CN111187149A - Method for preparing 2-alkoxy propylene - Google Patents

Method for preparing 2-alkoxy propylene Download PDF

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CN111187149A
CN111187149A CN202010097822.1A CN202010097822A CN111187149A CN 111187149 A CN111187149 A CN 111187149A CN 202010097822 A CN202010097822 A CN 202010097822A CN 111187149 A CN111187149 A CN 111187149A
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molecular sieve
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type molecular
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CN111187149B (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
    • Y02P20/00—Technologies relating to chemical industry
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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, carrying out cracking reaction on a raw material 2, 2-dialkoxypropane in a tower reactor, collecting the 2-alkoxy propylene at the top of the tower reactor, wherein the modified Y-type molecular sieve catalyst and the alkaline carrier are filled in the tower reactor in a way that: 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 of hydroxyl, oximido and amino groups in the synthesis of drug molecules and as protective agents, cyclizing agents, condensing agents and the like in the 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 the strong base catalyst is corrosive to equipment at high temperature, and the raw material of the propyne or propadiene is difficult to be sourced.
The ketal cracking method is to prepare 2-alkoxy propylene by taking 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 2-alkoxy propylene is prepared by using benzoic acid and pyridine mixed catalyst, ethylene glycol dimethyl ether as reaction solvent, phthalic anhydride as small molecular alcohol absorbent and reacted at the temperature of 120-145 ℃ for 0.25-2 h. 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-alkoxypropene by gas phase cracking 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 ℃. CN1660742A reports a process for continuously preparing 2-alkoxypropene at 120-160 ℃ and 2atm pressure by using acidic materials such as acidic ceramics, cationic resins, heteropoly acids 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, the reaction is carried out at the temperature of 280-340 ℃, 2-dimethoxypropane is adopted as the raw material, the conversion rate and the selectivity of the product 2-methoxypropene are both about 90 percent, and the activity of the catalyst is not obviously reduced after the catalyst is repeatedly used; US6211416 also employs a ZSM-5 molecular sieve catalyst, and adds propyne and propadiene to the cracking feedstock, increasing feedstock conversion and once-through yield. 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 of mixing and loading a modified Y-type molecular sieve catalyst and an alkaline carrier according to a certain proportion, and 2-alkoxy propylene is obtained by collecting at 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: taking 5.0g of NaY molecular sieve (the silica-alumina ratio is between 4.22 and 10.35, and the preferential ratio is 4.3 to 4.5) and placing the NaY molecular sieve into a 100mL three-neck bottle, adding 6.5g of ammonium sulfate and 50mL of water, heating and stirring in a water bath at 100 ℃ for 1h, filtering and washing for three times, then treating the obtained NaY molecular sieve once again under the same conditions, placing a filter cake (the water content is about 55%) into a covered crucible, and carrying out self-heating water vapor treatment at 500 to 650 ℃ for 2 h. 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 is 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 ultra-stabilization-sulfuric acid treatment.
The alkaline carrier is SiO treated by alkaline solution2The processing method comprises the following steps: will shape SiO2The carrier is dissolved in 0.001-2 mol/L, preferably 0.1-1 mol/L alkaline solution (preferably NaOH solution, Na solution) at 10-100 ℃, preferably 80-100 ℃2CO3Solution, NaHCO3Solutions, KOH solutions or K2CO3One of the solutions) for 1 to 12 hours, preferably 1 to 4 hours, and filtering, washing and drying the mixture 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 normal pressure to 2.0MPaG, preferably from 0.2 to 0.4 MPaG.
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 of the length of the tower reactor, preferably 1/4-1/3; the filling ratio of the second-stage modified Y-type molecular sieve catalyst to the alkaline carrier is 1: 4-4: 1, preferably 1: 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-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-1Preferably 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 (silica-alumina ratio: 4.4) was placed in a 100mL three-necked flask, 6.5g of ammonium sulfate and 50mL of water were added, and after heating and stirring in a water bath at 100 ℃ for 1 hour, filtration and washing were carried out three times, after which the resulting NaY molecular sieve was treated again under the same conditions, and the filter cake (water content: about 55%) was placed in a crucible with a lid and treated with 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 1mol/L) of sulfuric acid and ammonium sulfate (with the mass ratio of 2:3), stirring for 2h, filtering, washing for three times, drying the 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 type of the buffer solution is changed (the mass ratio of acid to ammonium is 2:3, the total concentration of the buffer solution is prepared to be 1mol/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 SiO2The carrier is heated at 85 ℃ under 0.6mol/L Na2CO3Soaking 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 controlled at 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 a 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, the filling mass is 60g, 1/3-2/3 parts are filled with 60g of a mixture of the catalyst A and an alkaline carrier in a mass ratio of 1:1, 2/3 parts are filled with 60g of the alkaline carrier to the top, 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 controlled at 0.2MPaG, and 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 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 2
In a tower reactor with the length of 1m and the diameter of 0.02m, catalyst B is filled from the bottom to 1/3, the filling mass is 40g, a mixture of the catalyst B and an alkaline carrier with the filling mass ratio of 1:1 is filled at 1/3-2/3, the filling mass is 100g, the alkaline carrier is filled at 2/3 to the top, the filling mass is 40g, and the catalyst and the carrier are filled together by 180 g. 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 controlled at 0.3MPaG, and after the gas collected at the top of the tower is cooled and rectified, 45.29g/h (the reaction conversion rate is 97.19%, the selectivity is 96.15%, and the yield is 93.45%) of a 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, the filling mass is 60g, 1/3-2/3 is filled with a mixture of the catalyst A and an alkaline carrier with the mass ratio of 1:1, the filling mass is 60g, 2/3 is filled with the alkaline carrier to the top, the filling mass is 60g, and the catalyst and the carrier are filled together by 180 g. 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 the 2-ethoxypropene product 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, catalyst C is filled from the bottom to 1/3, the filling mass is 50g, a mixture of the catalyst C and an alkaline carrier with the filling mass ratio of 1:1 is filled at 1/3-2/3, the filling mass is 80g, the alkaline carrier is filled at 2/3 to the top, the filling mass is 50g, and the catalyst and the carrier are filled together by 180 g. Raw material 2, 2-dimethoxypropane is fed from the bottom of the tower at the flow rate of 75g/h through a flow meter, the temperature of the bottom of the tower is controlled at 260 ℃, the pressure is controlled at 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 a 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, catalyst D is filled from the bottom to 1/3, the filling mass is 45g, a mixture of the catalyst D and an alkaline carrier with the filling mass ratio of 1:1 is filled at 1/3-2/3, the filling mass is 90g, the alkaline carrier is filled at 2/3 to the top, the filling mass is 45g, and the catalyst and the carrier are filled together by 180 g. Raw material 2, 2-dimethoxypropane is fed from the bottom of the tower through a flow meter at the flow rate of 90g/h, the temperature of the bottom of the tower is controlled at 270 ℃, the pressure is controlled at 0.2MPaG, and 61.67g/h (the reaction conversion rate is 99.65%, the selectivity is 99.32%, and the yield is 98.97%) of product 2-methoxypropene is collected after the gas collected at the top of the tower is cooled and rectified. 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, catalyst E is filled from the bottom to 1/3, the filling mass is 50g, 1/3-2/3 is filled with a mixture of the catalyst E and an alkaline carrier with the mass ratio of 1:1, the filling mass is 80g, 2/3 is filled with the alkaline carrier to the top, the filling mass is 50g, and the catalyst and the carrier are filled together by 180 g. Raw material 2, 2-dimethoxypropane is fed from the bottom of the tower through a flow meter at the flow rate of 80g/h, the temperature of the bottom of the tower is controlled at 270 ℃, the pressure is controlled at 0.2MPaG, and after the gas collected at the top of the tower is cooled and rectified, 53.92g/h (the reaction conversion rate is 98.53%, the selectivity is 98.80%, and the yield is 97.35%) of a product 2-methoxypropene is collected. The reaction was continued for 3200h without any catalyst deactivation.

