阅读说明：本技术 一种高纯度医用酒精的制备方法 (Preparation method of high-purity medical alcohol ) 是由 葛成斌 于 2021-08-11 设计创作，主要内容包括：本发明公开了一种高纯度医用酒精的制备方法,所述方法包括第一阶段：将95％的酒精溶液使用加热蒸馏法得到酒精I；第二阶段：将酒精I和吸水剂在容器中加热搅拌除水得到酒精II；第三阶段：将酒精II加热煮沸产生酒精II蒸汽,然后使用分离膜分离的方法对酒精II蒸汽进行除水处理,得到所述医用酒精。本发明制备方法得到的医用酒精其酒精含量均在99.89％以上,水含量均在0.1％以下。(The invention discloses a preparation method of high-purity medical alcohol, which comprises the following steps: heating and distilling 95% alcohol solution to obtain alcohol I; and a second stage: heating, stirring and dehydrating the alcohol I and the water absorbent in a container to obtain alcohol II; and a third stage: heating and boiling alcohol II to generate alcohol II steam, and then performing water removal treatment on the alcohol II steam by using a separation membrane separation method to obtain the medical alcohol. The medical alcohol prepared by the preparation method has the alcohol content of more than 99.89 percent and the water content of less than 0.1 percent.)

1. A process for the preparation of high purity medical alcohol, characterized in that it comprises a first stage: heating and distilling 95% alcohol solution to obtain alcohol I; and a second stage: heating, stirring and dehydrating the alcohol I and the water absorbent in a container to obtain alcohol II; and a third stage: heating and boiling alcohol II to generate alcohol II steam, and then performing water removal treatment on the alcohol II steam by using a separation membrane separation method to obtain the medical alcohol.

2. The method for preparing high-purity medical alcohol according to claim 1, wherein the method comprises the following specific steps:

the first stage is as follows: adding 95% alcohol solution into a distillation device, heating to 79-85 ℃ for distillation, condensing and collecting alcohol I;

and a second stage: adding alcohol I and a water absorbent into a container, then raising the temperature to 35-45 ℃, stirring for 2-4 h, filtering and collecting filtrate to obtain alcohol II;

and a third stage: and adding the alcohol II into a heating device, heating to 98-105 ℃, and removing water by using a separation membrane to generate steam to obtain the medical alcohol.

3. The method for producing high purity medical alcohol according to claim 1 or 2, wherein the water-absorbing agent is produced by:

s1: adding nickel acetate monohydrate into a deionized water solution, carrying out ultrasonic stirring, then adding potassium hydroxide and citric acid monohydrate, carrying out ultrasonic stirring for 30-45 min, then transferring into a high-pressure reaction kettle, then adding an alcohol solution, covering a high-pressure kettle reaction cover, placing in an oven, and carrying out reaction at 120-140 ℃ for two days to obtain Ni-MOF;

s2: adding polyvinyl alcohol into distilled water, ultrasonically dissolving, then adding humic acid, stirring and dissolving, standing for 1-2 h, adding Ni-MOF in the step S1 for dispersion, standing and aging for 6-8 h, then placing in a tubular furnace, and introducing a solvent with a volume ratio of 90: 10, calcining for 4-6 hours at 550-650 ℃ by using nitrogen and oxygen to obtain the water removing agent.

4. The method for preparing high-purity medical alcohol according to claim 3, wherein the mass-to-volume ratio of the nickel acetate monohydrate, the deionized water, the potassium hydroxide, the citric acid monohydrate and the alcohol is (1.23-1.45) g, (15-20) mL, (1.4-1.7) g, (1.37-1.68) g, (12-16) mL.

5. The method for preparing high-purity medical alcohol according to claim 3, wherein the mass ratio of the polyvinyl alcohol to the humic acid to the Ni-MOF is (16-22): (1.66-2.42): (4.2-4.6).

6. The method for preparing high purity medical alcohol according to claim 1 or 2, wherein the separation membrane is prepared by the following method:

1): adding gelatin, sodium chondroitin sulfate and sodium alginate into distilled water, ultrasonically stirring for dissolving, then adding a chelating agent, and continuously stirring for 15-25 min to obtain a gel solution;

2): transferring the gel solution obtained in the step 1) into an electrostatic spinning injection pump, wherein the injection voltage is 24-26 kV, the injection speed is 0.5-0.7L/h, the injection distance is 12-14 cm, obtaining a fiber membrane on a receiving roller, then putting the fiber membrane into a vacuum drying oven, and drying at 65-80 ℃ for 40-60 min to obtain the separation membrane.

