Post-treatment purification method and application of methylbutynol and purification method of methylbutynol

Abstract

The present invention relates to the field of synthesis of 2-methyl-3-butyn-2-ol (hereinafter referred to as methylbutynol), discloses a post-processing refining method of methylbutynol and an application thereof. The post-processing refining method comprises: (1) mixing a methylbutynol reaction mixture with a weakly basic carbonate for quenching, and flashing the obtained quencher; (2) recovering the crude liquid phase product obtained in step (1) with acetone, and rectifying the obtained methylbutynol crude product to obtain a pure methylbutynol. The present invention uses anhydrous weakly basic carbonate as a quenching agent, can reduce additional dehydration operations, shorten the production cycle, and improve production efficiency; can decompose diacetone alcohol into acetone, reduce acetone unit consumption, reduce impurity content, and improve the yield and purity of methylbutynol; can avoid causing diacetone alcohol to be dehydrated to generate mesityl oxide, and reduce the difficulty of rectifying methylbutynol.

Description

Technical Field

[0001] The invention relates to the field of methylbutynol synthesis, and in particular to a post-treatment purification method of methylbutynol and a purification method of methylbutynol applicable thereto. Background Art

[0002] Methylbutynol is an important intermediate in the pharmaceutical and chemical production field. Its main uses are in the synthesis of vitamin E, pesticides, spices, acid corrosion inhibitors, stabilizers and viscosity reducers.

[0003] The reaction route for synthesizing methylbutynol from acetylene and acetone is shown in the figure below:

[0004]

[0005] In the obtained reactants, there are by-products, which affect the quality of the target product.

[0006] CN106117010A discloses a new process for synthesizing acetylene alcohols from acetylene and ketone compounds. The process comprises: mixing acetylene with ammonia as a solvent, compressing the mixture, adding a ketone compound and a potassium hydroxide catalyst, and performing an acetylation reaction. The mixture is then subjected to pressurized degassing, atmospheric degassing, scraper evaporation, deketone removal, a crude acetylene alcohol product, and membrane separation to remove water to obtain an anhydrous acetylene alcohol product. The obtained methylbutynol product has a purity of 99.2% and a yield of 92.3% based on acetone.

[0007] CN104045518A discloses a method for preparing 2-methyl-3-butyn-2-ol. The method uses acetylene and acetone as starting materials and liquid potassium hydroxide as a catalyst to generate an acetylation reaction mixture, which is then subjected to flash evaporation, salting out to remove water, and distillation to obtain a finished product. The yield of the obtained 2-methyl-3-butyn-2-ol based on acetone is above 81%, and the product purity is above 99.5%.

[0008] The current mainstream process is to synthesize methylbutynol using acetylene and acetone as raw materials in the presence of a strong base (sodium hydroxide or potassium hydroxide). The reaction is often quenched with an aqueous solution of an acidic substance, which introduces a large amount of water into the reaction system and requires additional water removal, resulting in high equipment and plant investment and a long production cycle. In addition, the introduction of the acidic substance will promote further dehydration of the impurity diacetone alcohol to produce isopropylidene oxide. This impurity has a similar boiling point to methylbutynol, making distillation separation more difficult and reducing the yield and purity of methylbutynol.

[0009] Therefore, developing a simple, efficient, high-yield and high-purity post-treatment method for the preparation of methylbutynol is of great significance to promoting the industrial production of methylbutynol. Summary of the Invention

[0010] In view of the problems of low yield, low purity and high cost in the production of methylbutynol in the prior art, the present invention provides a post-treatment purification method for methylbutynol and a purification method for methylbutynol applied thereto, which are used to improve the yield, purity and production efficiency of methylbutynol and reduce investment cost and distillation difficulty.

[0011] In order to achieve the above object, the first aspect of the present invention provides a post-treatment purification method for methylbutynol, wherein the method comprises the following steps:

[0012] (1) quenching the methylbutynol reaction mixture by mixing it with a weakly alkaline carbonate, and flash evaporating the obtained quenched product;

[0013] (2) recovering the crude liquid product obtained in step (1) by acetone, and rectifying the crude methylbutynol product to obtain pure methylbutynol.

[0014] A second aspect of the present invention provides a post-treatment purification method for methylbutynol for use in the preparation of methylbutynol.

[0015] A third aspect of the present invention provides a method for preparing methylbutynol, wherein the preparation method comprises:

[0016] (1) reacting a compressed liquid containing acetylene and liquid ammonia with acetone in the presence of an aqueous alkali metal hydroxide solution to obtain a methylbutynol reaction mixture;

[0017] (2) post-processing and refining the methylbutynol reaction mixture to obtain pure methylbutynol, wherein the post-processing and refining method is the post-processing and refining method of the methylbutynol described above.

[0018] Through the above technical solution, the present invention uses a weakly alkaline carbonate solid as a quenching reagent, effectively avoiding the introduction of a large amount of water, requiring no additional water removal operation, resulting in a simple process, low investment cost, and a short production cycle; the weakly alkaline carbonate does not cause the impurity diacetone alcohol to be further dehydrated to produce mesityl oxide, and the method provided by the present invention has few side reactions, low distillation difficulty, high yield of methylbutynol, and high product purity, creating conditions for the industrial production of methylbutynol.

