WO2022016317A1 - Separation method for 2-methyl-3-butyne-2-ol - Google Patents

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

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WO2022016317A1
WO2022016317A1 PCT/CN2020/103014 CN2020103014W WO2022016317A1 WO 2022016317 A1 WO2022016317 A1 WO 2022016317A1 CN 2020103014 W CN2020103014 W CN 2020103014W WO 2022016317 A1 WO2022016317 A1 WO 2022016317A1
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content
methyl
butyn
product
separation
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PCT/CN2020/103014
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French (fr)
Chinese (zh)
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鲍元野
杨颖�
刘英俊
张永振
黎源
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万华化学集团股份有限公司
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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
    • C07C29/36—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
    • 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
    • C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/04—Acyclic alcohols with carbon-to-carbon triple bonds
    • C07C33/042—Acyclic alcohols with carbon-to-carbon triple bonds with only one triple bond

Definitions

  • the invention belongs to the technical field of acetylenic alcohol production, in particular to a method for separating high-purity 2-methyl-3-butyn-2-ol.
  • 2-Methyl-3-butyn-2-ol is one of the important acetylenic alcohol chemicals, which is mainly used in the fields of corrosion inhibitor, food and medicine, and other chemical products.
  • corrosion inhibitor application because the molecule of 2-methyl-3-butyn-2-ol has both polar groups and non-polar groups, it can be used as an adsorption corrosion inhibitor, which can effectively Prevent metal hydrogen embrittlement.
  • downstream product of 2-methyl-3-butyn-2-ol, methylheptenone is an important pharmaceutical intermediate and food intermediate, which can further produce linalool, citral and pseudoviolet ketones, and further preparation of vitamin A, vitamin E, vitamin K1 and various flavors and fragrances.
  • 2-methyl-3-butyn-2-ol can be hydrogenated to generate tertiary amyl alcohol, also known as tertiary amyl alcohol, which is mainly used in synthetic fragrances, color film colorants, plasticizers, pesticides, medicines , dyes and used as metal flotation agents and organic solvents.
  • 2-Methyl-3-butyn-2-ol is partially hydrogenated to give methylbutenol, the resulting monomer can be used to produce 1,4-cis polyisoprene, which can be used in the synthesis rubber.
  • the alkylation reaction of preparing 2-methyl-3-butyn-2-ol usually uses a strong base solution as a catalyst, reacts acetone and acetylene in liquid ammonia, and neutralizes it with a weakly acidic aqueous solution after the reaction. After the catalyst, the product post-treatment and separation work is carried out.
  • the reaction formula of the acetylation reaction is:
  • the concentration of 2-methyl-3-butyn-2-ol in the product obtained after removing water by this method could only reach 99 wt%, not only The loss of raw materials is large, and the purity does not meet the requirements.
  • benzene is used as an entrainer for azeotropic distillation, and an almost anhydrous 2-methyl-3-butyn-2-ol product can be successfully obtained. Therefore, the method is widely used for the industrial production of 2-methyl-3-butyn-2-ol, for example, the purification of 2-methyl- Method for 3-Butyn-2-ol.
  • patent document CN104470879A mentions reducing the amount of pervaporation therein by combining two, three or more pervaporation units and/or membranes in series and/or by passing the retentate two, three or more times through a pervaporation unit water content.
  • alcohol is a heat-sensitive substance and tends to polymerize under high temperature conditions.
  • 2-methyl-3-butyn-2-ol will further react with acetone to generate a by-product 2,5-dimethyl-3-hexyn-2 , 5-diol, its reaction formula is:
  • the content of 2,5-dimethyl-3-hexyn-2,5-diol has a significant effect on the service life of the separation membrane used in the pervaporation device.
  • the polyvinyl alcohol film and/or polyimide film used in such methods need to be replaced regularly, which leads to high industrial operation costs.
  • the existing technology for separating 2-methyl-3-butyne-2-ol mainly has the following deficiencies:
  • Solvent azeotropic distillation will form a ternary azeotrope of water/azeotrope/2-methyl-3-butyn-2-ol; the formation of ternary azeotrope is unavoidable, and benzene is used as an azeotrope
  • the separation of benzene is the best, with the lowest proportion of product carried out in the aqueous phase; however, the high toxicity of benzene limits its use.
  • the purpose of the present invention is to provide a separation method of high-purity 2-methyl-3-butyn-2-ol, which can effectively control the content of 2-methyl-3-butyn-2-ol.
  • a separation method of 2-methyl-3-butyn-2-ol comprising:
  • Pretreatment step The reaction solution containing 2-methyl-3-butyn-2-ol is pretreated to remove unreacted acetone and salts contained therein to obtain 2-methyl-3-butyne -2-ol crude product; in the reaction solution containing 2-methyl-3-butyn-2-ol, control the content of 2,5-dimethyl-3-hexyn-2,5-diol ⁇ 0.1wt%, preferably ⁇ 0.06wt%;
  • the separation method includes the following steps:
  • Pretreatment step after the reaction solution containing 2-methyl-3-butyn-2-ol is subjected to rectification to remove acetone and to desalination through distillation or rectification, 2-methyl- 3-butyn-2-ol crude product;
  • the content of water is 10wt% to 40wt%, the content of acetone is less than or equal to 1wt%, 2,5-dimethyl-3-hexyn-2, The content of 5-diol ⁇ 0.1wt%;
  • the process of removing acetone and desalting in step (1) in the pretreatment process is not sequential, that is, acetone can be removed first and then desalted, or acetone can be desalted first and then acetone removed.
  • the removal of acetone can be achieved by means of rectification.
  • the removal of acetone can optionally use a rectification column, which can be a tray column or a packed column, which is well known to those skilled in the art.
  • atmospheric distillation is used to remove acetone from the reaction solution obtained from the acetylation reaction.
  • the operating temperature of the column still of the rectification tower is 90-93° C.
  • the reflux ratio is 3:1
  • the acetone content in the reaction solution after the acetone removal treatment can be lower than 0.5 wt%.
  • desalination can be accomplished by distillation or rectification, as is well known to those skilled in the art.
  • a thin-film evaporator or a short-path distiller can be used as the device for the desalination process, preferably a horizontal thin-film evaporator, metal scraper operating at atmospheric pressure, and an external circulation 80-120°C oil bath.
  • the content of the by-product 2,5-dimethyl-3-hexyne-2,5-diol in the reaction solution obtained from the acetylation reaction can be controlled .
  • the content of 2,5-dimethyl-3-hexyn-2,5-diol in the final 2-methyl-3-butyn-2-ol product can also be controlled.
  • the content of 2,5-dimethyl-3-hexyn-2,5-diol ⁇ 0.01wt%.
  • At least one membrane separator for separating water and 2-methyl-3-butyn-2-ol is used; There are hydrophilic membranes (or permeable membranes).
  • the hydrophilic film is selected from polyvinyl alcohol film, polyimide film or ceramic film, more preferably polyvinyl alcohol film or polyimide film.
  • the operating temperature of the membrane separation process using the hydrophilic membrane is greater than or equal to 0°C and less than or equal to 100°C (eg, 20°C, 40°C, 60°C, 80°C).
  • the hydrophilic membrane may also be, for example, a zeolite A based ceramic membrane.
  • Ceramic membranes for pervaporation include a nanoporous layer on a macroporous support. The pores must be large enough to pass water molecules and small enough to retain 2-methyl-3-butyn-2-ol. The surface can be modified with specific coatings or treatments. This membrane has been used to remove water from organic reaction mixtures and is available from FOLEX, Switzerland.
  • the material of the hydrophilic membrane described here is well known to those skilled in the art, and will not be repeated here.
  • the operation process of step (2) includes:
  • the reconstituted stream here contains a high proportion of high molecular weight components and has a high viscosity. In order to ensure the fluidity of the stream, it is necessary to have a part of 2-methyl-3-butyn-2-ol product.
  • the crude distillation column here is a sufficiently ideal separation condition.
