isophorone and hydrogen peroxide are subjected to oxidation reaction in the presence of a solvent and a catalyst to obtain 4-oxo-isophorone. The method has the advantages of mild reaction conditions, simple process, high product yield, environmental protection, no generation of waste liquid containing heavy metal elements, and capability of effectively solving the problem that the catalyst prepared by the prior art cannot be recycled.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a method for preparing 4-oxoisophorone by catalytic oxidation of beta-isophorone with solid-liquid two phases.
Background
4-oxo-isophorone (KIP for short) is an important chemical intermediate product, not only can be used in cosmetics and perfumes, but also can be used for synthesizing carotenoid and vitamin. Because of the importance of 4-oxoisophorone in chemical products, the synthesis of 4-oxoisophorone has been a research hotspot for a long time.
At present, two methods for synthesizing KIP are commonly used, namely, beta-isophorone (beta-IP for short) or alpha-isophorone (alpha-IP for short) is oxidized to synthesize KIP.
Patent US4046813 describes a process for the preparation of KIP by catalytic oxidation of beta-isophorone using a vanadium, iron, cobalt, manganese acetylacetonate complex as catalyst in the presence of pyridine, which, although having a conversion of about 100%, involves conversion of beta-IP to alpha-IP during the reaction and the formation of a large amount of highly polymeric by-products, which makes the selectivity of the reaction not high.
Patent CN101417936A describes a method for preparing KIP by catalytic oxidation of α -IP under a metal-free catalytic system, but α -IP is difficult to oxidize and the reaction conversion rate is only 60% at the maximum.
Patent DE2526851 discloses a process for the catalytic oxidation of alpha-IP to produce KIP with the addition of molybdenum trioxide, but in order to achieve sufficiently high conversions, a time of 72 hours or more and a high temperature of 80 ℃ or more are required, and the yields achievable under these conditions are only within 50%.
Patent EP0425976 describes the oxidation of alpha-IP using phosphomolybdates as catalyst, with reaction results close to those of DE 2526851.
In US4898985, KIP is prepared by oxidation of beta-isophorone using porphyrin or phthalocyanine complexes of iron, copper, cobalt, manganese as catalyst, while triethylamine or ethylene glycol dimethyl ether is used as solvent. Although the method has high yield, the porphyrin or phthalocyanine transition metal catalyst is quite expensive and can be easily destroyed in the reaction, so that the reaction process has high cost. In addition, diethylene glycol dimethyl ether and triethylamine are dangerous under the operation condition, and the condition for realizing industrialization is not available at present.
U.S. Pat. No. 6,629,7404 describes a process for preparing 4-oxoisophorone by catalytic beta-IP oxidation using N, N-dimethylformamide and lithium acetate as catalytic system, which has the greatest disadvantage of easily generating o-KIP as a by-product of ortho-oxidation, which is close to KIP in physical properties and difficult to separate from KIP.
The above-described process for preparing 4-oxoisophorone is deficient in each of these two routes. The alpha-IP is directly oxidized into KIP, the required time is long, the conversion rate is low, and the selectivity is low; beta-IP can be easily oxidized by oxygen to prepare KIP, but a large amount of metal-containing waste liquid is generated by catalytic oxidation of a homogeneous catalyst, the catalyst is difficult to recycle, and the treatment difficulty and the environmental protection cost pressure are increased.
The prior publication does not mention a method for preparing 4-oxo-isophorone by using gamma-alumina loaded metal composite oxide as a catalyst to catalyze hydrogen peroxide to oxidize beta-isophorone.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for preparing 4-oxoisophorone by catalytic oxidation of beta-isophorone through solid-liquid two-phase catalysis. The method adopts gamma-aluminum oxide loaded metal composite oxide as a catalyst to catalyze hydrogen peroxide to oxidize beta-isophorone, so as to prepare 4-oxo-isophorone. The method has the advantages of simple reaction process, high reaction yield and capability of recycling the catalyst, and the catalytic activity of the catalyst can be kept stable after the catalyst is reused for many times.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for preparing 4-oxo-isophorone by catalytic oxidation of beta-isophorone with solid-liquid two-phase catalyst comprises the following steps: the beta-isophorone and hydrogen peroxide are subjected to oxidation reaction in the presence of a solvent and a catalyst to obtain 4-oxo-isophorone.