[0019] Specifically, the post-treatment purification method of methylbutynol provided by the present invention has the following effects:

[0020] (1) The method provided by the present invention uses a weakly alkaline carbonate solid as a quenching agent, which can avoid the introduction of water into the reaction system, reduce the difficulty of subsequent dehydration, shorten the production cycle, reduce unit operations, improve production efficiency, and reduce investment costs;

[0021] (2) The method provided by the present invention has few side reactions, avoids further dehydration of diacetone alcohol to form mesityl oxide, reduces the impurity content, and reduces the difficulty of distillation. The yield of methylbutynol can reach 93.3%, and the product purity can reach 99.7wt%;

[0022] (3) The method provided by the present invention generates a medium-strong alkaline carbonate by reacting a weak alkaline carbonate with an alkali metal hydroxide, so that diacetone alcohol can be decomposed into raw material acetone during distillation, thereby reducing the unit consumption of acetone. The recovered acetone can be directly recycled, thereby reducing production costs. DETAILED DESCRIPTION

[0023] The endpoints of the ranges and any values disclosed herein are not limited to the precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0024] A first aspect of the present invention provides a post-treatment purification method for methylbutynol, wherein the method comprises the following steps:

[0025] (1) quenching the methylbutynol reaction mixture by mixing it with a weakly alkaline carbonate, and flash evaporating the obtained quenched product;

[0026] (2) recovering the crude liquid product obtained in step (1) by acetone, and rectifying the crude methylbutynol product to obtain pure methylbutynol.

[0027] In some embodiments of the present invention, preferably, in step (1), the methylbutynol reaction mixture comprises: compressed liquids of acetylene and liquid ammonia, alkali metal hydroxide, and acetone.

[0028] In some embodiments of the present invention, preferably, in step (1), the weak alkaline carbonate is selected from at least one of ammonium carbonate, ammonium bicarbonate, sodium bicarbonate and potassium bicarbonate, preferably ammonium bicarbonate; and the molar ratio of the weak alkaline carbonate to the alkali metal hydroxide is 0.5-2:1, preferably 0.7-1.5:1.

[0029] In the present invention, a more preferred embodiment is that the weakly alkaline carbonate is bicarbonate, and the molar ratio of the weakly alkaline carbonate to the alkali metal hydroxide is 0.7-1.5:1. The use of bicarbonate as a quenching agent and the control of the dosage within the aforementioned range can reduce by-products in the post-treatment refining process of methylbutynol, and does not require an additional water removal process, which is beneficial to improving the purity and yield of methylbutynol.

[0030] In some embodiments of the present invention, preferably, in step (1), the quenching temperature is 30-60°C, preferably 40-60°C; the quenching time is 0.5-3h, preferably 1-2h; the flash temperature is 50-70°C, preferably 60-65°C; and the flash pressure is 0.05-0.1MPa.

[0031] In some embodiments of the present invention, preferably, in step (2), the acetone recovery pressure is atmospheric pressure, and the acetone recovery temperature is 55-60° C.; the methylbutynol distillation pressure is 10-100 kPa, preferably 50-100 kPa; and the methylbutynol distillation temperature is 40-104° C., preferably 80-104° C. In the present invention, atmospheric pressure is a pressure less than 0.1 MPa, and the recovered acetone can be directly recycled, significantly reducing production costs.

[0032] In the present invention, acetone can be removed by distillation. A distillation tower can be used to remove acetone, and a plate tower or a packed tower can be selected, which is well known to those skilled in the art. In some examples, the reaction liquid obtained by the acetylation reaction is often treated by atmospheric distillation to remove acetone during the use of a distillation tower. For example, the top temperature of the distillation tower is 55-60°C, and the acetone content in the reaction liquid after the acetone is removed is less than 0.2wt%.

[0033] A second aspect of the present invention provides a post-treatment purification method for methylbutynol for use in the preparation of methylbutynol.

[0034] A third aspect of the present invention provides a method for preparing methylbutynol, wherein the preparation method comprises:

[0035] (1) reacting a compressed liquid containing acetylene and liquid ammonia with acetone in the presence of an aqueous alkali metal hydroxide solution to obtain a methylbutynol reaction mixture;

[0036] (2) post-treating and refining the methylbutynol reaction mixture to obtain pure methylbutynol, wherein the post-treating and refining method is the post-treating and refining method for methylbutynol described in the first aspect.

[0037] In some embodiments of the present invention, preferably, the compressed liquid is obtained by compressing a mixture of acetylene and liquid ammonia; the volume fraction of acetylene in the mixture is 15-25%, preferably 16-18%; the compression pressure is 1.2-2.5 MPa, preferably 2-2.2 MPa; and the reaction temperature is 20-50°C, preferably 35-45°C. In the present invention, controlling the volume fraction of acetylene, the compression pressure, and the reaction temperature within the above-mentioned ranges is beneficial to reducing by-products during the post-treatment and refining process of methylbutynol, and is beneficial to higher yield and purity of methylbutynol. Controlling the volume fraction of acetylene, the compression pressure, and the reaction temperature within the above-mentioned preferred ranges has a better effect; preferably, in the present invention, the compression temperature is the same as the reaction temperature, and the reaction pressure is the same as the compression pressure.