  • the number of theoretical plates in the rectification section of the crude rectification column is ⁇ 5 (eg, 6, 8, 12, 14, 20), preferably 10-15.
  • the operating pressure of the crude rectification column is 50hPa ⁇ 300hPa (for example, 60hPa, 80hPa, 150hPa, 200hPa, 250hPa), preferably 100hPa ⁇ 200hPa;
  • the operating temperature of the column bottom of the crude rectification column is 100 hPa °C to 130°C (for example, 115°C, 120°C), preferably 110°C to 125°C.
  • the to-be-recombined fractions taken at the bottom of the crude rectification column enter from the middle of the column of the product separation column, and 2-methyl-3-butyn-2-ol is mixed with the product separation column in the product separation column.
  • the other components are separated.
  • the number of theoretical plates of the product separation column is ⁇ 5 (for example, 6, 8, 12, 14, 20), preferably 10-15;
  • the operating pressure of the product separation tower is 50hPa ⁇ 300hPa (for example, 60hPa, 80hPa, 150hPa, 200hPa, 250hPa), preferably 100hPa ⁇ 200hPa;
  • the operating temperature of the column kettle of the product separation tower is 100°C ⁇ 130°C (for example, 115°C, 120°C), preferably 110°C to 125°C.
  • the content of the by-product 2,5-dimethyl-3-hexyn-2,5-diol contained in the product affects the quality of the product 2-methyl-3-butyn-2-ol, i.e., for 2-
  • the color number and refractive index of the methyl-3-butyn-2-ol product will have adverse effects; therefore, in the process of removing water, the by-product can be further effectively controlled by adjusting the parameters of the process conditions. content.
  • the water content in the obtained 2-methyl-3-butyn-2-ol product is ⁇ 1 wt % (eg, 0.8 wt %, 0.5 wt %, 0.3 wt %, 0.1 wt % %) and the content of 2,5-dimethyl-3-hexyne-2,5-diol ⁇ 0.01wt% (eg, 0.008wt%, 0.005wt%, 0.003wt%, 0.001wt%).
  • the reaction solution containing 2-methyl-3-butyn-2-ol is prepared by a method comprising the following steps:
  • acetone, acetylene and a divalent metal salt are mixed in liquid ammonia for reaction; after the reaction is completed, a weakly acidic aqueous solution is added to neutralize the catalyst in the system to prepare a product containing 2-methyl-3-
  • the reaction solution of butyn-2-ol; in the reaction solution containing 2-methyl-3-butyn-2-ol, 2,5-dimethyl-3-hexyn-2,5-diol The content of ⁇ 0.1wt% (for example, its content is 0.08wt%, 0.06wt%, 0.04wt%, 0.02wt%).
  • Both the strong base and weakly acidic aqueous solutions here can be conventionally selected in the field.
  • the strong base can be selected from sodium hydroxide and potassium hydroxide;
  • the weakly acidic aqueous solution can be selected from ammonium sulfate aqueous solution.
  • the amount of the strong base in the reaction system is well known to those skilled in the art and will not be repeated here.
  • the amount of adding the weakly acidic aqueous solution for example, can just neutralize the strong base existing in the reaction system.
  • the reaction solution obtained from the alkylation reaction also contains various other components, such as the by-product 2,5-dimethyl-3-hexyn- 2,5-Diol, water, unreacted raw acetone, inorganic salts or other impurities.
  • the water content is 10-40 wt %, And it contains 1-20 wt% of unreacted raw material acetone.
  • the amount of the inorganic salt contained is related to the amount of the strong base and the weakly acidic aqueous solution added in the reaction process.
  • the divalent metal salt is selected from one or more of divalent zinc salt, divalent magnesium salt and divalent cobalt salt, preferably zinc acetate, magnesium sulfate and chlorine
  • the cobalt compounds more preferably zinc acetate and/or magnesium sulfate, more preferably zinc acetate.
  • the amount of the divalent metal salt is 0.01%-0.1% (eg, 0.015%, 0.03%, 0.05%, 0.08%, 0.09%) of the mass of acetone, preferably 0.02%-0.05%.
  • the molar ratio of acetylene to acetone is greater than or equal to 1:1 and less than or equal to 3:1 (for example, 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.
  • the 2,5-divalent metal salt in the prepared reaction solution containing 2-methyl-3-butyn-2-ol can be achieved. Effective control of methyl-3-hexyne-2,5-diol content ensures that it is in a lower content range ( ⁇ 0.1 wt%).
  • the effect of controlling the molar ratio of acetone to acetylene within this range is: under the condition of ensuring a certain acetylene content, the introduction of divalent metal salt can inhibit the generation of by-products and improve the selectivity of the product; at the same time, it can ensure safety. Reducing the molar ratio of acetylene to acetone can reduce energy loss and save costs.
  • the molar ratio of acetylene to acetone may be preferably 1.05:1 to 2:1.
  • the selectivity of the product of the acetylenic reaction can be improved, and the by-product 2,5-dimethylform in the reaction solution obtained can be effectively controlled.
  • the amount of divalent metal salt added also affects the content of 2,5-dimethyl-3-hexyne-2,5-diol in the reaction solution.
  • Controlling the content of 2,5-dimethyl-3-hexyne-2,5-diol in the reaction solution is less than or equal to 0.1 wt% can ensure the effect of membrane separation in the separation and purification process and prolong the service life of the permeable membrane.
  • the content of 2,5-dimethyl-3-hexyn-2,5-diol in the product obtained by separation can also be the same as that of the reaction solution containing 2-methyl-3-butyn-2-ol. In the process of separation, control is achieved to further reduce its content and ensure the quality of the obtained product.
  • the water in the 2-methyl-3-butyn-2-ol product can be removed and the 2,5-dimethyl-3-hexyne- 2,5-diol content, 2-methyl-3-butyn-2-ol with higher purity and higher conversion rate was prepared.
  • the membrane separation can be improved
  • the water removal effect in the process and the life of the permeable membrane used are significantly reduced, and the replacement frequency of the permeable membrane is significantly reduced. For example, the replacement is changed from monthly to every six months, which reduces the cost of separation.
  • the membrane separation process is used to replace the original azeotropic distillation process, which simplifies the operation process and has better industrial controllability.
  • FIG. 1 is a process flow diagram of the separation and purification steps in an embodiment of the separation method of the present invention.
  • 1--2-methyl-3-butyn-2-ol crude product 2--aqueous organic phase stream, 3--aqueous phase stream, 4--light component stream, 5--to be derecombined shunt, 6--product stream, 7--recombination shunt;
  • SEP-membrane separator SEP-membrane separator, RAC1-coarse distillation column, COOLER1-column top condenser, REBOILER1-column bottom reboiler;
  • composition of each component in the stream using gas chromatograph: Agilent7820A, chromatographic column HP-5 (30m ⁇ 320 ⁇ m ⁇ 0.25 ⁇ m), inlet temperature: 150°C; split ratio 50:1; carrier gas flow rate: 1.5ml/min;
  • Heating program hold 40°C for 1min, heat up to 90°C at 10°C/min, hold for 0min, then heat up to 160°C at 5°C/min, hold for 0min, then heat up to 280°C at 30°C/min, hold for 6min.
  • Detector temperature 280°C.
  • Refractive index test of the product METTLER TOLEDO refractometer Easy R40 is used.
  • the composition of the 1# reaction solution the content of inorganic salt is 2.16wt%, the content of water is 16.61wt%, the content of 2-methyl-3-butyn-2-ol is 77.30wt%, and the content of acetone is 3.56wt% %, the content of 2,5-dimethyl-3-hexyne-2,5-diol is 0.05wt%, the content of other components is 0.32wt%, and the total weight of each component of the 1# reaction solution is 100wt%.