As a specific implementation mode, adding beta-isophorone, solvent and catalyst into a reaction kettle, then dropwise adding hydrogen peroxide into the system, and carrying out oxidation reaction to obtain 4-oxo-isophorone.
The reaction equation for this reaction is as follows:
the catalyst is prepared by loading metal composite oxide in gamma-alumina powder (CuO-Co)2O3-Fe2O3-MgO/Al2O3) Wherein the mass content of the copper oxide is 1-10 percent, preferably 4-5 percent based on the total mass of the catalyst; the mass content of the ferric oxide is 0.5-2%, preferably 1-1.2%; the mass content of the cobalt oxide is 0.5-2 percent, preferably 1-1.2 percent; the content of magnesium oxide is 0.5-2 wt%, preferably 1-1.2 wt%. The average particle diameter of the catalyst is 10 to 80 μm, preferably 30 to 40 μm.
As a preferred technical scheme, beta-isophorone and hydrogen peroxide are subjected to oxidation reaction in the presence of a solvent, a catalyst and a cocatalyst to obtain 4-oxo-isophorone. The cocatalyst is selected from one or more of azodiisobutyl amidine hydrochloride, azodiisobutyl imidazoline hydrochloride and azoisobutyryl cyano formamide, and the azodiisobutyl imidazoline hydrochloride is preferred.
The cocatalyst is a water-soluble azo compound, and the cocatalyst has the function of improving the selectivity of a product 4-oxoisophorone obtained by catalyzing beta-isophorone oxidation by a metal composite oxide catalyst, and is different from the function of a conventional azo compound in the reaction. When no cocatalyst is added in the reaction system, most of the beta-isophorone is oxidized to generate 4-hydroxyisophorone, and the yield of the 4-oxoisophorone is low. When the cocatalyst is present in the reaction system, the 4-hydroxyisophorone can be oxidized to generate 4-oxoisophorone more easily, so that the selectivity of the main product is improved.
The catalyst used by the invention has a porous structure, the reaction sites of the catalyst reach the nanometer scale, and the catalyst can effectively catalyze the oxidation reaction of beta-IP. The reaction process is divided into four stages: hydrogen peroxide is catalyzed on the surface of the active component of the catalyst to generate hydroxyl radical, the hydroxyl radical oxidizes beta-isophorone to generate 4-hydroxyisophorone, the hydroxyl radical oxidizes 4-hydroxyisophorone to generate 4, 4-dihydroxyisophorone, and 4, 4-dihydroxyisophorone is dehydrated to generate 4-oxoisophorone. The above four stages occur simultaneously during the reaction.
The preparation method of the gamma-alumina powder catalyst loaded with the metal composite oxide comprises the following steps:
(1) dissolving metal salt in water according to a proportion to prepare a standard solution, and performing coprecipitation in a sodium carbonate and/or potassium carbonate standard solution;
(2) aging, drying and roasting the product obtained in the step (1);
wherein the metal salt is soluble salt of copper, cobalt, iron, magnesium and aluminum, preferably nitrate or chloride; the coprecipitation temperature in the step (1) is 60-80 ℃, and preferably 70-75 ℃.
The aging time in said step (2) is 20 to 30 hours, preferably 22 to 26 hours.
The drying temperature in the step (2) is 80-100 ℃, preferably 90-95 ℃, and the drying time is 18-36 hours, preferably 22-26 hours.
The roasting temperature in the step (2) is 300-500 ℃, preferably 375-425 ℃, and the roasting time is 6-12 hours, preferably 7-9 hours.
In the invention, the mass ratio of the beta-isophorone to the catalyst is 1:0.005-0.02, preferably 1: 0.008-0.012.
In the present invention, the solvent is selected from one or more of methanol, ethanol, n-propanol and isopropanol, preferably methanol.
In the invention, the mass ratio of the beta-isophorone to the solvent is 1:0.5-1, preferably 1: 0.6-0.8.
In the invention, the mass ratio of the beta-isophorone to the cocatalyst is 1:0.01-0.05, preferably 1: 0.02-0.03.
As a preferred embodiment, the oxidation reaction of the present invention is preferably carried out in the presence of an inorganic base. The inorganic base is one or more selected from potassium carbonate, sodium phosphate, potassium phosphate, sodium sulfide and the like, and sodium carbonate or potassium carbonate is preferred. Under the alkalescent environment, the method is favorable for the reaction and is favorable for the final dehydration reaction.
