CN109761761B - Preparation method of ethoxypropylene - Google Patents
Preparation method of ethoxypropylene Download PDFInfo
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Abstract
The invention relates to a preparation method of ethoxypropene, which solves the technical problems of high cost, low yield, low return, long reaction route, more byproducts and environmental pollution of the prior synthesis method of ethoxypropene. The invention provides a preparation method of ethoxypropylene, which comprises the following steps: step S1: in the reaction stage, acetone gas and ethylene gas are introduced into a fixed bed reactor, a modified catalyst is arranged in the fixed bed reactor, and the ethylene is catalyzed to carry out addition reaction under the conditions of normal pressure of 120-; step S2: and (4) product separation, namely condensing, separating and recycling the gas completely reacted in the step S1 to obtain a pure ethoxypropene product. The invention is widely applied to the technical field of organic synthesis.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of ethoxypropylene.
Background
2-ethoxy propylene is an important medical intermediate, and 2-methoxy propylene is gradually substituted to become a key intermediate for synthesizing clarithromycin in China at present. Clarithromycin is a macrolide antibiotic used for treating diseases such as upper and lower respiratory tract infection, subcutaneous soft tissue infection and the like.
2-ethoxypropene is a simple olefin ether, and the synthesis methods in the prior art mainly comprise four methods: the first method is to take acetaldehyde as a raw material to react with ethanol and hydrogen chloride to obtain alpha-chloroethyl ethyl ether, dibromoethyl ethyl ether and 1-bromo-2-ethoxypropane, and finally obtain the product. And the second method comprises the steps of using ethyl acetoacetate as a raw material, chlorinating by phosphorus trichloride to obtain beta-chloro-2-butenoic acid, reacting with sodium ethoxide to obtain beta-ethoxy-2-butenoic acid, and finally decarboxylating at high temperature to obtain the beta-ethoxy-2-butenoic acid. And thirdly, condensing triethyl orthoformate and acetone by using p-toluenesulfonic acid as a catalyst and absolute ethyl alcohol as a solvent to prepare the diacetone diethyl acetal, and performing high-temperature liquid-phase cracking on the diacetone diethyl acetal by using phenyl methyl silyl ether and the like as liquid-phase media or performing high-temperature gas-phase cracking on a solid catalyst to obtain the 2-ethoxypropene. And the fourth method is a DEP cracking method, which adopts 2, 2-diethoxypropane to crack and remove one molecule of ethanol to obtain the 2-ethoxypropylene. The method I and the method II have long reaction routes and more side reactions in the reaction process, so that the yield is low, more waste is generated, and the environmental pollution is great. The method III and the method IV are commonly used at present, but the raw materials triethyl orthoformate and 2, 2-diethoxypropane used in the methods have higher cost, larger investment and low return. Therefore, a method with low investment, simple reaction path, relatively high yield and environmental protection is urgently needed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the preparation method of the ethoxypropene, which has the advantages of low investment, simple reaction path, relatively high yield and environmental protection.
The technical scheme adopted by the invention for solving the technical problem is as follows:
a preparation method of ethoxypropylene comprises the following steps:
step S1: step S1: in the reaction stage, acetone gas and ethylene gas are introduced into a fixed bed reactor, a modified catalyst is arranged in the fixed bed reactor, and the ethylene is catalyzed to carry out addition reaction under the conditions of normal pressure of 120-;
step S2: and (4) product separation, namely condensing, separating and recycling the gas completely reacted in the step S1 to obtain a pure ethoxypropene product.
Preferably, in step S1, the mass ratio of the acetone gas to the ethylene gas is 0.25 to 2.00: 1.
Preferably, in step S1, the mass ratio of the acetone gas to the ethylene gas is 0.52 to 1.04: 1.
Preferably, in step S1, the reaction temperature is 130-170 ℃.
Preferably, in step S1, the reaction time is 0.77-1.43 h.
Preferably, in step S1, the reaction time is 1.12-1.43 h.
Preferably, the modified catalyst is a modified porous alumina, and the alumina is gamma-alumina or alpha-alumina.
Preferably, the specific surface area of the modified porous alumina is more than or equal to 200m2Per g, porosity 60-70%.
Preferably, in step S2, the separation is a rectification separation, and the condensate obtained by condensation is subjected to a rectification separation to obtain a fraction at 61-64 ℃, i.e., a pure ethoxypropene product.