  • the 500L autoclave was replaced with ammonia gas three times, the temperature in the reactor was lowered to -20°C, liquid ammonia (144.5Kg, 8500mol) was added, stirring was started, acetylene (16800L, 750mol) was introduced, and the concentration was 20wt% Zinc acetate aqueous solution 17.5g, then add the potassium hydroxide aqueous solution (1008g, the potassium hydroxide consumption as solute is 3mol% of acetone) that concentration is 50wt%, be warming up to 10 °C and add acetone (17.4Kg, 300mol), control The addition rate of acetone is completed in about 1h; the reaction temperature is 10 ° C, and 5Kg of ammonium sulfate aqueous solution with a concentration of 10wt% is added after the reaction for 2h for neutralization to obtain 2-methyl-3-butyn-2-ol. #Reaction solution, and sample the reaction solution by GC.
  • the composition of the 2# reaction solution the content of inorganic salt is 2.17wt%, the content of water is 16.62wt%, the content of 2-methyl-3-butyn-2-ol is 77.27wt%, and the content of acetone is 3.52wt% %, the content of 2,5-dimethyl-3-hexyne-2,5-diol is 0.02wt%, the content of other components is 0.40wt%, and the total weight of each component of the 2# reaction solution is 100wt%.
  • the 500L autoclave was replaced with ammonia gas three times, the temperature in the reactor was lowered to -20°C, liquid ammonia (144.5Kg, 8500mol) was added, stirring was started, acetylene (16800L, 750mol) was introduced, and the concentration was 20wt% Zinc acetate aqueous solution 8.7g, then add the potassium hydroxide aqueous solution (1008g, the potassium hydroxide consumption as solute is 3mol% of acetone) that concentration is 50wt%, be warming up to 10 °C and add acetone (17.4Kg, 300mol), control The addition rate of acetone is completed in about 1h; the reaction temperature is 10 ° C, and after 2h of reaction, 5Kg of ammonium sulfate aqueous solution with a concentration of 10wt% is added for neutralization to obtain 3-methyl-3-butyn-2-ol. #Reaction solution, and sample the reaction solution by GC.
  • the composition of the 3# reaction solution the content of inorganic salt is 2.17wt%, the content of water is 16.62wt%, the content of 2-methyl-3-butyn-2-ol is 77.41wt%, and the content of acetone is 3.32wt% %, the content of 2,5-dimethyl-3-hexyne-2,5-diol is 0.06wt%, the content of other components is 0.42wt%, and the total weight of each component of the 3# reaction solution is 100wt%.
  • the 500L autoclave was replaced with ammonia gas for 3 times, the temperature in the reactor was lowered to -20°C, liquefied ammonia (30.35Kg, 1785mol) was added, stirring was started, acetylene (7056L, 315mol) was introduced, and the concentration was 20wt% 87g of cobalt chloride aqueous solution, then add the potassium hydroxide aqueous solution that concentration is 50wt% (840g, the potassium hydroxide consumption as solute is 2.5mol% of acetone), be warming up to 10 °C and add acetone (17.4Kg, 300mol), The acetone addition rate was controlled to complete the feeding in about 1 hour; the reaction temperature was 10 ° C, and after the reaction for 2 hours, 4.5 Kg of ammonium sulfate aqueous solution with a concentration of 10 wt % was added for neutralization to obtain 2-methyl-3-butyn-2-ol containing 2-methyl-3-butyn-2-ol
  • the composition of the 4# reaction solution the content of inorganic salt is 1.81wt%, the content of water is 15.30wt%, the content of 2-methyl-3-butyn-2-ol is 76.57wt%, and the content of acetone is 5.75wt% %, the content of 2,5-dimethyl-3-hexyne-2,5-diol is 0.08wt%, the content of other components is 0.49wt%, and the total weight of each component in the 4# reaction solution is 100wt%.
  • the 1# reaction solution obtained by the acetylation reaction was desalted by a thin film evaporator.
  • the temperature of the external circulating oil bath of the thin film evaporator was 80°C, and the operating pressure was 800hPa.
  • the composition of the 1# reaction solution the content of inorganic salt is 2.16wt%, the content of water is 16.61wt%, the content of 2-methyl-3-butyn-2-ol is 77.30wt%, and the content of acetone is 3.56wt% %, the content of 2,5-dimethyl-3-hexyne-2,5-diol is 0.05wt%, and the content of other components is 0.32wt%.
  • the 1# reaction solution was passed into a thin film evaporator.
  • the feed rate of the 1# reaction liquid is 0.950kg/h
  • the extraction rate of the upper outlet of the thin film evaporator is 0.902kg/h
  • the composition of the extracted liquid phase the content of water is 16.98wt%, 2-methyl-3-
  • the content of butyn-2-ol is 79.01wt%
  • the content of acetone is 3.64wt%
  • the content of 2,5-dimethyl-3-hexyn-2,5-diol is 0.05wt%
  • other components Its content is 0.32wt%
  • the total weight of each component of the produced liquid phase at the above outlet is calculated as 100wt%.
  • the extraction rate of the lower outlet of the thin film evaporator is 0.048kg/h.
  • Liquid phase composition the content of water is 16.98wt%, the content of 2-methyl-3-butyn-2-ol is 79.01wt%, the content of acetone is 3.64wt%, the content of 2,5-dimethyl-3- The content of hexyne-2,5-diol was 0.05 wt %, and the content of other components was 0.32 wt %.
  • the produced liquid phase enters the rectification column from the feed line at the fourth theoretical plate in the lower part of the column.
  • the operating pressure of the distillation column is 1Kpa.
  • the top condenser uses 10°C cooling water as the refrigerant, and the operating temperature at the bottom of the tower is 92-93°C.
  • the ratio of reflux and production of the condensate flowing out of the top condenser of the rectification tower is 3:1.
  • the composition of the liquid phase produced at the top of the distillation column the content of water is 19.35wt%, the content of 2-methyl-3-butyn-2-ol is 48.27wt%, the content of acetone is 32.15wt%, and the other groups
  • the content of the components is 0.23 wt %, and the total weight of each component in the liquid phase drawn from the top of the tower is 100 wt %.
  • the composition of the liquid phase produced at the bottom of the distillation column the content of water is 16.72wt%, the content of 2-methyl-3-butyn-2-ol is 82.37wt%, the content of acetone is 0.52wt%, 2, The content of 5-dimethyl-3-hexyne-2,5-diol is 0.06wt%, the content of other components is 0.33wt%, and the total weight of each component in the liquid phase extracted from the column bottom is 100wt% %; that is, crude 2-methyl-3-butyn-2-ol was obtained.
  • the 2# reaction solution obtained by the acetylenic reaction is desalted by a thin film evaporator, the temperature of the external circulating oil bath of the thin film evaporator is 80°C, and the operating pressure is 800hPa.
  • the composition of the 2# reaction solution the content of inorganic salt is 2.17wt%, the content of water is 16.62wt%, the content of 2-methyl-3-butyn-2-ol is 77.27wt%, and the content of acetone is 3.52wt% %, the content of 2,5-dimethyl-3-hexyne-2,5-diol is 0.02wt%, and the content of other components is 0.40wt%.
  • the 2# reaction solution was passed into a thin film evaporator.
  • the feed rate of the 2# reaction liquid is 0.950kg/h
  • the extraction rate of the upper outlet of the thin film evaporator is 0.902kg/h
  • the composition of the extracted liquid phase the content of water is 16.99wt%, 2-methyl-3-
  • the content of butyn-2-ol is 78.98wt%
  • the content of acetone is 3.60wt%
  • the content of 2,5-dimethyl-3-hexyn-2,5-diol is 0.02wt%
  • other components Its content is 0.41wt%
  • the total weight of each component of the produced liquid phase at the above outlet is calculated as 100wt%.
  • the extraction rate of the lower outlet of the thin film evaporator is 0.048kg/h.
  • Phase composition the content of water is 16.99wt%, the content of 2-methyl-3-butyn-2-ol is 78.98wt%, the content of acetone is 3.60wt%, the content of 2,5-dimethyl-3-hexyl The content of alkyne-2,5-diol was 0.02 wt %, and the content of other components was 0.41 wt %.
  • the produced liquid enters the rectification column from the feed line at the fourth theoretical plate in the lower part of the column.