In the invention, the mass ratio of the beta-isophorone to the inorganic base is 1:0.001-0.005, preferably 1: 0.002-0.003.
In the invention, the concentration of the hydrogen peroxide is selected from 30-50%, preferably 35-40%.
The molar weight ratio of the beta-isophorone to hydrogen peroxide is 1:1-1.05, and preferably 1: 1.02-1.04.
In the invention, the temperature of the oxidation reaction is 40-75 ℃, preferably 55-60 ℃, and the time of the oxidation reaction is 4-12h, preferably 7-9 h.
Compared with the prior art, the method has the following outstanding effects: hydrogen peroxide is used as an oxidant, so that the process is simple, the operation is easy, the reaction condition is mild, and the process route is environment-friendly; the catalyst is cheap, easy to obtain and recyclable, and does not produce waste liquid containing heavy metals; the conversion rate of the raw materials can reach more than 99 percent, and the yield of the product can reach 84 to 86 percent. After the catalyst is reused for many times, the catalytic activity can be kept stable.
Detailed Description
The technical solutions of the present invention are further described below, but not limited thereto, and modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the scope of the technical solutions of the present invention.
Gas chromatography conditions:
the chromatographic type is as follows: agilent WAX 1701.42249
Carrier gas: high purity nitrogen gas
Sample introduction mode: automatic sample injector
Nitrogen flow rate: 64.5ml/min
Vaporization chamber temperature: 280 deg.C
Split-flow sample introduction, split-flow ratio: 1: 40
Sample introduction amount: 0.2. mu.l
Column flow rate 1.5ml/min
Column temperature: first-order temperature programming, wherein the initial temperature is 100 ℃, the temperature is kept for 2 minutes, then the temperature is raised to 230 ℃ at the speed of 15 ℃/min, and the temperature is kept for 15 minutes; the total running time is 25.67min
The detector temperature is 300 DEG C
And (4) selecting an external standard method for quantification.
ICP elemental spectrometry instrument manufacturers: jiangsu Wuxinjie Bokejiu
Model of ICP elemental spectrometer: JB-750 type
Some of the examples indicate the reagent specifications and sources
Example 1
Preparing a catalyst:
taking a certain amount of Cu (NO)3)2·H2O、Al(NO3)3·9H2O、Fe(NO3)3·9H2O、Co(NO3)3·6H2O、Mg(NO3)2·6H2O, anhydrous Na2CO3After dissolving in water, 1mol/L of standard aqueous solution is prepared respectively. 970mLNa is weighed2CO3Heating the aqueous solution in a constant temperature water bath kettle to 70 ℃, mixing 623mL of aluminum nitrate aqueous solution with 19mL of copper nitrate, 6.3mL of cobalt nitrate, 2.1mL of ferric nitrate and 2.5mL of magnesium nitrate aqueous solution, and slowly dripping Na2CO3In solution. The temperature is controlled at 70 +/-5 ℃ in the dripping process, constant-temperature stirring is continued for 40min after the dripping is finished, and then the precipitate is poured into a beaker and aged for 24h at room temperature. After the precipitate was filtered, the precipitate was washed with deionized water until the washing solution was neutral. The precipitate obtained by filtration was then dried at 90 ℃ for 24 hours and then calcined at a high temperature of 400 ℃ for 8 hours. Cooling to room temperature, taking out the catalyst, tabletting with a tabletting machine, and sufficiently pulverizing with a pulverizer to obtain 33.3g of CuO-Co2O3-Fe2O3-MgO/Al2O3Catalyst # 1. Obtaining the 1# catalyst with the average grain diameter of 35.4 μm after XDR scanning; the CuO content is 4 measured by ICP element spectral analysis.55％，Co2O3Content of 1.2% Fe2O3The content is 0.51%, and the MgO content is 1.81%.