Preferably, in step S1, the fixed bed reactor is a tubular fixed bed reactor having an internal tube diameter of 32 mm.
The invention has the beneficial effects that:
(1) the invention provides a preparation method of 2-ethoxy propylene, which takes the most commonly used industrial low-price raw materials of ethylene and acetone as initial raw materials, adds a modified catalyst at a proper temperature to make the ethylene generate addition reaction to generate ethoxy propylene in one step, and then carries out rectification operation to obtain the product, wherein the yield is up to 80 percent, compared with the yield (77 percent) of the conventional triethyl orthoformate preparation process, the yield is obviously improved by about 3 percent, the production process is simple and easy to implement, the three wastes are less generated, the preparation method is environment-friendly and energy-saving, meets the green energy-saving environment-friendly concept pursued by the current society, and is favorable for sustainable development.
(2) Compared with the prior art, the preparation method of the ethoxypropene has the following obvious advantages: firstly, the raw materials are cheap and easily available, and are basically low-price raw materials in industry as starting raw materials; secondly, the process is simple, the working procedure is short, the investment of production equipment is low, the production period is short, and the industrial popularization is easy; thirdly, the environment is friendly, and the utilization rate of raw materials is high. Therefore, the preparation method of the ethoxypropene is suitable for modern industrial production.
Drawings
FIG. 1 is a reaction scheme of the present invention.
Detailed Description
The invention is further described below in conjunction with the drawings and the specific embodiments to assist in understanding the contents of the invention. The method used in the invention is a conventional production method if no special provisions are made; the starting materials used, unless otherwise specified, are conventional commercial products.
Example one
A process for preparing an ethoxypropene comprising the steps of:
s0: in the preheating stage, 65ml of acetone and 4L of bottled ethylene gas are taken as reaction raw materials, and 60ml of a jacketed tubular fixed bed reactor with an inner tube diameter of 32mm is filled with a specific surface area of more than or equal to 200m2After the modified porous gamma-alumina with the porosity of 60-70 percent is treated by the method, firstly introducing nitrogen for 5 minutes, and completely replacing the air in the tubular fixed bed reactor; respectively opening a heating device on the tubular fixed bed reactor and a condensing device at the lower end of the tubular fixed bed reactor close to an outlet, so that the porous gamma-alumina of the modified catalyst in the tubular fixed bed reactor is heated to 120 ℃;
s1: in the reaction stage, 65ml of acetone solution is used, the acetone solution is conveyed into a coupling exchanger by a constant flow pump to be vaporized and heated, and then is heated to 120 ℃ by a superheater, the obtained acetone hot steam is introduced into the tubular fixed bed reactor heated to 120 ℃ in the step S0, and simultaneously, after the ethylene gas is heated to 120 ℃ by the superheater, the ethylene gas is introduced into the tubular fixed bed reactor heated to 120 ℃ in the step S0;
simultaneously introducing acetone hot steam at the rate of 23.8ml/h and ethylene gas at the rate of 30ml/h into the tubular fixed bed reactor heated to 120 ℃ in the step S0, controlling the mass ratio of acetone to ethylene to be 1.04:1, catalyzing ethylene to perform addition reaction at the reaction temperature of 120 ℃ under normal pressure, and performing heat preservation reaction for 1.12h until the reaction is completed;
s2: and (4) product separation, namely condensing the product completely reacted in the step S1, and then rectifying and separating: and (3) rectifying and separating the condensate obtained by condensation, and recovering to obtain 38.71g of fraction at 61-64 ℃, namely a pure ethoxypropene product with the calculated yield of 50.21%.
