CN111187149B - Method for preparing 2-alkoxy propylene - Google Patents

Method for preparing 2-alkoxy propylene Download PDF

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CN111187149B
CN111187149B CN202010097822.1A CN202010097822A CN111187149B CN 111187149 B CN111187149 B CN 111187149B CN 202010097822 A CN202010097822 A CN 202010097822A CN 111187149 B CN111187149 B CN 111187149B
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CN111187149A (en
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杨宗龙
张涛
吕英东
林龙
刘英瑞
郭劲资
张旭
程晓波
王延斌
朱龙龙
李莉
宋军伟
翟文超
黎源
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Wanhua Chemical Group Nutrition Technology Co.,Ltd.
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B01J23/04—Alkali metals
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • 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
    • B01J2229/37—Acid treatment
    • 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
    • B01J2229/42—Addition of matrix or binder particles
    • 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
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    • Y02P20/584—Recycling of catalysts

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Abstract

The present invention relates to a process for preparing 2-alkoxypropylene, comprising: in the presence of a modified Y-type molecular sieve catalyst and an alkaline carrier, a raw material 2,2-dialkoxypropane carries out cracking reaction in a tower reactor, 2-alkoxy propylene is collected from the top of the tower reactor, and the filling mode of the modified Y-type molecular sieve catalyst and the alkaline carrier in the tower reactor is as follows: the tower reactor is divided into three sections according to the length, and the modified Y-type molecular sieve catalyst, the mixture of the modified Y-type molecular sieve catalyst and the alkaline carrier are respectively filled from bottom to top. The method has the advantages of high conversion rate of cracking reaction, high selectivity and less by-products; the service life of the catalyst is long, and the catalytic activity is not obviously reduced after more than 3000 hours; in addition, the catalyst can be regenerated, so that the consumption of the catalyst is reduced, the generation of three wastes is reduced, and the method is a green and environment-friendly new method for synthesizing the 2-alkoxy propylene.

