CN111807929A - Separation method of 2-methyl-3-butyne-2-ol - Google Patents

Separation method of 2-methyl-3-butyne-2-ol Download PDF

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CN111807929A
CN111807929A CN202010700825.XA CN202010700825A CN111807929A CN 111807929 A CN111807929 A CN 111807929A CN 202010700825 A CN202010700825 A CN 202010700825A CN 111807929 A CN111807929 A CN 111807929A
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CN111807929B (en
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鲍元野
杨颖�
刘英俊
张永振
黎源
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Wanhua Chemical Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
    • C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
    • C07C29/42—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing triple carbon-to-carbon bonds, e.g. with metal-alkynes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
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Abstract

The invention belongs to the technical field of acetylene alcohol production, and particularly relates to a separation method of 2-methyl-3-butyne-2-alcohol, which comprises the following steps: pretreating reaction liquid containing 2-methyl-3-butyn-2-ol, and removing unreacted acetone and contained salt to obtain a crude product of 2-methyl-3-butyn-2-ol; in the reaction liquid containing the 2-methyl-3-butyne-2-ol, the content of the 2, 5-dimethyl-3-hexyne-2, 5-diol is controlled to be less than or equal to 0.1 wt%; separating and purifying the crude product of the 2-methyl-3-butyn-2-ol by membrane separation treatment and vacuum rectification treatment to obtain a 2-methyl-3-butyn-2-ol product. The method can remove water in the product and reduce the content of 2, 5-dimethyl-3-hexyne-2, 5-diol under the condition of reducing investment and energy consumption, and obtains the 2-methyl-3-butyne-2-ol with higher purity and conversion rate.

Description

Separation method of 2-methyl-3-butyne-2-ol
Technical Field
The invention belongs to the technical field of acetylene alcohol production, and particularly relates to a separation method of high-purity 2-methyl-3-butyne-2-alcohol.
Background
2-methyl-3-butyn-2-ol is one of important acetylene alcohol chemicals and is mainly applied to the fields of corrosion inhibitors, food and medicine, other chemical products and the like. In the application aspect of the corrosion inhibitor, the molecules of the 2-methyl-3-butyn-2-ol have both polar groups and nonpolar groups, so the corrosion inhibitor can be used as an adsorption type corrosion inhibitor and can effectively prevent metal hydrogen embrittlement.
In addition, the downstream product methyl heptenone of 2-methyl-3-butyn-2-ol is an important medical intermediate and food intermediate, and can be used for further preparing linalool, citral and pseudoionone, and further preparing vitamin A, vitamin E, vitamin K1 and various spice essences. Furthermore, the 2-methyl-3-butyn-2-ol can generate tert-amyl alcohol, also called tert-amyl alcohol, after hydrogenation, and is mainly applied to synthetic perfumes, color developing agents of color cinematographic films, plasticizers, pesticides, medicines, dyes, metal flotation agents, organic solvents and the like. The 2-methyl-3-butyn-2-ol is partially hydrogenated to generate methyl butenol, and the prepared monomer can be used for producing 1, 4-cis polyisoprene which can be used for synthesizing rubber.
In the prior art, the ethynylation reaction for preparing 2-methyl-3-butyn-2-ol usually uses strong base solution as a catalyst, acetone and acetylene react in liquid ammonia, and after the reaction is finished, weak acid aqueous solution is used for neutralizing the catalyst, and then the post-treatment separation work of the product is carried out. The reaction formula of the alkynylation reaction is:
Figure BDA0002592976360000011
a great deal of research is carried out at home and abroad on the preparation of 2-methyl-3-butine-2-alcohol by the acetylene-acetone method, and the water-containing azeotrope of the 2-methyl-3-butine-2-alcohol is obtained by the reaction. 2-methyl-3-butyne-2-alcohol and water are completely mutually soluble, the boiling point of the formed azeotrope is 91 ℃, and the water content is 20-30%. In order to develop downstream products of 2-methyl-3-butyn-2-ol, it is then necessary to obtain anhydrous 2-methyl-3-butyn-2-ol. The water in the calcium chloride is removed by salting out and distillation, but the concentration of the 2-methyl-3-butyn-2-ol in the product obtained by the method after water removal can only reach 99 wt%, so that the raw material loss is large, and the purity cannot meet the requirement. Later, referring to a method for preparing anhydrous alcohol by benzene azeotropic distillation, benzene is taken as an azeotropic distillation entrainer, and an approximately anhydrous 2-methyl-3-butyne-2-alcohol product can be successfully obtained. This process is therefore widely used for the industrial production of 2-methyl-3-butyn-2-ol, for example, in patent documents DE1193496 and GB1023856, which disclose the purification of 2-methyl-3-butyn-2-ol by distillation in the presence of benzene.
In recent years, with the development of acetylene chemical industry in China, a method for preparing anhydrous 2-methyl-3-butyn-2-ol is required in the market, the use of the method is limited due to the toxicity of benzene in the conventional benzene azeotropic distillation method, and other methods are required for dehydration.
For example, patent document CN104470879A mentions reducing the water content therein by combining two, three or more pervaporation devices and/or membranes in series and/or by passing the retentate through the pervaporation devices two, three or more times. However, alcohol is a heat-sensitive substance and is easily polymerized under high temperature conditions. In the preparation process, in the presence of a certain amount of strong base, 2-methyl-3-butyn-2-ol is further reacted with acetone to generate a byproduct 2, 5-dimethyl-3-hexyne-2, 5-diol, which has the reaction formula:
Figure BDA0002592976360000021
the content of 2, 5-dimethyl-3-hexyne-2, 5-diol has a significant influence on the service life of the separation membrane used in the pervaporation unit. In addition, in order to ensure the dehydration effect, the polyvinyl alcohol film and/or the polyimide film used in such a method needs to be replaced periodically, which results in high industrial operation cost.
The prior process for separating 2-methyl-3-butine-2-alcohol mainly has the following defects:
1. the solvent azeotropic distillation method can form a ternary azeotropic mixture of water/entrainer/2-methyl-3-butyne-2-alcohol; the formation of ternary azeotrope can not be avoided, the separation effect of benzene as the entrainer is the best, and the proportion of the product in the water phase is the lowest; however, benzene is highly toxic, which limits its use.
When other entrainers are used, the one-way yield of the product is reduced, the total energy consumption is improved, and the cost control is not facilitated.
2. Adopting a membrane separation mode to remove water; the molecular weight of the 2-methyl-3-butyne-2-alcohol is close to that of water, and the solubility of the 2-methyl-3-butyne-2-alcohol and the water is excellent, so that the membrane separation operation is difficult, and the used polyvinyl alcohol membrane and/or polyimide membrane needs to be replaced regularly, so that the industrial operation cost is higher than that of the solvent azeotropic distillation method.
In addition, in the existing preparation process of 2-methyl-3-butyn-2-ol, in order to achieve better product selectivity, the dosage of acetylene needs to be increased; for safety reasons, the amount of liquid ammonia needs to be increased while the amount of acetylene is increased, but this increases the reactor investment and energy consumption. In view of cost, some manufacturers reduce the molar ratio of acetylene to acetone to about 1, and although such raw material ratio adjustment can reduce energy loss, the conversion rate and selectivity of the product are also obviously reduced, and the content of the generated 2, 5-dimethyl-3-hexyne-2, 5-diol in the product is even higher than 1%.
In view of the above analysis, how to efficiently obtain high-purity and high-quality 2-methyl-3-butyn-2-ol has become an important research subject.
Disclosure of Invention
Aiming at the problems that the conversion rate and selectivity of products are reduced and the content of 2, 5-dimethyl-3-hexyne-2, 5-diol is higher in the preparation and separation processes of 2-methyl-3-butyne-2-ol in the prior art, the invention aims to provide a separation method of high-purity 2-methyl-3-butyne-2-ol, which can effectively control the content of 2, 5-dimethyl-3-hexyne-2, 5-diol in a reaction liquid containing 2-methyl-3-butyne-2-ol, ensure the separation effect of membrane separation treatment in the separation and purification procedures and the service life of a membrane, further realize effective separation and purification and obtain a high-purity 2-methyl-3-butyne-2-ol product, improve the color number and the refractive index of the 2-methyl-3-butine-2-alcohol product.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a method of isolating 2-methyl-3-butyn-2-ol comprising:
(1) a pretreatment procedure: pretreating reaction liquid containing 2-methyl-3-butyn-2-ol, and removing unreacted acetone and contained salt to obtain a crude product of 2-methyl-3-butyn-2-ol; in the reaction liquid containing the 2-methyl-3-butyn-2-ol, the content of the 2, 5-dimethyl-3-hexyne-2, 5-diol is controlled to be less than or equal to 0.1wt percent, preferably less than or equal to 0.06wt percent;
(2) separation and purification procedures: separating and purifying the crude product of the 2-methyl-3-butyn-2-ol by membrane separation treatment and vacuum rectification treatment to obtain a 2-methyl-3-butyn-2-ol product.
According to the separation method provided by the invention, in some examples, the separation method comprises the following steps:
(1) a pretreatment procedure: rectifying the reaction liquid containing the 2-methyl-3-butyn-2-ol to remove acetone, and distilling or rectifying to desalt to obtain a crude product of the 2-methyl-3-butyn-2-ol;
in the crude product of the 2-methyl-3-butyn-2-ol, the content of water is 10 to 40 weight percent, the content of acetone is less than or equal to 1 weight percent, and the content of 2, 5-dimethyl-3-hexyne-2, 5-diol is less than or equal to 0.1 weight percent;
(2) separation and purification procedures: performing membrane separation treatment on the crude product of the 2-methyl-3-butyn-2-ol to obtain a mixture containing the 2-methyl-3-butyn-2-ol, wherein the content of water is less than or equal to 5%; and then carrying out vacuum rectification treatment on the mixture containing the 2-methyl-3-butyn-2-ol to obtain a 2-methyl-3-butyn-2-ol product, wherein the content of water is less than or equal to 1 wt%.
In some examples, the acetone removal and desalination processes performed in the pretreatment step of step (1) are not in sequence, that is, the acetone may be removed first and then desalinated, or the acetone may be desalted first and then desalinated.
For example, the acetone removal can be achieved by means of rectification. Optionally, a rectification column, which may be a tray column or a packed column, is used for acetone removal, as is well known to those skilled in the art. In some examples, the reaction liquid obtained by the alkynylation reaction is subjected to acetone removal treatment by using an atmospheric distillation mode in the process of using the distillation tower. For example, the operation temperature of the bottom of the rectifying tower is 90-93 ℃, the reflux ratio is 3:1, and the acetone content in the reaction liquid after acetone removal treatment can be lower than 0.5 wt%.
