CN111939966A - Alkaline molecular sieve catalyst, preparation method thereof and application thereof in synthesis of N-methylmorpholine oxide - Google Patents

Alkaline molecular sieve catalyst, preparation method thereof and application thereof in synthesis of N-methylmorpholine oxide Download PDF

Info

Publication number
CN111939966A
CN111939966A CN202010854450.2A CN202010854450A CN111939966A CN 111939966 A CN111939966 A CN 111939966A CN 202010854450 A CN202010854450 A CN 202010854450A CN 111939966 A CN111939966 A CN 111939966A
Authority
CN
China
Prior art keywords
molecular sieve
methylmorpholine
sieve catalyst
basic
methylmorpholine oxide
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.)
Granted
Application number
CN202010854450.2A
Other languages
Chinese (zh)
Other versions
CN111939966B (en
Inventor
邢波
宋翔
杨郭
刘兴勇
王斌
罗文�
叶宇玲
莫莎
兰勇
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.)
SICHUAN INSTITUTE OF FINE CHEMICAL INDUSTRY RESEARCH AND DESIGN
Sichuan University of Science and Engineering
Original Assignee
SICHUAN INSTITUTE OF FINE CHEMICAL INDUSTRY RESEARCH AND DESIGN
Sichuan University of Science and Engineering
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 SICHUAN INSTITUTE OF FINE CHEMICAL INDUSTRY RESEARCH AND DESIGN, Sichuan University of Science and Engineering filed Critical SICHUAN INSTITUTE OF FINE CHEMICAL INDUSTRY RESEARCH AND DESIGN
Priority to CN202010854450.2A priority Critical patent/CN111939966B/en
Publication of CN111939966A publication Critical patent/CN111939966A/en
Application granted granted Critical
Publication of CN111939966B publication Critical patent/CN111939966B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • 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
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/22—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with hetero atoms directly attached to ring nitrogen atoms
    • C07D295/24—Oxygen 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
    • 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 basic molecular sieve, a preparation method thereof and application thereof in synthesizing N-methylmorpholine oxide. When the basic molecular sieve catalyst is prepared, the molecular sieve carrier is firstly put into an alkali metal salt solution for dipping, then dried and calcined in a nitrogen atmosphere, thus obtaining the basic molecular sieve catalyst. When preparing N-methylmorpholine oxide, mixing the prepared basic molecular sieve catalyst with N-methylmorpholine, then introducing ozone into the mixture, controlling the reaction temperature to be 30-90 ℃, and reacting for 3-9 hours to obtain the N-methylmorpholine oxide. The invention provides a basic molecular sieve, a preparation method thereof and application thereof in preparing N-methylmorpholine oxide (NMMO), wherein ozone is used for replacing H2O2The alkaline molecular sieve catalyst provided by the invention effectively improves the conversion rate and selectivity of the NMMO synthesized by ozone catalytic oxidation.