  • the operating pressure of the distillation column is 1Kpa.
  • the top condenser uses 10°C cooling water as the refrigerant, and the operating temperature at the bottom of the tower is 92-93°C.
  • the ratio of reflux and production of the condensate flowing out of the top condenser of the rectification tower is 3:1.
  • composition of the liquid phase produced at the top of the rectification tower the content of water is 19.38wt%, the content of 2-methyl-3-butyn-2-ol is 48.15wt%, the content of acetone is 32.12wt%, and the other groups
  • the content of the components is 0.35 wt %, and the total weight of each component in the liquid phase drawn from the top of the tower is 100 wt %.
  • the composition of the liquid phase produced at the bottom of the rectifying tower the content of water is 16.73wt%, the content of 2-methyl-3-butyn-2-ol is 82.35wt%, the content of acetone is 0.48wt%, 2, The content of 5-dimethyl-3-hexyne-2,5-diol is 0.02wt%, the content of other components is 0.42wt%, and the total weight of each component in the liquid phase extracted from the column bottom is 100wt% %; that is, crude 2-methyl-3-butyn-2-ol was obtained.
  • the 3# reaction solution obtained by the reaction is subjected to deacetone treatment by using a corrugated packing column of plate mesh, the diameter of the rectifying column (packing column) is 100mm, the height of the packing layer is 0.5m, and the number of theoretical plates is 5;
  • the 3# reaction liquid is fed into the rectification tower from the feed line at the fourth theoretical plate in the lower part of the tower.
  • the operating pressure of the distillation column is 1Kpa.
  • the top condenser uses 10°C cooling water as the refrigerant, and the operating temperature at the bottom of the tower is 92-93°C.
  • the ratio of reflux and production of the condensate flowing out of the top condenser of the rectification tower is 3:1.
  • composition of the liquid phase produced at the top of the rectification tower the content of water is 19.37wt%, the content of 2-methyl-3-butyn-2-ol is 48.05wt%, the content of acetone is 32.19wt%, and the other groups
  • the content of the components is 0.39 wt %, and the total weight of each component in the liquid phase drawn from the top of the tower is 100 wt %.
  • the composition of the liquid phase produced at the bottom of the distillation column the content of inorganic salts is 2.40wt%, the content of water is 16.33wt%, the content of 2-methyl-3-butyn-2-ol is 80.46wt%, the content of acetone The content of 0.32wt%, the content of 2,5-dimethyl-3-hexyne-2,5-diol is 0.07wt%, and the content of other components is 0.42wt%, and the liquid phase is extracted from the bottom of the tower The total weight of each component is calculated as 100 wt%.
  • a thin film evaporator is used to desalt the produced liquid at the bottom of the rectification tower.
  • the temperature of the external circulating oil bath of the thin film evaporator is 80°C and the operating pressure is 800hPa.
  • the produced liquid from the bottom of the rectifying tower is passed into the thin film evaporator, the feed rate is 0.861kg/h, the production rate of the upper outlet of the thin film evaporator is 0.817kg/h, and the composition of the produced liquid phase: the content of water is 16.74wt%, the content of 2-methyl-3-butyn-2-ol is 82.44wt%, the content of acetone is 0.32wt%, 2,5-dimethyl-3-hexyn-2,5-di
  • the content of alcohol is 0.07 wt %, the content of other components is 0.43 wt %, and the total weight of each component of the produced liquid phase at the above outlet is 100 wt %; that is, 2-methyl-3-butyne-2 is obtained - Crude alcohol.
  • the extraction rate of the lower outlet of the thin film evaporator is 0.044kg/h.
  • the 4# reaction solution obtained by the reaction is subjected to deacetone treatment by using a corrugated packing column of plate mesh.
  • Composition The content of inorganic salt is 1.81wt%, the content of water is 15.30wt%, the content of 2-methyl-3-butyn-2-ol is 76.57wt%, the content of acetone is 5.75wt%, the content of 2,5 - The content of dimethyl-3-hexyn-2,5-diol was 0.08 wt %, and the content of other components was 0.49 wt %.
  • the 4# reaction liquid is fed into the rectification tower from the feed line at the 4th theoretical plate in the lower part of the tower.
  • the operating pressure of the distillation column is 1Kpa.
  • the top condenser uses 10°C cooling water as the refrigerant, and the operating temperature at the bottom of the tower is 92-93°C.
  • the ratio of reflux and production of the condensate flowing out of the top condenser of the rectification tower is 3:1.
  • composition of the liquid phase produced at the top of the rectification tower the content of water is 19.38wt%, the content of 2-methyl-3-butyn-2-ol is 47.89wt%, the content of acetone is 32.21wt%, and the other groups
  • the content of the components is 0.52 wt %, and the total weight of each component in the liquid phase drawn from the top of the tower is 100 wt %.
  • the composition of the liquid phase produced at the bottom of the distillation column the content of inorganic salts is 2.14wt%, the content of water is 14.56wt%, the content of 2-methyl-3-butyn-2-ol is 81.79wt%, the content of acetone The content of 0.93wt%, the content of 2,5-dimethyl-3-hexyne-2,5-diol is 0.09wt%, and the content of other components is 0.49wt%, and the liquid phase is extracted from the bottom of the tower The total weight of each component is calculated as 100 wt%.
  • a thin film evaporator is used to desalt the produced liquid at the bottom of the rectification tower.
  • the temperature of the external circulating oil bath of the thin film evaporator in the morning is 80°C and the operating pressure is 800hPa.
  • the produced liquid from the bottom of the rectifying tower is passed into the thin film evaporator, the feed rate is 0.794kg/h, the production rate of the upper outlet of the thin film evaporator is 0.763kg/h, the composition of the produced liquid phase: the content of water is 14.87wt%, the content of 2-methyl-3-butyn-2-ol is 83.58wt%, the content of acetone is 0.95wt%, 2,5-dimethyl-3-hexyn-2,5-di
  • the content of alcohol is 0.10 wt %, the content of other components is 0.50 wt %, and the total weight of each component of the produced liquid phase at the above outlet is 100 wt %; that is, 2-methyl-3-butyne-2 is obtained - Crude alcohol.
  • the extraction rate of the lower outlet of the thin film evaporator was 0.031 kg/h.
  • the separation and purification process includes the following steps:
  • the membrane separator SEP consists of the following components (not shown in the figure): a feed vessel with a circulating pump, a membrane permeation unit with a hydrophilic membrane ((CMC-E, Celfa AG, Switzerland), which is passed through the hydrophilic membrane in gaseous form Water rich permeate is removed.
  • a feed vessel with a circulating pump a membrane permeation unit with a hydrophilic membrane ((CMC-E, Celfa AG, Switzerland)
  • Aqueous organic phase stream 2 ie, retentate
  • aqueous phase stream 3 ie, permeate
  • retentate flow rate 0.695 kg/h , which contains 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 of 100 wt%; the permeate flow rate was 0.118 kg/h, which contained about 0.31 wt% of 2-methyl -3-butyn-2-ol, 1.34 wt % acetone, 0.14 wt % other impurities and the remainder water, based on the total weight of the permeate components as 100 wt %.
  • the resulting aqueous organic phase stream 2 (ie, retentate) was fed into the crude rectification column RAC1 from the feed line at the 10th theoretical plate in the lower part of the column at a flow rate of 0.695 kg/h.
  • the distillation column adopts the corrugated packing column of plate mesh, the diameter of the column is 100mm, the height of the packing layer is 2m, and the number of theoretical plates is 15.
  • the operating pressure of the crude distillation column was 100 hPa.
  • the column top condenser COOLER1 uses 10 °C cooling water as the refrigerant, and the column bottom reboiler REBOILER1 realizes the regulation of the column bottom temperature, and the operating temperature of the column bottom is 119-120 °C.
  • the ratio of condensate reflux and extraction from the top condenser of the crude rectification tower is 1:1, the operating temperature at the top of the column is 42-43 ° C, and the top of the column is drawn with a light component stream 4, and the extraction flow rate is 0.0725kg/h .