Example two
A process for preparing an ethoxypropene comprising the steps of:
s0: in the preheating stage, 65ml of acetone and 4L of bottled ethylene gas are taken as reaction raw materials, and 60ml of a jacketed tubular fixed bed reactor with an inner tube diameter of 32mm is filled with a specific surface area of more than or equal to 200m2After the modified porous gamma-alumina with the porosity of 60-70 percent is treated by the method of the invention, firstly introducing nitrogen for 5 minutes, and completely replacing the air in the tubular fixed bed reactor; respectively opening a heating device on the tubular fixed bed reactor and a condensing device at the lower end of the tubular fixed bed reactor close to an outlet, so that the porous gamma-alumina of the modified catalyst in the tubular fixed bed reactor is heated to 130 ℃;
s1: in the reaction stage, 65ml of acetone solution is used, the acetone solution is conveyed into a coupling exchanger by a constant flow pump to be vaporized and heated, then the acetone solution is heated to 130 ℃ by a superheater, the obtained acetone hot steam is introduced into the tubular fixed bed reactor heated to 130 ℃ in the step S0, and simultaneously, the ethylene gas is also heated to 130 ℃ by the superheater and then introduced into the tubular fixed bed reactor heated to 130 ℃ in the step S0;
simultaneously introducing acetone hot steam at the rate of 23.8ml/h and ethylene gas at the rate of 30ml/h into the tubular fixed bed reactor heated to 130 ℃ in the step S0, controlling the mass ratio of acetone to ethylene to be 1.04:1, catalyzing ethylene to perform addition reaction under the condition of controlling the reaction temperature at normal pressure and 130 ℃, and performing heat preservation reaction for 1.12h until the reaction is completed;
s2: and (4) product separation, namely condensing the product completely reacted in the step S1, and then rectifying and separating: and (3) rectifying and separating the condensate obtained by condensation, and recovering to obtain 60.36g of fraction at 61-64 ℃, namely a pure ethoxypropene product, wherein the calculated yield is 78.29%.
EXAMPLE III
A process for preparing an ethoxypropene comprising the steps of:
s0: preheating stage, taking 65ml acetone and 4L bottled ethylene gas as raw materials for reaction,the specific surface area of 60ml filled in a jacketed tubular fixed bed reactor with the inner tube diameter of 32mm is more than or equal to 200m2After the modified porous gamma-alumina with the porosity of 60-70 percent is treated by the method of the invention, firstly introducing nitrogen for 5 minutes, and completely replacing the air in the tubular fixed bed reactor; respectively opening a heating device on the tubular fixed bed reactor and a condensing device at the lower end of the tubular fixed bed reactor close to an outlet, so that the porous gamma-alumina of the modified catalyst in the tubular fixed bed reactor is heated to 150 ℃;
s1: in the reaction stage, 65ml of acetone solution is used, the acetone solution is conveyed into a coupling exchanger by an advection pump to be vaporized and heated, then the acetone solution is heated to 150 ℃ by a superheater, the obtained acetone hot steam is introduced into the tubular fixed bed reactor which is heated to 150 ℃ in the step S0, and simultaneously, after the ethylene gas is heated to 150 ℃ by the superheater, the ethylene gas is introduced into the tubular fixed bed reactor which is heated to 150 ℃ in the step S0;
simultaneously introducing acetone hot steam at the rate of 23.8ml/h and ethylene gas at the rate of 30ml/h into the tubular fixed bed reactor heated to 150 ℃ in the step S0, controlling the mass ratio of acetone to ethylene to be 1.04:1, catalyzing ethylene to perform addition reaction under the condition of controlling the reaction temperature at normal pressure and 150 ℃, and performing heat preservation reaction for 1.12h until the reaction is completed;
s2: and (5) product separation, namely condensing the product after the reaction in the step S1, and then rectifying and separating: and (3) rectifying and separating the condensate obtained by condensation, and recovering 61.31g of fraction at 61-64 ℃, namely pure ethoxypropylene, wherein the calculated yield is 79.52%.
Example four
A process for preparing an ethoxypropene comprising the steps of:
s0: in the preheating stage, 65ml of acetone and 4L of bottled ethylene gas are taken as reaction raw materials, and 60ml of a jacketed tubular fixed bed reactor with an inner tube diameter of 32mm is filled with a specific surface area of more than or equal to 200m2After the modified porous gamma-alumina with the porosity of 60-70 percent is treated by the method of the invention, firstly introducing nitrogen for 5 minutes, and completely replacing the air in the tubular fixed bed reactor; respectively opening the heating on the tube array type fixed bed reactorThe device and a condensing device at the lower end close to the outlet of the device enable the modified catalyst porous gamma-alumina in the tubular fixed bed reactor to be heated to 170 ℃;
s1: in the reaction stage, 65ml of acetone solution is used, the acetone solution is conveyed into a coupling exchanger by a constant flow pump to be vaporized and heated, then the acetone solution is heated to 170 ℃ by a superheater, the obtained acetone hot steam is introduced into the tubular fixed bed reactor which is heated to 170 ℃ in the step S0, and simultaneously, the ethylene gas is also heated to 170 ℃ by the superheater and then introduced into the tubular fixed bed reactor which is heated to 170 ℃ in the step S0;
simultaneously introducing acetone hot steam at the rate of 23.8ml/h and ethylene gas at the rate of 30ml/h into the tubular fixed bed reactor heated to 170 ℃ in the step S0, controlling the mass ratio of acetone to ethylene to be 1.04:1, catalyzing ethylene to perform addition reaction under the condition of controlling the reaction temperature to be 170 ℃ at normal pressure, and performing heat preservation reaction for 1.12h until the reaction is completed;
s2: and (5) product separation, namely condensing the product after the reaction in the step S1, and then rectifying and separating: and (3) rectifying and separating the condensate obtained by condensation, and recovering to obtain 61.71g of fraction at 61-64 ℃, namely pure ethoxypropylene, wherein the calculated yield is 80.03%.