Description

Method for preparing 2-alkoxy propylene
Technical Field
The invention relates to a method for preparing 2-alkoxy propylene, in particular to a novel green and environment-friendly method which takes modified acidic Y-type molecular sieve and alkaline carrier as catalysts and 2,2-dialkoxy propane as raw materials to carry out cracking reaction at a certain temperature and pressure to synthesize the 2-alkoxy propylene.
Background
2-alkoxy propylene is an important chemical raw material, and the chemical property of the 2-alkoxy propylene is very active because the molecule contains bifunctional groups: a double bond and an ether linkage, which gives it the general properties of both olefins and ethers. 2-alkoxy propylene has wide application, and is commonly used as a solvent and an auxiliary agent in the paint, textile and leather industries; also commonly used as key intermediates for the synthesis of medicines, foods and feeds; in addition, the compounds are also commonly used as protective agents for hydroxyl, oximido and amino groups in the synthesis of drug molecules and as protective agents, cyclizing agents, condensing agents and the like in the application of sugar chemistry. Wherein, 2-methoxy propylene is the most important alkenyl ether compound with the most extensive application, and is applied to synthesizing compounds such as clarithromycin, pseudoionone, ionone, vitamin A, vitamin E, vitamin K2 and the like in industrial production.
The technical literature for synthesizing 2-alkoxy propylene is more, and the method is mainly divided into three types: alkynol addition method, aldol synthesis method and ketal cracking method, wherein the aldol synthesis method is only reported in literature at present, and no industrial production is reported. The alkynol addition method is to perform addition reaction on propyne or allene and small molecular alcohol under the action of a catalyst (usually strong alkali) at a certain temperature and pressure. The alkynol addition method has the advantages that only one-step reaction is needed, and the yield is about 70 percent; the disadvantages are that strong base catalyst is corrosive to equipment at high temperature, and the source of propyne or propadiene is difficult.
The ketal cracking method is to prepare 2-alkoxy propylene by using 2,2-dialkoxy propane as a raw material and cracking at high temperature in the presence of a catalyst. The prior ketal cracking method mainly comprises a gas phase cracking method and a liquid phase cracking method. For the liquid phase cracking method, hydrocarbons are mostly adopted as solvent in the early period, sulfonic acid is taken as catalyst to carry out reaction, and the mode of aftertreatment is troublesome. The liquid phase cracking method reported at present mainly adopts fatty acid such as neononanoic acid or aromatic acid such as benzoic acid as a catalyst, and acetic anhydride, succinic anhydride and the like are added into a reaction system as absorbents of cracking by-product small molecular alcohols to promote the reaction. For example, CN1850760A reports that benzoic acid and pyridine are mixed for catalysis, ethylene glycol dimethyl ether is used as a reaction solvent, phthalic anhydride is added as a small molecular alcohol absorbent to prepare 2-alkoxy propylene, and the 2-alkoxy propylene is reacted for 0.25 to 2 hours at the temperature of between 120 and 145 ℃. Compared with a gas phase cracking method, the liquid phase cracking method has the advantage of low reaction temperature, but increases the recovery work of corresponding ester, and simultaneously, reaction products have the problems of difficult separation, high acid anhydride price and easy impurity carrying in reaction, so the process competitiveness of the liquid phase cracking method still has certain question.
The most widely used method for preparing 2-alkoxy propylene in industry is gas phase cracking method. Patent US3218359 reports the preparation of 2-alkoxypropylene by gas phase cracking reaction at 300 ℃ using magnesium pyrophosphate as catalyst; similarly, wolfgang et al reported that 90% conversion of the starting material and selectivity of the reaction were obtained using an aluminum phosphate salt as the catalyst at 300-350 deg.C. CN1660742A reports a process for continuously preparing 2-alkoxy propylene at 120-160 ℃ and 2atm pressure by using acidic materials such as acidic ceramics, cationic resin, heteropoly acid and the like as catalysts. The process has the advantages that the catalyst can be simultaneously used as a separating agent, and the reaction rectification technology is adopted, so that the reaction flow is simplified; the disadvantages are low yield of product and many by-products. Compared with the general cracking reaction by adopting an acid catalyst, US5767325A reports that in an alkaline environment, a self-made ZSM-5 type molecular sieve is adopted as the catalyst to react at 280-340 ℃,2,2-dimethoxypropane is adopted as a raw material, the conversion rate and the selectivity of a product 2-methoxypropene are both about 90%, and the activity of the catalyst is not obviously reduced after the catalyst is repeatedly used; the US6211416 also adopts ZSM-5 molecular sieve catalyst, adds propine and propadiene in cracking raw material, and increases conversion rate and once-through yield of raw material. In summary, the gas phase cracking method has the advantages of high reaction conversion rate and simple operation; the disadvantages are that the reaction needs high temperature, which is above 300 ℃, thus causing more side reactions, great separation difficulty and raising the requirement for equipment.