7. The method for preparing high-purity medical alcohol according to claim 6, wherein the mass ratio of the gelatin to the sodium chondroitin sulfate to the sodium alginate is (0.8-0.9) to (0.5-0.7) to (0.7-0.86).

8. The method for preparing high purity medical alcohol according to claim 6, wherein the chelating agent is any one of citric acid and fumaric acid, and the addition amount of the chelating agent is 16-22 wt%.

Technical Field

The invention belongs to the technical field of chemical substance purification, and particularly relates to a preparation method of high-purity medical alcohol.

Background

Alcohol is a flammable, volatile, colorless, transparent liquid at ambient temperature and pressure, and its aqueous solution has a special, pleasant fragrance and is slightly irritating. The alcohol has wide application range, and can be used for preparing acetic acid, beverage, essence, dye, fuel, etc. The alcohol is a bulk chemical raw material, and can be used for producing a plurality of high value-added chemical products such as ethyl acetate, alcohol amine, ethylene and the like from alcohol, and the alcohol can be used as a fuel additive and can also be used as a raw material for preparing products such as dyes, coatings, detergents and the like. In addition, the alcohol also has wide application in the industrial fields of chemical industry, food, national defense, medicine, printing and dyeing and the like.

However, it is difficult to prepare medical alcohol by a general distillation method due to the azeotropic point of the alcohol-water system. At present, the common preparation methods of medical alcohol mainly comprise azeotropic distillation, membrane separation, molecular sieve adsorption, extractive distillation and extraction distillation with salt. Although the azeotropic distillation is suitable for large-scale production, the required energy consumption is high, the number of tower plates is large, and the problems of high energy consumption, entrainment of toxic solvent benzene and the like, which are easy to cause pollution, exist; although the membrane separation can reduce energy consumption, the temperature required by the operation is higher, the device is miniaturized, and the production scale is limited; molecular sieve adsorption is suitable for large-scale production, but the energy consumption required during regeneration is very high; the amount of the added extraction agent is large in the extraction and rectification, so that the energy consumption in the separation process is increased; the salt-added extractive distillation can improve the solvent effect and reduce the solvent ratio by adding salt into the solvent, but in industrial production, the metal material is corroded by the ring section of the salt in the adding process.

Disclosure of Invention

The invention aims to provide a preparation method of high-purity medical alcohol, which comprises the following steps: heating and distilling 95% alcohol solution to obtain alcohol I; and a second stage: heating, stirring and dehydrating the alcohol I and the water absorbent in a container to obtain alcohol II; and a third stage: heating and boiling alcohol II to generate alcohol II steam, and then performing water removal treatment on the alcohol II steam by using a separation membrane separation method to obtain the medical alcohol.

A preparation method of high-purity medical alcohol comprises the following specific steps:

the first stage is as follows: adding 95% alcohol solution into a distillation device, heating to 79-85 ℃ for distillation, condensing and collecting alcohol I.

And a second stage: adding alcohol I and a water absorbent into a container, then raising the temperature to 35-45 ℃, stirring for 2-4 h, filtering and collecting filtrate to obtain alcohol II.

And a third stage: and adding the alcohol II into a heating device, heating to 98-105 ℃, and removing water by using a separation membrane to generate steam to obtain the medical alcohol.

Preferably, the water absorbing agent is prepared by the following method:

s1: adding nickel acetate monohydrate into a deionized water solution, carrying out ultrasonic stirring, then adding potassium hydroxide and citric acid monohydrate, carrying out ultrasonic stirring for 30-45 min, then transferring into a high-pressure reaction kettle, then adding an alcohol solution, covering a high-pressure kettle reaction cover, placing in an oven, and carrying out reaction at 120-140 ℃ for two days to obtain the Ni-MOF.

S2: adding polyvinyl alcohol into distilled water, ultrasonically dissolving, then adding humic acid, stirring and dissolving, standing for 1-2 h, adding Ni-MOF in the step S1 for dispersion, standing and aging for 6-8 h, then placing in a tubular furnace, and introducing a solvent with a volume ratio of 90: 10, calcining for 4-6 hours at 550-650 ℃ by using nitrogen and oxygen to obtain the water removing agent.

More preferably, the mass-to-volume ratio of the nickel acetate monohydrate, the deionized water, the potassium hydroxide, the citric acid monohydrate and the alcohol is (1.23-1.45) g, (15-20) mL, (1.4-1.7) g, (1.37-1.68) g and (12-16) mL.