Claims (10)

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, the raw material 2, 2-dialkoxypropane is subjected to cracking reaction in a tower reactor, and 2-alkoxy propylene is obtained by collecting the top of the tower reactor.
2. The method of claim 1, wherein the 2-alkoxypropene has the structure shown in the following formula, wherein R includes but is not limited to methyl, ethyl, propyl, isopropyl, butyl,
Figure FDA0002385928030000011
3. the method according to claim 1 or 2, 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 in the second section is 1: 4-4: 1, preferably 1: 1-1: 1.5.
4. The process according to claim 3, characterized in that the filling height of each section is 1/8 to 1/3, preferably 1/4 to 1/3 of the length of the column reactor.
5. The method of any one of claims 1-4, wherein the modified Y-type molecular sieve catalyst is selected from one or more of a hydrothermally hyperstabilized-sulfuric acid treated modified Y-type molecular sieve, a hydrothermally hyperstabilized-hydrochloric acid treated modified Y-type molecular sieve, a hydrothermally hyperstabilized-acetic acid treated modified Y-type molecular sieve, a hydrothermally hyperstabilized-sulfonic acid treated modified Y-type molecular sieve, and a hydrothermally hyperstabilized-p-toluenesulfonic acid treated modified Y-type molecular sieve.
6. The method according to any one of claims 1 to 5, wherein the basic carrier is SiO treated with a basic solution2The processing method comprises the following steps: will shape SiO2Soaking the carrier in 0.001-2 mol/L alkaline solution at the temperature of 10-100 ℃ for 1-12 h, and filtering, washing and drying to obtain the carrier; wherein the alkaline solution is selected from NaOH solution, Na2CO3Solution, NaHCO3Solution, KOH solution, K2CO3And (3) solution.
7. A process according to any one of claims 1 to 6, characterized in that the starting material 2, 2-dialkoxypropane is fed from the lower part of the column reactor.
8. A process according to any one of claims 1 to 7, wherein the reaction temperature of the cleavage reaction is 150 to 350 ℃, preferably 250 to 300 ℃.
9. The process according to any one of claims 1 to 8, wherein the reaction pressure is from atmospheric pressure to 2.0MPaG, preferably from 0.2 to 0.4 MPaG.
10. The method of any one of claims 1 to 9, wherein the mass space velocity of the feed rate of the 2, 2-dialkoxypropane is 0.1 to 10 hours relative to the total mass of the modified Y-type molecular sieve catalyst and the basic carrier-1Preferably 0.25 to 2.0 hours-1。
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CN111701539A (en) * 2020-06-28 2020-09-25 安徽威驰化工有限责任公司 2-ethoxy propylene bed reactor and reaction method
CN112337503A (en) * 2020-10-23 2021-02-09 山东新和成维生素有限公司 Modified molecular sieve and preparation method and application thereof

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CN111686670A (en) * 2020-06-28 2020-09-22 安徽威驰化工有限责任公司 Cold treatment device and method for 2-ethoxypropylene
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