Preparation of 4-oxoisophorone:
a reaction kettle provided with a six-blade turbine high-speed stirring paddle is used as a reactor. 1380g of beta-isophorone, 970g of methanol, 3.45g of sodium carbonate, 13.8g of No. 1 catalyst and 34.5g of azobisisobutyrimidazoline hydrochloride are sequentially added into a reaction kettle; starting electric heating and mechanical stirring, heating the temperature of the reaction solution to 60 ℃, dropwise adding 2267g of 30% hydrogen peroxide solution for 6 hours, and continuously preserving the temperature for 2 hours. After the reaction, gas chromatography analysis shows that the conversion rate of the raw material beta-isophorone is 99.71%, the reaction solution is filtered, the catalyst is washed by methanol, and the catalyst washing solution is combined with the reaction solution. After the solvent is removed by a rotary evaporator, a packed tower with 16 theoretical plates is used for rectifying the reaction liquid after the solvent is removed under the condition of 1KPa, the reflux ratio is 3:1, and the fraction at 83-86 ℃ at the top of the tower is collected to obtain the 4-oxoisophorone, wherein the yield is 85.61%.
Example 2
Preparation of 4-oxoisophorone:
the catalyst obtained in example 1 was washed and then air-dried to prepare a catalyst of example 2.
A reaction kettle provided with a six-blade turbine high-speed stirring paddle is used as a reactor. 1380g of beta-isophorone, 970g of ethanol, 1.38g of sodium carbonate, 13.8g of No. 1 catalyst and 13.8g of azobisisobutyrimidazoline hydrochloride are sequentially added into a reaction kettle; starting electrical heating and mechanical stirring, heating the temperature of the reaction solution to 75 ℃, dropwise adding 2289g of 30% hydrogen peroxide solution for 6 hours, and continuously preserving the heat for 2 hours. After the reaction, gas chromatography analysis shows that the conversion rate of the raw material beta-isophorone is 99.33%, the reaction solution is filtered, the catalyst is washed by ethanol, and the catalyst washing solution is combined with the reaction solution. After the solvent is removed by a rotary evaporator, a packed tower with 16 theoretical plates is used for rectifying the reaction liquid after the solvent is removed under the condition of 1KPa, the reflux ratio is 3:1, and the fraction at 83-86 ℃ at the top of the tower is collected to obtain the 4-oxoisophorone, wherein the yield is 86.04%.
Example 3
Preparation of 4-oxoisophorone:
the catalyst obtained in example 2 was washed and then air-dried to prepare a catalyst of example 3.
A reaction kettle provided with a six-blade turbine high-speed stirring paddle is used as a reactor. 1380g of beta-isophorone, 690g of methanol, 3.45g of potassium carbonate, 13.8g of No. 1 catalyst and 34.5g of azobisisobutyrimidazoline hydrochloride are sequentially added into a reaction kettle; starting electric heating and mechanical stirring, heating the temperature of the reaction solution to 60 ℃, dropwise adding 1387g of 50% hydrogen peroxide solution for 6h, and continuously preserving the heat for 2 h. After the reaction, gas chromatography analysis shows that the conversion rate of the raw material beta-isophorone is 99.25%, the reaction solution is filtered, the catalyst is washed by methanol, and the catalyst washing solution is combined with the reaction solution. After the solvent is removed by a rotary evaporator, a packed tower with 16 theoretical plates is used for rectifying the reaction liquid after the solvent is removed under the condition of 1KPa, the reflux ratio is 3:1, and the fraction at 83-86 ℃ at the top of the tower is collected to obtain the 4-oxoisophorone, wherein the yield is 85.13%.
Examples 4 to 8
The catalyst obtained in example 3 was washed and then naturally air-dried, and the catalyst application experiment was repeated under the conditions of example 3, with the following results:
| examples | Number of times of catalyst application | Conversion of feedstock | Yield of the reaction |
| 4 | 4 | 99.15％ | 84.69％ |
| 5 | 5 | 99.23％ | 85.62％ |
| 6 | 6 | 99.06％ | 85.33％ |
| 7 | 7 | 99.24％ | 85.10％ |
| 8 | 8 | 99.18％ | 84.98％ |
The catalyst has stable property in the continuous application process, the catalyst is continuously applied for 8 times, the conversion rate of the raw material is more than 99 percent, and the reaction yield is between 84 and 86 percent.