Description

Alkaline molecular sieve catalyst, preparation method thereof and application thereof in synthesis of N-methylmorpholine oxide
Technical Field
The invention belongs to the technical field of catalytic oxidation synthesis, and particularly relates to an alkaline molecular sieve, a preparation method thereof and application thereof in synthesizing N-methylmorpholine oxide.
Background
N-methylmorpholine N-oxide (NMMO) is a solvent commonly used for preparing Lyocell fibers, the yield of the Lyocell fibers exceeds that of the terylene of the current chemical fiber variety with the largest yield, the economic benefit is remarkable, and the further development of the NMMO is inevitably driven. NMMO is a tertiary amine oxide, and H is used as the main process for industrially synthesizing NMMO2O2As an oxidant, N-methylmorpholine (NMM) is catalytically oxidized under the action of a basic catalyst to synthesize NMMO. Most of the traditional base catalysis reaction adopts NaOH, KOH or Na2CO3The solution is used as a catalyst to carry out catalytic reaction. However, the process has major problems: (1) h2O2Easy decomposition and difficult storage, obtains high-quality NMMO, needs to add excessive oxidant into a reaction system, and increases the risk of cost and production safety; (2) h for reaction2O2A certain amount of water is brought into the reaction, so that the pressure of the subsequent rectification is increased; (3) the liquid catalyst is difficult to separate from the product, and has great industrial limitation. Therefore, the development of the efficient synthesis process of the NMMO has important practical significance for the development of the textile industry, and simultaneously provides raw material support for the rapid development of Lyocell fibers in China.
Disclosure of Invention
Aiming at the prior art, the invention provides a basic molecular sieve, a preparation method thereof and application thereof in synthesizing N-methylmorpholine oxide (NMMO), wherein ozone is used for replacing H2O2And the introduction of moisture is avoided. The alkaline molecular sieve catalyst provided by the invention effectively improves the conversion rate and selectivity of the NMMO synthesized by ozone catalytic oxidation.
In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of a basic molecular sieve catalyst is provided, which comprises the following steps:
s1: putting the molecular sieve carrier into an alkali metal salt solution with the concentration of 0.1-1 mol/L for soaking for 0.5-3 h, filtering, and drying at 75-85 ℃ for 10-15 h to obtain an alkaline molecular sieve precursor; the mass ratio of the molecular sieve carrier to the solute of the alkali metal salt solution is 100: 5-20;
in N2And under protection, calcining the alkaline molecular sieve precursor at 400-650 ℃ for 2-4 h to obtain the alkaline molecular sieve catalyst.
On the basis of the technical scheme, the invention can be further improved as follows.
Furthermore, the molecular sieve carrier is an MCM-41 mesoporous molecular sieve or an SBA-15 mesoporous molecular sieve.
Further, the solute of the alkali metal salt solution is MgCl2、CaCl2、Ca(NO3)2、SrCl2、Sr(NO3)2、RbCl、RbNO3、AlCl3、Al(NO3)3、TiCl4、Cs2CO3Or Ti (NO)3)4。
The method of the invention can obtain the basic molecular sieve catalyst with excellent catalytic performance. The basic metal salt shows excellent catalytic activity in olefin epoxidation, alcohol oxidation, aniline oxidation and a process for synthesizing tertiary amine oxide, and the basic metal salt is used as a main active component and loaded on a medium-pore molecular sieve. The mesoporous molecular sieve material not only has excellent properties of large specific surface area, developed pore structure, easy-to-regulate surface property, hydrothermal resistance and the like, but also has larger pore diameter compared with the traditional microporous molecular sieve, thereby being more beneficial to the mass transfer of reactants and products. Therefore, after the mesoporous molecular sieve is loaded with the alkaline metal salt, the dispersion degree of the alkaline metal salt on the mesoporous molecular sieve can be improved, the number of catalytic active sites of the mesoporous molecular sieve is increased, and the catalytic activity is obviously improved.
The basic molecular sieve catalyst prepared by the invention can be used for olefin epoxidation, alcohol oxidation, aniline oxidation and a process for synthesizing tertiary amine oxide. Particularly, the method has higher yield for synthesizing the N-methylmorpholine oxide, and the quality of the obtained product can be well ensured. The method for synthesizing N-methylmorpholine oxide by adopting the basic molecular sieve catalyst comprises the following steps:
s1: uniformly mixing an alkaline molecular sieve catalyst and N-methylmorpholine according to a mass ratio of 0.1-5: 100 to obtain a reaction substrate;
s2: and continuously introducing ozone into the reaction substrate at the speed of 20-50 mL/min under normal pressure, controlling the reaction temperature to be 30-90 ℃, and reacting for 3-9 hours to obtain the N-methylmorpholine oxide.
The preparation of the N-methylmorpholine oxide can be improved as follows on the basis of the technical scheme.
Further, the mass ratio of the basic molecular sieve catalyst to the N-methylmorpholine in the reaction substrate is 1: 100.
Further, the introduction rate of ozone in S2 is 40 mL/min; the reaction temperature was 60 ℃.
In the invention, alkaline molecular sieve is adopted to catalyze ozone to replace homogeneous catalyst to catalyze H2O2Can effectively solve the problems existing in the prior art. Alkaline molecular sieve catalyzed ozone compared with homogeneous catalyst for catalyzing H2O2Has the advantages that: (1) ozone is a gaseous substance, and does not bring moisture into the reaction; (2) ozone oxidation ratio H2O2The method has the advantages that the use cost of the oxidant is saved and the reaction time is shortened under the same reaction condition, so that the generation of side reactions of the NMMO is further reduced, and the quality of the NMMO is improved; (3) the basic molecular sieve is a kind of one kind of gathering agentCompared with a liquid alkali homogeneous catalyst, the heterogeneous catalyst has the advantages of strong alkalinity, easy separation after reaction, high catalytic selectivity, small corrosion to equipment and recycling.