More preferably, the mass ratio of the polyvinyl alcohol to the humic acid to the Ni-MOF is (16-22): (1.66-2.42): (4.2-4.6).

More preferably, the above-mentioned

Preferably, the separation membrane is prepared by the following method:

1): adding gelatin, sodium chondroitin sulfate and sodium alginate into distilled water, ultrasonically stirring for dissolving, then adding a chelating agent, and continuously stirring for 15-25 min to obtain a gel solution.

2): transferring the gel solution obtained in the step 1) into an electrostatic spinning injection pump, wherein the injection voltage is 24-26 kV, the injection speed is 0.5-0.7L/h, the injection distance is 12-14 cm, obtaining a fiber membrane on a receiving roller, then putting the fiber membrane into a vacuum drying oven, and drying at 65-80 ℃ for 40-60 min to obtain the separation membrane.

More preferably, the mass ratio of the gelatin to the sodium chondroitin sulfate to the sodium alginate is (0.8-0.9): (0.5-0.7): 0.7-0.86).

More preferably, the chelating agent is any one of citric acid and fumaric acid, and the addition amount of the chelating agent is 16-22 wt%.

Compared with the prior art, the invention has the following beneficial effects:

(1) in the invention, the medical alcohol solution with the concentration of more than 99.90 percent is prepared by adopting a method of combining a distillation method, a water absorbent dehydration method and a membrane separation dehydration method to carry out dehydration treatment on the 95 percent alcohol solution, the preparation method is simple, and the prepared alcohol solution has high concentration and the water concentration is lower than 0.1 percent.

(2) According to the invention, the 95% alcohol solution is firstly subjected to dehydration by adopting a distillation method, then the water absorbent is used for dehydration treatment, and finally the membrane separation method is used for dehydration, so that the phenomenon that a small amount of water absorbent impurities are remained in the medical alcohol solution when the water is removed by using the traditional water absorbent is effectively avoided.

(3) According to the invention, the used water removing agent is a nickel metal organic framework material, the outer surface of the nickel metal organic framework material is coated with polyvinyl alcohol which is a hydrophilic and hydrophobic material, so that water molecules in an alcohol solution can be in better surface contact with the water removing agent, hydrophilic metal sites are arranged in Ni-MOF, the metal sites are exposed after calcination, and the water removing agent is added into medical alcohol as the water removing agent, has better affinity with the water molecules, and further has more excellent water removing effect.

(4) According to the invention, through the first stage and the second stage of the water removal process, the water content in alcohol is reduced, then three kinds of hydrophobic and alcohol hydrophilic substances, namely gelatin, sodium chondroitin sulfate and sodium alginate, are used for preparing the fiber separation membrane through an electrostatic spinning method, and the water removal treatment is carried out on the alcohol, so that a very small amount of water molecules in the alcohol solution separation membrane can be removed by the separation membrane, and the alcohol content of the medical alcohol solution is further improved.

Detailed Description

The following embodiments of the present invention are described in detail, and the embodiments are implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, it should be noted that, for those skilled in the art, a plurality of modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Example 1

A preparation method of high-purity medical alcohol specifically comprises the following steps:

the water absorbent is prepared by the following method:

s1: adding nickel acetate monohydrate into a deionized water solution, carrying out ultrasonic stirring, then adding potassium hydroxide and citric acid monohydrate, carrying out ultrasonic stirring for 30min, then transferring into a high-pressure reaction kettle, then adding an alcohol solution, covering a reaction cover of the high-pressure reaction kettle, placing in an oven, and reacting at 120 ℃ for two days to obtain Ni-MOF, wherein the mass-volume ratio of the nickel acetate monohydrate to the deionized water to the potassium hydroxide to the citric acid monohydrate to the alcohol is 1.23g:15mL:1.4g:1.37g:12 mL.

S2: adding polyvinyl alcohol into distilled water, carrying out ultrasonic dissolution, then adding humic acid, wherein the mass ratio of the polyvinyl alcohol to the humic acid to the Ni-MOF is 16:1.66:4.2, stirring and dissolving, standing for 1h, adding Ni-MOF in the step S1 for dispersion, standing and aging for 6h, then placing the mixture in a tube furnace, and introducing a mixture with the volume ratio of 90: calcining 10 parts of nitrogen and oxygen at 550 ℃ for 4 hours to obtain the water removal agent.

The separation membrane is prepared by the following method:

1): adding gelatin, sodium chondroitin sulfate and sodium alginate into distilled water, ultrasonically stirring for dissolving, then adding 16 wt% of citric acid or fumaric acid, wherein the mass ratio of the gelatin to the sodium chondroitin sulfate to the sodium alginate is 0.8:0.5:0.7, and continuously stirring for 15min to obtain a gel solution.