Disclosure of Invention
The invention aims to provide a novel synthesis process of 2-alkoxy propylene, which has high conversion rate and selectivity, less byproducts and low production cost.
The invention achieves the above purpose through the following scheme:
the process for preparing 2-alkoxy propylene comprises the following steps: the raw material 2,2-dialkoxypropane is subjected to cracking reaction in a reactor, the filling mode of a catalyst in the reactor is a mode that a modified Y-type molecular sieve catalyst and an alkaline carrier are mixed and loaded according to a certain proportion, and 2-alkoxy propylene is collected from the top of the reactor.
In the invention, the structure of the 2-alkoxy propylene is shown as a formula 1,
Figure BDA0002385928040000031
wherein R is a group such as methyl, ethyl, propyl, isopropyl, butyl, etc., preferably methyl, ethyl.
In the method, the modified Y-type molecular sieve catalyst is selected from one or more of a modified Y-type molecular sieve (catalyst A) treated by hydrothermal hyperstabilization-sulfuric acid, a modified Y-type molecular sieve (catalyst B) treated by hydrothermal hyperstabilization-hydrochloric acid, a modified Y-type molecular sieve (catalyst C) treated by hydrothermal hyperstabilization-acetic acid, a modified Y-type molecular sieve (catalyst D) treated by hydrothermal hyperstabilization-sulfonic acid and a modified Y-type molecular sieve (catalyst E) treated by hydrothermal hyperstabilization-p-toluenesulfonic acid.
The preparation method of the modified Y-type molecular sieve catalyst comprises the following steps:
(1) Performing ammonium salt ion exchange on a Y-type molecular sieve (preferably an NaY molecular sieve, and the silicon-aluminum ratio is between 4.22 and 10.35) in an ammonium salt aqueous solution;
(2) Carrying out hydrothermal treatment on the ammonium exchanged Y molecular sieve obtained in the step (1);
(3) Repeating the step (1) and the step (2);
(4) Drying and roasting the Y molecular sieve obtained in the step (3);
(5) Repeating the steps (1) to (4) to obtain a 'four-exchange two-roasting' hydrothermal ultra-stabilized Y-type molecular sieve;
(6) And (3) carrying out acid treatment on the Y-type molecular sieve obtained in the step (5) by using an acid-ammonium buffer solution:
(7) And (4) drying and roasting the molecular sieve obtained in the step (6) to obtain the modified Y-type molecular sieve subjected to hydrothermal hyperstabilization-acid treatment.
Taking the modified Y-type molecular sieve treated by hydrothermal hyperstabilization and sulfuric acid as an example, the specific preparation process can be as follows: 5.0g of NaY molecular sieve (the silica-alumina ratio is between 4.22 and 10.35, preferably between 4.3 and 4.5) is placed in a 100mL three-necked bottle, 6.5g of ammonium sulfate and 50mL of water are added, after heating and stirring in a water bath at 100 ℃ for 1h, filtration and washing are carried out three times, the NaY molecular sieve obtained is treated once more under the same conditions, the filter cake (the water content is about 55%) is placed in a crucible with a cover, and autothermal steam treatment is carried out at 500 to 650 ℃ for 2h. The process is repeated again to obtain the 'four-exchange two-roasting' hydrothermal ultra-stabilized NaY molecular sieve. And (2) putting 5g of the obtained hydrothermal ultra-stabilized NaY molecular sieve into a three-necked bottle, adding 50mL of ammonium sulfate solution with the concentration of 1mol/L, adding 50mL of buffer solution of sulfuric acid and ammonium sulfate (the mass ratio of 2:3), stirring for 2h, filtering, washing for three times, drying a filter cake at 120 ℃ for 4h, and roasting at 600 ℃ for 2h to obtain the hydrothermal ultra-stabilized-sulfuric acid treated modified Y-type molecular sieve (catalyst A).
The alkaline carrier is SiO treated by alkaline solution 2 The treatment method comprises the following steps: will shape SiO 2 The carrier is heated at 10-100 deg.C, preferably 80-100 deg.C, in 0.001-2 mol/L, preferably 0.1-1 mol/L alkaline solution (preferably NaOH solution, na solution) 2 CO 3 Solution, naHCO 3 Solution, KOH solution or K 2 CO 3 One of the solutions) for 1 to 12 hours, preferably 1 to 4 hours, filtered, washed and dried for later use.
The cracking reaction is carried out in a tower reactor, and the reaction temperature is usually 150-350 ℃, preferably 250-300 ℃; the reaction pressure is from atmospheric pressure to 2.0MPaG, preferably from 0.2 to 0.4MPaG.
The cracking reaction is continuously carried out in a tower reactor, and the feeding mode is that the cracking reaction is carried out from bottom to top.