The invention has the beneficial effects that:
1. the invention adopts the basic molecular sieve catalyst, and since the basic metal salt is used as a basic catalyst, the basic molecular sieve catalyst is commonly used for the base catalytic reaction (olefin epoxidation, alcohol oxidation, aniline oxidation, synthesis of tertiary amine oxide and the like); meanwhile, the molecular sieve carrier has rich pore structure and large specific surface area, thereby effectively easing reaction conditions and improving the activity of synthesizing N-methylmorpholine oxide by catalytic oxidation of ozone.
2. The invention adopts ozone to replace H2O2Catalytic oxidation synthesis of N-methyl morpholine oxide, ozone being compared with H2O2The oxidizing property is stronger, the subsequent separation and purification are easy, and the generated wastewater is less.
3. The method for synthesizing N-methylmorpholine oxide by catalyzing ozone oxidation based on the alkaline molecular sieve is simple, easy to operate and suitable for industrial production.
Detailed Description
The following examples are provided to illustrate specific embodiments of the present invention.
Example 1
A process for synthesizing N-methylmorpholine oxide includes preparing basic molecular sieve catalyst and synthesizing N-methylmorpholine oxide. Wherein, the synthesis of the basic molecular sieve catalyst comprises the following steps:
s1: placing a molecular sieve carrier MCM-41 mesoporous molecular sieve into Cs with the concentration of 0.25mol/L2CO3Soaking the solution for 0.5h, filtering, and drying at 80 ℃ for 12h to obtain an alkaline molecular sieve precursor; MCM-41 mesoporous molecular sieve and Cs2CO3Cs in solution2CO3The ratio of the mass of (a) to (b) is shown in table 1;
s2: in N2And under protection, calcining the precursor of the basic molecular sieve at 500 ℃ for 3h to obtain the basic molecular sieve catalyst.
The method for preparing N-methylmorpholine oxide by using the prepared basic molecular sieve catalyst comprises the following steps:
s1: uniformly mixing an alkaline molecular sieve catalyst and N-methylmorpholine according to a mass ratio of 1:100 to obtain a reaction substrate;
s2: under normal pressure, continuously introducing ozone into a reaction substrate at the speed of 50mL/min, controlling the reaction temperature to be 30 ℃, and reacting for 4 hours to obtain the N-methylmorpholine oxide.
TABLE 1 influence of basic molecular sieve catalysts on N-methylmorpholine conversion and N-methylmorpholine oxide selectivity
MCM-41 and Cs2CO3Mass ratio of Conversion of N-methylmorpholine (%) N-methylmorpholine oxide selectivity (%)
100:0 54.8 72.6
100:5 69.2 81.3
100:10 78.1 84.2
100:15 87.1 94.6
100:20 82.3 91.7
The high performance liquid chromatography analysis of the conversion rate of N-methylmorpholine (NMM) and the selectivity of N-methylmorpholine oxide (NMMO) under 5 basic molecular sieve catalysts shows that (Table 1 above), when NMMO is prepared by simply adopting a molecular sieve (100:0) without loading alkali metal, the conversion rate of NMM and the selectivity of NMMO are both low, because few catalytic active sites exist on the molecular sieve, the reaction of NMM and ozone cannot be promoted. When MCM-41 and Cs2CO3When the mass ratio of (A) to (B) is 100: 5-100: 15, the conversion rate of N-methylmorpholine and the selectivity of N-methylmorpholine oxide show an increasing trend along with the increase of the alkali content on the molecular sieve, which shows that the introduction of alkaline metal on the molecular sieve carrier is favorable for improving the activity of the alkaline molecular sieve for catalyzing the ozone oxidation to synthesize the N-methylmorpholine oxide. When MCM-41 and Cs2CO3When the mass ratio of (a) to (b) exceeds 100:15, a large amount of alkali metal is attached to the molecular sieve, which not only does not improve the reaction efficiency, but also causes problems such as catalyst poisoning and the like, but also reduces the conversion rate of NMM and the selectivity of NMMO.
Example 2
A process for synthesizing N-methylmorpholine oxide includes preparing basic molecular sieve catalyst and synthesizing N-methylmorpholine oxide. Wherein, the synthesis of the basic molecular sieve catalyst comprises the following steps:
s1: putting a molecular sieve carrier SBA-15 mesoporous molecular sieve into RbNO with the concentration of 0.5mol/L3Soaking the solution for 1h, filtering, and drying at 80 ℃ for 12h to obtain an alkaline molecular sieve precursor; SBA-15 mesoporous molecular sieve and RbNO3RbNO in solution3The mass ratio of (A) to (B) is 100: 10;
s2: in N2And under protection, calcining the basic molecular sieve precursor at the temperature shown in the table 2 for 3 hours to obtain the basic molecular sieve catalyst.
The method for preparing N-methylmorpholine oxide by using the prepared basic molecular sieve catalyst comprises the following steps:
s1: uniformly mixing an alkaline molecular sieve catalyst and N-methylmorpholine according to a mass ratio of 5:100 to obtain a reaction substrate;
s2: under normal pressure, continuously introducing ozone into a reaction substrate at the speed of 40mL/min, controlling the reaction temperature to be 40 ℃, and reacting for 5 hours to obtain the N-methylmorpholine oxide.
TABLE 2 influence of temperature on the conversion of N-methylmorpholine and the selectivity of N-methylmorpholine oxide
Figure BDA0002645893760000051
Figure BDA0002645893760000061