Desalination can be achieved, for example, by distillation or rectification, as is well known to those skilled in the art. In some examples, the desalting device can be a thin film evaporator or a short path distiller, preferably a horizontal thin film evaporator, a metal scraper operated at normal pressure, and an external circulating 80-120 ℃ oil bath.
In order to increase the lifetime of the permeable membrane used in the membrane separation process, the content of 2, 5-dimethyl-3-hexyne-2, 5-diol contained in the crude 2-methyl-3-butyn-2-ol needs to be strictly limited to less than 0.1 wt%. The content of 2, 5-dimethyl-3-hexyne-2, 5-diol has a very adverse effect on the service life of the osmotic membrane, and if the content of 2, 5-dimethyl-3-hexyne-2, 5-diol is too high, the pore channels of the osmotic membrane are blocked, so that the flux is reduced, the service life of the membrane is influenced, and the water removal effect is influenced. Therefore, in order to ensure the service life of the permeable membrane used in the membrane separation process and the separation and water removal effects, the content of the byproduct 2, 5-dimethyl-3-hexyne-2, 5-diol in the reaction liquid obtained by the ethynylation reaction can be controlled.
In order to ensure the product quality, the content of 2, 5-dimethyl-3-hexyne-2, 5-diol in the finally obtained 2-methyl-3-butyne-2-ol product can be controlled. In some preferred embodiments, the 2-methyl-3-butyn-2-ol product of step (2) has a 2, 5-dimethyl-3-hexyn-2, 5-diol content of 0.01 wt% or less.
In some examples, in the membrane separation treatment of step (2), at least one membrane separator for separating water from 2-methyl-3-butyn-2-ol is used; the membrane separator is provided with a hydrophilic membrane (or a permeable membrane).
In some preferred embodiments, the hydrophilic membrane is selected from a polyvinyl alcohol membrane, a polyimide membrane, or a ceramic membrane, more preferably a polyvinyl alcohol membrane or a polyimide membrane.
In some examples, the operating temperature of the membrane separation process using the hydrophilic membrane is 0 ℃ or higher and 100 ℃ or lower (e.g., 20 ℃, 40 ℃, 60 ℃, 80 ℃).
Alternatively, the hydrophilic membrane may also be, for example, a ceramic membrane based on zeolite a. The ceramic membrane used for pervaporation comprises a nanoporous layer on a macroporous support. The pores must be large enough to allow the passage of water molecules and small enough to retain 2-methyl-3-butyn-2-ol. The surface may be modified by a specific coating or treatment. Such films have been used to remove water from organic reaction mixtures and are available from FOLEX, switzerland. The material of the hydrophilic membrane is well known to those skilled in the art and will not be described herein.
According to the separation method provided by the invention, in some preferred embodiments, the operation process of the step (2) comprises:
(i) treating the crude 2-methyl-3-butyn-2-ol product by a membrane separator, and separating an aqueous organic phase stream and an aqueous phase stream; wherein, in the aqueous organic phase stream (based on the total weight of all components in the aqueous organic phase stream being 100 wt%), the content of water is less than or equal to 5 wt%, and the content of 2-methyl-3-butyn-2-ol is greater than or equal to 90 wt%; in the water phase stream, the content of water is more than or equal to 95 wt%, and the content of 2-methyl-3-butyn-2-ol is less than or equal to 1 wt% (based on the total weight of all components in the water phase stream as 100 wt%);
(ii) the organic phase flow strand containing water enters a crude distillation column for treatment, a light component flow is extracted from the top of the crude distillation column, and the content of water in the light component flow (calculated by the total weight of all components in the light component flow being 100 wt%) is 5-30 wt%; a stream to be subjected to heavy component removal is extracted from the bottom of the crude rectifying tower, wherein the content of water in the stream to be subjected to heavy component removal is less than or equal to 1 wt% (based on the total weight of all components in the stream to be subjected to heavy component removal being 100 wt%);
(iii) the stream of the heavy components to be removed enters a product separation tower for treatment, and a product stream is collected from the top of the product separation tower; in the product stream (based on the total weight of all components in the product stream being 100 wt%), the content of 2-methyl-3-butyn-2-ol is more than or equal to 99 wt%, the content of water is less than or equal to 1 wt%, and the content of 2, 5-dimethyl-3-hexyne-2, 5-diol is less than or equal to 0.01 wt%; and (3) a heavy component stream is produced at the bottom of the product separation tower, wherein the content of the 2-methyl-3-butyne-2-ol in the heavy component stream (calculated by taking the total weight of all components in the heavy component stream as 100 wt%) is less than or equal to 70 wt%.
The heavy component stream has high molecular weight component ratio and high viscosity, so that a part of 2-methyl-3-butyn-2-ol product is required to be present for ensuring the fluidity of the stream.
The crude distillation column here is such that sufficiently ideal separation conditions can be achieved. In some examples, the number of theoretical plates in the rectifying section of the crude rectifying tower is more than or equal to 5 (for example, 6, 8, 12, 14, 20), and preferably 10 to 15.
In some examples, the crude rectification column is operated at a pressure of 50hPa to 300hPa (e.g., 60hPa, 80hPa, 150hPa, 200hPa, 250hPa), preferably 100hPa to 200 hPa; the operation temperature of the bottom of the crude distillation column is 100 ℃ to 130 ℃ (for example, 115 ℃ and 120 ℃), preferably 110 ℃ to 125 ℃.
In some examples, the heavy component to be removed stream from the bottom of the crude distillation column enters from the middle of the product separation column, and 2-methyl-3-butyn-2-ol is separated from other components in the product separation column.
In some examples, the product separation column has a theoretical plate number of 5 or more (e.g., 6, 8, 12, 14, 20), preferably 10 to 15;
in some examples, the product separation column is operated at a pressure of 50hPa to 300hPa (e.g., 60hPa, 80hPa, 150hPa, 200hPa, 250hPa), preferably 100hPa to 200 hPa; the operating temperature of the bottom of the product separation tower is 100 ℃ to 130 ℃ (for example, 115 ℃ and 120 ℃), and is preferably 110 ℃ to 125 ℃.
The quality of the product 2-methyl-3-butyn-2-ol can be influenced by the content of the byproduct 2, 5-dimethyl-3-hexyne-2, 5-diol contained in the product, namely, the color number and the refractive index of the 2-methyl-3-butyn-2-ol product can be adversely influenced; therefore, the content of the by-product can be further effectively controlled by adjusting the parameters of the process conditions during the process of removing water therefrom. In some examples, after the separation and purification steps, the resulting 2-methyl-3-butyn-2-ol product has a water content of less than or equal to 1 wt.% (e.g., 0.8 wt.%, 0.5 wt.%, 0.3 wt.%, 0.1 wt.%) and a 2, 5-dimethyl-3-hexyne-2, 5-diol content of less than or equal to 0.01 wt.% (e.g., 0.008 wt.%, 0.005 wt.%, 0.003 wt.%, 0.001 wt.%).
According to the separation method provided by the invention, in some preferred embodiments, the reaction liquid containing 2-methyl-3-butyn-2-ol is prepared by a method comprising the following steps:
mixing acetone, acetylene and divalent metal salt in liquid ammonia to react by using strong base as a catalyst; after the reaction is finished, adding a weakly acidic aqueous solution to neutralize the catalyst in the system, and preparing a reaction solution containing 2-methyl-3-butyne-2-ol; the reaction solution containing 2-methyl-3-butyn-2-ol contains 2, 5-dimethyl-3-hexyne-2, 5-diol in an amount of 0.1 wt% or less (for example, in an amount of 0.08 wt%, 0.06 wt%, 0.04 wt%, 0.02 wt%).
In the preparation of the reaction solution, the reaction temperature and time are well known to those skilled in the art and will not be described herein.
Both strong and weak acidic aqueous solutions herein can be routinely selected in the art. For example, the strong base may be selected from sodium hydroxide, potassium hydroxide; the weakly acidic aqueous solution may be selected from aqueous ammonium sulfate solutions. The amount of the strong base to be used in the reaction system is well known to those skilled in the art and will not be described herein. The amount of the weakly acidic aqueous solution to be added is, for example, an amount capable of neutralizing a strong base present in the reaction system just enough.
The reaction solution obtained by the ethynylation reaction contains various other components, such as a by-product of 2, 5-dimethyl-3-hexyne-2, 5-diol, water, unreacted raw material acetone, inorganic salts or other impurities, in addition to 2-methyl-3-butyn-2-ol. In some examples, the reaction liquid containing 2-methyl-3-butyn-2-ol contains 10-40 wt% of water and 1-20 wt% of unreacted raw material acetone (based on 100 wt% of the total weight of the components in the reaction liquid). In the reaction solution, the amount of the inorganic salt contained is related to the amounts of the strong base and the weakly acidic aqueous solution added during the reaction.
According to the separation method provided by the present invention, in some examples, the divalent metal salt is selected from one or more of a divalent zinc salt, a divalent magnesium salt and a divalent cobalt salt, preferably one or more of zinc acetate, magnesium sulfate and cobalt chloride, more preferably zinc acetate and/or magnesium sulfate, and more preferably zinc acetate.
In some examples, the divalent metal salt is used in an amount of 0.01% to 0.1% (e.g., 0.015%, 0.03%, 0.05%, 0.08%, 0.09%) by mass of acetone, preferably 0.02% to 0.05%.
In some examples, the molar ratio of acetylene to acetone is greater than or equal to 1:1 and less than or equal to 3:1 (e.g., 1.1:1, 1.3:1, 1.5:1, 1.8:1, 2.2:1, 2.5:1, 2.8:1), preferably 1.05:1 to 2:1, during the preparation of the reaction solution. Under the condition of proper molar ratio of acetylene to acetone, the divalent metal salt is added into the system, so that the content of 2, 5-dimethyl-3-hexyne-2, 5-diol in the reaction liquid containing the 2-methyl-3-butyn-2-ol can be effectively controlled, and the reaction liquid is ensured to be in a lower content range (less than or equal to 0.1 wt%).
During the reaction, the effect of controlling the molar ratio of acetone to acetylene within this range is: under the condition of ensuring a certain acetylene content, divalent metal salt is introduced to inhibit the generation of byproducts and improve the selectivity of the product; meanwhile, on the premise of ensuring safety, the energy loss can be reduced by reducing the molar ratio of acetylene to acetone, and the cost is saved. In order to integrate the selectivity of the product and the energy consumption, the molar ratio of acetylene to acetone is preferably 1.05: 1-2: 1.