Example 9
Preparing a catalyst:
taking a certain amount of Cu (NO)3)2·H2O、Al(NO3)3·9H2O、Fe(NO3)3·9H2O、Co(NO3)3·6H2O、Mg(NO3)2·6H2O, anhydrous Na2CO3After dissolving in water, 1mol/L of standard aqueous solution is prepared respectively. Weigh 985mLNa2CO3Heating the aqueous solution in a constant temperature water bath kettle to 60 ℃, and mixing 645mL of aluminum nitrate aqueous solution with 5.7mL of copper nitrate, 7.6mL of cobalt nitrate, 5.0mL of ferric nitrate and 2.2mL of nitric acidAfter mixing the magnesium aqueous solution, slowly adding Na dropwise2CO3In solution. The temperature is controlled at 60 +/-5 ℃ in the dripping process, constant-temperature stirring is continued for 40min after the dripping is finished, and then the precipitate is poured into a beaker and aged for 20h at room temperature. After the precipitate was filtered, the precipitate was washed with deionized water until the washing solution was neutral. The precipitate obtained by filtration was then dried at 100 ℃ for 18 hours and then calcined at a high temperature of 300 ℃ for 12 hours. Cooling to room temperature, taking out the catalyst, tabletting with a tabletting machine, and sufficiently pulverizing with a pulverizer to obtain 34.1g of CuO-Co2O3-Fe2O3-MgO/Al2O3Catalyst # 2. Obtaining the average grain diameter of the 2# catalyst to be 11.6 mu m after XDR scanning; the content of CuO is 1.35 percent and the content of Co is measured by ICP element spectral analysis2O3Content of 1.79% Fe2O3The content is 1.14%, and the MgO content is 0.53%.
Preparation of 4-oxoisophorone:
a reaction kettle provided with a six-blade turbine high-speed stirring paddle is used as a reactor. 1380g of beta-isophorone, 970g of isopropanol, 6.9g of sodium phosphate, 27.6g of 2# catalyst and 69g of azodiisobutyl amidine hydrochloride are sequentially added into a reaction kettle; starting electric heating and mechanical stirring, heating the temperature of the reaction solution to 40 ℃, dropwise adding 2001g of 35% hydrogen peroxide solution for 10 hours, and continuously preserving the heat for 2 hours. After the reaction, gas chromatography analysis shows that the conversion rate of the raw material beta-isophorone is 99.54%, the reaction solution is filtered, the catalyst is washed by isopropanol, and the catalyst washing solution is combined with the reaction solution. After the solvent is removed by a rotary evaporator, a packed tower with 16 theoretical plates is used for rectifying the reaction liquid after the solvent is removed under the condition of 1KPa, the reflux ratio is 3:1, and the fraction at 83-86 ℃ at the top of the tower is collected to obtain the 4-oxoisophorone, wherein the yield is 84.12%.
Example 10
Preparation of 4-oxoisophorone:
the catalyst obtained in example 9 was washed and then air-dried to prepare a catalyst of example 10.
A reaction kettle provided with a six-blade turbine high-speed stirring paddle is used as a reactor. 1380g of beta-isophorone, 718g of ethanol, 6.9g of potassium phosphate, 27.6g of 2# catalyst and 69g of azodiisobutyl amidine hydrochloride are sequentially added into a reaction kettle; starting electric heating and mechanical stirring, heating the temperature of the reaction solution to 40 ℃, dropwise adding 2357g of 30% hydrogen peroxide solution for 10 hours, and continuously preserving the heat for 2 hours. After the reaction, gas chromatography analysis shows that the conversion rate of the raw material beta-isophorone is 99.18%, the reaction solution is filtered, the catalyst is washed by isopropanol, and the catalyst washing solution is combined with the reaction solution. After the solvent is removed by a rotary evaporator, a packed tower with 16 theoretical plates is used for rectifying the reaction liquid after the solvent is removed under the condition of 1KPa, the reflux ratio is 3:1, and the fraction at 83-86 ℃ at the top of the tower is collected to obtain the 4-oxoisophorone, wherein the yield is 86.97%.