The high performance liquid chromatography analysis of the conversion rate of N-methylmorpholine and the selectivity of N-methylmorpholine oxide under 5 basic molecular sieve catalysts (Table 2 above) shows that the conversion rate of NMM and the selectivity of NMMO are low at a calcination temperature of 300 ℃, because the temperature is low, and stable catalytic active sites are not sufficiently formed on the surface of the molecular sieve during the calcination process, so that the catalytic efficiency is low during the reaction process. When the calcination temperature is 400-600 ℃, the conversion rate of the N-methylmorpholine and the selectivity of the N-methylmorpholine oxide show an increasing trend along with the increase of the calcination temperature, which shows that the increase of the calcination temperature is beneficial to improving the activity of the alkaline molecular sieve for catalyzing the ozone oxidation to synthesize the N-methylmorpholine oxide. After the calcination temperature exceeds 600 ℃, the structure of the molecular sieve can be damaged in the calcination process, and meanwhile, the adhesion state of alkali metal on the molecular sieve is changed, so that the catalytic activity of the basic molecular sieve catalyst is reduced, and further the conversion rate of NMM and the selectivity of NMMO are influenced.
Example 3
A process for synthesizing N-methylmorpholine oxide includes preparing basic molecular sieve catalyst and synthesizing N-methylmorpholine oxide. Wherein, the synthesis of the basic molecular sieve catalyst comprises the following steps:
s1: will be provided withSrCl with the concentration of 1mol/L is put into a molecular sieve carrier SBA-15 mesoporous molecular sieve2Soaking the solution for 0.5h, filtering, and drying at 75 ℃ for 15h to obtain an alkaline molecular sieve precursor; SBA-15 mesoporous molecular sieve and SrCl2SrCl in solution2The mass ratio of (A) to (B) is 100: 10;
s2: in N2And under protection, calcining the precursor of the basic molecular sieve at 500 ℃ for 4h to obtain the basic molecular sieve catalyst.
The method for preparing N-methylmorpholine oxide by using the prepared basic molecular sieve catalyst comprises the following steps:
s1: uniformly mixing an alkaline molecular sieve catalyst and N-methylmorpholine according to the mass ratio shown in the table 3 to obtain a reaction substrate;
s2: under normal pressure, continuously introducing ozone into a reaction substrate at the speed of 45mL/min, controlling the reaction temperature at 50 ℃, and reacting for 4 hours to obtain the N-methylmorpholine oxide.
TABLE 3 influence of the mass ratio of basic molecular sieves to N-methylmorpholine on the conversion of N-methylmorpholine and the selectivity of N-methylmorpholine oxide
Mass ratio of basic molecular sieve to N-methylmorpholine Conversion of N-methylmorpholine (%) N-methylmorpholine oxide selectivity (%)
0.1:100 47.2 66.4
1:100 69.8 78.3
2:100 77.6 84.1
3.5:100 82.5 95.12
5:100 88.2 98.7
The high performance liquid chromatography is used for analyzing the N-methylmorpholine conversion rate and the N-methylmorpholine oxide selectivity under the mass ratio of 5 basic molecular sieve catalysts to N-methylmorpholine (shown in the table 3), wherein the mass ratio is 0.1-5: 100, more basic molecular sieve catalysts are added to facilitate the increase of the N-methylmorpholine conversion rate and the N-methylmorpholine oxide selectivity, and the improvement of the addition of the basic molecular sieves is beneficial to the improvement of the activity of the basic molecular sieves for catalyzing ozone oxidation to synthesize the N-methylmorpholine oxide.
Example 4
A process for synthesizing N-methylmorpholine oxide includes preparing basic molecular sieve catalyst and synthesizing N-methylmorpholine oxide. Wherein, the synthesis of the basic molecular sieve catalyst comprises the following steps:
s1: putting a molecular sieve carrier MCM-41 mesoporous molecular sieve into CaCl with the concentration of 0.1mol/L2Soaking the solution for 3h, filtering and drying at 85 ℃ for 10h to obtain an alkaline molecular sieve precursor; SBA-15 mesoporous molecular sieve and CaCl2CaCl in solution2The mass ratio of (A) to (B) is 100: 15;
s2: in N2And under protection, calcining the precursor of the basic molecular sieve at 400 ℃ for 4h to obtain the basic molecular sieve catalyst.
The method for preparing N-methylmorpholine oxide by using the prepared basic molecular sieve catalyst comprises the following steps:
s1: uniformly mixing an alkaline molecular sieve catalyst and N-methylmorpholine according to a mass ratio of 3:100 to obtain a reaction substrate;
s2: under normal pressure, continuously introducing ozone into the reaction substrate at the speed of 35mL/min, controlling the reaction temperature to be 80 ℃, and reacting under the reaction time shown in the table 4 to obtain the N-methylmorpholine oxide.
TABLE 4 influence of reaction time on N-methylmorpholine conversion and N-methylmorpholine oxide selectivity
Reaction time (hours) Conversion of N-methylmorpholine (%) N-methylmorpholine oxide selectivity (%)
3 49.4 65.7
5 89.2 94.3
7 92.6 98.5
9 84.5 93.8
The conversion rate of N-methylmorpholine (NMM) and the selectivity of N-methylmorpholine oxide (NMMO) in 4 reaction times are analyzed through high performance liquid chromatography, and when the reaction time is 3-7 hours, the conversion rate of N-methylmorpholine and the selectivity of N-methylmorpholine oxide show an increasing trend along with the increase of the reaction time, which indicates that the increase of the reaction time is beneficial to improving the activity of synthesizing N-methylmorpholine oxide through catalytic ozonation by using an alkaline molecular sieve. When the reaction time exceeds 7 hours, side reactions increase, which not only does not improve the reaction efficiency, but also reduces the conversion rate of NMM and the selectivity of NMMO.
While the present invention has been described in detail with reference to the embodiments, it should not be construed as limited to the scope of the patent. Various modifications and changes may be made by those skilled in the art without inventive step within the scope of the appended claims.

