CN116212943A - Preparation method of novel alkaline catalyst and application of novel alkaline catalyst in preparation of methyl heptenone - Google Patents

Preparation method of novel alkaline catalyst and application of novel alkaline catalyst in preparation of methyl heptenone Download PDF

Info

Publication number
CN116212943A
CN116212943A CN202211547557.8A CN202211547557A CN116212943A CN 116212943 A CN116212943 A CN 116212943A CN 202211547557 A CN202211547557 A CN 202211547557A CN 116212943 A CN116212943 A CN 116212943A
Authority
CN
China
Prior art keywords
molecular sieve
methyl
novel
basic catalyst
preparation
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.)
Pending
Application number
CN202211547557.8A
Other languages
Chinese (zh)
Inventor
刘晓涛
王�锋
张建洋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu Hongbang Chemical Technology Co ltd
Original Assignee
Jiangsu Hongbang Chemical Technology Co ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Jiangsu Hongbang Chemical Technology Co ltd filed Critical Jiangsu Hongbang Chemical Technology Co ltd
Priority to CN202211547557.8A priority Critical patent/CN116212943A/en
Publication of CN116212943A publication Critical patent/CN116212943A/en
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7007—Zeolite Beta
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/082—X-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/60—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the type L, as exemplified by patent document US3216789
    • 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
    • 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
    • B01J37/30—Ion-exchange
    • 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
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/34—Reaction with organic or organometallic compounds
    • 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

Abstract

The invention discloses a preparation method of a novel alkaline catalyst, which comprises the following steps: soaking a silicon-aluminum molecular sieve into a solution containing alkali metal ions for ion exchange, drying and roasting to obtain an alkaline molecular sieve; according to the method of isovolumetric impregnation, organic amine is impregnated on the obtained basic molecular sieve, and the novel basic catalyst is obtained by drying. The prepared novel alkaline catalyst catalyzes methyl butenol to react with methyl acetoacetate to prepare methyl heptenone, so that the reaction speed of transesterification is greatly improved, the reaction condition is milder, the catalyst can be recycled, the catalyst is clean and environment-friendly, the side reaction is less, and the residue of a kettle is reduced.