2): transferring the gel solution obtained in the step 1) into an electrostatic spinning injection pump, wherein the injection voltage is 24kV, the injection speed is 0.5L/h, the injection distance is 12cm, obtaining a fiber membrane on a receiving roller, then putting the fiber membrane into a vacuum drying oven, and drying for 40min at 65 ℃ to obtain the separation membrane.

The first stage is as follows: adding 95% alcohol solution into a distillation device, heating to 79 ℃ for distillation, and condensing to collect alcohol I.

And a second stage: adding alcohol I and water absorbent into a container, raising the temperature to 35 ℃, stirring for 2h, filtering and collecting filtrate to obtain alcohol II.

And a third stage: adding alcohol II into a heating device, heating to 98 deg.C, and removing water from the generated steam with a separation membrane to obtain medical alcohol.

Example 2

A preparation method of high-purity medical alcohol specifically comprises the following steps:

the water absorbent is prepared by the following method:

s1: adding nickel acetate monohydrate into a deionized water solution, carrying out ultrasonic stirring, then adding potassium hydroxide and citric acid monohydrate, carrying out ultrasonic stirring for 45min, then transferring into a high-pressure reaction kettle, then adding an alcohol solution, covering a reaction cover of the high-pressure reaction kettle, placing in an oven, and reacting at 140 ℃ for two days to obtain Ni-MOF, wherein the mass-volume ratio of the nickel acetate monohydrate to the deionized water to the potassium hydroxide to the citric acid monohydrate to the alcohol is 1.45g:20mL:1.7g:1.68g:16 mL.

S2: adding polyvinyl alcohol into distilled water, carrying out ultrasonic dissolution, then adding humic acid, wherein the mass ratio of the polyvinyl alcohol to the humic acid to the Ni-MOF is 22:2.42:4.6, stirring and dissolving, standing for 2 hours, adding Ni-MOF in the step S1 for dispersion, standing and aging for 8 hours, then placing the mixture in a tube furnace, and introducing a mixture with the volume ratio of 90: calcining 10 parts of nitrogen and oxygen at 650 ℃ for 6 hours to obtain the water removal agent.

The separation membrane is prepared by the following method:

1): adding gelatin, sodium chondroitin sulfate and sodium alginate into distilled water, ultrasonically stirring for dissolving, then adding 22 wt% of citric acid or fumaric acid, wherein the mass ratio of the gelatin to the sodium chondroitin sulfate to the sodium alginate is 0.9:0.7:0.86, and continuously stirring for 25min to obtain a gel solution.

2): transferring the gel solution obtained in the step 1) into an electrostatic spinning injection pump, wherein the injection voltage is 26kV, the injection speed is 0.7L/h, the injection distance is 14cm, obtaining a fiber membrane on a receiving roller, then putting the fiber membrane into a vacuum drying oven, and drying for 60min at 80 ℃ to obtain the separation membrane.

The first stage is as follows: adding 95% alcohol solution into a distillation device, heating to 85 ℃ for distillation, and condensing to collect alcohol I.

And a second stage: adding alcohol I and water absorbent into a container, then raising the temperature to 45 ℃, stirring for 4h, filtering and collecting filtrate to obtain alcohol II.

And a third stage: adding alcohol II into a heating device, heating to 105 deg.C, and removing water from the generated steam with a separation membrane to obtain medical alcohol.

Example 3

A preparation method of high-purity medical alcohol specifically comprises the following steps:

the water absorbent is prepared by the following method:

s1: adding nickel acetate monohydrate into a deionized water solution, carrying out ultrasonic stirring, then adding potassium hydroxide and citric acid monohydrate, carrying out ultrasonic stirring for 35min, then transferring into a high-pressure reaction kettle, then adding an alcohol solution, covering a reaction cover of the high-pressure reaction kettle, placing in an oven, and reacting at 130 ℃ for two days to obtain Ni-MOF, wherein the mass-volume ratio of the nickel acetate monohydrate to the deionized water to the potassium hydroxide to the citric acid monohydrate to the alcohol is 1.29g:16mL:1.5g:1.46g:13 mL.