  • a flow rate of 0.6225kg/h is taken out of the sub-stream 5 to be removed and entered into the product separation tower.
  • the content of -hexyne-2,5-diol is 0.07 wt %, and the content of other components is 0.41 wt %, and the total weight of each component in the liquid phase extracted from the bottom of the tower is 100 wt %.
  • the operating pressure of the product separation column was 100 hPa.
  • the column top condenser COOLER2 uses 10°C cooling water as the refrigerant, and the column bottom reboiler REBOILER2 realizes the regulation of the column bottom temperature, and the column bottom operating temperature is 119-120°C.
  • the ratio of reflux and production of condensate flowing out of the tower top condenser is 1:1, the operating temperature of the tower top is 53-54°C, and the product stream 6 is produced from the top of the tower, and its production flow rate is 0.6127kg/h.
  • the composition of the produced liquid phase at the top of the product separation tower the content of water is 0.27% by weight, the content of 2-methyl-3-butyn-2-ol is 99.73% by weight, and the components of the liquid phase are taken from the top of the tower.
  • the total weight is 100wt%.
  • the bottom of the product separation tower draws out the reorganization branch 7 with the flow velocity of 0.0098kg/h, and the liquid phase composition at the bottom of the product separation tower: the content of 2-methyl-3-butyn-2-ol is 69.72wt %, the content of 2,5-dimethyl-3-hexyne-2,5-diol is 4.6wt%, and the content of other components is 25.68wt%.
  • the weight is based on 100 wt%.
  • the membrane permeation unit including the membrane separator was continuously fed for 3000 hours, and no obvious abnormality was observed.
  • the separation and purification process includes the following steps:
  • the membrane separator SEP consists of the following components (not shown in the figure): a feed vessel with a circulating pump, a membrane permeation unit with a hydrophilic membrane (CMC-E, Celfa AG, Switzerland), which is removed in gaseous form by a hydrophilic membrane Water-rich permeate.
  • a feed vessel with a circulating pump a membrane permeation unit with a hydrophilic membrane (CMC-E, Celfa AG, Switzerland), which is removed in gaseous form by a hydrophilic membrane Water-rich permeate.
  • CMC-E hydrophilic membrane
  • Aqueous organic phase stream 2 ie, retentate
  • aqueous phase stream 3 ie, permeate
  • the retentate flow rate was 0.692 kg/h, which contained 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-hexyn-2,5-diol and 0.45wt% of other impurities, based on the total weight of the retentate components as 100wt%;
  • the permeate flow rate is 0.121kg/h, containing about 0.35wt% of 2-methyl-3-butyn-2-ol , 1.12 wt % of acetone, 0.18 wt % of other impurities and the remainder being water, based on the total weight of the permeate components as 100 wt %.
  • the resulting aqueous organic phase stream 2 (ie, retentate) was fed into the crude rectification column RAC1 from the feed line at the 10th theoretical plate in the lower part of the column at a flow rate of 0.695 kg/h.
  • the distillation column adopts the corrugated packing column of plate mesh, the diameter of the column is 100mm, the height of the packing layer is 2m, and the number of theoretical plates is 15.
  • the operating pressure of the crude distillation column was 100 hPa.
  • the column top condenser COOLER1 uses 10 °C cooling water as the refrigerant, and the column bottom reboiler REBOILER1 realizes the regulation of the column bottom temperature, and the operating temperature of the column bottom is 119-120 °C.
  • the ratio of condensate reflux and extraction from the top condenser of the crude rectification tower is 1:1, the operating temperature at the top of the column is 42-43 ° C, and the top of the column draws a light component stream 4, and the extraction flow rate is 0.0519kg/h .
  • a flow rate of 0.6401kg/h is taken out of the fractional stream 5 to be deweighted, and enters the product separation tower.
  • the content of -hexyne-2,5-diol is 0.03 wt %, and the content of other components is 0.50 wt %, and the total weight of each component in the liquid phase extracted from the bottom of the tower is 100 wt %.
  • the fractional stream 5 to be taken off at the bottom of the crude rectifying tower enters from the middle of the tower of the product separation tower RAC2;
  • the number of plates is 7, and the crude distillation column bottom liquid enters the product separation column from the feed line at the fourth theoretical plate.
  • the operating pressure of the product separation column was 100 hPa.
  • the column top condenser COOLER2 uses 10 °C cooling water as the refrigerant, and the column bottom reboiler REBOILER2 realizes the regulation of the column bottom temperature, and the operating temperature of the column bottom is 119-120 °C.
  • the ratio of reflux and production of the condensate flowing out of the tower top condenser is 1:1, the operating temperature of the tower top is 53-54°C, and the product stream 6 is produced from the top of the tower, and its production flow rate is 0.6316kg/h.
  • the composition of the produced liquid phase at the top of the product separation tower the content of water is 0.61 wt%, the content of 2-methyl-3-butyn-2-ol is 99.39 wt%, and the components of the liquid phase are taken from the top of the tower.
  • the total weight is 100wt%.
  • the reorganization branch 7 is extracted at a flow rate of 0.0085kg/h, and the liquid phase composition at the bottom of the product separation tower is: the content of 2-methyl-3-butyn-2-ol is 60.60wt% , the content of 2,5-dimethyl-3-hexyne-2,5-diol is 2.12wt%, the content of other components is 37.28wt%, and the total weight of each component in the liquid phase is obtained from the bottom of the tower 100% by weight.
  • the membrane permeation unit including the membrane separator was continuously fed for 4000 hours, and no obvious abnormality was observed.
  • the separation and purification process includes the following steps:
  • the membrane separator SEP consists of the following components (not shown in the figure): a feed vessel with a circulating pump, a membrane permeation unit with a hydrophilic membrane (CMC-E, Celfa AG, Switzerland), which is removed in gaseous form by a hydrophilic membrane Water-rich permeate.
  • a feed vessel with a circulating pump a membrane permeation unit with a hydrophilic membrane (CMC-E, Celfa AG, Switzerland), which is removed in gaseous form by a hydrophilic membrane Water-rich permeate.
  • CMC-E hydrophilic membrane
  • Aqueous organic phase stream 2 ie, retentate
  • aqueous phase stream 3 ie, permeate
  • the retentate flow rate was 0.714 kg/h, which contained about 94.29 wt% of 2-methyl-3-butyn-2-ol, 4.93 wt % water, 0.24 wt % acetone, 0.08 wt % 2,5-dimethyl-3-hexyn-2,5-diol and 0.46 wt% of other impurities, based on the total weight of the retentate components as 100 wt%;
  • the permeate flow rate was 0.103 kg/h, containing 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 is water, based on the total weight of the permeate components as 100 wt %.
  • the resulting aqueous organic phase stream 2 (ie, retentate) was fed into the crude rectification column RAC1 from the feed line at the 10th theoretical plate in the lower part of the column at a flow rate of 0.714 kg/h.
  • the distillation column adopts the corrugated packing column of plate mesh, the diameter of the column is 100mm, the height of the packing layer is 2m, and the number of theoretical plates is 15.
  • the operating pressure of the crude distillation column was 100 hPa.
  • the column top condenser COOLER1 uses 10 °C cooling water as the refrigerant, and the column bottom reboiler REBOILER1 realizes the regulation of the column bottom temperature, and the operating temperature of the column bottom is 119-120 °C.
  • the ratio of reflux and extraction of the condensate flowing out of the top condenser of the crude rectification tower is 1:1, the operating temperature at the top of the column is 42-43 ° C, and the top of the column is drawn with a light component stream 4, and the extraction flow rate is 0.1225kg/h .
  • a flow rate of 0.5915kg/h is taken out of the fractional stream 5 to be deweighted, and enters the product separation tower.
  • the content of -hexyne-2,5-diol is 0.09wt%
  • the content of other components is 0.56wt%
  • the total weight of each component in the liquid phase extracted from the bottom of the tower is 100wt%.