On one hand, the selectivity of the ethynylation reaction product can be improved by adjusting the adding amount of acetylene in the ethynylation reaction and adding divalent metal salt in the system, and the content of the byproduct 2, 5-dimethyl-3-hexyne-2, 5-diol in the prepared reaction liquid can be effectively controlled. The amount of the divalent metal salt added also affects the content of 2, 5-dimethyl-3-hexyne-2, 5-diol in the reaction solution. The content of the 2, 5-dimethyl-3-hexyne-2, 5-diol in the reaction liquid is controlled to be less than or equal to 0.1 weight percent, so that the membrane separation effect in the separation and purification procedures can be ensured, and the service life of the permeable membrane can be prolonged. On the other hand, the content of the 2, 5-dimethyl-3-hexyne-2, 5-diol in the separated product can be controlled in the process of separating the reaction liquid containing the 2-methyl-3-butyne-2-ol, so that the content of the reaction liquid is further reduced, and the quality of the obtained product is ensured.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
by the separation method, water in the 2-methyl-3-butyn-2-ol product can be removed and the content of 2, 5-dimethyl-3-hexyne-2, 5-diol can be reduced under the condition of reducing investment and energy consumption, and the 2-methyl-3-butyn-2-ol with higher purity and conversion rate can be prepared.
Under the working condition that the molar ratio of acetylene to acetone is low, by adding divalent metal salt into the system, the generation of byproducts in the reaction process can be effectively inhibited, so that the content of 2, 5-dimethyl-3-hexyne-2, 5-diol in the obtained reaction liquid containing 2-methyl-3-butyne-2-ol is controlled to be in a lower range (for example, less than or equal to 0.1wt percent), and the product selectivity is improved; meanwhile, the energy consumption and the purification difficulty can be reduced.
By strictly controlling the content of the key component 2, 5-dimethyl-3-hexyne-2, 5-diol in the obtained reaction liquid containing 2-methyl-3-butyne-2-ol, the water removal effect in the membrane separation process and the service life of the used permeable membrane can be improved, the replacement frequency of the permeable membrane is obviously reduced, for example, the replacement is changed from monthly replacement to once every half year, and the separation cost is reduced.
By controlling the content of a key component 2, 5-dimethyl-3-hexyne-2, 5-diol in the obtained reaction liquid containing the 2-methyl-3-butyne-2-ol, powerful conditions are provided for further membrane separation treatment and rectification treatment of a crude product of the 2-methyl-3-butyne-2-ol, so that the 2-methyl-3-butyne-2-ol in the product is fully separated from the water, meanwhile, the content of 2, 5-dimethyl-3-hexyne-2, 5-diol (for example, less than or equal to 0.01 wt%) is further reduced, the purpose of controlling the quality of the product 2-methyl-3-butyne-2-ol is achieved, and qualified products with high quality and high purity can be obtained.
The membrane separation process is adopted to replace the original azeotropic distillation process, so that the operation process is simplified, and the industrial controllability is better.
Drawings
FIG. 1 is a process flow diagram of a separation and purification process in one embodiment of the separation method of the present invention.
The reference numerals in the figures are explained below:
1-2-methyl-3-butyn-2-ol crude product, 2-aqueous organic phase stream, 3-aqueous phase stream, 4-light components stream, 5-heavy components to be removed stream, 6-product stream, 7-heavy components stream;
SEP-membrane separator, RAC 1-crude distillation column, COOLER 1-overhead condenser, REBOILER 1-bottom REBOILER;
RAC2 product splitter, COOLER2 overhead condenser, REBOILER2 bottoms REBOILER.
Detailed Description
In order that the technical features and contents of the present invention can be understood in detail, preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention have been described in the examples, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.
< sources of raw materials >
99 wt% of acetone and Shandong vitamin chemical industry;
acetylene, 98 wt%, Qingdao acetylene gas, Inc.;
99 wt% of liquid ammonia, Dongying Hengsheng chemical Co., Ltd;
magnesium sulfate, 99 wt%, carbofuran technologies ltd;
zinc acetate, 99 wt%, welfare technologies ltd;
potassium hydroxide, denna blooms chemical ltd;
ammonium sulfate, 99 wt%, largeway technologies ltd.
< analytical method >
The test methods for each example and comparative example are as follows:
1. the composition of each component in the stream adopts a gas chromatograph: agilent7820A, column HP-5(30 m.times.320. mu.m.times.0.25 μm), injection port temperature: 150 ℃; the split ratio is 50: 1; carrier gas flow: 1.5 ml/min;
temperature rising procedure: keeping at 40 deg.C for 1min, heating to 90 deg.C at 10 deg.C/min for 0min, heating to 160 deg.C at 5 deg.C/min for 0min, heating to 280 deg.C at 30 deg.C/min for 6 min. Detector temperature: 280 ℃.
2. Refractive index test of the product: METTLER TOLEDO refractometer Easy R40 was used.
3. Color number test of the product: a HANNA platinum cobalt (Pt-Co) colorimeter was used.
Example 1: preparation of No. 1 reaction solution
Firstly, replacing a 500L high-pressure kettle with ammonia gas for 3 times, reducing the temperature in the reaction kettle to-20 ℃, adding liquid ammonia (144.5Kg, 8500mol), starting stirring, introducing acetylene (16800L, 750mol), adding 43.5g of magnesium sulfate aqueous solution with the concentration of 20 wt% and potassium hydroxide aqueous solution with the concentration of 50 wt% (1008g, the using amount of potassium hydroxide as solute is 3 mol% of acetone), heating to 10 ℃, adding acetone (17.4Kg, 300mol), and controlling the adding rate of the acetone to finish feeding within about 1 hour; the reaction temperature is 10 ℃, 5Kg of ammonium sulfate aqueous solution with the concentration of 10 wt% is added for neutralization after 2 hours of reaction, 1# reaction solution containing 2-methyl-3-butyn-2-ol is obtained, and the reaction solution is sampled and detected by GC.
Composition of # 1 reaction solution: the inorganic salt content is 2.16 wt%, the water content is 16.61 wt%, the 2-methyl-3-butyn-2-ol content is 77.30 wt%, the acetone content is 3.56 wt%, the 2, 5-dimethyl-3-hexyne-2, 5-diol content is 0.05 wt%, and the other components content is 0.32 wt%, based on the total weight of the components of the No. 1 reaction liquid as 100 wt%.
Example 2: preparation of 2# reaction solution
Firstly, replacing a 500L high-pressure kettle with ammonia gas for 3 times, reducing the temperature in the reaction kettle to-20 ℃, adding liquid ammonia (144.5Kg, 8500mol), starting stirring, introducing acetylene (16800L, 750mol), adding 17.5g of zinc acetate aqueous solution with the concentration of 20 wt%, adding 50 wt% of potassium hydroxide aqueous solution (1008g, the using amount of potassium hydroxide as solute is 3 mol% of acetone), heating to 10 ℃, adding acetone (17.4Kg, 300mol), and controlling the adding rate of the acetone to finish feeding within about 1 hour; the reaction temperature is 10 ℃, 5Kg of ammonium sulfate aqueous solution with the concentration of 10 wt% is added for neutralization after 2 hours of reaction, 2# reaction liquid containing 2-methyl-3-butyn-2-ol is obtained, and the reaction liquid is sampled and detected by GC.
Composition of # 2 reaction solution: the inorganic salt content is 2.17 wt%, the water content is 16.62 wt%, the 2-methyl-3-butyn-2-ol content is 77.27 wt%, the acetone content is 3.52 wt%, the 2, 5-dimethyl-3-hexyne-2, 5-diol content is 0.02 wt%, and the other components content is 0.40 wt%, based on the total weight of the components of the 2# reaction solution as 100 wt%.
Example 3: preparation of 3# reaction solution
Firstly, replacing a 500L high-pressure kettle with ammonia gas for 3 times, reducing the temperature in the reaction kettle to-20 ℃, adding liquid ammonia (144.5Kg, 8500mol), starting stirring, introducing acetylene (16800L, 750mol), adding 8.7g of zinc acetate aqueous solution with the concentration of 20 wt%, adding 50 wt% potassium hydroxide aqueous solution (1008g, the using amount of potassium hydroxide as solute is 3 mol% of acetone), heating to 10 ℃, adding acetone (17.4Kg, 300mol), and controlling the adding rate of the acetone to finish feeding within about 1 hour; the reaction temperature is 10 ℃, 5Kg of ammonium sulfate aqueous solution with the concentration of 10 wt% is added for neutralization after 2 hours of reaction, 3# reaction liquid containing 2-methyl-3-butyn-2-ol is obtained, and the reaction liquid is sampled and detected by GC.
Composition of reaction solution # 3: the inorganic salt content is 2.17 wt%, the water content is 16.62 wt%, the 2-methyl-3-butyn-2-ol content is 77.41 wt%, the acetone content is 3.32 wt%, the 2, 5-dimethyl-3-hexyne-2, 5-diol content is 0.06 wt%, and the other components content is 0.42 wt%, based on the total weight of the components of the No. 3 reaction liquid as 100 wt%.
Example 4: preparation of No. 4 reaction solution
Firstly, replacing a 500L high-pressure kettle with ammonia gas for 3 times, reducing the temperature in the reaction kettle to-20 ℃, adding liquid ammonia (30.35Kg, 1785mol), starting stirring, introducing acetylene (7056L, 315mol), adding 87g of a cobalt chloride aqueous solution with the concentration of 20 wt%, adding a potassium hydroxide aqueous solution with the concentration of 50 wt% (840g, wherein the using amount of potassium hydroxide as a solute is 2.5 mol% of acetone), heating to 10 ℃, adding acetone (17.4Kg, 300mol), and controlling the adding rate of the acetone to finish feeding within about 1 hour; the reaction temperature is 10 ℃, 4.5Kg of ammonium sulfate aqueous solution with the concentration of 10 wt% is added for neutralization after 2 hours of reaction, 4# reaction solution containing 2-methyl-3-butyn-2-ol is obtained, and the reaction solution is sampled and detected by GC.
Composition of # 4 reaction solution: the content of inorganic salt is 1.81 wt%, the content of water is 15.30 wt%, the content of 2-methyl-3-butyn-2-ol is 76.57 wt%, the content of acetone is 5.75 wt%, the content of 2, 5-dimethyl-3-hexyne-2, 5-diol is 0.08 wt%, the content of other components is 0.49 wt%, and the total weight of all the components of the No. 4 reaction liquid is 100 wt%.