Example 11
Preparing a catalyst:
taking a certain amount of Cu (NO)3)2·H2O、Al(NO3)3·9H2O、Fe(NO3)3·9H2O、Co(NO3)3·6H2O、Mg(NO3)2·6H2O, anhydrous Na2CO3After dissolving in water, 1mol/L of standard aqueous solution is prepared respectively. Weigh 985mLNa2CO3Heating the aqueous solution in a constant temperature water bath to 80 ℃, mixing 595mL of aluminum nitrate aqueous solution with 38mL of copper nitrate, 2.2mL of cobalt nitrate, 8.3mL of ferric nitrate and 4.2mL of magnesium nitrate aqueous solution, and slowly dripping Na2CO3In solution. The temperature is controlled at 60 +/-5 ℃ in the dripping process, constant-temperature stirring is continued for 40min after the dripping is finished, and then the precipitate is poured into a beaker and aged for 30h at room temperature. After the precipitate was filtered, the precipitate was washed with deionized water until the washing solution was neutral. The precipitate obtained by filtration was then dried at 80 ℃ for 36 hours and then calcined at a high temperature of 500 ℃ for 6 hours. Cooling to room temperature, taking out the catalyst, tabletting with a tabletting machine, and sufficiently crushing with a crusher to obtain 32.9g of CuO-Co2O3-Fe2O3-MgO/Al2O3Catalyst # 3. Obtaining the average grain diameter of the 3# catalyst to be 70.3 mu m after XDR scanning; the content of CuO is 9.15 percent and the content of Co is measured by ICP element spectral analysis2O30.54% of Fe2O3The content is 1.88%, and the MgO content is 1.07%.
Preparation of 4-oxoisophorone:
a reaction kettle provided with a six-blade turbine high-speed stirring paddle is used as a reactor. 1380g of beta-isophorone, 970g of n-propanol, 3.45g of sodium sulfide, 6.9g of 3# catalyst and 34.5g of azo-isobutyryl cyano formamide are sequentially added into a reaction kettle; starting electric heating and mechanical stirring, heating the temperature of the reaction solution to 60 ℃, dropwise adding 1428g of 50% hydrogen peroxide solution for 3 hours, and continuously preserving the heat for 1 hour. After the reaction, gas chromatography analysis shows that the conversion rate of the raw material beta-isophorone is 99.66%, the reaction solution is filtered, the catalyst is washed by isopropanol, and the catalyst washing solution is combined with the reaction solution. After the solvent is removed by a rotary evaporator, a packed tower with 16 theoretical plates is used for rectifying the reaction liquid after the solvent is removed under the condition of 1KPa, the reflux ratio is 3:1, and the fraction at 83-86 ℃ at the top of the tower is collected to obtain the 4-oxoisophorone, wherein the yield is 85.88%.
Claims (18)
1. A method for preparing 4-oxo-isophorone by catalytic oxidation of beta-isophorone with solid-liquid two-phase catalyst comprises the following steps: carrying out oxidation reaction on the beta-isophorone and hydrogen peroxide in the presence of a solvent and a catalyst to obtain 4-oxo-isophorone; the catalyst is CuO-Co2O3-Fe2O3-MgO/Al2O3Wherein the mass content of the copper oxide is 1-10 percent; the mass content of the ferric oxide is 0.5-2%; the mass content of the cobalt oxide is 0.5-2%; the mass content of the magnesium oxide is 0.5 to 2 percent; based on the total mass of the catalyst; the oxidation reaction is carried out in the presence of a cocatalyst and an inorganic base, wherein the cocatalyst is selected from one or more of azobisisobutyramidine hydrochloride, azobisisobutyrimidazoline hydrochloride and azobisisobutyronitrile formamide; the inorganic base is one or more selected from potassium carbonate, sodium phosphate, potassium phosphate and sodium sulfide.
2. The method of claim 1, wherein the copper oxide content of the catalyst is 4-5% by mass; the mass content of the ferric oxide is 1 to 1.2 percent; the mass content of the cobalt oxide is 1 to 1.2 percent; the mass content of the magnesium oxide is 1 to 1.2 percent; based on the total mass of the catalyst.
3. The process of claim 1 wherein the catalyst has an average particle size of from 10 to 80 μm.
4. The process of claim 3 wherein the catalyst has an average particle size of from 30 to 40 μm.
5. The process of claim 1 wherein said cocatalyst is azobisisobutyrimidazoline hydrochloride.
6. The method according to any one of claims 1 to 4, wherein the solvent is selected from one or more of methanol, ethanol, n-propanol and isopropanol; the mass ratio of the beta-isophorone to the solvent is 1: 0.5-1.
7. The method of claim 6, wherein the solvent is selected from the group consisting of methanol; the mass ratio of the beta-isophorone to the solvent is 1: 0.6-0.8.
8. The method of any one of claims 1 to 4, wherein the mass ratio of the beta-isophorone to the catalyst is 1: 0.005-0.02.