  • the fractional stream 5 to be taken off at the bottom of the crude rectifying tower enters from the middle of the tower of the product separation tower RAC2;
  • the number of plates is 7, and the crude distillation column bottom liquid enters the product separation column from the feed line at the fourth theoretical plate.
  • the operating pressure of the product separation column was 100 hPa.
  • the column top condenser COOLER2 uses 10 °C cooling water as the refrigerant, and the column bottom reboiler REBOILER2 realizes the regulation of the column bottom temperature, and the operating temperature of the column bottom is 119-120 °C.
  • the ratio of reflux and production of condensate flowing out of the tower top condenser is 1:1, the operating temperature of the tower top is 53-54°C, and the product stream 6 is produced from the top of the tower, and its production flow rate is 0.5819kg/h.
  • the composition of the produced liquid phase at the top of the product separation tower the content of water is 0.64% by weight, the content of 2-methyl-3-butyn-2-ol is 99.36% by weight, and the components of the liquid phase are taken from the top of the tower.
  • the total weight is 100wt%.
  • the bottom of the product separation tower draws out the reorganization branch 7 with the flow velocity of 0.096kg/h, and the liquid phase composition at the bottom of the product separation tower: the content of 2-methyl-3-butyn-2-ol is 59.48wt %, the content of 2,5-dimethyl-3-hexyne-2,5-diol is 5.96wt%, and the content of other components is 34.56wt%.
  • the weight is based on 100 wt%.
  • the membrane permeation unit including the membrane separator was continuously fed for 3500 hours without any obvious abnormality.
  • the produced liquid at the top of the product separation tower namely the obtained product 2-methyl-3-butyn-2-ol, measured its refractive index: n20/D 1.4215, color number: 16 (Pt-Co).
  • the separation and purification process includes the following steps:
  • the membrane separator SEP consists of the following components (not shown in the figure): a feed vessel with a circulating pump, a membrane permeation unit with a hydrophilic membrane ((CMC-E, Celfa AG, Switzerland), passing through the hydrophilic membrane in gaseous form Water-rich permeate was removed.
  • a feed vessel with a circulating pump a membrane permeation unit with a hydrophilic membrane ((CMC-E, Celfa AG, Switzerland)
  • Aqueous organic phase stream 2 ie, retentate
  • aqueous phase stream 3 ie, permeate
  • retentate flow rate was 0.658 kg/h , which contains about 96.86 wt% 2-methyl-3-butyn-2-ol, 1.61 wt% water, 0.87 wt% acetone, 0.11 wt% 2,5-dimethyl-3-hexyne -2,5-diol and 0.55 wt% of other impurities, based on the total weight of the retentate components of 100 wt%;
  • the permeate flow rate was 0.105 kg/h, which contained about 0.36 wt% of 2-methyl -3-butyn-2-ol, 1.45 wt % acetone, 0.22 wt % other impurities and the remainder water, based on the total weight of the permeate components as 100 wt %.
  • the resulting aqueous organic phase stream 2 (ie, retentate) was fed into the crude distillation column RAC1 from the feed line at the 10th theoretical plate in the lower part of the column at a flow rate of 0.658 kg/h.
  • the distillation column adopts the corrugated packing column of plate mesh, the diameter of the column is 100mm, the height of the packing layer is 2m, and the number of theoretical plates is 15.
  • the operating pressure of the crude distillation column was 100 hPa.
  • the column top condenser COOLER1 uses 10 °C cooling water as the refrigerant, and the column bottom reboiler REBOILER1 realizes the regulation of the column bottom temperature, and the operating temperature of the column bottom is 119-120 °C.
  • the ratio of condensate reflux and extraction from the top condenser of the crude rectification tower is 1:1, the operating temperature at the top of the column is 42-43 ° C, and the top of the column is drawn with a light component stream 4, and the extraction flow rate is 0.0725kg/h .
  • a flow rate of 0.6255kg/h is taken out of the sub-stream 5 to be deweighted, and enters the product separation tower.
  • the content of -hexyne-2,5-diol is 0.12 wt %, and the content of other components is 0.57 wt %, and the total weight of each component in the liquid phase extracted from the bottom of the tower is 100 wt %.
  • the fractional stream 5 to be taken off at the bottom of the crude rectifying tower enters from the middle of the tower of the product separation tower RAC2;
  • the number of plates is 7, and the crude distillation column bottom liquid enters the product separation column from the feed line at the fourth theoretical plate.
  • the operating pressure of the product separation column was 100 hPa.
  • the column top condenser COOLER2 uses 10 °C cooling water as the refrigerant, and the column bottom reboiler REBOILER2 realizes the regulation of the column bottom temperature, and the operating temperature of the column bottom is 119-120 °C.
  • the ratio of reflux and production of the condensate flowing out of the tower top condenser is 1:1, the operating temperature of the tower top is 53-54°C, and the product stream 6 is produced from the top of the tower, and its production flow rate is 0.6134kg/h.
  • the total weight is based on 100 wt%.
  • the reorganization branch 7 is extracted at a flow rate of 0.121 kg/h, and the liquid phase composition at the bottom of the product separation tower is: the content of 2-methyl-3-butyn-2-ol is 64.07wt% , the content of 2,5-dimethyl-3-hexyne-2,5-diol is 6.31wt%, the content of other components is 29.62wt%, and the total weight of each component in the liquid phase is obtained from the bottom of the tower 100% by weight.
  • the membrane permeation unit including the membrane separator was continuously fed for 2000 hours, and no obvious abnormality was observed.
  • the 500L autoclave was replaced with ammonia gas three times, the temperature in the reactor was lowered to -20°C, liquefied ammonia (144.5Kg, 8500mol) was added, stirring was started, acetylene (16800L, 750mol) was introduced, and the concentration was 50wt%
  • the potassium hydroxide aqueous solution (1008g, as the potassium hydroxide consumption of solute is 3mol% of acetone), be warming up to 10 DEG C and add acetone (17.4Kg, 300mol), control the acetone addition rate to complete the feeding at about 1h; the reaction temperature is At 10°C, after 2 hours of reaction, 5Kg of ammonium sulfate aqueous solution with a concentration of 10wt% was added for neutralization to obtain a 5# reaction solution containing 2-methyl-3-butyn-2-ol, and the reaction solution was sampled and detected by GC.
  • the composition of the 5# reaction solution the content of inorganic salt is 2.17wt%, the content of water is 16.62wt%, the content of 2-methyl-3-butyn-2-ol is 75.31wt%, and the content of acetone is 4.68wt% %, the content of 2,5-dimethyl-3-hexyne-2,5-diol is 0.59wt%, the content of other components is 0.63wt%, and the total weight of each component of the 5# reaction solution is 100wt%.
  • the 5# reaction solution obtained by the acetylation reaction was desalted by a thin film evaporator, the temperature of the external circulating oil bath of the thin film evaporator was 80°C, and the operating pressure was 800hPa.
  • the composition of the 5# reaction solution the content of inorganic salt is 2.17wt%, the content of water is 16.62wt%, the content of 2-methyl-3-butyn-2-ol is 75.31wt%, and the content of acetone is 4.68wt% %, the content of 2,5-dimethyl-3-hexyne-2,5-diol is 0.59wt%, and the content of other components is 0.63wt%.
  • the feed rate of the 5# reaction liquid is 0.950kg/h
  • the extraction rate of the upper outlet of the thin film evaporator is 0.902kg/h
  • the composition of the extracted liquid phase the content of water is 16.99wt%, 2-methyl-3-
  • the content of butyn-2-ol is 76.98wt%
  • the content of acetone is 4.79wt%
  • the content of 2,5-dimethyl-3-hexyn-2,5-diol is 0.60wt%
  • Its content is 0.64 wt %, calculated on the basis of the total weight of each component of the produced liquid phase as 100 wt %.
  • the extraction rate of the lower outlet of the thin film evaporator is 0.048kg/h.
  • Phase composition the content of water is 16.99wt%, the content of 2-methyl-3-butyn-2-ol is 76.98wt%, the content of acetone is 4.79wt%, 2,5-dimethyl-3-hexyl The content of alkyne-2,5-diol was 0.60 wt %, and the content of other components was 0.64 wt %.