Description

Preparation method of novel alkaline catalyst and application of novel alkaline catalyst in preparation of methyl heptenone
Technical Field
The invention belongs to the technical field of catalyst preparation and organic synthesis, relates to preparation of an alkaline catalyst, and particularly relates to a preparation method of a novel alkaline catalyst and application of the novel alkaline catalyst in preparation of methyl heptenone.
Background
Methyl heptenone, chemical name 6-methyl-5-hepten-2-one, molecular formula C 8 H 14 O is colorless or pale yellow liquid, has strong oil smell, and has fresh green fragrance and orange fragrance. Methyl heptenone is mainly used in the formulation of essence for soap and is used for preparing a plurality of fruit-flavored edible essences. Meanwhile, the methyl heptenone is an important intermediate for synthesizing various medicines, essences and fragrances, and is also a main raw material for preparing linalool, citral, pseudoionone and other fragrance products, so that vitamin A, vitamin E and various essence fragrances can be prepared synthetically.
The method for synthesizing methyl heptenone in the prior art mainly comprises an isobutene method, a Saucy-Marbet method and a Carrol method;
the isobutene method, german BASF takes isobutene, acetone and formaldehyde as raw materials, alpha-methyl heptenone is directly synthesized under the condition of 300 ℃ and 30MPa, and then methyl heptenone is obtained by heating isomerization under the action of iron and palladium catalysts (DE 1277848B, DE 1267682B).
Figure 959850DEST_PATH_IMAGE002
The method has the advantages of short reaction steps, simple route, wide and easily available raw material sources, high temperature and high pressure are needed for the reaction conditions of the method, a large amount of byproducts are generated in the reaction process, the separation and purification difficulties are high, the raw material recovery process is complex, and the requirements on equipment are quite high.
The Saucy-Marbet method is to synthesize methyl heptenone by using methyl butenol and alkyl (methoxy) propylene, and the main reaction process is as follows:
Figure 829322DEST_PATH_IMAGE004
chinese patent CN108299171A synthesizes methyl heptenone without catalyst under the critical conditions of high temperature of 250-300 ℃ and 5-10Mpa, and the selectivity is more than 92%. Under the protection of inert gas, the Chinese patent CN106478514A uses unsaturated alcohol and 2-alkoxy propylene as raw materials and uses Bronsted acid as a catalyst to carry out rearrangement reaction in a mode of connecting autoclaves in series, the selectivity reaches more than 97%, but the method has higher requirements on equipment.
The method has the advantages of good atom economy, high selectivity and simple route, but the raw material methoxypropene is not a large number of commodities, has fewer sources, is not easy to transport and store, and is not favorable for large-scale industrial production and application at present.
The Carrol method is industrialized by Roche company in Switzerland, after the process is improved by BASF in Germany, the catalyst of the Carrol reaction in the method of U.S. Pat. No. 3,979A is an aluminum alcoholate such as aluminum isobutanol and aluminum isopropoxide, and the modified alkyl acetoacetate aluminum compound is used as the catalyst in China patent CN1173917C to prepare gamma-delta unsaturated ketone by the Carrol reaction, wherein the related alkyl acetoacetate comprises methyl ester, ethyl ester, isopropyl ester, tertiary butyl ester, secondary butyl ester and the like.
The Chinese patent CN102503790A adopts methyl butenyl alcohol and methyl acetoacetate as raw materials, and adopts a diethanol amine/aluminum isopropoxide composite catalyst to synthesize methyl heptenone and modify aluminum isopropoxide, wherein the aluminum isopropoxide accounts for 2-3% of the feeding amount of the methyl acetoacetate, the method also inhibits the cracking of the methyl heptenone, improves the yield of the methyl heptenone, and the diethanol amine can be recycled through rectification, but aluminum isopropoxide in the rectification generates aluminum-containing organic foot oil which cannot be recycled well, so that certain pressure is brought to environmental protection treatment.
Chinese patent CN107673959a discloses that methyl butenyl alcohol and methyl acetoacetate are used as raw materials, diazabicyclo and aluminum isopropoxide are used as catalysts to prepare methyl heptenone, and the two kettles are used for sectional temperature control, so that the yield is more than 90%, but the aluminum isopropoxide is larger in dosage and accounts for 6-8.5% of the total materials, the aluminum-containing waste liquid in the later stage is more, and the environmental protection treatment difficulty is high.
The technical personnel find that in the Carrol method, the improvement of the reaction speed of transesterification is the key for improving the whole reaction speed, the reaction speed of claisen rearrangement and decarboxylation is more related to the concentration of a transesterification product and the reaction temperature, the reaction speed of transesterification is reduced, the concentration of the transesterification product is lower, the claisen rearrangement and decarboxylation reaction is reduced, the whole reaction time is overlong, meanwhile, the side reactions such as dehydration, polymerization and the like of the methyl butenol are more caused at high temperature for a long time, and the dehydrated water also damages the aluminum isopropoxide catalyst, so that the reaction yield is reduced. New catalysts are therefore needed to solve this problem, and the recovery of the catalyst is also particularly important.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of a novel alkaline catalyst, which is characterized in that an organic amine is used for treating an alkaline molecular sieve to prepare the novel alkaline catalyst, and the novel alkaline catalyst is used for catalyzing the reaction of methyl butenol and methyl acetoacetate to prepare methyl heptenone, so that the reaction speed of transesterification is greatly improved, the reaction condition is milder, the catalyst can be recycled, the catalyst is clean and environment-friendly, the side reaction is less, and the residue of a kettle is reduced.
The invention is realized by the following technical scheme:
a method for preparing a novel alkaline catalyst, comprising the following steps: soaking a silicon-aluminum molecular sieve into a solution containing alkali metal ions for ion exchange, drying and roasting to obtain an alkaline molecular sieve; according to the method of isovolumetric impregnation, organic amine is impregnated on the obtained basic molecular sieve, and the novel basic catalyst is obtained by drying.
The invention further improves the scheme as follows:
the silicon-aluminum molecular sieve is one or more than two of Beta type molecular sieve, L type molecular sieve, X type molecular sieve or Y type molecular sieve.
Preferably, the silicon-aluminum molecular sieve is an L-type molecular sieve or an X-type molecular sieve.