9. The method of claim 8, wherein the mass ratio of the beta-isophorone to the catalyst is 1: 0.008-0.012.
10. The method of claim 1, wherein the mass ratio of the beta-isophorone to the co-catalyst is 1: 0.01-0.05.
11. The method of claim 10, wherein the mass ratio of the beta-isophorone to the co-catalyst is 1: 0.02-0.03.
12. The process according to claim 1, wherein the inorganic base is selected from sodium carbonate.
13. The method of claim 1, wherein the mass ratio of the beta-isophorone to inorganic base is 1: 0.001-0.005.
14. The method of claim 13, wherein the mass ratio of the beta-isophorone to inorganic base is 1: 0.002-0.003.
15. The method according to any one of claims 1 to 4, wherein the molar weight ratio of the beta-isophorone to hydrogen peroxide is 1: 2-2.1.
16. The method of claim 15, wherein the molar weight ratio of the beta-isophorone to hydrogen peroxide is 1: 2.04-2.08.
17. The process according to any one of claims 1 to 4, wherein the temperature of the oxidation reaction is 40 to 75 ℃ and the time of the oxidation reaction is 4 to 12 hours.
18. The method according to claim 17, wherein the temperature of the oxidation reaction is 55-60 ℃ and the time of the oxidation reaction is 7-9 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810322296.7A CN108440262B (en) | 2018-04-11 | 2018-04-11 | Method for preparing 4-oxoisophorone by catalytic oxidation of beta-isophorone with solid-liquid two-phase |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810322296.7A CN108440262B (en) | 2018-04-11 | 2018-04-11 | Method for preparing 4-oxoisophorone by catalytic oxidation of beta-isophorone with solid-liquid two-phase |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108440262A CN108440262A (en) | 2018-08-24 |
| CN108440262B true CN108440262B (en) | 2021-04-20 |
Family
ID=63199394
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810322296.7A Active CN108440262B (en) | 2018-04-11 | 2018-04-11 | Method for preparing 4-oxoisophorone by catalytic oxidation of beta-isophorone with solid-liquid two-phase |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108440262B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110075894B (en) * | 2019-04-03 | 2022-02-15 | 万华化学集团股份有限公司 | Metal/composite metal oxide/g-C3N4Catalyst and preparation method of 4-oxoisophorone |
| CN110721696B (en) * | 2019-10-01 | 2020-06-05 | 山东新和成维生素有限公司 | Method for catalytically synthesizing tea scented ketone by adopting perovskite type composite oxide |
| CN111777497B (en) * | 2020-07-08 | 2022-07-12 | 万华化学集团股份有限公司 | Method for preparing 4-oxo-isophorone by catalytic oxidation of beta-isophorone |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2300065B1 (en) * | 1975-02-04 | 1977-07-22 | Rhone Poulenc Ind | |
| US4970347A (en) * | 1988-12-17 | 1990-11-13 | Huels Aktiengesellschaft | Method of producing 2,6,6-trimethyl-2-cyclohexane-1,4-dione |
| US5545761A (en) * | 1994-11-14 | 1996-08-13 | Aristech Chemical Corporation | Method of making ketoisophorone via oxidation of isophorone with tert-butyl hydroperoxide |
| CN105601490A (en) * | 2014-11-13 | 2016-05-25 | 四川大学 | Oxo-isophorone preparation through efficient catalytic oxidation of alpha-isophorone |
| CN108147952A (en) * | 2016-12-02 | 2018-06-12 | 赢创德固赛有限公司 | With catalytic oxidation of hydrogen peroxide β-isophorone generation 2,6,6- trimethyl -2- cyclohexene -1,4- diketone |
-
2018
- 2018-04-11 CN CN201810322296.7A patent/CN108440262B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2300065B1 (en) * | 1975-02-04 | 1977-07-22 | Rhone Poulenc Ind | |
| US4970347A (en) * | 1988-12-17 | 1990-11-13 | Huels Aktiengesellschaft | Method of producing 2,6,6-trimethyl-2-cyclohexane-1,4-dione |
| US5545761A (en) * | 1994-11-14 | 1996-08-13 | Aristech Chemical Corporation | Method of making ketoisophorone via oxidation of isophorone with tert-butyl hydroperoxide |
| CN105601490A (en) * | 2014-11-13 | 2016-05-25 | 四川大学 | Oxo-isophorone preparation through efficient catalytic oxidation of alpha-isophorone |