The filling mode of the catalyst in the tower reactor is preferably as follows: the tower reactor is divided into three sections according to the length, and the modified Y-type molecular sieve catalyst, the mixture of the modified Y-type molecular sieve catalyst and the alkaline carrier are filled from bottom to top respectively. The filling height of each section is 1/8-1/3, preferably 1/4-1/3 of the length of the tower reactor; the loading ratio of the second-stage modified Y-type molecular sieve catalyst to the alkaline carrier is 1:4-4:1, preferably 1:1-1.5.
The filling mode has the advantages of simple reaction operation, avoiding the problems of more side reactions and low selectivity caused by single use of an acid catalyst, and improving the selectivity of a gas phase cracking method, thereby simplifying product separation.
In the present invention, 2,2-dialkoxypropane, which is a starting material, can be obtained by condensation of alcohol and acetone according to a known method, and will not be described in detail.
In the invention, the mass space velocity of the feeding speed of the raw material 2,2-dialkoxypropane relative to the total mass of the modified Y-type molecular sieve catalyst and the alkaline carrier is 0.1-10 h -1 Preferably 0.25 to 2.0 hours -1 。
The invention has the advantages that: 1) The catalyst adopts a mixture of a self-made modified acidic molecular sieve catalyst and an alkaline carrier, and has the advantages of high conversion rate of cracking reaction, high selectivity and less by-products; 2) The service life of the catalyst is long, and the catalytic activity is not obviously reduced after more than 3000 hours; 3) The catalyst can be regenerated, and the consumption of the catalyst is reduced, so that the generation of three wastes is reduced.
Detailed Description
The present invention is described in detail below with reference to examples, but the present invention should not be construed as being limited thereto.
Preparing a modified molecular sieve catalyst:
the method for preparing the modified Y-shaped molecular sieve (catalyst A) by hydrothermal hyperstabilization-sulfuric acid treatment comprises the following specific steps: 5.0g of NaY molecular sieve (silicon-aluminum ratio is 4.4) is placed in a 100mL three-necked flask, 6.5g of ammonium sulfate and 50mL of water are added, the mixture is heated and stirred in a water bath at 100 ℃ for 1 hour, then the mixture is filtered and washed for three times, the obtained NaY molecular sieve is treated under the same conditions once again, and a filter cake (the water content is about 55 percent) is placed in a crucible which is covered and is treated by autothermal steam at 570 ℃ for 2 hours. The process is repeated again to obtain the 'four-exchange two-roasting' hydrothermal ultra-stabilized NaY molecular sieve. And (2) putting 5g of the obtained super-stabilized NaY molecular sieve into a three-necked bottle, adding 50mL of ammonium sulfate solution with the concentration of 1mol/L, adding 50mL of buffer solution (with the concentration of 1 mol/L) of sulfuric acid and ammonium sulfate (with the mass ratio of 2:3), stirring for 2h, filtering, washing for three times, drying a filter cake at 120 ℃ for 4h, and roasting at 600 ℃ for 2h to obtain the modified Y-type molecular sieve (catalyst A) subjected to hydrothermal super-stabilization-sulfuric acid treatment.
Catalyst B-catalyst E:
according to the method, the types of the buffer solutions are changed (the buffer solution is acid/ammonium mass ratio 2:3, the total concentration of the buffer solution is prepared to be 1 mol/L), and the modified Y-type molecular sieve (catalyst B) treated by hydrothermal hyperstabilization-hydrochloric acid, the modified Y-type molecular sieve (catalyst C) treated by hydrothermal hyperstabilization-acetic acid, the modified Y-type molecular sieve (catalyst D) treated by hydrothermal hyperstabilization-sulfonic acid and the modified Y-type molecular sieve (catalyst E) treated by hydrothermal hyperstabilization-p-toluenesulfonic acid are respectively prepared.
Preparing an alkaline carrier:
will shape SiO 2 The carrier is heated at 85 ℃ under 0.6mol/L Na 2 CO 3 Soaking in the solution for 2.5h, filtering, washing, and drying.
Gas chromatography conditions: an Agilent gas chromatography polysiloxane column HP-5 is subjected to online measurement, the temperature of a gasification chamber is 250 ℃, the temperature of a detector is 250 ℃, and the column temperature is programmed temperature: initial temperature 40 deg.C, raising to 80 deg.C at a rate of 5 deg.C/min; then the temperature is increased to 240 ℃ at the speed of 15 ℃/min, the temperature is kept for 5min, and the sample injection amount is 0.2 mu L.
Comparative example 1
A total of 90g of catalyst A was packed in a column reactor having a length of 1m and a diameter of 0.02 m. The raw material 2,2-dimethoxypropane is fed from the bottom of the tower at the flow rate of 90g/h through a flow meter, the temperature of the bottom of the tower is controlled at 280 ℃, the pressure is 0.2MPaG, and after the gas collected at the top of the tower is cooled and rectified, 50.26g/h (the reaction conversion rate is 93.49%, the selectivity is 86.28%, and the yield is 80.66%) of the product 2-methoxypropene is collected.
Example 1