Further, the solute in the solution containing alkali metal ions is one or more than two of nitrate, acetate, carbonate and hydroxide of alkali metal; the alkali metal ion is one or more than two of potassium ion, rubidium ion or cesium ion.
Further, the Si/Al molar ratio of the silicon-aluminum molecular sieve is 1-20.
Preferably, the Si/Al molar ratio of the silicon-aluminum molecular sieve is 3-5.
Further, the organic amine is one or more than two of 1, 2-propylene diamine, triethylamine, triethanolamine or 4-dimethylaminopyridine.
Further, the solid-liquid ratio in g: ml is 1:5-30, the mass concentration of alkali metal ions is 1-30%, the exchange temperature is 60-80 ℃, and the exchange time is 2-6 h.
Further, the degree of exchange of the alkali metal ions is 10-20%.
Preferably, the degree of exchange of the alkali metal ions is 50%, 45%, 35%, 40%, 30% or 20%.
The invention further improves the scheme as follows:
the application of the novel alkaline catalyst prepared by the method in the preparation of methyl heptenone comprises the following steps: methyl butenol is reacted with methyl acetoacetate in the presence of the novel basic catalyst to form methyl heptenone.
Further, the reaction temperature is 140-170 ℃ and the reaction time is 6-12 hours.
Further, the molar ratio of the methyl butenol to the methyl acetoacetate is 1.2-2.0: 1, wherein the mass ratio of the methyl acetoacetate to the novel alkaline catalyst is 5-60: 1.
compared with the prior art, the invention has the beneficial effects that:
1) The novel alkaline catalyst is adopted to catalyze the condensation of methyl butenol to prepare methyl heptenone, so that the problem that the catalyst can not be recycled mechanically is avoided, and the route is clean and environment-friendly;
2) The catalyst is a metal catalyst loaded by an alkaline molecular sieve, the shape selective effect of the molecular sieve is utilized to improve the reaction speed of transesterification, effectively inhibit the dehydration of methyl butenol, reduce the consumption of methyl acetoacetate, and show excellent selectivity in the synthesis of methyl heptenone;
3) The preparation method provided by the invention is simple and convenient to operate, meets the industrial application requirements, and is convenient for industrial production.
Detailed Description
The present invention will be described in detail with reference to specific examples.
The original NaX, naY, naL, naBeta type molecular sieves in the examples of the present invention were all commercially available.
The analytical methods, conversions, selectivities in the examples were calculated as follows:
analysis was performed using a Shimadzu gas chromatograph.
In some embodiments of the invention, both conversion and yield are calculated on a molar basis:
methyl acetoacetate conversion = [ (moles of methyl butenol in feed) - (moles of methyl butenol in discharge) ]/(moles of methyl butenol in feed) ×100%
Methyl heptenone yield (p-methyl butenol) = (moles of methyl heptenone in discharge)/(moles of methyl butenol converted) ×100%
Methyl heptenone yield (methyl acetoacetate) = (moles of methyl heptenone in the discharge)/(moles of methyl acetoacetate converted) ×100%
Examples 1 to 10: preparation of basic molecular sieves
Step 1, dissolving alkali metal salt in water to obtain a precursor solution with the concentration of 0.1-0.5 mol/L, wherein the alkali metal salt is selected from one of potassium nitrate, rubidium nitrate and cesium nitrate;
step 2, weighing 20g of unshaped molecular sieve, wherein the molecular sieve is selected from one of NaX, naY, naL, naBeta type molecular sieves;
step 3, carrying out ion exchange on the molecular sieve weighed in the step 2) by using the alkali metal ion precursor solution in the step 1) according to the solid-liquid ratio of 1:5, stirring for 5 hours at the constant temperature of 90 ℃ under normal pressure, filtering, washing, drying in a 100 ℃ oven for 2 hours, and calcining the obtained solid in a muffle furnace at 160 ℃ and 450 ℃ for 1 hour respectively;
and 4, changing the molecular sieve weighed in the step 2 into a molecular sieve obtained after roasting the ion-exchanged object in the step 3, and repeating the step 3 for two times to obtain an alkaline molecular sieve sample, wherein the obtained sample is marked as A-l-A-10.
The sample numbers, corresponding molecular sieves, alkali metal salts and concentrations used for the corresponding precursor solutions, and the degree of exchange are shown in table 1. Performing element analysis on the obtained sample by adopting an XRF element analyzer, and calculating the ion exchange degree according to the K element content of the sample before and after exchange, wherein the calculation formula is as follows:
ion exchange = (mole percent of Na (K) element in molecular sieve before exchange-mole percent of Na (K) element in molecular sieve after exchange): the mole percentage of Na (K) element in the molecular sieve before exchange is multiplied by 100 percent.
TABLE 1 parameters for the preparation of basic molecular sieves
Figure 218847DEST_PATH_IMAGE006
Examples 11 to 10: preparation of organic amine treated basic molecular sieve catalyst
20g of basic molecular sieve is suspended in 100mL of toluene, a certain mass of organic amine is added, reflux is carried out for 15 hours at 85 ℃, the cooled product is washed by methanol, filtered and dried in an oven at 70 ℃ for 6 hours. The types and the masses of the carrier and the organic amine are shown in Table 2.
Table 2 parameters for the preparation of organic amine treated basic molecular sieve catalysts
Figure 286160DEST_PATH_IMAGE008
Examples 25 to 38: evaluation of organic amine treated basic molecular sieve catalysts in methyl heptenone synthesis reactions
Adding a catalyst into a reaction kettle, and adding a certain amount of methyl butenol and methyl acetoacetate into the reaction kettle to carry out Carrol condensation reaction, wherein the methyl butenol is as follows: methyl acetoacetate molar ratio is 1.5:1, reaction temperature is 165 ℃, reaction time is 8 hours, the catalyst accounts for 8.0% of the mass of methyl acetoacetate, methanol and unconverted methyl butenol generated by reaction are condensed and collected along with a rectifying column, and CO is generated 2 Cooling, discharging to atmosphere, cooling after the reaction is finished, filtering out catalyst, decompressing and rectifying,the product was obtained and analyzed by sampling, and the reaction results are shown in Table 3;
TABLE 3 reactivity of the catalysts prepared in examples 25-38
Figure 303794DEST_PATH_IMAGE010
As shown in Table 3, the catalyst provided by each embodiment of the invention shows excellent selectivity to methyl acetoacetate in the reaction of synthesizing methyl heptenone from methyl butenol and methyl acetoacetate, the yield of methyl heptenone (p-methyl butenol) can reach 96.5%, and the highest conversion rate of methyl acetoacetate can reach 96.5%; when the NaX molecular sieve for basic molecular screening has an ion exchange degree of 35.0-40.0 and an organic amine content of 0.15-0.2 mol, the yield of methyl heptenone (methyl acetoacetate) can be 92.5% or more.
The foregoing embodiments are merely illustrative of the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and to implement the same, not to limit the scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.