[0038] In some embodiments of the present invention, preferably, the alkali metal hydroxide is selected from sodium hydroxide and / or potassium hydroxide, preferably sodium hydroxide; the molar ratio of the alkali metal hydroxide to acetone is 0.003-0.02:1, preferably 0.005-0.01:1; and the concentration of the alkali metal hydroxide in the alkali metal hydroxide aqueous solution is 10-50 wt%, preferably 30-50 wt%.

[0039] In the present invention, a more preferred embodiment is that the alkali metal hydroxide is sodium hydroxide, the molar ratio of sodium hydroxide to acetone is 0.005-0.01:1, and the concentration is 30-50wt%. The obtained methylbutynol has a higher yield and product purity.

[0040] The present invention will be described in detail below through examples.

[0041] The raw materials, acids, bases, solvents, etc. used in the following examples and comparative examples were all purchased commercially.

[0042] The purity of methylbutynol was determined by gas chromatography.

[0043] The yield of methylbutynol (%) is calculated as follows: actual yield / theoretical yield×100%.

[0044] Example 1

[0045] (1) A mixture of acetylene and liquid ammonia with an acetylene volume fraction of 18% in a gas cabinet is compressed to 2.2 MPa to form a compressed liquid, and the compressed liquid is transported to an acetylation reactor. After the system pressure is stabilized and the temperature rises to 35°C, acetone is added to the acetylation reactor at a flow rate of 8 L / h through a metering pump. At the same time, a 30% sodium hydroxide aqueous solution is added to the acetylation reactor at a flow rate of 0.055 L / h. The system temperature is maintained between 35°C and 45°C for reaction. A methylbutynol reaction mixture is generated through continuous reaction, and the material is transferred to a turnover pipe.

[0046] (2) The reaction mixture in the turnover tank is transferred to the quenching receiving tank, and ammonium bicarbonate solid is added to the quenching receiving tank at a rate of 30 g / h through a high-pressure solid feeder. The temperature is raised to 50-60°C and stirred for 1 hour. The quenched material is then transferred to a flash kettle to start recovering ammonia and acetylene. The temperature is raised to 60-65°C and ammonia is removed by flash evaporation until the residual ammonia is less than 0.1 wt%.

[0047] (3) The crude product after ammonia removal was transferred to an acetone recovery tower, the tower top temperature was controlled at 55-60° C., and acetone was recovered by atmospheric distillation until the acetone residual in the tower bottom material was less than 0.2 wt %. The crude methylbutynol product was transferred to a methylbutynol distillation tower through a pipeline filter, the tower top pressure was controlled at 80 kPa, the tower top temperature was controlled at 80-82° C., 0.15 kg of azeotrope of methylbutynol and water was removed by azeotropic distillation, and the fraction with a top temperature of 86-88° C. was collected to obtain 8.54 kg of pure methylbutynol with a purity of 99.7 wt % and a yield of 93.3%.

[0048] Example 2

[0049] (1) A mixture of acetylene and liquid ammonia with an acetylene volume fraction of 18% in a gas cabinet is compressed to 2.1 MPa to form a compressed liquid, and the compressed liquid is transported to an acetylation reactor. After the system pressure is stabilized and the temperature rises to 35°C, acetone is added to the acetylation reactor at a flow rate of 8 L / h through a metering pump. At the same time, a 30% sodium hydroxide aqueous solution is added to the acetylation reactor at a flow rate of 0.11 L / h. The system temperature is maintained between 35°C and 45°C for reaction. A methylbutynol reaction mixture is generated through continuous reaction, and the material is transferred to a turnover pipe.

[0050] (2) The reaction mixture in the turnover tank is transferred to the quenching receiving tank, and ammonium carbonate solid is added to the quenching receiving tank at a rate of 72 g / h through a high-pressure solid feeder. The temperature is raised to 40-50°C and stirred for 2 hours. The quenched material is then transferred to a flash kettle to start recovering ammonia and acetylene. The temperature is raised to 60-65°C and ammonia is removed by flash evaporation until the residual ammonia is less than 0.1 wt%.

[0051] (3) The crude product after ammonia removal was transferred to an acetone recovery tower, the tower top temperature was controlled at 55-60° C., and acetone was recovered by atmospheric distillation until the acetone residual in the tower bottom material was less than 0.2 wt %. The crude methylbutynol product was transferred to a methylbutynol distillation tower through a pipeline filter, the tower top pressure was controlled at 80 kPa, the tower top temperature was controlled at 80-82° C., 0.3 kg of azeotrope of methylbutynol and water was removed by azeotropic distillation, and the fraction with a top temperature of 86-88° C. was collected to obtain 8.35 kg of pure methylbutynol with a purity of 99.7 wt % and a yield of 91.2%.