  • the produced liquid enters the rectification column from the feed line at the fourth theoretical plate in the lower part of the column.
  • the operating pressure of the distillation column is 1Kpa.
  • the top condenser uses 10°C cooling water as the refrigerant, and the operating temperature at the bottom of the tower is 92-93°C.
  • the ratio of reflux and production of the condensate flowing out of the top condenser of the rectification tower is 3:1.
  • composition of the liquid phase produced at the top of the distillation column the content of water is 19.36wt%, the content of 2-methyl-3-butyn-2-ol is 46.58wt%, the content of acetone is 33.72wt%, and the other groups
  • the content of the fractions is 0.34 wt %, and the total weight of each component of the liquid phase produced at the top of the tower is 100 wt %.
  • the composition of the liquid phase produced at the bottom of the distillation column the content of water is 16.68wt%, the content of 2-methyl-3-butyn-2-ol is 80.99wt%, the content of acetone is 0.98wt%, 2, The content of 5-dimethyl-3-hexyne-2,5-diol is 0.67wt%, the content of other components is 0.68wt%, and the total weight of each component in the liquid phase extracted from the column bottom is 100wt% Calculation; that is, crude 2-methyl-3-butyn-2-ol was obtained.
  • the separation and purification process includes the following steps:
  • the membrane separator SEP consists of the following components (not shown in the figure): a feed vessel with a circulating pump, a membrane permeation unit with a hydrophilic membrane (CMC-E, Celfa AG, Switzerland), which is removed in gaseous form by a hydrophilic membrane Water-rich permeate.
  • a feed vessel with a circulating pump a membrane permeation unit with a hydrophilic membrane (CMC-E, Celfa AG, Switzerland), which is removed in gaseous form by a hydrophilic membrane Water-rich permeate.
  • CMC-E hydrophilic membrane
  • Aqueous organic phase stream 2 ie, retentate
  • aqueous phase stream 3 ie, permeate
  • the retentate flow rate was 0.689 kg/h, which contained 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-hexyn-2,5-diol and 0.76 wt% of other impurities, based on the total weight of the retentate components as 100 wt%;
  • the permeate flow was 0.108 kg/h, which contained about 0.31 wt% of 2-methyl-3-butyne-2- Alcohol, 1.34 wt% acetone, 0.18 wt% other impurities and the remainder water, based on the total weight of the permeate components as 100 wt%.
  • the resulting aqueous organic phase stream 2 (ie, retentate) was fed into the crude rectification column RAC1 from the feed line at the 10th theoretical plate in the lower part of the column at a flow rate of 0.689 kg/h.
  • the distillation column adopts the corrugated packing column of plate mesh, the diameter of the column is 100mm, the height of the packing layer is 2m, and the number of theoretical plates is 15.
  • the operating pressure of the crude distillation column was 100 hPa.
  • the column top condenser COOLER1 uses 10 °C cooling water as the refrigerant, and the column bottom reboiler REBOILER1 realizes the regulation of the column bottom temperature, and the operating temperature of the column bottom is 119-120 °C.
  • the ratio of reflux and extraction of the condensate flowing out of the top condenser of the crude rectification tower is 1:1, the operating temperature at the top of the column is 42-43 ° C, and the top of the column is drawn with a light component stream 4, and the extraction flow rate is 0.0878kg/h .
  • a flow rate of 0.6012kg/h is taken out of the fractional stream 5 to be removed and entered into the product separation tower.
  • the content of -hexyne-2,5-diol is 0.91 wt %, and the content of other components is 0.87 wt %, and the total weight of each component in the liquid phase extracted from the bottom of the tower is 100 wt %.
  • the fractional stream 5 to be taken off at the bottom of the crude rectifying tower enters from the middle of the tower of the product separation tower RAC2;
  • the number of plates is 7, and the crude distillation column bottom liquid enters the product separation column from the feed line at the fourth theoretical plate.
  • the operating pressure of the product separation column was 100 hPa.
  • the column top condenser COOLER2 uses 10 °C cooling water as the refrigerant, and the column bottom reboiler REBOILER2 realizes the regulation of the column bottom temperature, and the operating temperature of the column bottom is 119-120 °C.
  • the ratio of reflux and production of the condensate flowing out of the tower top condenser is 1:1, the operating temperature of the tower top is 53-54°C, and the product stream 6 is produced from the top of the tower, and its production flow rate is 0.5736kg/h.
  • Composition of the produced liquid phase at the top of the product separation tower the content of water is 0.80%, the content of 2-methyl-3-butyn-2-ol is 99.18wt%, 2,5-dimethyl-3-hexanol
  • the content of alkyne-2,5-diol is 0.01wt%, the content of other components is 0.01wt%, and the total weight of each component in the liquid phase extracted from the top of the column is 100wt%.
  • the reorganization branch 7 is extracted at a flow rate of 0.0276kg/h, and the liquid phase composition at the bottom of the product separation tower is: 2-methyl-3-butyn-2-ol is 61.32wt% , the content of 2,5-dimethyl-3-hexyne-2,5-diol is 19.61wt%, the content of other components is 19.07wt%, and the total weight of each component in the liquid phase is obtained from the bottom of the tower 100% by weight.
  • the produced liquid at the top of the product separation tower namely the obtained product 2-methyl-3-butyn-2-ol, measured its refractive index: n20/D 1.4500, color number: 35 (Pt-Co).
  • Example 1 From the experimental results of Example 1 and Comparative Example 1, it can be seen that by adding a divalent metal salt in the system of the preparation process, the by-product 2,5-dimethyl-3-hexyne-2,5 in the reaction process can be effectively suppressed - the formation of diol, and then control the content of 2,5-dimethyl-3-hexyne-2,5-diol in the obtained reaction solution to a lower range ( ⁇ 0.1wt%), which improves the product selectivity .
  • Example 2 It can be seen from the experimental results of Example 2 and Example 3 that under the same molar ratio of acetone and acetylene, as the amount of added divalent metal salt decreases, the by-product 2,5-dimethyl-3-hexyne- The content of 2,5-diol increased, indicating that the addition amount of divalent metal salt in the system could regulate the content of 2,5-dimethyl-3-hexyne-2,5-diol in the obtained reaction solution.
  • the divalent metal salt selected in Example 2-3 is zinc acetate, and as the preferred divalent metal salt species, it reduces the by-product 2,5-dimethyl-3-hexyne-2,5-diol The effect of content is more obvious.

Abstract

The present invention relates to the technical field of acetylene alcohol production, and in particular, to a separation method for 2-methyl-3-butyne-2-ol, comprising: pretreating a reaction liquid containing 2-methyl-3-butyne-2-ol to remove unreacted acetone and contained salt therein so as to obtain a 2-methyl-3-butyne-2-ol crude product; controlling the content of 2,5-dimethyl-3-hexyne-2,5-diol to be less than or equal to 0.1 wt% in the reaction liquid containing 2-methyl-3-butyne-2-ol; and separating and purifying the 2-methyl-3-butyne-2-ol crude product by means of membrane separation treatment and reduced pressure distillation treatment to obtain a 2-methyl-3-butyne-2-ol product. According to the method of the present invention, water in the product can be removed and the content of the 2,5-dimethyl-3-hexyne-2,5-diol can be decreased with reduced investment and energy consumption, thereby obtaining 2-methyl-3-butyne-2-ol having relatively high purity and conversion rate.

Description

一种2-甲基-3-丁炔-2-醇的分离方法A kind of separation method of 2-methyl-3-butyn-2-ol 技术领域technical field
本发明属于炔属醇类生产的技术领域，尤其涉及一种高纯度的2-甲基-3-丁炔-2-醇的分离方法。The invention belongs to the technical field of acetylenic alcohol production, in particular to a method for separating high-purity 2-methyl-3-butyn-2-ol.