Claims (10)

1. The preparation method of the novel alkaline catalyst is characterized by comprising the following steps: soaking a silicon-aluminum molecular sieve into a solution containing alkali metal ions for ion exchange, drying and roasting to obtain an alkaline molecular sieve; according to the method of isovolumetric impregnation, organic amine is impregnated on the obtained basic molecular sieve, and the novel basic catalyst is obtained by drying.
2. The method for preparing a novel basic catalyst according to claim 1, wherein: the silicon-aluminum molecular sieve is one or more than two of Beta type molecular sieve, L type molecular sieve, X type molecular sieve or Y type molecular sieve.
3. The method for preparing a novel basic catalyst according to claim 1, wherein: the solute in the solution containing alkali metal ions is one or more than two of nitrate, acetate, carbonate and hydroxide of alkali metal; the alkali metal ion is one or more than two of potassium ion, rubidium ion or cesium ion.
4. The method for preparing a novel basic catalyst according to any one of claims 1 or 2, characterized in that: the Si/Al molar ratio of the silicon-aluminum molecular sieve is 1-20.
5. The method for preparing a novel basic catalyst according to claim 1, wherein: the organic amine is one or more than two of 1, 2-propylene diamine, triethylamine, triethanolamine or 4-dimethylaminopyridine.
6. The method for preparing a novel basic catalyst according to claim 1, wherein: the solid-liquid ratio in g: ml is 1:5-30, the mass concentration of alkali metal ion is 1-30%, the exchange temperature is 60-80 deg.C, and the exchange time is 2-6 h.
7. The method for preparing a novel basic catalyst according to claim 1, wherein: the degree of exchange of the alkali metal ions is 10-20%.
8. Use of the novel basic catalyst prepared by the process according to claim 1 for the preparation of methyl heptenone, comprising the steps of: methyl butenol is reacted with methyl acetoacetate in the presence of the novel basic catalyst to form methyl heptenone.
9. Use of the novel basic catalyst according to claim 8 for the preparation of methyl heptenone, characterized in that: the reaction temperature is 140-170 ℃ and the reaction time is 6-12 hours.
10. Use of the novel basic catalyst according to claim 8 for the preparation of methyl heptenone, characterized in that: the molar ratio of the methyl butenol to the methyl acetoacetate is 1.2-2.0: 1, wherein the mass ratio of the methyl acetoacetate to the novel alkaline catalyst is 5-60: 1.
CN202211547557.8A 2022-12-05 2022-12-05 Preparation method of novel alkaline catalyst and application of novel alkaline catalyst in preparation of methyl heptenone Pending CN116212943A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211547557.8A CN116212943A (en) 2022-12-05 2022-12-05 Preparation method of novel alkaline catalyst and application of novel alkaline catalyst in preparation of methyl heptenone