[0052] Example 3

[0053] (1) A mixture of acetylene and liquid ammonia with an acetylene volume fraction of 16% in a gas cabinet is compressed to 2.0 MPa to form a compressed liquid, and the compressed liquid is transported to an acetylation reactor. After the system pressure is stabilized and the temperature is stabilized at 35°C, acetone is added to the acetylation reactor at a flow rate of 8 L / h through a metering pump. At the same time, a 30% sodium hydroxide aqueous solution is added to the acetylation reactor at a flow rate of 0.16 L / h. The system temperature is maintained between 35°C and 45°C for reaction. A methylbutynol reaction mixture is generated through continuous reaction, and the material is transferred to a turnover pipe.

[0054] (2) The reaction mixture in the turnover tank is transferred to the quenching receiving tank, and sodium bicarbonate solid is added to the quenching receiving tank at a rate of 200 g / h through a high-pressure solid feeder. The temperature is raised to 50-60°C and stirred for 2 hours. The quenched material is then transferred to a flash kettle to start recovering ammonia and acetylene. The temperature is raised to 60-65°C and ammonia is removed by flash evaporation until the residual ammonia is less than 0.1 wt%.

[0055] (3) The crude product after ammonia removal was transferred to an acetone recovery tower, the tower top temperature was controlled at 55-60° C., and acetone was recovered by atmospheric distillation until the acetone residual in the tower bottom material was less than 0.2 wt %. The crude methylbutynol product was obtained in the tower bottom. The crude methylbutynol product was transferred to a methylbutynol distillation tower through a pipeline filter, the tower top pressure was controlled at 80 kPa, the tower top temperature was controlled at 80-82° C., 0.5 kg of methylbutynol and water azeotrope were removed by azeotropic distillation, and the fraction with a top temperature of 86-88° C. was collected to obtain 8.16 kg of pure methylbutynol with a purity of 99.6 wt % and a yield of 89.2%.

[0056] Example 4

[0057] (1) A mixture of acetylene and liquid ammonia with an acetylene volume fraction of 18% in a gas cabinet is compressed to 2.2 MPa to form a compressed liquid, and the compressed liquid is transported to an acetylation reactor. After the system pressure is stabilized and the temperature is stabilized at 35°C, acetone is added to the acetylation reactor at a flow rate of 8 L / h through a metering pump. At the same time, a 30% sodium hydroxide aqueous solution is added to the acetylation reactor at a flow rate of 0.22 L / h. The system temperature is maintained between 25°C and 35°C for reaction. A methylbutynol reaction mixture is generated through continuous reaction, and the material is transferred to a turnover pipe.

[0058] (2) The reaction mixture in the turnover tank is transferred to the quenching receiving tank, and potassium bicarbonate solid is added to the quenching receiving tank at a rate of 320 g / h through a high-pressure solid feeder. The temperature is raised to 40-50°C and stirred for 3 hours. The quenched material is then transferred to a flash kettle to start recovering ammonia and acetylene. The temperature is raised to 60-65°C and ammonia is removed by flash evaporation until the residual ammonia is less than 0.1 wt%.

[0059] (3) The crude product after ammonia removal is transferred to an acetone recovery tower, the tower top temperature is controlled at 55-60°C, and acetone is recovered by atmospheric distillation until the acetone residue in the bottom material is less than 0.2wt%. The crude methylbutynol product is obtained in the bottom of the tower. The crude methylbutynol product is transferred to a methylbutynol distillation tower through a pipeline filter, the tower top pressure is controlled at 80kPa, and the tower top temperature is controlled at 80-82°C. Azeotropic distillation is performed to remove 0.6kg of azeotrope of methylbutynol and water, and the fraction with a top temperature of 86-88°C is collected to obtain 8.11kg of pure methylbutynol with a purity of 99.5wt% and a yield of 88.6%.

[0060] Example 5

[0061] (1) A mixture of acetylene and liquid ammonia with an acetylene volume fraction of 18% in a gas cabinet is compressed to 2.1 MPa to form a compressed liquid, and the compressed liquid is transported to an acetylation reactor. After the system pressure is stabilized and the temperature is stabilized at 35°C, acetone is added to the acetylation reactor at a flow rate of 8 L / h through a metering pump. At the same time, a 50% potassium hydroxide aqueous solution is added to the acetylation reactor at a flow rate of 0.04 L / h. The system temperature is maintained between 35°C and 45°C for reaction. A methylbutynol reaction mixture is generated through continuous reaction, and the material is transferred to a turnover pipe.

[0062] (2) The reaction mixture in the turnover tank is transferred to the quenching receiving tank, and ammonium bicarbonate solid is added to the quenching receiving tank at a rate of 30 g / h through a high-pressure solid feeder. The temperature is raised to 50-60°C and stirred for 1 hour. The quenched material is then transferred to a flash kettle to start recovering ammonia and acetylene. The temperature is raised to 60-65°C and ammonia is removed by flash evaporation until the residual ammonia is less than 0.1 wt%.