Example 5: pretreatment of No. 1 reaction solution
1) Desalting the No. 1 reaction liquid obtained by the ethynylation reaction by adopting a thin film evaporator, wherein the temperature of an external circulating oil bath of the thin film evaporator is 80 ℃, and the operating pressure of the thin film evaporator is 800 hPa. Composition of # 1 reaction solution: the content of inorganic salt was 2.16 wt%, the content of water was 16.61 wt%, the content of 2-methyl-3-butyn-2-ol was 77.30 wt%, the content of acetone was 3.56 wt%, the content of 2, 5-dimethyl-3-hexyne-2, 5-diol was 0.05 wt%, and the content of other components was 0.32 wt%.
The No. 1 reaction solution was passed to a thin film evaporator. The feeding rate of the No. 1 reaction liquid is 0.950kg/h, the extraction rate of the upper outlet of the thin film evaporator is 0.902kg/h, and the composition of the extracted liquid phase is as follows: the content of water was 16.98 wt%, the content of 2-methyl-3-butyn-2-ol was 79.01 wt%, the content of acetone was 3.64 wt%, the content of 2, 5-dimethyl-3-hexyne-2, 5-diol was 0.05 wt%, the content of other components was 0.32 wt%, and the total weight of the components of the above-outlet produced liquid phase was 100 wt%. The take-off rate at the lower outlet of the thin-film evaporator was 0.048 kg/h.
2) The produced liquid phase at the outlet of the thin film evaporator is subjected to acetone removal treatment by adopting a plate mesh corrugated packed tower, the tower diameter of a rectifying tower (or the packed tower) is 100mm, the height of a packing layer is 0.5m, the number of theoretical plates is 5, and the produced liquid phase comprises: the water content was 16.98 wt.%, the 2-methyl-3-butyn-2-ol content was 79.01 wt.%, the acetone content was 3.64 wt.%, the 2, 5-dimethyl-3-hexyne-2, 5-diol content was 0.05 wt.%, and the other components were 0.32 wt.%.
The produced liquid phase enters a rectifying tower from a feed pipeline at the 4 th theoretical plate at the lower part of the tower. The operating pressure of the rectification column was 1 Kpa. The condenser at the top of the tower uses cooling water of 10 ℃ as a refrigerant, and the operation temperature at the bottom of the tower is 92-93 ℃. The reflux and extraction ratio of the condensate flowing out of the condenser at the top of the rectifying tower is 3: 1.
The composition of the liquid phase extracted from the top of the rectifying tower is as follows: the content of water was 19.35 wt%, the content of 2-methyl-3-butyn-2-ol was 48.27 wt%, the content of acetone was 32.15 wt%, and the content of other components was 0.23 wt%, based on 100 wt% of the total weight of the components in the overhead produced liquid phase.
The composition of liquid phase extracted from the bottom of the rectifying tower is as follows: the content of water is 16.72 wt%, the content of 2-methyl-3-butyn-2-ol is 82.37 wt%, the content of acetone is 0.52 wt%, the content of 2, 5-dimethyl-3-hexyne-2, 5-diol is 0.06 wt%, the content of other components is 0.33 wt%, and the total weight of all components in a tower bottom produced liquid phase is 100 wt%; thus obtaining the crude product of 2-methyl-3-butyne-2-ol.
Example 6: pretreatment of 2# reaction solution
1) Desalting the No. 2 reaction liquid obtained by the ethynylation reaction by adopting a thin film evaporator, wherein the temperature of an external circulating oil bath of the thin film evaporator is 80 ℃, and the operating pressure of the thin film evaporator is 800 hPa. Composition of # 2 reaction solution: the content of inorganic salt was 2.17 wt%, the content of water was 16.62 wt%, the content of 2-methyl-3-butyn-2-ol was 77.27 wt%, the content of acetone was 3.52 wt%, the content of 2, 5-dimethyl-3-hexyne-2, 5-diol was 0.02 wt%, and the content of other components was 0.40 wt%.
And (3) introducing the No. 2 reaction solution into a thin film evaporator. The feeding rate of the No. 2 reaction liquid is 0.950kg/h, the extraction rate of the upper outlet of the thin film evaporator is 0.902kg/h, and the composition of the extracted liquid phase is as follows: the content of water was 16.99 wt%, the content of 2-methyl-3-butyn-2-ol was 78.98 wt%, the content of acetone was 3.60 wt%, the content of 2, 5-dimethyl-3-hexyne-2, 5-diol was 0.02 wt%, the content of other components was 0.41 wt%, and the total weight of the components of the above-outlet extraction liquid phase was 100 wt%. The take-off rate at the lower outlet of the thin-film evaporator was 0.048 kg/h.
2) The produced liquid at the outlet of the thin film evaporator is subjected to acetone removal treatment by adopting a plate mesh corrugated packed tower, the tower diameter of a rectifying tower (or the packed tower) is 100mm, the height of a packing layer is 0.5m, the number of theoretical plates is 5, and the produced liquid phase composition is as follows: the water content was 16.99% by weight, the 2-methyl-3-butyn-2-ol content was 78.98% by weight, the acetone content was 3.60% by weight, the 2, 5-dimethyl-3-hexyne-2, 5-diol content was 0.02% by weight, and the other components were 0.41% by weight.
The produced liquid enters the rectifying tower from a feed line at the 4 th theoretical plate at the lower part of the tower. The operating pressure of the rectification column was 1 Kpa. The condenser at the top of the tower uses cooling water of 10 ℃ as a refrigerant, and the operation temperature at the bottom of the tower is 92-93 ℃. The reflux and extraction ratio of the condensate flowing out of the condenser at the top of the rectifying tower is 3: 1.
The composition of the liquid phase extracted from the top of the rectifying tower is as follows: the content of water was 19.38 wt%, the content of 2-methyl-3-butyn-2-ol was 48.15 wt%, the content of acetone was 32.12 wt%, and the content of other components was 0.35 wt%, based on 100 wt% of the total weight of the components in the overhead produced liquid phase.
The composition of liquid phase extracted from the bottom of the rectifying tower is as follows: the content of water is 16.73 wt%, the content of 2-methyl-3-butyn-2-ol is 82.35 wt%, the content of acetone is 0.48 wt%, the content of 2, 5-dimethyl-3-hexyne-2, 5-diol is 0.02 wt%, the content of other components is 0.42 wt%, and the total weight of all components in a tower bottom produced liquid phase is 100 wt%; thus obtaining the crude product of 2-methyl-3-butyne-2-ol.
Example 7: pretreatment of 3# reaction solution
1) The 3# reaction liquid obtained by the reaction is subjected to acetone removal treatment by adopting a plate mesh corrugated packed tower, the tower diameter of a rectifying tower (packed tower) is 100mm, the height of a packing layer is 0.5m, and the number of theoretical plates is 5; composition of reaction solution # 3: 2.17 wt% of inorganic salt, 16.62 wt% of water, 77.41 wt% of 2-methyl-3-butyn-2-ol, 3.32 wt% of acetone, 0.06 wt% of 2, 5-dimethyl-3-hexyne-2, 5-diol and 0.42 wt% of other components.
The No. 3 reaction liquid enters the rectifying tower from a feed line at the 4 th theoretical plate at the lower part of the tower. The operating pressure of the rectification column was 1 Kpa. The condenser at the top of the tower uses cooling water of 10 ℃ as a refrigerant, and the operation temperature at the bottom of the tower is 92-93 ℃. The reflux and extraction ratio of the condensate flowing out of the condenser at the top of the rectifying tower is 3: 1.
The composition of the liquid phase extracted from the top of the rectifying tower is as follows: the content of water is 19.37 wt%, the content of 2-methyl-3-butyn-2-ol is 48.05 wt%, the content of acetone is 32.19 wt%, and the content of other components is 0.39 wt%, based on the total weight of all components in the liquid phase extracted from the top of the tower as 100 wt%.
The composition of liquid phase extracted from the bottom of the rectifying tower is as follows: the content of inorganic salt is 2.40 wt%, the content of water is 16.33 wt%, the content of 2-methyl-3-butyn-2-ol is 80.46 wt%, the content of acetone is 0.32 wt%, the content of 2, 5-dimethyl-3-hexyne-2, 5-diol is 0.07 wt%, and the content of other components is 0.42 wt%, based on the total weight of all components in a produced liquid phase at the bottom of the tower being 100 wt%.
2) Desalting the bottom extracted liquid of the rectifying tower by using a thin film evaporator, wherein the temperature of an external circulating oil bath of the thin film evaporator is 80 ℃, and the operating pressure is 800 hPa. The composition of the distillate at the bottom of the rectifying tower is as follows: 2.40 wt% of inorganic salt, 16.33 wt% of water, 80.46 wt% of 2-methyl-3-butyn-2-ol, 0.32 wt% of acetone, 0.07 wt% of 2, 5-dimethyl-3-hexyne-2, 5-diol and 0.42 wt% of other components.
Introducing the bottom extract of the rectifying tower into a thin film evaporator, wherein the feeding rate is 0.861kg/h, the extraction rate of an upper outlet of the thin film evaporator is 0.817kg/h, and the composition of the extract liquid phase is as follows: 16.74 percent of water, 82.44 percent of 2-methyl-3-butyn-2-ol, 0.32 percent of acetone, 0.07 percent of 2, 5-dimethyl-3-hexyne-2, 5-diol and 0.43 percent of other components, wherein the total weight of all the components of the extracted liquid phase at the outlet is 100 percent; thus obtaining the crude product of 2-methyl-3-butyne-2-ol. The take-off rate at the lower outlet of the thin-film evaporator was 0.044 kg/h.
Example 8: pretreatment of No. 4 reaction solution
1) The 4# reaction liquid prepared by the reaction is subjected to acetone removal treatment by adopting a plate mesh corrugated packed tower, the tower diameter of a rectifying tower (packed tower) is 100mm, the height of a packing layer is 0.5m, the number of theoretical plates is 5, and the composition of the 4# reaction liquid is as follows: the content of inorganic salt was 1.81 wt%, the content of water was 15.30 wt%, the content of 2-methyl-3-butyn-2-ol was 76.57 wt%, the content of acetone was 5.75 wt%, the content of 2, 5-dimethyl-3-hexyne-2, 5-diol was 0.08 wt%, and the content of other components was 0.49 wt%.
The No. 4 reaction liquid enters the rectifying tower from a feed line at the 4 th theoretical plate at the lower part of the tower. The operating pressure of the rectification column was 1 Kpa. The condenser at the top of the tower uses cooling water of 10 ℃ as a refrigerant, and the operation temperature at the bottom of the tower is 92-93 ℃. The reflux and extraction ratio of the condensate flowing out of the condenser at the top of the rectifying tower is 3: 1.
The composition of the liquid phase extracted from the top of the rectifying tower is as follows: the content of water was 19.38 wt%, the content of 2-methyl-3-butyn-2-ol was 47.89 wt%, the content of acetone was 32.21 wt%, and the content of other components was 0.52 wt%, based on 100 wt% of the total weight of the components in the overhead produced liquid phase.