In a tower reactor with the length of 1m and the diameter of 0.02m, catalyst A is filled from the bottom to 1/3 of the tower, the filling mass is 60g, the mixture 60g of the catalyst A and the alkaline carrier with the filling mass ratio of 1:1 at 1/3-2/3 is mixed, 60g of the alkaline carrier is filled from 2/3 to the top of the tower, and 180g of the catalyst and the carrier are filled together. The raw material 2,2-dimethoxypropane is fed from the bottom of the tower at the flow rate of 90g/h through a flow meter, the temperature of the bottom of the tower is controlled at 280 ℃, the pressure is 0.2MPaG, and after cooling and rectifying the gas collected at the top of the tower, 59.81g/h (the reaction conversion rate is 98.25%, the selectivity is 97.70%, and the yield is 95.99%) of the product 2-methoxypropene is collected. The reaction was continued for 3000h without any catalyst deactivation.
Example 2
In a tower reactor with the length of 1m and the diameter of 0.02m, a mixture of catalyst B and an alkaline carrier is filled from the bottom to 1/3 of the tower, the filling mass is 40g, the filling mass ratio of 1:1 at 1/3-2/3 of the tower is 100g, the filling mass is 40g, and the catalyst and the carrier are co-filled by 180g. The raw material 2,2-dimethoxypropane is fed from the bottom of the tower at the flow rate of 70g/h through a flow meter, the temperature of the bottom of the tower is controlled at 270 ℃, the pressure is 0.3MPaG, and after cooling and rectifying the gas collected at the top of the tower, 45.29g/h (the reaction conversion rate is 97.19%, the selectivity is 96.15%, and the yield is 93.45%) of the product 2-methoxypropene is collected. The reaction was continued for 3500h without any catalyst deactivation.
Example 3
In a tower reactor with the length of 1m and the diameter of 0.02m, catalyst A is filled from the bottom to 1/3 of the tower, the filling mass is 60g, the mixture of the catalyst A and an alkaline carrier with the filling mass ratio of 1:1 at 1/3-2/3 is mixed, the filling mass is 60g, the basic carrier is filled from 2/3 to the top of the tower, the filling mass is 60g, and the catalyst and the carrier are co-filled by 180g. The raw material 2,2-diethoxypropane is fed from the bottom of the tower at the flow rate of 90g/h through a flow meter, the temperature of the bottom of the tower is controlled at 300 ℃, the pressure is 0.25MPaG, and 53.74g/h (the reaction conversion rate is 99.46%, the selectivity is 92.15%, and the yield is 91.65%) of a product 2-ethoxypropene is collected after the gas collected at the top of the tower is cooled and rectified. The reaction was continued for 3000h without any catalyst deactivation.
Example 4
In a tower reactor with the length of 1m and the diameter of 0.02m, a mixture of catalyst C and an alkaline carrier is filled from the bottom to 1/3 of the tower, the filling mass is 50g, the filling mass ratio of the catalyst C to the 1:1 at 1/3-2/3 of the tower is 80g, the filling mass is 50g, and the catalyst and the carrier are co-filled by 180g. The raw material 2,2-dimethoxypropane is fed from the bottom of the tower at the flow rate of 75g/h through a flowmeter, the temperature of the bottom of the tower is controlled at 260 ℃, the pressure is 0.35MPaG, and after the gas collected at the top of the tower is cooled and rectified, 45.32g/h (the reaction conversion rate is 88.69%, the selectivity is 98.41%, and the yield is 87.28%) of the product 2-methoxypropene is collected. The reaction was continued for 4200h and no catalyst deactivation was observed.
Example 5
In a tower reactor with the length of 1m and the diameter of 0.02m, a mixture of catalyst D and an alkaline carrier is filled from the bottom to 1/3 of the tower, the filling mass is 45g, the filling mass ratio of 1:1 at 1/3 to 2/3 is 5363, the filling mass is 90g, the filling mass is 45g from the top of the tower, and the catalyst and the carrier are co-filled by 180g. The raw material 2,2-dimethoxypropane is fed from the bottom of the tower at the flow rate of 90g/h through a flow meter, the temperature of the bottom of the tower is controlled at 270 ℃, the pressure is 0.2MPaG, and after cooling and rectifying the gas collected at the top of the tower, 61.67g/h (the reaction conversion rate is 99.65%, the selectivity is 99.32%, and the yield is 98.97%) of the product 2-methoxypropene is collected. The reaction was continued for 3100h without any catalyst deactivation.
Example 6
In a tower reactor with the length of 1m and the diameter of 0.02m, a mixture of catalyst E and an alkaline carrier is filled from the bottom to 1/3 of the tower, the filling mass is 50g, the filling mass ratio of the catalyst E to the 1:1 at 1/3-2/3 of the tower is 80g, the filling mass is 50g, and the catalyst and the carrier are filled together by 180g. The raw material 2,2-dimethoxypropane is fed from the bottom of the tower at the flow rate of 80g/h through a flow meter, the temperature of the bottom of the tower is controlled at 270 ℃, the pressure is 0.2MPaG, and after cooling and rectifying the gas collected at the top of the tower, 53.92g/h (the reaction conversion rate is 98.53%, the selectivity is 98.80%, and the yield is 97.35%) of the product 2-methoxypropene is collected. The reaction was continued for 3200h without any catalyst deactivation.