Claims (8)

1. A preparation method of a basic molecular sieve catalyst is characterized by comprising the following steps: the method comprises the following steps:
s1: putting the molecular sieve carrier into an alkali metal salt solution with the concentration of 0.1-1 mol/L for soaking for 0.5-3 h, filtering, and drying at 75-85 ℃ for 10-15 h to obtain an alkaline molecular sieve precursor; the mass ratio of the molecular sieve carrier to the solute of the alkali metal salt solution is 100: 5-20;
s2: in N2And under protection, calcining the alkaline molecular sieve precursor at 400-650 ℃ for 2-4 h to obtain the alkaline molecular sieve catalyst.
2. The method of claim 1, wherein: the molecular sieve carrier is an MCM-41 mesoporous molecular sieve or an SBA-15 mesoporous molecular sieve.
3. The method of claim 1, wherein: the solute of the alkali metal salt solution is MgCl2、CaCl2、Ca(NO3)2、SrCl2、Sr(NO3)2、RbCl、RbNO3、AlCl3、Al(NO3)3、TiCl4、Cs2CO3Or Ti (NO)3)4。
4. The basic molecular sieve catalyst prepared by the preparation method of any one of claims 1 to 3.
5. The use of the basic molecular sieve catalyst of claim 4 in the synthesis of N-methylmorpholine-N-oxide.
6. Use according to claim 5, characterized in that it comprises the following steps:
s1: uniformly mixing an alkaline molecular sieve catalyst and N-methylmorpholine according to a mass ratio of 0.1-5: 100 to obtain a reaction substrate;
s2: and continuously introducing ozone into the reaction substrate at the speed of 20-50 mL/min under normal pressure, controlling the reaction temperature to be 30-90 ℃, and reacting for 3-9 hours to obtain the N-methylmorpholine oxide.
7. Use according to claim 6, characterized in that: the mass ratio of the basic molecular sieve catalyst to the N-methylmorpholine in the reaction substrate is 1: 100.
8. Use according to claim 6, characterized in that: the ozone introducing speed in the S2 is 40 mL/min; the reaction temperature was 60 ℃.
CN202010854450.2A 2020-08-24 2020-08-24 Alkaline molecular sieve catalyst, preparation method thereof and application thereof in synthesis of N-methylmorpholine oxide Active CN111939966B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010854450.2A CN111939966B (en) 2020-08-24 2020-08-24 Alkaline molecular sieve catalyst, preparation method thereof and application thereof in synthesis of N-methylmorpholine oxide