The composition of liquid phase extracted from the bottom of the rectifying tower is as follows: the content of inorganic salt is 2.14 wt%, the content of water is 14.56 wt%, the content of 2-methyl-3-butyn-2-ol is 81.79 wt%, the content of acetone is 0.93 wt%, the content of 2, 5-dimethyl-3-hexyne-2, 5-diol is 0.09 wt%, and the content of other components is 0.49 wt%, based on the total weight of all components in the liquid phase extracted from the bottom of the tower being 100 wt%.
2) And desalting the bottom extracted liquid of the rectifying tower by using a thin film evaporator, wherein the temperature of an external circulating oil bath of the thin film evaporator in the morning is 80 ℃, and the operating pressure is 800 hPa. The composition of the distillate at the bottom of the rectifying tower is as follows: 2.14 wt% of inorganic salt, 14.56 wt% of water, 81.79 wt% of 2-methyl-3-butyn-2-ol, 0.93 wt% of acetone, 0.09 wt% of 2, 5-dimethyl-3-hexyne-2, 5-diol and 0.49 wt% of other components.
Introducing the bottom extracted liquid of the rectifying tower into a thin film evaporator, wherein the feeding rate is 0.794kg/h, the extraction rate of an upper outlet of the thin film evaporator is 0.763kg/h, and the extracted liquid phase composition is as follows: the content of water is 14.87 wt%, the content of 2-methyl-3-butyn-2-ol is 83.58 wt%, the content of acetone is 0.95 wt%, the content of 2, 5-dimethyl-3-hexyne-2, 5-diol is 0.10 wt%, the content of other components is 0.50 wt%, and the total weight of all the components of the extracted liquid phase at the outlet is 100 wt%; thus obtaining the crude product of 2-methyl-3-butyne-2-ol. The withdrawal rate at the lower outlet of the thin-film evaporator was 0.031 kg/h.
Example 9
As shown in fig. 1, the separation and purification process comprises the steps of:
(i) the crude 2-methyl-3-butyn-2-ol 1 obtained in example 5 (water 16.72 wt%, 2-methyl-3-butyn-2-ol 82.37 wt%, acetone 0.52 wt%, 2, 5-dimethyl-3-hexyne-2, 5-diol 0.06 wt%, other components 0.33 wt%) was passed through a membrane separator SEP at a feed rate of 0.813kg/h and subjected to a membrane separation operation at an operating temperature of 95 ℃.
The membrane separator SEP comprises the following components (not shown in the figures): a feed vessel with a circulation pump, a membrane permeation unit with a hydrophilic membrane ((CMC-E, Celfa AG, Switzerland) through which a water-rich permeate is removed in gaseous form, an aqueous organic phase stream 2 (i.e., retentate) and an aqueous phase stream 3 (i.e., permeate) are separated by a membrane separator, the retentate flow rate being 0.695kg/h, comprising about 96.31 wt.% 2-methyl-3-butyn-2-ol, 2.89 wt.% water, 0.38 wt.% acetone, 0.06 wt.% 2, 5-dimethyl-3-hexyne-2, 5-diol and 0.36 wt.% of other impurities, based on the total weight of the retentate components being 100 wt.%, the permeate flow rate being 0.118kg/h, comprising about 0.31 wt.% 2-methyl-3-butyn-2-ol, 2-ol, 1.34 wt% acetone, 0.14 wt% other impurities and the remainder water, based on the total weight of the permeate components taken as 100 wt%.
(ii) The resulting aqueous organic phase stream 2 (i.e.the retentate) was fed at a flow rate of 0.695kg/h from the feed line at the 10 th theoretical plate from the lower part of the column into a crude rectification column RAC1, which employs a plate-mesh corrugated packed column having a column diameter of 100mm and a packing layer height of 2m and a theoretical plate number of 15. The operating pressure of the crude rectification column is 100 hPa. The condenser COOLER1 at the top of the tower uses cooling water at 10 ℃ as a refrigerant, the REBOILER REBOILER1 at the bottom of the tower realizes the regulation and control of the temperature at the bottom of the tower, and the operation temperature at the bottom of the tower is 119-120 ℃. The reflux and extraction ratio of the condensate flowing out of the condenser at the top of the coarse rectifying tower is 1:1, the operating temperature at the top of the tower is 42-43 ℃, a light component stream 4 is extracted at the top of the tower, and the extraction flow speed is 0.0725 kg/h. The composition of liquid phase extracted from the top of the crude distillation tower is as follows: the content of water is 25.35 wt%, the content of acetone is 3.64 wt%, and the content of 2-methyl-3-butyn-2-ol is 71.01 wt%, based on 100 wt% of the total weight of the components of the liquid phase obtained by the top of the tower.
And (3) taking out a stream 5 to be removed with heavy components at the bottom of the crude rectifying tower at the flow speed of 0.6225kg/h, and entering a product separating tower. The liquid phase is extracted from the bottom of the coarse rectifying tower: the content of water is 0.27 wt%, the content of 2-methyl-3-butyn-2-ol is 99.25 wt%, the content of 2, 5-dimethyl-3-hexyne-2, 5-diol is 0.07 wt%, the content of other components is 0.41 wt%, and the total weight of all components of a liquid phase extracted from the bottom of the tower is 100 wt%.
(iii) Heavy component streams to be removed are extracted from the bottom of the coarse rectifying tower and enter the middle of a product separation tower RAC 2; the product separation tower adopts a plate mesh corrugated packing tower, the diameter of the tower is 100mm, the height of a packing layer is 1m, the number of theoretical plates is 7, and the tower bottom liquid of the crude distillation tower enters the product separation tower from a feeding pipeline at the 4 th theoretical plate. The operating pressure of the product separation column was 100 hPa. The condenser COOLER2 at the top of the tower uses cooling water at 10 ℃ as a refrigerant, the REBOILER REBOILER2 at the bottom of the tower realizes the regulation and control of the temperature at the bottom of the tower, and the operation temperature at the bottom of the tower is 119-120 ℃. The reflux and extraction ratio of the condensate flowing out of the condenser at the top of the tower is 1:1, the operating temperature at the top of the tower is 53-54 ℃, a product stream 6 is extracted from the top of the tower, and the extraction flow speed is 0.6127 kg/h. The produced liquid phase at the top of the product separation tower comprises: the content of water is 0.27 wt%, the content of 2-methyl-3-butyn-2-ol is 99.73 wt%, and the total weight of the components extracted from the top of the tower is 100 wt%.
Heavy component stream 7 is extracted from the bottom of the product separation tower at the flow velocity of 0.0098kg/h, and the extracted liquid phase at the bottom of the product separation tower comprises: the content of 2-methyl-3-butyn-2-ol is 69.72 wt%, the content of 2, 5-dimethyl-3-hexyne-2, 5-diol is 4.6 wt%, the content of other components is 25.68 wt%, and the total weight of the components of the liquid phase obtained by the bottom of the tower is 100 wt%.
The membrane permeation unit containing the membrane separator was fed for 3000 hours with no significant abnormalities. The refractive index of the produced liquid at the top of the product separation tower, namely the obtained product 2-methyl-3-butyne-2-ol, is measured as follows: n 20/D1.4215, color number: 16 (Pt-Co).
Example 10
As shown in fig. 1, the separation and purification process comprises the steps of:
(i) the crude 2-methyl-3-butyn-2-ol 1 obtained in example 6 (water 16.73 wt%, 2-methyl-3-butyn-2-ol 82.35 wt%, acetone 0.48 wt%, 2, 5-dimethyl-3-hexyne-2, 5-diol 0.02 wt%, other components 0.42 wt%) was passed through a membrane separator SEP at a feed rate of 0.813kg/h and subjected to a membrane separation operation at 95 ℃.
The membrane separator SEP comprises the following components (not shown in the figures): a feed vessel with a circulation pump, a membrane permeation unit with a hydrophilic membrane (CMC-E, Celfa AG, switzerland) through which the water-rich permeate is removed in gaseous form. An aqueous organic phase stream 2 (i.e., retentate) and an aqueous phase stream 3 (i.e., permeate) are separated by a membrane separator: the retentate flow was 0.692kg/h, comprising about 96.69 wt% 2-methyl-3-butyn-2-ol, 2.46 wt% water, 0.37 wt% acetone, 0.03 wt% 2, 5-dimethyl-3-hexyne-2, 5-diol and 0.45 wt% other impurities, based on the total weight of the retentate components of 100 wt%; the permeate flow was 0.121kg/h and contained about 0.35 wt% of 2-methyl-3-butyn-2-ol, 1.12 wt% of acetone, 0.18 wt% of other impurities and the remainder water, based on the total weight of the components of the permeate as 100 wt%.
(ii) The resulting aqueous organic phase stream 2 (i.e.the retentate) was fed at a flow rate of 0.695kg/h from the feed line at the 10 th theoretical plate from the lower part of the column into a crude rectification column RAC1, which employs a plate-mesh corrugated packed column having a column diameter of 100mm and a packing layer height of 2m and a theoretical plate number of 15. The operating pressure of the crude rectification column is 100 hPa. The condenser COOLER1 at the top of the tower uses cooling water at 10 ℃ as a refrigerant, the REBOILER REBOILER1 at the bottom of the tower realizes the regulation and control of the temperature at the bottom of the tower, and the operation temperature at the bottom of the tower is 119-120 ℃. The reflux and extraction ratio of the condensate flowing out of the condenser at the top of the coarse rectifying tower is 1:1, the operating temperature at the top of the tower is 42-43 ℃, a light component stream 4 is extracted at the top of the tower, and the extraction flow speed is 0.0519 kg/h. The composition of liquid phase extracted from the top of the crude distillation tower is as follows: the content of water is 25.35 wt%, the content of acetone is 4.87 wt%, and the content of 2-methyl-3-butyn-2-ol is 69.78 wt%, based on 100 wt% of the total weight of the components of the liquid phase extracted from the top of the tower.
And taking out a stream 5 to be removed with heavy components from the bottom of the crude distillation tower at the flow rate of 0.6401kg/h, and entering a product separation tower. The liquid phase is extracted from the bottom of the coarse rectifying tower: the content of water is 0.60 wt%, the content of 2-methyl-3-butyn-2-ol is 98.87 wt%, the content of 2, 5-dimethyl-3-hexyne-2, 5-diol is 0.03 wt%, the content of other components is 0.50 wt%, and the total weight of all components of a liquid phase extracted from the bottom of the tower is 100 wt%.