[0063] (3) The crude product after ammonia removal was transferred to an acetone recovery tower, the tower top temperature was controlled at 55-60° C., and acetone was recovered by atmospheric distillation until the acetone residual in the tower bottom material was less than 0.2 wt %. The crude methylbutynol product was transferred to a methylbutynol distillation tower through a pipeline filter, the tower top pressure was controlled at 80 kPa, the tower top temperature was controlled at 80-82° C., 0.1 kg of azeotrope of methylbutynol and water was removed by azeotropic distillation, and the fraction with a top temperature of 86-88° C. was collected to obtain 8.47 kg of pure methylbutynol with a purity of 99.7 wt % and a yield of 92.6%.

[0064] Example 6

[0065] (1) A mixture of acetylene and liquid ammonia with an acetylene volume fraction of 18% in a gas cabinet is compressed to 2.1 MPa to form a compressed liquid, and the compressed liquid is transported to an acetylation reactor. After the system pressure is stabilized and the temperature is stabilized at 35°C, acetone is added to the acetylation reactor at a flow rate of 8 L / h through a metering pump. At the same time, a 30% sodium hydroxide aqueous solution is added to the acetylation reactor at a flow rate of 0.08 L / h. The system temperature is maintained between 35°C and 45°C for reaction. A methylbutynol reaction mixture is generated through continuous reaction, and the material is transferred to a turnover pipe.

[0066] (2) The reaction mixture in the turnover tank is transferred to the quenching receiving tank, and ammonium carbonate solid is added to the quenching receiving tank at a rate of 72 g / h through a high-pressure solid feeder. The temperature is raised to 40-50°C and stirred for 2 hours. The quenched material is then transferred to a flash kettle to start recovering ammonia and acetylene. The temperature is raised to 60-65°C and ammonia is removed by flash evaporation until the residual ammonia is less than 0.1 wt%.

[0067] (3) The crude product after ammonia removal was transferred to an acetone recovery tower, the tower top temperature was controlled at 55-60° C., and acetone was recovered by atmospheric distillation until the acetone residual in the tower bottom material was less than 0.2 wt %. The crude methylbutynol product was transferred to a methylbutynol distillation tower through a pipeline filter, the tower top pressure was controlled at 80 kPa, the tower top temperature was controlled at 80-82° C., 0.2 kg of azeotrope of methylbutynol and water was removed by azeotropic distillation, and the fraction with a top temperature of 86-88° C. was collected to obtain 8.37 kg of pure methylbutynol with a purity of 99.6 wt % and a yield of 91.5%.

[0068] Example 7

[0069] (1) A mixture of acetylene and liquid ammonia with an acetylene volume fraction of 16% in a gas cabinet is compressed to 2.0 MPa to form a compressed liquid, and the compressed liquid is transported to an acetylation reactor. After the system pressure is stabilized and the temperature is stabilized at 35°C, acetone is added to the acetylation reactor at a flow rate of 8 L / h through a metering pump. At the same time, a 30% sodium hydroxide aqueous solution is added to the acetylation reactor at a flow rate of 0.12 L / h. The system temperature is maintained between 35°C and 45°C for reaction. A methylbutynol reaction mixture is generated through continuous reaction, and the material is transferred to a turnover pipe.

[0070] (2) The reaction mixture in the turnover tank is transferred to the quenching receiving tank, and sodium bicarbonate solid is added to the quenching receiving tank at a rate of 200 g / h through a high-pressure solid feeder. The temperature is raised to 50-60°C and stirred for 1 hour. The quenched material is then transferred to a flash kettle to start recovering ammonia and acetylene. The temperature is raised to 60-65°C and ammonia is removed by flash evaporation until the residual ammonia is less than 0.1 wt%.

[0071] (3) The crude product after ammonia removal was transferred to an acetone recovery tower, the tower top temperature was controlled at 55-60° C., and acetone was recovered by atmospheric distillation until the acetone residue in the tower bottom material was less than 0.2 wt %. The crude methylbutynol product was transferred to a methylbutynol distillation tower through a pipeline filter, the tower top pressure was controlled at 80 kPa, the tower top temperature was controlled at 80-82° C., 0.3 kg of azeotrope of methylbutynol and water was removed by azeotropic distillation, and the fraction with a top temperature of 86-88° C. was collected to obtain 8.23 kg of pure methylbutynol with a purity of 99.5 wt % and a yield of 89.9%.

[0072] Example 8

[0073] (1) A mixture of acetylene and liquid ammonia with an acetylene volume fraction of 18% in a gas cabinet is compressed to 2.2 MPa to form a compressed liquid, and the compressed liquid is transported to an acetylation reactor. After the system pressure is stabilized and the temperature is stabilized at 25°C, acetone is added to the acetylation reactor at a flow rate of 8 L / h through a metering pump. At the same time, a sodium hydroxide aqueous solution with a concentration of 30 wt% is added to the acetylation reactor at a flow rate of 0.16 L / h. The system temperature is maintained between 25°C and 35°C for reaction. A methylbutynol reaction mixture is generated through continuous reaction, and the material is transferred to a turnover pipe.