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211547557.8A CN116212943A (en) 2022-12-05 2022-12-05 Preparation method of novel alkaline catalyst and application of novel alkaline catalyst in preparation of methyl heptenone

Publications (1)

Publication Number Publication Date
CN116212943A true CN116212943A (en) 2023-06-06

Family

ID=86568595

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211547557.8A Pending CN116212943A (en) 2022-12-05 2022-12-05 Preparation method of novel alkaline catalyst and application of novel alkaline catalyst in preparation of methyl heptenone

Country Status (1)

Country Link
CN (1) CN116212943A (en)

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2729975A1 (en) * 1977-07-02 1979-01-18 Basf Ag 2-Methyl-2-heptenone-6 prodn. from 2-methyl-3-buten-2-ol - and alkyl acetoacetate over organic aluminium catalyst, intermediate for perfumes and vitamin(s) esp. vitamin=A
US4467112A (en) * 1979-01-30 1984-08-21 Kawasaki Kasei Chemicals Ltd. Process for producing p-n-alkylbenzoic acid
US4954621A (en) * 1988-06-14 1990-09-04 Mitsubushi Kasei Corporation Process for producing sucrose fatty acid polyester
KR20020027812A (en) * 2000-10-05 2002-04-15 유승렬 Method for removing the residual catalyst from Carroll reaction mixture by using adsorption technology
CN1348434A (en) * 1998-09-07 2002-05-08 Basf公司 Method for producing upsilon, delta unsaturated ketones by carroll reaction
CN102030626A (en) * 2010-11-16 2011-04-27 上海应用技术学院 Method for preparing 5-methyl-2-hepten-4-one
CN102503790A (en) * 2011-10-11 2012-06-20 上海博鹤企业发展有限公司 Method for producing methyl heptenone
CN104711007A (en) * 2013-12-11 2015-06-17 中国科学院大连化学物理研究所 Preparation method of aviation kerosene or diesel oil scope liquid alkane
CN107673959A (en) * 2017-10-27 2018-02-09 西南化工研究设计院有限公司 A kind of method and system for preparing methyl heptenone
CN108129314A (en) * 2017-12-20 2018-06-08 沈阳化工大学 By the method for ethylene carbonate, methanol and ethyl alcohol one-step synthesis methyl ethyl carbonate
US20180370896A1 (en) * 2015-07-20 2018-12-27 Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences Methyl acetate preparation method
CN113877562A (en) * 2020-07-03 2022-01-04 中国石油化工股份有限公司 Solid base catalyst for synthesizing methyl acrylate and preparation method and application thereof