(iii) A stream 5 to be subjected to heavy component removal is extracted from the bottom of the crude rectifying tower and enters the middle of a product separation tower RAC 2; the product separation tower adopts a plate mesh corrugated packing tower, the diameter of the tower is 100mm, the height of a packing layer is 1m, the number of theoretical plates is 7, and the tower bottom liquid of the crude distillation tower enters the product separation tower from a feeding pipeline at the 4 th theoretical plate. The operating pressure of the product separation column was 100 hPa. The condenser COOLER2 at the top of the tower uses cooling water at 10 ℃ as a refrigerant, the REBOILER REBOILER2 at the bottom of the tower realizes the regulation and control of the temperature at the bottom of the tower, and the operation temperature at the bottom of the tower is 119-120 ℃. The reflux and extraction ratio of the condensate flowing out of the condenser at the top of the tower is 1:1, the operating temperature at the top of the tower is 53-54 ℃, a product stream 6 is extracted from the top of the tower, and the extraction flow speed is 0.6316 kg/h. The produced liquid phase at the top of the product separation tower comprises: the content of water is 0.61 wt%, the content of 2-methyl-3-butyn-2-ol is 99.39 wt%, and the total weight of the components extracted from the top of the tower is 100 wt%.
Heavy component stream 7 is extracted from the bottom of the product separation tower at the flow velocity of 0.0085kg/h, and the extracted liquid phase at the bottom of the product separation tower comprises: the content of 2-methyl-3-butyn-2-ol is 60.60 wt%, the content of 2, 5-dimethyl-3-hexyne-2, 5-diol is 2.12 wt%, the content of other components is 37.28 wt%, and the total weight of the components of the liquid phase extracted from the tower bottom is 100 wt%.
The membrane permeation unit containing the membrane separator was fed for 4000 hours with no significant abnormalities. The refractive index of the produced liquid at the top of the product separation tower, namely the obtained product 2-methyl-3-butyne-2-ol, is measured as follows: n 20/D1.4215, color number: 15 (Pt-Co).
Example 11
As shown in fig. 1, the separation and purification process comprises the steps of:
(i) the crude 2-methyl-3-butyn-2-ol 1 obtained in example 7 (water 16.74 wt%, 2-methyl-3-butyn-2-ol 82.44 wt%, acetone 0.32 wt%, 2, 5-dimethyl-3-hexyne-2, 5-diol 0.07 wt%, other components 0.43 wt%) was passed through a membrane separator SEP at a feed rate of 0.817kg/h and subjected to a membrane separation operation at 95 ℃.
The membrane separator SEP comprises the following components (not shown in the figures): a feed vessel with a circulation pump, a membrane permeation unit with a hydrophilic membrane (CMC-E, Celfa AG, switzerland) through which the water-rich permeate is removed in gaseous form. An aqueous organic phase stream 2 (i.e., retentate) and an aqueous phase stream 3 (i.e., permeate) are separated by a membrane separator: the retentate flow was 0.714kg/h, comprising about 94.29 wt% of 2-methyl-3-butyn-2-ol, 4.93 wt% of water, 0.24 wt% of acetone, 0.08 wt% of 2, 5-dimethyl-3-hexyne-2, 5-diol and 0.46 wt% of other impurities, based on the total weight of the retentate components of 100 wt%; the permeate flow was 0.103kg/h and contained about 0.34 wt% of 2-methyl-3-butyn-2-ol, 0.86 wt% of acetone, 0.19 wt% of other impurities and the remainder water, based on the total weight of the components of the permeate as 100 wt%.
(ii) The resulting aqueous organic phase stream 2 (i.e., the retentate) was fed at a flow rate of 0.714kg/h from the feed line at the 10 th theoretical plate from the lower part of the column into a crude rectification column RAC1, which employs a plate-mesh corrugated packed column having a column diameter of 100mm, a packed bed height of 2m and a theoretical plate number of 15. The operating pressure of the crude rectification column is 100 hPa. The condenser COOLER1 at the top of the tower uses cooling water at 10 ℃ as a refrigerant, the REBOILER REBOILER1 at the bottom of the tower realizes the regulation and control of the temperature at the bottom of the tower, and the operation temperature at the bottom of the tower is 119-120 ℃. The reflux and extraction ratio of the condensate flowing out of the condenser at the top of the coarse rectifying tower is 1:1, the operating temperature at the top of the tower is 42-43 ℃, a light component stream 4 is extracted at the top of the tower, and the extraction flow speed is 0.1225 kg/h. The composition of liquid phase extracted from the top of the crude distillation tower is as follows: the content of water is 25.69 wt%, the content of acetone is 1.41 wt%, and the content of 2-methyl-3-butyn-2-ol is 72.90 wt%, based on 100 wt% of the total weight of the components of the liquid phase obtained by the top of the tower.
And taking out a stream 5 to be removed with heavy components from the bottom of the crude distillation tower at the flow rate of 0.5915kg/h, and entering a product separation tower. The liquid phase is extracted from the bottom of the coarse rectifying tower: the content of water is 0.64 wt%, the content of 2-methyl-3-butyn-2-ol is 98.71 wt%, the content of 2, 5-dimethyl-3-hexyne-2, 5-diol is 0.09 wt%, the content of other components is 0.56 wt%, and the total weight of all components of a liquid phase extracted from the bottom of the tower is 100 wt%.
(iii) A stream 5 to be subjected to heavy component removal is extracted from the bottom of the crude rectifying tower and enters the middle of a product separation tower RAC 2; the product separation tower adopts a plate mesh corrugated packing tower, the diameter of the tower is 100mm, the height of a packing layer is 1m, the number of theoretical plates is 7, and the tower bottom liquid of the crude distillation tower enters the product separation tower from a feeding pipeline at the 4 th theoretical plate. The operating pressure of the product separation column was 100 hPa. The condenser COOLER2 at the top of the tower uses cooling water at 10 ℃ as a refrigerant, the REBOILER REBOILER2 at the bottom of the tower realizes the regulation and control of the temperature at the bottom of the tower, and the operation temperature at the bottom of the tower is 119-120 ℃. The reflux and extraction ratio of the condensate flowing out of the condenser at the top of the tower is 1:1, the operating temperature at the top of the tower is 53-54 ℃, a product stream 6 is extracted from the top of the tower, and the extraction flow speed is 0.5819 kg/h. The produced liquid phase at the top of the product separation tower comprises: the content of water is 0.64 wt%, the content of 2-methyl-3-butyn-2-ol is 99.36 wt%, and the total weight of the components extracted from the top of the tower is 100 wt%.
A heavy component stream 7 is extracted from the bottom of the product separation tower at a flow rate of 0.096kg/h, and the extracted liquid phase at the bottom of the product separation tower comprises: the content of 2-methyl-3-butyn-2-ol is 59.48 wt%, the content of 2, 5-dimethyl-3-hexyne-2, 5-diol is 5.96 wt%, the content of other components is 34.56 wt%, and the total weight of the components of the liquid phase extracted from the tower bottom is 100 wt%.
The membrane permeation unit containing the membrane separator continued feeding for 3500 hours with no significant abnormalities. The refractive index of the produced liquid at the top of the product separation tower, namely the obtained product 2-methyl-3-butyne-2-ol, is measured as follows: n 20/D1.4215, color number: 16 (Pt-Co).
Example 12
As shown in fig. 1, the separation and purification process comprises the steps of:
(i) the crude 2-methyl-3-butyn-2-ol 1 obtained in example 8 (water 14.87 wt%, 2-methyl-3-butyn-2-ol 83.58 wt%, acetone 0.95 wt%, 2, 5-dimethyl-3-hexyne-2, 5-diol 0.10 wt%, other components 0.50 wt%) was passed through a membrane separator SEP at a feed rate of 0.763kg/h and subjected to a membrane separation operation at 95 ℃.
The membrane separator SEP comprises the following components (not shown in the figures): a feed vessel with a circulation pump, a membrane permeation unit with a hydrophilic membrane ((CMC-E, Celfa AG, Switzerland) through which a water-rich permeate is removed in gaseous form, an aqueous organic phase stream 2 (i.e., retentate) and an aqueous phase stream 3 (i.e., permeate) are separated by a membrane separator, the retentate stream having a mass flow of 0.658kg/h, which contains about 96.86 wt.% of 2-methyl-3-butyn-2-ol, 1.61 wt.% of water, 0.87 wt.% of acetone, 0.11 wt.% of 2, 5-dimethyl-3-hexyne-2, 5-diol and 0.55 wt.% of other impurities, based on the total weight of the retentate components being 100 wt.%, and the permeate stream having a mass flow of 0.105kg/h, which contains about 0.36 wt.% of 2-methyl-3-butyn-2-ol, 2-ol, 1.45 wt% acetone, 0.22 wt% other impurities and the remainder water, based on the total weight of the permeate components taken as 100 wt%.
(ii) The resulting aqueous organic phase stream 2 (i.e., the retentate) was fed at a flow rate of 0.658kg/h from the feed line at the 10 th theoretical plate from the lower part of the column into a crude rectification column RAC1, which employs a plate-mesh corrugated packed column having a column diameter of 100mm, a packed layer height of 2m and a theoretical plate number of 15. The operating pressure of the crude rectification column is 100 hPa. The condenser COOLER1 at the top of the tower uses cooling water at 10 ℃ as a refrigerant, the REBOILER REBOILER1 at the bottom of the tower realizes the regulation and control of the temperature at the bottom of the tower, and the operation temperature at the bottom of the tower is 119-120 ℃. The reflux and extraction ratio of the condensate flowing out of the condenser at the top of the coarse rectifying tower is 1:1, the operating temperature at the top of the tower is 42-43 ℃, a light component stream 4 is extracted at the top of the tower, and the extraction flow speed is 0.0725 kg/h. The composition of liquid phase extracted from the top of the crude distillation tower is as follows: the content of water is 19.59 wt%, the content of acetone is 17.62 wt%, and the content of 2-methyl-3-butyn-2-ol is 62.79 wt%, based on 100 wt% of the total weight of the components of the liquid phase extracted from the top of the tower.
And taking out a stream 5 to be removed with heavy components from the bottom of the crude distillation tower at the flow rate of 0.6255kg/h, and entering a product separation tower. The liquid phase is extracted from the bottom of the coarse rectifying tower: the content of water is 0.68 wt%, the content of 2-methyl-3-butyn-2-ol is 98.63 wt%, the content of 2, 5-dimethyl-3-hexyne-2, 5-diol is 0.12 wt%, the content of other components is 0.57 wt%, and the total weight of all components of a liquid phase extracted from the bottom of the tower is 100 wt%.