EXAMPLE five
A process for preparing an ethoxypropene comprising the steps of:
s0: in the preheating stage, 65ml of acetone and 4L of bottled ethylene gas are taken as reaction raw materials, and 60ml of a jacketed tubular fixed bed reactor with an inner tube diameter of 32mm is filled with a specific surface area of more than or equal to 200m2After the modified porous gamma-alumina with the porosity of 60-70 percent is treated by the method of the invention, firstly introducing nitrogen for 5 minutes, and completely replacing the air in the tubular fixed bed reactor; respectively opening a heating device on the tubular fixed bed reactor and a condensing device at the lower end of the tubular fixed bed reactor close to an outlet, so that the porous gamma-alumina of the modified catalyst in the tubular fixed bed reactor is heated to 200 ℃;
s1: in the reaction stage, 65ml of acetone solution is used, the acetone solution is conveyed into a coupling exchanger by a constant flow pump to be vaporized and heated, then the acetone solution is heated to 200 ℃ by a superheater, the obtained acetone hot steam is introduced into the tubular fixed bed reactor which is heated to 200 ℃ in the step S0, and simultaneously, the ethylene gas is also heated to 200 ℃ by the superheater and then introduced into the tubular fixed bed reactor which is heated to 200 ℃ in the step S0;
simultaneously introducing acetone hot steam at the rate of 23.8ml/h and ethylene gas at the rate of 30ml/h into the tubular fixed bed reactor heated to 200 ℃ in the step S0, controlling the mass ratio of acetone to ethylene to be 1.04:1, catalyzing ethylene to perform addition reaction under the conditions of normal pressure, controlling the reaction temperature to be 200 ℃, and performing heat preservation reaction for 0.77-1.43h until the reaction is completed;
s2: and (4) product separation, namely condensing the product completely reacted in the step S1, and then rectifying and separating: and (3) rectifying and separating the condensate obtained by condensation, and recovering 52.96g of fraction at 61-64 ℃, namely pure ethoxypropylene, wherein the calculated yield is 68.69%.
EXAMPLE six
A process for preparing an ethoxypropene comprising the steps of:
s0: in the preheating stage, 130ml of acetone and 4L of bottled ethylene gas are taken as reaction raw materials, and 60ml of specific surface area more than or equal to 200m is filled in a jacketed tubular fixed bed reactor with the inner tube diameter of 32mm2After the modified porous gamma-alumina with the porosity of 60-70 percent is treated by the method of the invention, firstly introducing nitrogen for 5 minutes, and completely replacing the air in the tubular fixed bed reactor; respectively opening a heating device on the tubular fixed bed reactor and a condensing device at the lower end of the tubular fixed bed reactor close to an outlet, so that the porous gamma-alumina of the modified catalyst in the tubular fixed bed reactor is heated to 170 ℃;
s1: in the reaction stage, 65ml of acetone solution is used, the acetone solution is conveyed into a coupling exchanger by a constant flow pump to be vaporized and heated, then the acetone solution is heated to 170 ℃ by a superheater, the obtained acetone hot steam is introduced into the tubular fixed bed reactor which is heated to 170 ℃ in the step S0, and simultaneously, the ethylene gas is also heated to 170 ℃ by the superheater and then introduced into the tubular fixed bed reactor which is heated to 170 ℃ in the step S0;
simultaneously introducing acetone hot steam at a rate of 47.5ml/h and ethylene gas at a rate of 30ml/h into the tubular fixed bed reactor heated to 170 ℃ in the step S0, controlling the mass ratio of acetone to ethylene to be 2.08:1, catalyzing ethylene to perform addition reaction at the reaction temperature of 170 ℃ under normal pressure, and performing heat preservation reaction for 0.77h until the reaction is completed;
s2: and (4) product separation, namely condensing the product completely reacted in the step S1, and then rectifying and separating: and (3) rectifying and separating the condensate obtained by condensation, and recovering to obtain 115.89g of fraction at 61-64 ℃, namely pure ethoxypropylene, wherein the calculated yield is 75.15%.