[0074] (2) The reaction mixture in the turnover tank is transferred to the quenching receiving tank, and potassium bicarbonate solid is added to the quenching receiving tank at a rate of 320 g / h through a high-pressure solid feeder. The temperature is raised to 40-50°C and stirred for 3 hours. The quenched material is then transferred to a flash kettle to start recovering ammonia and acetylene. The temperature is raised to 60-65°C and ammonia is removed by flash evaporation until the residual ammonia is less than 0.1 wt%.

[0075] (3) The crude product after ammonia removal was transferred to an acetone recovery tower, the tower top temperature was controlled at 55-60° C., and acetone was recovered by atmospheric distillation until the acetone residue in the tower bottom material was less than 0.2 wt %. The crude methylbutynol product was transferred to a methylbutynol distillation tower through a pipeline filter, the tower top pressure was controlled at 80 kPa, the tower top temperature was controlled at 80-82° C., 0.4 kg of azeotrope of methylbutynol and water was removed by azeotropic distillation, and the fraction with a top temperature of 86-88° C. was collected to obtain 8.08 kg of pure methylbutynol with a purity of 99.5 wt % and a yield of 88.3%.

[0076] Example 9

[0077] (1) A mixture of acetylene and liquid ammonia with an acetylene volume fraction of 25% in a gas cabinet is compressed to 2.5 MPa to form a compressed liquid, and the compressed liquid is transported to an acetylation reactor. After the system pressure is stabilized and the temperature is stabilized at 45°C, acetone is added to the acetylation reactor at a flow rate of 8 L / h through a metering pump. At the same time, a 30% sodium hydroxide aqueous solution is added to the acetylation reactor at a flow rate of 0.055 L / h. The system temperature is maintained between 45°C and 50°C for reaction. A methylbutynol reaction mixture is generated through continuous reaction, and the material is transferred to a turnover pipe.

[0078] (2) The reaction mixture in the turnover tank is transferred to the quenching receiving tank, and ammonium bicarbonate solid is added to the quenching receiving tank at a rate of 85 g / h through a high-pressure solid feeder. The temperature is raised to 50-60°C and stirred for 3 hours. The quenched material is then transferred to a flash kettle to start recovering ammonia and acetylene. The temperature is raised to 60-65°C and ammonia is removed by flash evaporation until the residual ammonia is less than 0.1 wt%.

[0079] (3) The crude product after ammonia removal was transferred to an acetone recovery tower, the tower top temperature was controlled at 55-60° C., and acetone was recovered by atmospheric distillation until the acetone residual in the tower bottom material was less than 0.2 wt %. The crude methylbutynol product was transferred to a methylbutynol distillation tower through a pipeline filter, the tower top pressure was controlled at 80 kPa, the tower top temperature was controlled at 80-82° C., 0.15 kg of methylbutynol and water azeotrope were removed by azeotropic distillation, and the fraction with a top temperature of 86-88° C. was collected to obtain 7.81 kg of pure methylbutynol with a purity of 99.5 wt % and a yield of 85.3%.

[0080] Example 10

[0081] (1) A mixture of acetylene and liquid ammonia with an acetylene volume fraction of 15% in a gas cabinet is compressed to 2.5 MPa to form a compressed liquid, and the compressed liquid is transported to an acetylation reactor. After the system pressure is stabilized and the temperature is stabilized at 20°C, acetone is added to the acetylation reactor at a flow rate of 8 L / h through a metering pump. At the same time, a 50% potassium hydroxide aqueous solution is added to the acetylation reactor at a flow rate of 0.04 L / h. The system temperature is maintained between 20°C and 25°C for reaction. A methylbutynol reaction mixture is generated through continuous reaction, and the material is transferred to a turnover pipe.

[0082] (2) The reaction mixture in the turnover tank is transferred to the quenching receiving tank, and ammonium bicarbonate solid is added to the quenching receiving tank at a rate of 85 g / h through a high-pressure solid feeder. The temperature is raised to 40-50°C and stirred for 3 hours. The quenched material is then transferred to a flash kettle to start recovering ammonia and acetylene. The temperature is raised to 60-65°C and ammonia is removed by flash evaporation until the residual ammonia is less than 0.1 wt%.

[0083] (3) The crude product after ammonia removal was transferred to an acetone recovery tower, the tower top temperature was controlled at 55-60° C., and acetone was recovered by atmospheric distillation until the acetone residual in the tower bottom material was less than 0.2 wt %. The crude methylbutynol product was obtained in the tower bottom. The crude methylbutynol product was transferred to a methylbutynol distillation tower through a pipeline filter, the tower top pressure was controlled at 80 kPa, the tower top temperature was controlled at 80-82° C., 0.1 kg of azeotrope of methylbutynol and water was removed by azeotropic distillation, and the fraction with a top temperature of 86-88° C. was collected to obtain 7.67 kg of pure methylbutynol with a purity of 99.5 wt % and a yield of 83.8%.