(iii) A stream 5 to be subjected to heavy component removal is extracted from the bottom of the crude rectifying tower and enters the middle of a product separation tower RAC 2; the product separation tower adopts a plate mesh corrugated packing tower, the diameter of the tower is 100mm, the height of a packing layer is 1m, the number of theoretical plates is 7, and the tower bottom liquid of the crude distillation tower enters the product separation tower from a feeding pipeline at the 4 th theoretical plate. The operating pressure of the product separation column was 100 hPa. The condenser COOLER2 at the top of the tower uses cooling water at 10 ℃ as a refrigerant, the REBOILER REBOILER2 at the bottom of the tower realizes the regulation and control of the temperature at the bottom of the tower, and the operation temperature at the bottom of the tower is 119-120 ℃. The reflux and extraction ratio of the condensate flowing out of the condenser at the top of the tower is 1:1, the operating temperature at the top of the tower is 53-54 ℃, a product stream 6 is extracted from the top of the tower, and the extraction flow speed is 0.6134 kg/h. The produced liquid at the top of the product separation tower comprises: the content of water is 0.69 wt%, the content of 2-methyl-3-butyn-2-ol is 99.31 wt%, and the total weight of the components extracted from the top of the tower is 100 wt%.
A heavy component stream 7 is extracted from the bottom of the product separation tower at a flow rate of 0.121kg/h, and the extracted liquid phase at the bottom of the product separation tower comprises: the content of 2-methyl-3-butyn-2-ol is 64.07 wt%, the content of 2, 5-dimethyl-3-hexyne-2, 5-diol is 6.31 wt%, the content of other components is 29.62 wt%, and the total weight of all components of the liquid phase obtained by the bottom of the tower is 100 wt%.
The membrane permeation unit containing the membrane separator was fed for 2000 hours with no significant abnormalities. The refractive index of the produced liquid at the top of the product separation tower, namely the obtained product 2-methyl-3-butyne-2-ol, is measured as follows: n 20/D1.4216, color number: 18 (Pt-Co).
Comparative example 1:
preparation of # 5 reaction solution:
firstly, replacing a 500L high-pressure kettle with ammonia gas for 3 times, reducing the temperature in the reaction kettle to-20 ℃, adding liquid ammonia (144.5Kg, 8500mol), starting stirring, introducing acetylene (16800L, 750mol), adding a 50 wt% potassium hydroxide aqueous solution (1008g, the using amount of potassium hydroxide as a solute is 3 mol% of acetone), heating to 10 ℃, adding acetone (17.4Kg, 300mol), and controlling the adding speed of the acetone to finish feeding within about 1 hour; the reaction temperature is 10 ℃, 5Kg of ammonium sulfate aqueous solution with the concentration of 10 wt% is added for neutralization after 2 hours of reaction, 5# reaction liquid containing 2-methyl-3-butyn-2-ol is obtained, and the reaction liquid is sampled and detected by GC.
Composition of reaction solution # 5: the inorganic salt content is 2.17 wt%, the water content is 16.62 wt%, the 2-methyl-3-butyn-2-ol content is 75.31 wt%, the acetone content is 4.68 wt%, the 2, 5-dimethyl-3-hexyne-2, 5-diol content is 0.59 wt%, and the other components content is 0.63 wt%, based on the total weight of the components of the No. 5 reaction liquid being 100 wt%.
Pretreatment of No. 5 reaction solution:
1) desalting the 5# reaction solution obtained by the ethynylation reaction by adopting a thin film evaporator, wherein the temperature of an external circulating oil bath of the thin film evaporator is 80 ℃, and the operating pressure is 800 hPa. Composition of reaction solution # 5: the content of inorganic salt was 2.17 wt%, the content of water was 16.62 wt%, the content of 2-methyl-3-butyn-2-ol was 75.31 wt%, the content of acetone was 4.68 wt%, the content of 2, 5-dimethyl-3-hexyne-2, 5-diol was 0.59 wt%, and the content of other components was 0.63 wt%.
And (3) introducing the 5# reaction solution into a thin film evaporator. The feeding rate of the No. 5 reaction liquid is 0.950kg/h, the extraction rate of the upper outlet of the thin film evaporator is 0.902kg/h, and the composition of the extracted liquid phase is as follows: the content of water was 16.99 wt%, the content of 2-methyl-3-butyn-2-ol was 76.98 wt%, the content of acetone was 4.79 wt%, the content of 2, 5-dimethyl-3-hexyne-2, 5-diol was 0.60 wt%, and the content of other components was 0.64 wt%, based on 100 wt% of the total weight of the components of the liquid phase taken. The take-off rate at the lower outlet of the thin-film evaporator was 0.048 kg/h.
2) The produced liquid at the outlet of the thin film evaporator is subjected to acetone removal treatment by adopting a plate mesh corrugated packed tower, the tower diameter of a rectifying tower (or the packed tower) is 100mm, the height of a packing layer is 0.5m, the number of theoretical plates is 5, and the produced liquid phase composition is as follows: the water content was 16.99% by weight, the 2-methyl-3-butyn-2-ol content was 76.98% by weight, the acetone content was 4.79% by weight, the 2, 5-dimethyl-3-hexyne-2, 5-diol content was 0.60% by weight, and the other components were 0.64% by weight.
The produced liquid enters the rectifying tower from a feed line at the 4 th theoretical plate at the lower part of the tower. The operating pressure of the rectification column was 1 Kpa. The condenser at the top of the tower uses cooling water of 10 ℃ as a refrigerant, and the operation temperature at the bottom of the tower is 92-93 ℃. The reflux and extraction ratio of the condensate flowing out of the condenser at the top of the rectifying tower is 3: 1.
The composition of the liquid phase extracted from the top of the rectifying tower is as follows: the content of water was 19.36 wt%, the content of 2-methyl-3-butyn-2-ol was 46.58 wt%, the content of acetone was 33.72 wt%, and the content of other components was 0.34 wt%, based on 100 wt% of the total weight of the components of the liquid phase taken at the top of the column.
The composition of liquid phase extracted from the bottom of the rectifying tower is as follows: the content of water is 16.68 wt%, the content of 2-methyl-3-butyn-2-ol is 80.99 wt%, the content of acetone is 0.98 wt%, the content of 2, 5-dimethyl-3-hexyne-2, 5-diol is 0.67 wt%, the content of other components is 0.68 wt%, and the total weight of all components of a liquid phase extracted from the bottom of the tower is 100 wt%; thus obtaining the crude product of 2-methyl-3-butyne-2-ol.
Comparative example 2:
as shown in fig. 1, the separation and purification process comprises the steps of:
(i) the crude 2-methyl-3-butyn-2-ol 1 obtained in comparative example 1 (water 16.68 wt%, 2-methyl-3-butyn-2-ol 80.99 wt%, acetone 0.98 wt%, 2, 5-dimethyl-3-hexyne-2, 5-diol 0.67 wt%, other components 0.68 wt%) was passed through a membrane separator SEP at a feed rate of 0.797kg/h to conduct a membrane separation operation at 95 ℃.
The membrane separator SEP comprises the following components (not shown in the figures): a feed vessel with a circulation pump, a membrane permeation unit with a hydrophilic membrane (CMC-E, Celfa AG, switzerland) through which the water-rich permeate is removed in gaseous form. An aqueous organic phase stream 2 (i.e., retentate) and an aqueous phase stream 3 (i.e., permeate) are separated by a membrane separator: the retentate flow was 0.689kg/h, comprising about 93.63 wt% 2-methyl-3-butyn-2-ol, 3.90 wt% water, 0.92 wt% acetone, 0.79 wt% 2, 5-dimethyl-3-hexyne-2, 5-diol and 0.76 wt% other impurities, based on the total weight of the retentate components of 100 wt%; the permeate flow was 0.108kg/h, which contained about 0.31 wt% of 2-methyl-3-butyn-2-ol, 1.34 wt% of acetone, 0.18 wt% of other impurities and the remainder water, based on the total weight of the components of the permeate as 100 wt%.
(ii) The resulting aqueous organic phase stream 2 (i.e., the retentate) was fed at a flow rate of 0.689kg/h from the feed line at the 10 th theoretical plate from the lower part of the column into a crude rectification column RAC1, which employs a plate-mesh corrugated packed column having a column diameter of 100mm and a packing layer height of 2m and a theoretical plate number of 15. The operating pressure of the crude rectification column is 100 hPa. The condenser COOLER1 at the top of the tower uses cooling water at 10 ℃ as a refrigerant, the REBOILER REBOILER1 at the bottom of the tower realizes the regulation and control of the temperature at the bottom of the tower, and the operation temperature at the bottom of the tower is 119-120 ℃. The reflux and extraction ratio of the condensate flowing out of the condenser at the top of the coarse rectifying tower is 1:1, the operating temperature at the top of the tower is 42-43 ℃, a light component stream 4 is extracted at the top of the tower, and the extraction flow speed is 0.0878 kg/h. The composition of liquid phase extracted from the top of the crude distillation tower is as follows: the content of water is 25.35 wt%, the content of acetone is 7.24 wt%, and the content of 2-methyl-3-butyn-2-ol is 67.41 wt%, based on 100 wt% of the total weight of the components of the liquid phase obtained by the top of the tower.
And taking out a stream 5 to be removed with heavy components from the bottom of the crude distillation tower at the flow rate of 0.6012kg/h, and entering a product separation tower. The liquid phase is extracted from the bottom of the coarse rectifying tower: the content of water is 0.76 wt%, the content of 2-methyl-3-butyn-2-ol is 97.46 wt%, the content of 2, 5-dimethyl-3-hexyne-2, 5-diol is 0.91 wt%, the content of other components is 0.87 wt%, and the total weight of all components of a liquid phase extracted from the bottom of the tower is 100 wt%.
(iii) A stream 5 to be subjected to heavy component removal is extracted from the bottom of the crude rectifying tower and enters the middle of a product separation tower RAC 2; the product separation tower adopts a plate mesh corrugated packing tower, the diameter of the tower is 100mm, the height of a packing layer is 1m, the number of theoretical plates is 7, and the tower bottom liquid of the crude distillation tower enters the product separation tower from a feeding pipeline at the 4 th theoretical plate. The operating pressure of the product separation column was 100 hPa. The condenser COOLER2 at the top of the tower uses cooling water at 10 ℃ as a refrigerant, the REBOILER REBOILER2 at the bottom of the tower realizes the regulation and control of the temperature at the bottom of the tower, and the operation temperature at the bottom of the tower is 119-120 ℃. The reflux and extraction ratio of the condensate flowing out of the condenser at the top of the tower is 1:1, the operating temperature at the top of the tower is 53-54 ℃, a product stream 6 is extracted from the top of the tower, and the extraction flow speed is 0.5736 kg/h. The produced liquid phase at the top of the product separation tower comprises: the content of water is 0.80%, the content of 2-methyl-3-butine-2-alcohol is 99.18 wt%, the content of 2, 5-dimethyl-3-hexine-2, 5-diol is 0.01 wt%, the content of other components is 0.01 wt%, and the total weight of all components of a liquid phase extracted from the top of the tower is 100 wt%.