EXAMPLE seven
A process for preparing an ethoxypropene comprising the steps of:
s0: in the preheating stage, 162.5ml of acetone and 4L of bottled ethylene gas are taken as raw materials for reaction, and 60ml of a jacketed tubular fixed bed reactor with the inner tube diameter of 32mm is filled in the jacketed tubular fixed bed reactor, and the specific surface area of the reactor is more than or equal to 200m2After the modified porous gamma-alumina with the porosity of 60-70 percent is treated by the method of the invention, firstly introducing nitrogen for 5 minutes, and completely replacing the air in the tubular fixed bed reactor; respectively opening a heating device on the tubular fixed bed reactor and a condensing device at the lower end of the tubular fixed bed reactor close to an outlet, so that the porous gamma-alumina of the modified catalyst in the tubular fixed bed reactor is heated to 170 ℃;
s1: in the reaction stage, 65ml of acetone solution is used, the acetone solution is conveyed into a coupling exchanger by a constant flow pump to be vaporized and heated, then the acetone solution is heated to 170 ℃ by a superheater, the obtained acetone hot steam is introduced into the tubular fixed bed reactor which is heated to 170 ℃ in the step S0, and simultaneously, the ethylene gas is also heated to 170 ℃ by the superheater and then introduced into the tubular fixed bed reactor which is heated to 170 ℃ in the step S0;
controlling acetone hot steam to flow into the tubular fixed bed reactor heated to 170 ℃ in the step S0 at the speed of 59.4ml/h and ethylene gas at the speed of 30ml/h at the same time, controlling the mass ratio of acetone to ethylene to be 2.6:1, catalyzing ethylene to perform addition reaction under the condition of controlling the reaction temperature to be 170 ℃ at normal pressure, and performing heat preservation reaction for 0.67h until the reaction is completed;
s2: and (4) product separation, namely condensing the product completely reacted in the step S1, and then rectifying and separating: and (3) rectifying and separating the condensate obtained by condensation, and recovering to obtain 115.89g of fraction at 61-64 ℃, namely pure ethoxypropylene, wherein the calculated yield is 75.15%.
Example eight
A process for preparing an ethoxypropene comprising the steps of:
s0: in the preheating stage, 65ml of acetone and 4L of bottled ethylene gas are taken as reaction raw materials, and 60ml of specific surface area more than or equal to 200m is filled in a jacketed tubular fixed bed reactor with the inner tube diameter of 32mm2After the modified porous gamma-alumina with the porosity of 60-70 percent is treated by the method of the invention, firstly introducing nitrogen for 5 minutes, and completely replacing the air in the tubular fixed bed reactor; respectively opening a heating device on the tubular fixed bed reactor and a condensing device at the lower end of the tubular fixed bed reactor close to an outlet, so that the porous gamma-alumina of the modified catalyst in the tubular fixed bed reactor is heated to 170 ℃;
s1: in the reaction stage, 65ml of acetone solution is used, the acetone solution is conveyed into a coupling exchanger by a constant flow pump to be vaporized and heated, then the acetone solution is heated to 170 ℃ by a superheater, the obtained acetone hot steam is introduced into the tubular fixed bed reactor which is heated to 170 ℃ in the step S0, and simultaneously, the ethylene gas is also heated to 170 ℃ by the superheater and then introduced into the tubular fixed bed reactor which is heated to 170 ℃ in the step S0;
controlling the acetone hot steam to flow into the tubular fixed bed reactor heated to 170 ℃ in the step S0 at the speed of 11.9ml/h and the ethylene gas at the speed of 30ml/h at the same time, controlling the mass ratio of acetone to ethylene to be 0.52:1, catalyzing ethylene to perform addition reaction under the condition of controlling the reaction temperature to be 170 ℃ at normal pressure, and performing heat preservation reaction for 1.43h until the reaction is completed;
s2: and (4) product separation, namely condensing the product completely reacted in the step S1, and then rectifying and separating: and (3) rectifying and separating the condensate obtained by condensation, and recovering to obtain 61.64g of fraction at 61-64 ℃, namely pure ethoxypropylene, wherein the calculated yield is 79.95%.