[0084] Comparative Example 1

[0085] (1) A mixture of acetylene and liquid ammonia with an acetylene volume fraction of 18% in a gas cabinet is compressed to 2.2 MPa to form a compressed liquid, and the compressed liquid is transported to an acetylation reactor. After the system pressure is stabilized and the temperature is stabilized at 35°C, acetone is added to the acetylation reactor at a flow rate of 8 L / h through a metering pump. At the same time, a 30% sodium hydroxide aqueous solution is added to the acetylation reactor at a flow rate of 0.055 L / h. The system temperature is maintained between 35°C and 45°C for reaction. A methylbutynol reaction mixture is generated through continuous reaction, and the material is transferred to a turnover pipe.

[0086] (2) The reaction mixture in the turnover tank is transferred to the quenching receiving tank, and a 10 wt% ammonium chloride aqueous solution is added to the quenching receiving tank at a rate of 580 g / h through a high-pressure solid feeder. The temperature is raised to 50-60 ° C and stirred for 1 hour. The quenched material is then transferred to a flash kettle to start recovering ammonia and acetylene. The temperature is raised to 60-65 ° C and ammonia is removed by flash evaporation until the residual ammonia is less than 0.1 wt%.

[0087] (3) The crude product after ammonia removal is transferred to an acetone recovery tower, the tower top temperature is controlled at 55-60°C, and the acetone is recovered by atmospheric distillation until the acetone residue in the tower bottom material is less than 0.2wt%.

[0088] (4) The crude methylbutynol product containing water obtained in the bottom of the tower was transferred to a dehydration tank, the temperature was controlled at 60-70°C, 3 kg of 50 wt% potassium carbonate was added, the mixture was stirred for 0.5 h, and the mixture was allowed to stand for 0.5 h. The upper organic phase was transferred to a methylbutynol tower for distillation and separation. The tower top pressure was controlled at 80 kPa and the tower top temperature was controlled at 80-82°C. 0.15 kg of azeotrope of methylbutynol and water was removed by azeotropic distillation. The fraction with a top temperature of 86-88°C was collected to obtain 7.64 kg of pure methylbutynol with a purity of 99.3 wt% and a yield of 83.5%.

[0089] Comparative Example 2

[0090] (1) A mixture of acetylene and liquid ammonia with an acetylene volume fraction of 18% in a gas cabinet is compressed to 2.2 MPa to form a compressed liquid, and the compressed liquid is transported to an acetylation reactor. After the system pressure is stabilized and the temperature is stabilized at 35°C, acetone is added to the acetylation reactor at a flow rate of 8 L / h through a metering pump. At the same time, a 50% potassium hydroxide aqueous solution is added to the acetylation reactor at a flow rate of 0.04 L / h. The system temperature is maintained between 35°C and 45°C for reaction. A methylbutynol reaction mixture is generated through continuous reaction, and the material is transferred to a turnover pipe.

[0091] (2) The reaction mixture in the turnover tank is transferred to the quenching receiving tank, and a 10 wt% ammonium chloride aqueous solution is added to the quenching receiving tank at a rate of 580 g / h through a high-pressure solid feeder. The temperature is raised to 50-60 ° C and stirred for 1 hour. The quenched material is then transferred to a flash kettle to start recovering ammonia and acetylene. The temperature is raised to 60-65 ° C and ammonia is removed by flash evaporation until the residual ammonia is less than 0.1 wt%.

[0092] (3) The crude product after ammonia removal is transferred to an acetone recovery tower, the tower top temperature is controlled at 55-60°C, and the acetone is recovered by atmospheric distillation until the acetone residue in the tower bottom material is less than 0.2wt%.

[0093] (4) The crude methylbutynol product containing water obtained in the bottom of the tower was transferred to a dehydration tank, the temperature was controlled at 60-70°C, 3 kg of 50% potassium carbonate was added, stirred for 0.5 h, allowed to stand for 0.5 h, and separated. The upper organic phase was transferred to a methylbutynol tower for distillation and separation. The tower top pressure was controlled at 80 kPa and the tower top temperature was controlled at 80-82°C. 0.15 kg of azeotrope of methylbutynol and water was removed by azeotropic distillation. The fraction with the top temperature of 86-88°C was collected to obtain 7.6 kg of pure methylbutynol with a purity of 99.3 wt% and a yield of 83.1%.