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010854450.2A CN111939966B (en) 2020-08-24 2020-08-24 Alkaline molecular sieve catalyst, preparation method thereof and application thereof in synthesis of N-methylmorpholine oxide

Publications (2)

Publication Number Publication Date
CN111939966A true CN111939966A (en) 2020-11-17
CN111939966B CN111939966B (en) 2023-03-31

Family

ID=73359906

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010854450.2A Active CN111939966B (en) 2020-08-24 2020-08-24 Alkaline molecular sieve catalyst, preparation method thereof and application thereof in synthesis of N-methylmorpholine oxide

Country Status (1)

Country Link
CN (1) CN111939966B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113604823A (en) * 2021-09-13 2021-11-05 四川之江高新材料股份有限公司 Method for producing N-methyl morpholine oxide

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1043096A (en) * 1988-11-23 1990-06-20 国际壳牌研究有限公司 Basic metal-zeolite compositions, its method for making and the application in base catalyzed reactions thereof
US5403800A (en) * 1993-05-28 1995-04-04 Mobil Oil Corp. Multiple impregnation technique for the preparation of ex situ selectivated zeolite catalysts
CN110088064A (en) * 2016-12-23 2019-08-02 奥若泰克股份有限公司 Amine oxide is prepared by the oxidation of tertiary amine
CN110283145A (en) * 2019-07-22 2019-09-27 山东英利实业有限公司 A kind of preparation method of N-methylmorpholine-N- oxide
CN110467587A (en) * 2019-08-30 2019-11-19 四川轻化工大学 One kind being catalyzed O based on ruthenium/N doping porous carbon2The method of oxidative synthesis N- methyl morpholine oxide