Example nine
A process for preparing an ethoxypropene comprising the steps of:
s0: in the preheating stage, 100ml of acetone and 4L of bottled ethylene gas are taken as reaction raw materials, and 60ml of a jacketed tubular fixed bed reactor with an inner tube diameter of 32mm is filled with a specific surface area of more than or equal to 200m2After the modified porous gamma-alumina with the porosity of 60-70 percent is treated by the method of the invention, firstly introducing nitrogen for 5 minutes, and completely replacing the air in the tubular fixed bed reactor; respectively opening a heating device on the tubular fixed bed reactor and a condensing device at the lower end of the tubular fixed bed reactor close to an outlet, so that the porous gamma-alumina of the modified catalyst in the tubular fixed bed reactor is heated to 170 ℃;
s1: in the reaction stage, 65ml of acetone solution is used, the acetone solution is conveyed into a coupling exchanger by an advection pump to be vaporized and heated, then the acetone solution is heated to 170 ℃ by a superheater, the obtained acetone hot steam is introduced into the tubular fixed bed reactor which is heated to 170 ℃ in the step S0, and simultaneously, the ethylene gas is also heated to 170 ℃ by the superheater and then introduced into the tubular fixed bed reactor which is heated to 170 ℃ in the step S0;
controlling the acetone hot steam to flow into the tubular fixed bed reactor heated to 170 ℃ in the step S0 at the rate of 18.3ml/h and the ethylene gas at the rate of 30ml/h at the same time, controlling the mass ratio of acetone to ethylene to be 0.8:1, catalyzing ethylene to perform addition reaction under the condition of controlling the reaction temperature to be 170 ℃ at normal pressure, and performing heat preservation reaction for 1.24h until the reaction is completed;
s2: and (4) product separation, namely condensing the product completely reacted in the step S1, and then rectifying and separating: and (3) rectifying and separating the condensate obtained by condensation, and recovering 94.08g of fraction at 61-64 ℃, namely pure ethoxypropylene, wherein the calculated yield is 79.31%.
The following further analysis of the experimental data and the statistical results of the yield in the above examples one to nine is summarized as follows:
table 1 experimental data and yield statistics for examples one-nine are as follows:
| examples | Reaction temperature C | Mass ratio of acetone to ethylene | Reaction time h of heat preservation | Yield of |
| Example one | 120 | 1.04:1 | 1.12 | 50.21％ |
| Example two | 130 | 1.04:1 | 1.12 | 78.29％ |
| EXAMPLE III | 150 | 1.04:1 | 1.12 | 79.52％ |
| Example four | 170 | 1.04:1 | 1.12 | 80.03％ |
| EXAMPLE five | 200 | 1.04:1 | 1.12 | 68.69％ |
| Example six | 170 | 2.08:1 | 0.77 | 75.15％ |
| EXAMPLE seven | 170 | 2.6:1 | 0.67 | 62.34％ |
| Example eight | 170 | 0.52:1 | 1.43 | 79.95％ |
| Example nine | 170 | 0.8:1 | 1.24 | 79.31％ |
The experimental data and the data results in the yield statistical table in the above examples one to nine show that the reaction temperature, the mass ratio of acetone to ethylene, the reaction holding time and other factors have a great influence on the final reaction yield.
Effect of reaction temperature on reaction yield: in the experimental data of the first to ninth examples, the mass ratio of acetone to ethylene, the reaction time of the reaction incubation, and the like are the same, except that the reaction temperatures are 120 ℃, 130 ℃, 150 ℃, 170 ℃ and 200 ℃, respectively, and the comparison result with the final reaction yield shows that the reaction yield is increased with the increase of the temperature, but after the reaction temperature exceeds 170 ℃, the yield is decreased due to the increase of impurities generated at high temperature, so the reaction temperature should be controlled at 180 ℃ of 120-.
The reaction yield is influenced by the changes of the mass ratio of acetone to ethylene and the reaction holding time: in the experimental data of the fourth example, the sixth example, the seventh example, the eighth example and the ninth example, the reaction temperature is the same, the mass ratio of acetone to ethylene and the reaction holding time are changed, which affects the reaction yield result, the mass ratio of acetone to ethylene is increased or decreased, that is, the reaction has side reactions with different degrees in the reaction of insufficient ethylene or excessive ethylene, which causes the reaction yield to be decreased; and the reaction raw material conversion is insufficient when the heat preservation reaction time is too short, side reaction is generated when the heat preservation reaction time is too long, self polymerization reaction is generated, and the reaction yield is reduced, so the mass ratio of the acetone to the ethylene is controlled to be 0.25-2.00:1, the optimal mass ratio of acetone to ethylene is 0.52-1.04: 1; the reaction time is kept at 0.77-1.43h, and the optimal reaction time is 1.12-1.43 h.