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2729975A1 (en) * 1977-07-02 1979-01-18 Basf Ag 2-Methyl-2-heptenone-6 prodn. from 2-methyl-3-buten-2-ol - and alkyl acetoacetate over organic aluminium catalyst, intermediate for perfumes and vitamin(s) esp. vitamin=A
US4467112A (en) * 1979-01-30 1984-08-21 Kawasaki Kasei Chemicals Ltd. Process for producing p-n-alkylbenzoic acid
US4954621A (en) * 1988-06-14 1990-09-04 Mitsubushi Kasei Corporation Process for producing sucrose fatty acid polyester
CN1348434A (en) * 1998-09-07 2002-05-08 Basf公司 Method for producing upsilon, delta unsaturated ketones by carroll reaction
KR20020027812A (en) * 2000-10-05 2002-04-15 유승렬 Method for removing the residual catalyst from Carroll reaction mixture by using adsorption technology
CN102030626A (en) * 2010-11-16 2011-04-27 上海应用技术学院 Method for preparing 5-methyl-2-hepten-4-one
CN102503790A (en) * 2011-10-11 2012-06-20 上海博鹤企业发展有限公司 Method for producing methyl heptenone
CN104711007A (en) * 2013-12-11 2015-06-17 中国科学院大连化学物理研究所 Preparation method of aviation kerosene or diesel oil scope liquid alkane
US20180370896A1 (en) * 2015-07-20 2018-12-27 Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences Methyl acetate preparation method
CN107673959A (en) * 2017-10-27 2018-02-09 西南化工研究设计院有限公司 A kind of method and system for preparing methyl heptenone
CN108129314A (en) * 2017-12-20 2018-06-08 沈阳化工大学 By the method for ethylene carbonate, methanol and ethyl alcohol one-step synthesis methyl ethyl carbonate
CN113877562A (en) * 2020-07-03 2022-01-04 中国石油化工股份有限公司 Solid base catalyst for synthesizing methyl acrylate and preparation method and application thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
ANNA 等: "Impact of Bronsted acid sites in MWW zeolites modified with cecium and amine species on Knoevenagel condensation", 《MICROPOROUS AND MESOPOROUS MATERIALS》, vol. 280, 12 February 2019 (2019-02-12), pages 288 - 296, XP085620659, DOI: 10.1016/j.micromeso.2019.02.007 *
宋华民;徐桂转;张百良;: "固体碱催化制备生物柴油的研究进展", 安徽农业科学, no. 05, 10 February 2008 (2008-02-10), pages 2005 - 2007 *
许慎敏: "固体碱催化合成生物柴油基本规律的研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, 15 March 2009 (2009-03-15), pages 18 - 19 *
雷经新, 石秋杰: "固体碱催化剂在有机合成中的应用及进展", 化工时刊, no. 02, 25 February 2005 (2005-02-25), pages 51 - 55 *

Similar Documents

Publication Publication Date Title
Corma et al. One-step synthesis of citronitril on hydrotalcite derived base catalysts
Climent et al. Synthesis of pseudoionones by acid and base solid catalysts
CN106582788B (en) A kind of modified zsm-5 zeolite and preparation method and catalysis prepare the synthetic method of 3- methyl-3-butene-1-alcohol
CN103221380B (en) Process for production of methacrylic acid ester
WO2016135605A1 (en) Process for the dehydration of oxygenated compounds
CN109534977A (en) One kind synthesizing α, γ-unsaturation dienone method and the catalyst for this method by propargyl alcohol
CN103130768B (en) Preparation method of compound with 1,3-dioxane structure
CN111187149B (en) Method for preparing 2-alkoxy propylene
JP5705236B2 (en) A novel method for the synthesis of acrolein from glycerol
CN111215138A (en) catalyst, preparation method and application of catalyst in preparation of β -isophorone
CN114656345A (en) Synthesis method of 4-methyl-1-pentene
CN116212943A (en) Preparation method of novel alkaline catalyst and application of novel alkaline catalyst in preparation of methyl heptenone
CN107722030B (en) Method for preparing isohexide
CN112898156B (en) Method for recovering 1- (3, 3-dimethylcyclohexyl) ethanol and method for preparing musk eden
Sato et al. Synthesis of α-Hydroxy Ketones from Vicinal Diols by Selective Dehydrogenation over Ir–ReO x/SiO2 Catalyst
CN111217704B (en) Method for preparing butyl butyrate by directly catalyzing and converting n-butyraldehyde
US4694107A (en) Preparation of ketones by isomerization of aldehydes
CN113698284B (en) Synthesis method of pseudo ionone
CN108299171B (en) Method for synthesizing methyl heptenone from 2-methyl-3-butene-2-ol
CN112961051A (en) Method for purifying methyl 3-methoxypropionate
CN109134485B (en) Method for preparing isosorbide
WO2015095999A1 (en) Method for preparing polyoxymethylene dimethyl ether carbonyl compound and methyl methoxyacetate
CN111992200B (en) Lithium doped solid base catalyst and preparation method and application thereof
CN109608426B (en) Method for synthesizing lilypan by using waste liquid from citral production as raw material
CN110479257B (en) Catalyst and preparation method thereof, and hydrogenation treatment method of vanillin tar

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