| CN108147952A (en) * | 2016-12-02 | 2018-06-12 | 赢创德固赛有限公司 | With catalytic oxidation of hydrogen peroxide β-isophorone generation 2,6,6- trimethyl -2- cyclohexene -1,4- diketone |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108440262A (en) | 2018-08-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108236955B (en) | Preparation method of catalyst for synthesizing ethanol by dimethyl oxalate hydrogenation, catalyst obtained by preparation method and application of catalyst | |
| CN108440262B (en) | Method for preparing 4-oxoisophorone by catalytic oxidation of beta-isophorone with solid-liquid two-phase | |
| CN102773097B (en) | Preparation of loaded bimetallic nano-catalyst | |
| CN107376997B (en) | Preparation and application of catalyst for preparing benzaldehyde by oxidizing benzyl alcohol | |
| Leng et al. | A novel heteropolyanion-based amino-containing cross-linked ionic copolymer catalyst for epoxidation of alkenes with H2O2 | |
| CN106345530A (en) | Magnetic core-shell nanocatalyst, preparation method thereof and application thereof in catalyzing 5-hydroxymethylfurfural to prepare 2, 5-diformyl furan | |
| CN106622316B (en) | A kind of vanadium-phosphor oxide catalyst, preparation method and application | |
| CN105562046B (en) | Methanol and the ethanol condensed catalyst for preparing propyl alcohol and butanol and preparation method and application | |
| CN104667913A (en) | Macroporous aluminum oxide assembled nano metal catalyst as well as preparation and application to methanol liquid-phase catalytic reaction | |
| CN101966460A (en) | Supported catalyst for synthesis of dimethyl carbonate, preparation method and using method thereof | |
| CN101134163A (en) | Method for synthesizing formic ester and specific catalyzer thereof | |
| CN102863335B (en) | Preparation method of diethyl succinate | |
| CN106582666B (en) | Gamma-valerolactone hydrogenation catalyst, preparation method and the method for being used to prepare 1,4- pentanediol and 2- methyltetrahydrofuran | |
| CN108435171A (en) | The preparation method and a kind of method of selective catalytic oxidation glycerine DHA of a kind of bimetallic Pt-Bi catalyst | |
| CN109894140A (en) | A kind of preparation method and its catalytic applications of solid base hydrotalcite supported precious metal catalyst | |
| CN108722455B (en) | Preparation method of vanadium phosphorus oxide catalyst | |
| CN110482607B (en) | High-grain boundary density MoO3Nanocrystalline, preparation thereof and application thereof in catalytic oxidation of aromatic primary alcohol | |
| Yang et al. | Improved olefin epoxidation performance of a discrete bis (8-quinolinol) oxovanadium (IV) complex covalently attached on SBA-15 by a metal-template/metal-exchange method | |
| CN103706398A (en) | supported vanadium-substituted phosphotungstic acid catalyst and preparation method and application of catalyst | |
| CN108067230A (en) | A kind of preparation method of non-precious metal catalyst | |
| CN110256230A (en) | Efficient catalytic glycerol prepares catalyst of glyceric acid and preparation method thereof under the conditions of a kind of alkali-free | |
| CN113171798B (en) | Heterogeneous iron catalyst, preparation method thereof and process for preparing 2-methyl-1, 4-naphthoquinone by catalysis | |
| Yue et al. | Ag–Cu nanoparticles as efficient catalysts for transesterification of β-keto esters under acid/base-free conditions | |
| CN113786837A (en) | Method for preparing cyclopentanone and cyclopentanol through furfural hydrogenation rearrangement | |
| Oberhauser et al. | Aerobic diol lactonization by Au-nanoparticles supported onto an anion-exchange resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A solid-liquid two-phase catalytic oxidation b- Method for preparing 4-oxo isophorone from Isophorone Effective date of registration: 20211123 Granted publication date: 20210420 Pledgee: Bank of China Limited by Share Ltd. Yantai branch Pledgor: Wanhua Chemical Group Co.,Ltd. Registration number: Y2021980013026 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20220622 Granted publication date: 20210420 Pledgee: Bank of China Limited by Share Ltd. Yantai branch Pledgor: Wanhua Chemical Group Co.,Ltd. Registration number: Y2021980013026 |