[0094] Table 1

[0095]

[0096] Table 1 - continued

[0097]

[0098]

[0099] The results in Table 1 show that the method of the present invention can achieve a higher yield and purity of methylbutynol. As can be seen from Examples 1-8 in Table 1, when the acetylene volume fraction, system pressure, and reaction temperature are within the preferred ranges of the present invention, the yield and purity of methylbutynol can be higher. In Examples 9 and 10, the acetylene volume fraction, system pressure, and reaction temperature are not within the preferred ranges, and therefore the yield and purity of methylbutynol are slightly reduced, indicating that the acetylene volume fraction, system pressure, and reaction temperature have an impact on the yield of methylbutynol, and that a higher yield can be achieved when the acetylene volume fraction, system pressure, and reaction temperature are within the preferred ranges of the present invention. As can be seen from Examples 1-8 in Table 1, the system The acetylene volume fraction, pressure, and reaction temperature are the same, and the methylbutynol obtained by using sodium hydroxide as the alkaline metal hydroxide has a higher yield and product purity; the difference between Comparative Examples 1 and 2 in Table 1 and Example 1 is that Comparative Examples 1 and 2 do not use the weakly alkaline carbonate defined in the present invention as a quenching agent, resulting in lower yield and purity of methylbutynol, and an additional salting-out and water separation operation is added, which increases investment costs and reduces production efficiency. In addition, the yield and purity of the product obtained by using solid ammonium bicarbonate as a quenching agent are higher than those obtained by using ammonium carbonate, sodium bicarbonate, and potassium bicarbonate as quenching agents.

[0100] In summary, in the method of the present invention for improving the yield and purity of methylbutynol, the above-mentioned effects are achieved by the combined action of the acetylene volume fraction, system pressure, reaction temperature, type of alkali metal hydroxide, and type of quenching agent.

[0101] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. A post-treatment purification method for methylbutynol, characterized in that, The method comprises the following steps: (1) quenching the methylbutynol reaction mixture by mixing it with a weakly alkaline carbonate, and flash evaporating the obtained quenched product; The methylbutynol reaction mixture comprises: compressed liquids of acetylene and liquid ammonia, alkali metal hydroxide, and acetone; The weak alkaline carbonate is selected from at least one of ammonium carbonate, ammonium bicarbonate, sodium bicarbonate and potassium bicarbonate; the molar ratio of the weak alkaline carbonate to the alkali metal hydroxide is 0.5-2:1; (2) The crude liquid product obtained in step (1) is subjected to acetone recovery, and the crude methylbutynol obtained is subjected to distillation to obtain pure methylbutynol.

2. The method according to claim 1, wherein In step (1), the weakly alkaline carbonate is ammonium bicarbonate.

3. The method according to claim 1, wherein The molar ratio of the weakly alkaline carbonate to the alkali metal hydroxide is 0.7-1.5:

1.

4. The method according to claim 1, wherein In step (1), the quenching temperature is 30-60°C.

5. The method according to claim 4, wherein In step (1), the quenching temperature is 40-60°C.

6. The method according to claim 1, wherein The quenching time is 0.5-3h.

7. The method according to claim 6, wherein: The quenching time is 1-2h.

8. The method according to claim 1, wherein The flash evaporation temperature is 50-70°C; the flash evaporation pressure is 0.05-0.1MPa.

9. The method according to claim 8, wherein The flash temperature is 60-65°C.

10. The method according to claim 1, wherein In step (2), the pressure of acetone recovery is normal pressure and the temperature is 55-60°C.

11. The method according to claim 1, wherein The distillation pressure is 10-100 kPa; the temperature is 40-104°C.

12. The method according to claim 11, wherein The distillation pressure is 50-100 kPa; the temperature is 80-104°C.

13. Use of the post-treatment purification method of methylbutynol according to any one of claims 1 to 12 in the preparation of methylbutynol.

14. A method for preparing methylbutynol, characterized in that: The preparation method comprises: (1) reacting a compressed liquid containing acetylene and liquid ammonia with acetone in the presence of an aqueous alkali metal hydroxide solution to obtain a methylbutynol reaction mixture; (2) post-treating and refining the methylbutynol reaction mixture to obtain pure methylbutynol, wherein the post-treating and refining method is the post-treating and refining method for methylbutynol according to any one of claims 1 to 12.

15. The method according to claim 14, wherein The compressed liquid is obtained by compressing a mixed gas of acetylene and liquid ammonia.

16. The method according to claim 15, wherein The volume fraction of acetylene in the mixed gas is 15-25%.

17. The method according to claim 16, wherein The volume fraction of acetylene in the mixed gas is 16-18%.

18. The method according to claim 14, wherein The compression pressure is 1.2-2.5 MPa.

19. The method according to claim 18, wherein The compression pressure is 2-2.2 MPa.

20. The method according to claim 14, wherein The reaction temperature is 20-50°C.

21. The method according to claim 20, wherein The reaction temperature is 35-45°C.

22. The method according to claim 14, wherein The alkali metal hydroxide is selected from sodium hydroxide and / or potassium hydroxide.

23. The method according to claim 22, wherein The alkali metal hydroxide is sodium hydroxide.

24. The method according to claim 14, wherein The molar ratio of the alkali metal hydroxide to acetone is 0.003-0.02:

1.

25. The method according to claim 24, wherein The molar ratio of the alkali metal hydroxide to acetone is 0.005-0.01:

1.

26. The method according to claim 14, wherein In the alkali metal hydroxide aqueous solution, the concentration of alkali metal hydroxide is 10-50 wt %.

27. The method according to claim 26, wherein In the alkali metal hydroxide aqueous solution, the concentration of alkali metal hydroxide is 30-50 wt %.

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