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1043096A (en) * 1988-11-23 1990-06-20 国际壳牌研究有限公司 Basic metal-zeolite compositions, its method for making and the application in base catalyzed reactions thereof
US5403800A (en) * 1993-05-28 1995-04-04 Mobil Oil Corp. Multiple impregnation technique for the preparation of ex situ selectivated zeolite catalysts
CN110088064A (en) * 2016-12-23 2019-08-02 奥若泰克股份有限公司 Amine oxide is prepared by the oxidation of tertiary amine
CN110283145A (en) * 2019-07-22 2019-09-27 山东英利实业有限公司 A kind of preparation method of N-methylmorpholine-N- oxide
CN110467587A (en) * 2019-08-30 2019-11-19 四川轻化工大学 One kind being catalyzed O based on ruthenium/N doping porous carbon2The method of oxidative synthesis N- methyl morpholine oxide

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
李露等: "中孔分子筛催化剂的研究进展", 《现代化工》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113604823A (en) * 2021-09-13 2021-11-05 四川之江高新材料股份有限公司 Method for producing N-methyl morpholine oxide
CN113604823B (en) * 2021-09-13 2022-06-24 四川之江高新材料股份有限公司 Method for producing N-methyl morpholine oxide

Also Published As

Publication number Publication date
CN111939966B (en) 2023-03-31

Similar Documents

Publication Publication Date Title
CN110467587B (en) Based on ruthenium/nitrogen doped porous carbon catalysis O2Method for synthesizing N-methylmorpholine oxide by oxidation
CN103896302A (en) Silicon molecular sieve and preparation method thereof
CN111939966B (en) Alkaline molecular sieve catalyst, preparation method thereof and application thereof in synthesis of N-methylmorpholine oxide
CN103182322A (en) Treatment method of inactivated titanium silicon molecular sieve
CN107445831B (en) Process for producing glyoxylic acid esters
CN112206808B (en) Catalyst for synthesizing isobutyl isobutyrate and preparation method and application thereof
CN111909116B (en) Method for synthesizing N-methylmorpholine oxide by catalytic oxidation
CN110170333B (en) Catalyst for preparing ethylene from ethane in carbon dioxide atmosphere and preparation method thereof
CN110498778B (en) Method for preparing cyclohexene oxide by epoxidation of cyclohexene
CN112206811A (en) Catalyst for preparing propylene by methanol conversion and preparation method and application thereof
CN112237946A (en) Terephthalic acid hydrofining reaction and catalyst thereof
CN113694916B (en) Method for synthesizing paranitroaniline based on hierarchical pore carbon fiber supported phase transfer catalyst
CN103508845A (en) Method for oxidizing cyclohexane
CN1218915C (en) Solid acid catalyst for preparing ethylene glycol by ethylene oxide hydration
CN114054079B (en) Preparation method and application of catalyst for preparing acetaldehyde by ethanol dehydrogenation
CN101148397B (en) Method for preparing dimethyl ether
CN114425367B (en) Catalyst system for preparing acrylic ester by carbonylation of acetylene, preparation and application thereof
CN1218917C (en) Process for preparing ethylene glycol by ethylene oxide catalytic hydration
CN103664486A (en) Method for preparing ethylbenzene from benzene and ethylene
CN108586202B (en) Synthesis method of intermediate 4-phenylbutanol
CN112299959A (en) Method for preparing diethoxymethane by solid superacid catalysis
CN114632539B (en) Catalyst for preparing acetonitrile by ammonification and dehydrogenation of ethanol, and preparation method and application thereof
CN113461652B (en) Method for preparing epsilon-caprolactone by catalytically oxidizing cyclohexanone in presence of molecular oxygen
CN114618567B (en) Ytterbium strontium barium supported catalyst and preparation method and application thereof
CN113042025B (en) Non-metal porous carbon material catalyst prepared by taking saccharides as raw materials and preparation method and application thereof

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