Claims (14)

1. A process for preparing a 2-alkoxypropene, characterized in that it comprises: in the presence of a modified Y-type molecular sieve catalyst and an alkaline carrier, a raw material 2,2-dialkoxypropane is subjected to a cracking reaction in a tower reactor, and 2-alkoxy propylene is collected from the top of the tower reactor;
the modified Y-type molecular sieve catalyst is selected from one or more of a modified Y-type molecular sieve treated by hydrothermal hyperstabilization-sulfuric acid, a modified Y-type molecular sieve treated by hydrothermal hyperstabilization-hydrochloric acid, a modified Y-type molecular sieve treated by hydrothermal hyperstabilization-acetic acid, a modified Y-type molecular sieve treated by hydrothermal hyperstabilization-sulfonic acid and a modified Y-type molecular sieve treated by hydrothermal hyperstabilization-p-toluenesulfonic acid;
the alkaline carrier is SiO treated by alkaline solution 2 。
2. The method according to claim 1, wherein the 2-alkoxypropene has the following structure, wherein R is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl,
Figure FDA0003777318610000011
3. the method according to claim 1, wherein the modified Y-type molecular sieve catalyst and the basic carrier are filled in the tower reactor in a way that: the tower reactor is divided into three sections according to the length, the modified Y-type molecular sieve catalyst, the mixture of the modified Y-type molecular sieve catalyst and the alkaline carrier are respectively filled from bottom to top, and the mass ratio of the modified Y-type molecular sieve catalyst to the alkaline carrier at the second section is 1:4-4:1.
4. The method of claim 3, wherein the mass ratio of the second-stage modified Y-type molecular sieve catalyst to the basic carrier is 1:1-1.5.
5. The process according to claim 3, wherein the filling height of each stage is 1/8 to 1/3 of the length of the column reactor.
6. The process according to claim 5, wherein the filling height of each stage is 1/4 to 1/3 of the length of the column reactor.
7. The method according to claim 1, wherein the alkaline carrier is treated by: will shape SiO 2 The carrier is dipped in 0.001-2 mol/L alkaline solution for 1-12 h at the temperature of 10-100 ℃, and is obtained by filtration, washing and drying; wherein the alkaline solution is selected from NaOH solution, na 2 CO 3 Solution, naHCO 3 Solution, KOH solution, K 2 CO 3 And (3) solution.
8. The process according to any one of claims 1 to 7, wherein the feed 2,2-dialkoxypropane enters from the lower portion of the column reactor.
9. The process according to any one of claims 1 to 7, wherein the reaction temperature of the cleavage reaction is 150 to 350 ℃.
10. The method of claim 9, wherein the reaction temperature of the cracking reaction is 250 to 300 ℃.
11. The process of any one of claims 1-7, 10, wherein the reaction pressure is from atmospheric pressure to 2.0MPaG.
12. The process of claim 11, wherein the reaction pressure is 0.2 to 0.4MPaG.
13. The process of any one of claims 1 to 7 wherein the feed rate of the feedstock 2,2-dialkoxypropane is from 0.1 to 10 hours relative to the mass space velocity of the combined mass of the modified Y-type molecular sieve catalyst and the basic support -1 。
14. The process of claim 13 wherein the feed rate of the feedstock 2,2-dialkoxypropane is 0.25 to 2.0h mass space velocity relative to the total mass of the modified Y-type molecular sieve catalyst and the basic support -1 。
CN202010097822.1A 2020-02-18 2020-02-18 Method for preparing 2-alkoxy propylene Active CN111187149B (en)

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CN1660742A (en) * 2004-12-30 2005-08-31 浙江大学 New technique for synthesizing 2-alkoxyl propylene
CN107790172A (en) * 2016-08-30 2018-03-13 中国石油化工股份有限公司 Transalkylation catalyst and its production and use
CN109020789A (en) * 2017-06-12 2018-12-18 浙江医药股份有限公司新昌制药厂 A method of preparing 2- methoxyl group propylene
CN110240540A (en) * 2018-03-07 2019-09-17 中国科学院化学研究所 A kind of continuous method for preparing 2- methoxyl group propylene

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US5767325A (en) * 1995-11-29 1998-06-16 Basf Aktiengesellschaft Preparation of enol ethers
CN1660742A (en) * 2004-12-30 2005-08-31 浙江大学 New technique for synthesizing 2-alkoxyl propylene
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CN110240540A (en) * 2018-03-07 2019-09-17 中国科学院化学研究所 A kind of continuous method for preparing 2- methoxyl group propylene

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