S2: adding polyvinyl alcohol into distilled water, carrying out ultrasonic dissolution, then adding humic acid, wherein the mass ratio of the polyvinyl alcohol to the humic acid to the Ni-MOF is 18:1.96:4.4, standing for 2 hours after stirring and dissolving, adding the Ni-MOF in the step S1 for dispersion, standing and aging for 7 hours, then placing the mixture in a tube furnace, and introducing the mixture in a volume ratio of 90: calcining 10 parts of nitrogen and oxygen at 600 ℃ for 5 hours to obtain the water removal agent.

The separation membrane is prepared by the following method:

1): adding gelatin, sodium chondroitin sulfate and sodium alginate into distilled water, ultrasonically stirring for dissolving, then adding 18 wt% of citric acid or fumaric acid, wherein the mass ratio of the gelatin to the sodium chondroitin sulfate to the sodium alginate is 0.83:0.6:0.76, and continuously stirring for 20min to obtain a gel solution.

2): transferring the gel solution obtained in the step 1) into an electrostatic spinning injection pump, wherein the injection voltage is 25kV, the injection speed is 0.6L/h, the injection distance is 13cm, obtaining a fiber membrane on a receiving roller, then putting the fiber membrane into a vacuum drying oven, and drying for 45min at 70 ℃ to obtain the separation membrane.

The first stage is as follows: adding 95% alcohol solution into a distillation device, heating to 82 ℃ for distillation, and condensing to collect alcohol I.

And a second stage: adding alcohol I and water absorbent into a container, heating to 40 deg.C, stirring for 3 hr, filtering, and collecting filtrate to obtain alcohol II.

And a third stage: adding alcohol II into a heating device, heating to 100 deg.C, and removing water from the generated steam with a separation membrane to obtain medical alcohol.

Example 4

A preparation method of high-purity medical alcohol specifically comprises the following steps:

the water absorbent is prepared by the following method:

s1: adding nickel acetate monohydrate into a deionized water solution, carrying out ultrasonic stirring, then adding potassium hydroxide and citric acid monohydrate, carrying out ultrasonic stirring for 40min, then transferring into a high-pressure reaction kettle, then adding an alcohol solution, covering a reaction cover of the high-pressure reaction kettle, placing in an oven, and reacting at 130 ℃ for two days to obtain Ni-MOF, wherein the mass-volume ratio of the nickel acetate monohydrate to the deionized water to the potassium hydroxide to the citric acid monohydrate to the alcohol is 1.42g:18mL:1.6g:1.58g:15 mL.

S2: adding polyvinyl alcohol into distilled water, carrying out ultrasonic dissolution, then adding humic acid, wherein the mass ratio of the polyvinyl alcohol to the humic acid to the Ni-MOF is 20:2.21:4.5, standing for 2h after stirring and dissolving, adding the Ni-MOF in the step S1 for dispersion, standing and aging for 8h, then placing the mixture in a tube furnace, and introducing the mixture in a volume ratio of 90: calcining 10 parts of nitrogen and oxygen at 500 ℃ for 6 hours to obtain the water removal agent.

The separation membrane is prepared by the following method:

1): adding gelatin, sodium chondroitin sulfate and sodium alginate into distilled water, ultrasonically stirring for dissolving, then adding 20 wt% of citric acid or fumaric acid, wherein the mass ratio of the gelatin to the sodium chondroitin sulfate to the sodium alginate is 0.86:0.69:0.81, and continuously stirring for 23min to obtain a gel solution.

2): transferring the gel solution obtained in the step 1) into an electrostatic spinning injection pump, wherein the injection voltage is 25kV, the injection speed is 0.65L/h, the injection distance is 14cm, obtaining a fiber membrane on a receiving roller, then putting the fiber membrane into a vacuum drying oven, and drying for 55min at 75 ℃ to obtain the separation membrane.

The first stage is as follows: adding 95% alcohol solution into a distillation device, heating to 82 ℃ for distillation, and condensing to collect alcohol I.

And a second stage: adding alcohol I and water absorbent into a container, then raising the temperature to 45 ℃, stirring for 4h, filtering and collecting filtrate to obtain alcohol II.

And a third stage: adding alcohol II into a heating device, heating to 103 deg.C, and removing water from the generated steam with a separation membrane to obtain medical alcohol.

Examples of the experiments

And (3) performance testing: the components and contents of the medical alcohol prepared in examples 1 to 4 were measured by a mass spectrometer, and the results are shown in table 1,

TABLE 1 test data

As can be seen from Table 1, the medical alcohol prepared by the preparation methods of examples 1 to 4 of the present invention has an alcohol content of 99.89% or more, a water content of 0.1% or less, a methanol content of about 170ppm, and a lipid content of about 5ppm, which indicates that the methanol prepared by the method of the present invention has a high methanol content.