A heavy component stream 7 is extracted from the bottom of the product separation tower at a flow rate of 0.0276kg/h, and an extracted liquid phase at the bottom of the product separation tower comprises: the content of 2-methyl-3-butyn-2-ol is 61.32 wt%, the content of 2, 5-dimethyl-3-hexyne-2, 5-diol is 19.61 wt%, the content of other components is 19.07 wt%, and the total weight of the components of the liquid phase obtained by the bottom of the tower is 100 wt%.
The refractive index of the produced liquid at the top of the product separation tower, namely the obtained product 2-methyl-3-butyne-2-ol, is measured as follows: n 20/D1.4500, color number: 35 (Pt-Co).
After the membrane permeation unit containing the membrane separator was continuously fed for 710 hours, the pressure fluctuation was abnormal and clogging occurred. The presence of clogging affects the purity of the isolated product 2-methyl-3-butyn-2-ol as well as its refractive index and color number.
From the experimental results of example 1 and comparative example 1, it is known that the formation of a by-product 2, 5-dimethyl-3-hexyne-2, 5-diol during the reaction can be effectively inhibited by adding a divalent metal salt to the system of the preparation process, and the content of 2, 5-dimethyl-3-hexyne-2, 5-diol in the obtained reaction solution is controlled to be in a lower range (less than or equal to 0.1 wt%), thereby improving the product selectivity.
From the experimental results of example 2 and example 3, it is understood that under the same molar ratio of acetone to acetylene, the content of the by-product 2, 5-dimethyl-3-hexyne-2, 5-diol increases as the amount of the divalent metal salt to be added decreases, indicating that the amount of the divalent metal salt to be added in the system can control the content of the 2, 5-dimethyl-3-hexyne-2, 5-diol in the obtained reaction solution. In addition, the divalent metal salt selected for examples 2 to 3 was zinc acetate, which is more effective in reducing the content of 2, 5-dimethyl-3-hexyne-2, 5-diol as a preferred divalent metal salt species.
From the experimental results of examples 1-3 and 4, it can be seen that a lower acetylene ratio during the ethynylation reaction is not favorable for controlling the content of 2, 5-dimethyl-3-hexyne-2, 5-diol, and a larger amount of divalent metal salt needs to be added.
From the experimental results of examples 9 to 12, it is known that the service life of the permeable membrane used in the membrane separation treatment can be prolonged by controlling the content of the key component 2, 5-dimethyl-3-hexyne-2, 5-diol in the reaction solution containing 2-methyl-3-butyn-2-ol during the separation process; for example, if the 2, 5-dimethyl-3-hexyne-2, 5-diol content of the crude 2-methyl-3-butyn-2-ol is less than 0.10 wt%, the membrane separator can be operated for more than 2000 hours without changing the permeable membrane.
As can be seen from comparative example 2, when the content of by-products in the reaction solution was high, that is, the content of 2, 5-dimethyl-3-hexyne-2, 5-diol in the crude 2-methyl-3-butyn-2-ol was increased to 0.67 wt%, the life of the permeable membrane used in the membrane separation treatment was shortened to 710 hours, and the running cost was increased. It is demonstrated that when the content of 2, 5-dimethyl-3-hexyne-2, 5-diol, which is a key component in the reaction solution containing 2-methyl-3-butyn-2-ol, is more than 0.10 wt%, the membrane separation treatment is adversely affected.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the spirit of the invention.

Claims (11)

1. A method for separating 2-methyl-3-butyn-2-ol, comprising:
(1) a pretreatment procedure: pretreating reaction liquid containing 2-methyl-3-butyn-2-ol, and removing unreacted acetone and contained salt to obtain a crude product of 2-methyl-3-butyn-2-ol; in the reaction liquid containing the 2-methyl-3-butyn-2-ol, the content of the 2, 5-dimethyl-3-hexyne-2, 5-diol is controlled to be less than or equal to 0.1wt percent, preferably less than or equal to 0.06wt percent;
(2) separation and purification procedures: separating and purifying the crude product of the 2-methyl-3-butyn-2-ol by membrane separation treatment and vacuum rectification treatment to obtain a 2-methyl-3-butyn-2-ol product.
2. The separation method according to claim 1, characterized in that it comprises the steps of:
(1) a pretreatment procedure: rectifying the reaction liquid containing the 2-methyl-3-butyn-2-ol to remove acetone, and distilling or rectifying to desalt to obtain a crude product of the 2-methyl-3-butyn-2-ol;
in the crude product of the 2-methyl-3-butyn-2-ol, the content of water is 10 to 40 weight percent, the content of acetone is less than or equal to 1 weight percent, and the content of 2, 5-dimethyl-3-hexyne-2, 5-diol is less than or equal to 0.1 weight percent;
(2) separation and purification procedures: performing membrane separation treatment on the crude product of the 2-methyl-3-butyn-2-ol to obtain a mixture containing the 2-methyl-3-butyn-2-ol, wherein the content of water is less than or equal to 5%; then carrying out vacuum rectification treatment on the mixture containing the 2-methyl-3-butyn-2-ol to obtain a 2-methyl-3-butyn-2-ol product, wherein the content of water is less than or equal to 1 wt%;
preferably, the 2-methyl-3-butyn-2-ol product in the step (2) has the content of 2, 5-dimethyl-3-hexyne-2, 5-diol of less than or equal to 0.01 wt%.
3. The separation method according to claim 1 or 2, wherein in the membrane separation treatment of step (2), at least one membrane separator for separating water from 2-methyl-3-butyn-2-ol is used; a hydrophilic membrane is arranged in the membrane separator;
preferably, the hydrophilic membrane is selected from a polyvinyl alcohol membrane, a polyimide membrane or a ceramic membrane, more preferably a polyvinyl alcohol membrane or a polyimide membrane;
preferably, the operating temperature of the membrane separation treatment using the hydrophilic membrane is 0 ℃ or higher and 100 ℃ or lower.
4. The separation method according to any one of claims 1 to 3, wherein the operation process of step (2) comprises:
(i) treating the crude 2-methyl-3-butyn-2-ol product by a membrane separator, and separating an aqueous organic phase stream and an aqueous phase stream; wherein, in the aqueous organic phase stream, the content of water is less than or equal to 5 wt%, and the content of 2-methyl-3-butyn-2-ol is more than or equal to 90 wt%; in the water phase stream, the content of water is more than or equal to 95 wt%, and the content of 2-methyl-3-butyn-2-ol is less than or equal to 1 wt%;
(ii) the organic phase flow strand containing water enters a crude rectifying tower for treatment, and a light component flow is extracted from the top of the crude rectifying tower, wherein the content of water in the light component flow is 5-30 wt%; a heavy component stream to be removed is extracted from the bottom of the crude rectifying tower, and the content of water in the heavy component stream to be removed is less than or equal to 1 wt%;
(iii) the stream of the heavy components to be removed enters a product separation tower for treatment, and a product stream is collected from the top of the product separation tower; in the product stream, the content of 2-methyl-3-butyn-2-ol is more than or equal to 99 wt%, the content of water is less than or equal to 1 wt%, and the content of 2, 5-dimethyl-3-hexyne-2, 5-diol is less than or equal to 0.01 wt%; a heavy component stream is extracted from the bottom of the product separation tower, wherein the content of the 2-methyl-3-butyne-2-ol in the heavy component stream is less than or equal to 70 wt%;
preferably, the stream of the heavy component to be removed enters from the middle of the product separation column.
5. The separation method according to claim 4, wherein the number of theoretical plates of the rectifying section of the crude rectifying tower is more than or equal to 5, preferably 10 to 15;
preferably, the operating pressure of the crude distillation column is 50hPa to 300hPa, more preferably 100hPa to 200 hPa; the operation temperature of the tower kettle of the crude rectifying tower is 100-130 ℃, and more preferably 110-125 ℃.
6. The separation process according to claim 4, wherein the product separation column has a theoretical plate number of 5 or more, preferably 10 to 15;
preferably, the operating pressure of the product separation column is 50hPa to 300hPa, more preferably 100hPa to 200 hPa; the operation temperature of the tower kettle of the product separation tower is 100-130 ℃, and more preferably 110-125 ℃.
7. The separation method according to any one of claims 1 to 6, wherein the obtained 2-methyl-3-butyn-2-ol product has a water content of 1 wt.% or less and a 2, 5-dimethyl-3-hexyn-2, 5-diol content of 0.01 wt.% or less after the separation and purification steps.
8. The separation method according to any one of claims 1 to 7, wherein the reaction liquid containing 2-methyl-3-butyn-2-ol is prepared by a method comprising:
mixing acetone, acetylene and divalent metal salt in liquid ammonia to react by using strong base as a catalyst; after the reaction is finished, adding a weakly acidic aqueous solution to neutralize the catalyst in the system, and preparing a reaction solution containing 2-methyl-3-butyne-2-ol; in the reaction liquid containing the 2-methyl-3-butyne-2-ol, the content of the 2, 5-dimethyl-3-hexyne-2, 5-diol is less than or equal to 0.1 wt%.
9. The separation method according to claim 8, wherein the divalent metal salt is selected from one or more of a divalent zinc salt, a divalent magnesium salt and a divalent cobalt salt, preferably one or more of zinc acetate, magnesium sulfate and cobalt chloride, further preferably zinc acetate and/or magnesium sulfate, more preferably zinc acetate.
10. The separation method according to claim 8 or 9, wherein the divalent metal salt is used in an amount of 0.01% to 0.1%, preferably 0.02% to 0.05% by mass of acetone.
11. The separation process according to any one of claims 8 to 10, wherein the molar ratio of acetylene to acetone is greater than or equal to 1:1 and less than or equal to 3:1, preferably from 1.05:1 to 2: 1.
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CN112574018A (en) * 2020-11-30 2021-03-30 万华化学集团股份有限公司 Low-color-number citral and preparation method thereof
CN112661586A (en) * 2020-12-29 2021-04-16 山东铂源药业有限公司 Preparation method of 3,3-dimethyl-1-butyne
CN113121315A (en) * 2021-04-15 2021-07-16 万华化学集团股份有限公司 Recycling method of unsaturated alcohol in kettle residue in preparation of methyl butenol by hydrogenating 2-methyl-3-butyn-2-ol
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CN112574018A (en) * 2020-11-30 2021-03-30 万华化学集团股份有限公司 Low-color-number citral and preparation method thereof
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