According to the reaction structure formula shown in fig. 1, in the preparation method of ethoxypropene, ethylene is catalyzed by a catalyst, enolated ketone attacks a double bond polarized by hydrogen ions, the double bond is opened, and a chemical bond is formed with acetone, namely ethoxypropene. The acetone is gasified, the ethylene gas is heated to the same temperature, and then the ethylene gas and the acetone gas are led to pass through the modified catalyst to react under the catalytic action of the catalyst. The modified catalyst has great activity and is convenient for the contact reaction of ethylene and acetone, and when the modified catalyst is porous gamma-alumina, the modified catalyst has the best catalytic effect on the reaction.
The invention provides a preparation method of 2-ethoxy propylene, which takes the most commonly used industrial low-price raw materials of ethylene and acetone as initial raw materials, adds a modified catalyst at a proper temperature to make the ethylene generate addition reaction to generate ethoxy propylene in one step, and then carries out rectification operation to obtain the product, wherein the yield is up to 80 percent, compared with the yield (77 percent) of the conventional triethyl orthoformate preparation process, the yield is obviously improved by about 3 percent, the production process is simple and easy to implement, the three wastes are less generated, the preparation method is environment-friendly and energy-saving, meets the green energy-saving environment-friendly concept pursued by the current society, and is favorable for sustainable development.
In conclusion, the invention provides the preparation method of the 2-ethoxypropylene, which has low investment cost, short reaction period and environmental friendliness. The method adopts a reaction route completely different from the prior method, and uses industrial raw materials of ethylene and acetone to react under the condition of a modified catalyst to directly generate the 2-ethoxypropylene. Compared with the prior art, the preparation method of the ethoxypropene has the following obvious advantages: firstly, the raw materials are cheap and easily available, and are basically low-price raw materials in industry as starting raw materials; secondly, the process is simple, the working procedure is short, the investment of production equipment is low, the production period is short, and the industrial popularization is easy; thirdly, the environment is friendly, and the utilization rate of raw materials is high. Therefore, the preparation method of the ethoxypropene is suitable for modern industrial production.
The above are only examples of the present invention, and for example, the specific surface area is 200m or more2A modified porous catalyst with a porosity of 60-70%; the modified porous alumina is gamma-alumina or alpha-alumina, and the preparation method of the ethoxypropene can be realized.
However, the above description is only an embodiment of the present invention, and the scope of the present invention should not be limited by this, and all equivalent changes and modifications made in the claims of the present invention should be covered by the present invention.
Claims (7)
1. The preparation method of the ethoxypropene is characterized by comprising the following steps of:
step S1: in the reaction stage, acetone gas and ethylene gas are introduced into a fixed bed reactor, a modified catalyst is arranged in the fixed bed reactor, the ethylene is catalyzed to carry out addition reaction under the condition of normal pressure of 130-;
step S2: and (4) product separation, namely condensing, separating and recycling the gas completely reacted in the step S1 to obtain a pure ethoxypropene product.
2. The method according to claim 1, wherein in step S1, the mass ratio of the acetone gas to the ethylene gas is 0.25-2.00: 1.
3. The method according to claim 2, wherein in step S1, the mass ratio of the acetone gas to the ethylene gas is 0.52-1.04: 1.
4. The method according to claim 1, wherein the reaction time in step S1 is 1.12-1.43 h.
5. The method for preparing ethoxypropene according to claim 1, wherein the specific surface area of the modified porous alumina is not less than 200m2Per g, porosity 60-70%.
6. The method for preparing ethoxypropene according to claim 1, wherein in step S2, the separation is a rectification separation, and a condensate obtained by condensation is subjected to a rectification separation to obtain a fraction of 61-64 ℃, i.e., a pure ethoxypropene product.
7. The method for preparing ethoxypropylene according to claim 1, wherein in step S1, the fixed bed reactor is a tubular fixed bed reactor, and an internal tube diameter of the tubular fixed bed reactor is 32 mm.
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