背景技术Background technique
2-甲基-3-丁炔-2-醇是重要的炔属醇类化学品之一，主要应用于缓蚀剂、食品医药、其它化工产品等领域。在缓蚀剂应用方面，因2-甲基-3-丁炔-2-醇的分子中既有极性基团，又有非极性基团，所以可以作为吸附型缓蚀剂，可有效防止金属氢脆。2-Methyl-3-butyn-2-ol is one of the important acetylenic alcohol chemicals, which is mainly used in the fields of corrosion inhibitor, food and medicine, and other chemical products. In terms of corrosion inhibitor application, because the molecule of 2-methyl-3-butyn-2-ol has both polar groups and non-polar groups, it can be used as an adsorption corrosion inhibitor, which can effectively Prevent metal hydrogen embrittlement.
另外，2-甲基-3-丁炔-2-醇的下游产品甲基庚烯酮，是一种重要的医药中间体、食品中间体，可以进一步制得芳樟醇、柠檬醛和假紫罗兰酮，以及进一步制备维生素A、维生素E、维生素K1及多种香料香精。而且，2-甲基-3-丁炔-2-醇加氢后可生成叔戊醇，又名特戊醇，主要应用于合成香料、彩色电影胶片呈色剂、增塑剂、农药、医药、染料以及用做金属浮选剂和有机溶剂等。2-甲基-3-丁炔-2-醇经部分加氢后生成甲基丁烯醇，制成的单体可以用于生产1,4-顺式聚异戊二烯，其可用于合成橡胶。In addition, the downstream product of 2-methyl-3-butyn-2-ol, methylheptenone, is an important pharmaceutical intermediate and food intermediate, which can further produce linalool, citral and pseudoviolet ketones, and further preparation of vitamin A, vitamin E, vitamin K1 and various flavors and fragrances. Moreover, 2-methyl-3-butyn-2-ol can be hydrogenated to generate tertiary amyl alcohol, also known as tertiary amyl alcohol, which is mainly used in synthetic fragrances, color film colorants, plasticizers, pesticides, medicines , dyes and used as metal flotation agents and organic solvents. 2-Methyl-3-butyn-2-ol is partially hydrogenated to give methylbutenol, the resulting monomer can be used to produce 1,4-cis polyisoprene, which can be used in the synthesis rubber.
现有技术中，制备2-甲基-3-丁炔-2-醇的炔化反应通常使用强碱溶液作为催化剂，将丙酮与乙炔在液氨中反应，反应结束后使用弱酸性水溶液中和催化剂后进行产物后处理分离工作。炔化反应的反应式为：In the prior art, the alkylation reaction of preparing 2-methyl-3-butyn-2-ol usually uses a strong base solution as a catalyst, reacts acetone and acetylene in liquid ammonia, and neutralizes it with a weakly acidic aqueous solution after the reaction. After the catalyst, the product post-treatment and separation work is carried out. The reaction formula of the acetylation reaction is:
Figure PCTCN2020103014-appb-000001
Figure PCTCN2020103014-appb-000001
国内外对乙炔-丙酮法制备2-甲基-3-丁炔-2-醇进行了大量的研究，反应得到的是2-甲基-3-丁炔-2-醇的含水共沸物。2-甲基-3-丁炔-2-醇与水完全互溶，所形成共沸物的沸点为91℃，含水量为20％～30％。为了发展2-甲基-3-丁炔-2-醇的下游产品，则需要获得无水的2-甲基-3-丁炔-2-醇。最初采用氯化钙通过盐析加蒸馏的方法除去其中的水，但是，这种方法除水后所得产物中2-甲基-3-丁炔-2-醇的浓度仅能达到99wt％，不仅原料损失较大，纯度也达不到要求。后来，参考苯共沸精馏制无水酒精的方法，以 苯作共沸精馏夹带剂，可成功得到近乎无水的2-甲基-3-丁炔-2-醇产品。因此，该方法便被广泛应用到2-甲基-3-丁炔-2-醇的工业生产，例如，在专利文件DE1193496和GB1023856中公开了在苯的存在下通过蒸馏纯化2-甲基-3-丁炔-2-醇的方法。A lot of research has been done on the preparation of 2-methyl-3-butyn-2-ol by acetylene-acetone method at home and abroad, and the reaction obtained is the aqueous azeotrope of 2-methyl-3-butyn-2-ol. 2-Methyl-3-butyn-2-ol is completely miscible with water, the boiling point of the formed azeotrope is 91° C., and the water content is 20% to 30%. In order to develop the downstream products of 2-methyl-3-butyn-2-ol, it is necessary to obtain anhydrous 2-methyl-3-butyn-2-ol. At first, calcium chloride was used to remove the water in it by salting out and distillation. However, the concentration of 2-methyl-3-butyn-2-ol in the product obtained after removing water by this method could only reach 99 wt%, not only The loss of raw materials is large, and the purity does not meet the requirements. Later, with reference to the method for azeotropic distillation of benzene to make anhydrous alcohol, benzene is used as an entrainer for azeotropic distillation, and an almost anhydrous 2-methyl-3-butyn-2-ol product can be successfully obtained. Therefore, the method is widely used for the industrial production of 2-methyl-3-butyn-2-ol, for example, the purification of 2-methyl- Method for 3-Butyn-2-ol.
近年来，随着国内乙炔化工的发展，市场上需要制备无水2-甲基-3-丁炔-2-醇的方法，原有的苯共沸精馏法会因苯的毒性而使得该方法的使用受到限制，需要改用其它方法进行脱水。In recent years, with the development of domestic acetylene chemical industry, there is a need for a method for preparing anhydrous 2-methyl-3-butyn-2-ol in the market. The use of the method is limited and other methods need to be used for dehydration.
例如，专利文件CN104470879A提到通过串联组合两个、三个或更多个渗透蒸发装置和/或膜和/或通过使渗余物两次、三次或更多次通过渗透蒸发装置来降低其中的水含量。但是，醇是一种热敏性物质，在高温条件下容易发生聚合。在该制备过程中，有一定量的强碱存在下，2-甲基-3-丁炔-2-醇会进一步与丙酮反应，生成副产物2,5-二甲基-3-己炔-2,5-二醇，其反应式为：For example, patent document CN104470879A mentions reducing the amount of pervaporation therein by combining two, three or more pervaporation units and/or membranes in series and/or by passing the retentate two, three or more times through a pervaporation unit water content. However, alcohol is a heat-sensitive substance and tends to polymerize under high temperature conditions. In the preparation process, in the presence of a certain amount of strong base, 2-methyl-3-butyn-2-ol will further react with acetone to generate a by-product 2,5-dimethyl-3-hexyn-2 , 5-diol, its reaction formula is:
Figure PCTCN2020103014-appb-000002
Figure PCTCN2020103014-appb-000002
2,5-二甲基-3-己炔-2,5-二醇的含量对于渗透蒸发装置所使用的分离膜的使用寿命影响明显。此外，为了确保脱水效果，此类方法使用的聚乙烯醇膜和/或聚酰亚胺膜需定期更换，这就导致了工业运行成本较高。The content of 2,5-dimethyl-3-hexyn-2,5-diol has a significant effect on the service life of the separation membrane used in the pervaporation device. In addition, in order to ensure the dehydration effect, the polyvinyl alcohol film and/or polyimide film used in such methods need to be replaced regularly, which leads to high industrial operation costs.
现有对2-甲基-3-丁炔-2-醇进行分离的工艺主要存在以下不足：The existing technology for separating 2-methyl-3-butyne-2-ol mainly has the following deficiencies:
1、溶剂共沸精馏法会形成水/共沸剂/2-甲基-3-丁炔-2-醇的三元共沸混合物；三元共沸物的形成无法避免，苯作为共沸剂进行分离的效果最好，带出水相中产物比例最低；然而，苯的毒性高，这使其使用受到限制。1. Solvent azeotropic distillation will form a ternary azeotrope of water/azeotrope/2-methyl-3-butyn-2-ol; the formation of ternary azeotrope is unavoidable, and benzene is used as an azeotrope The separation of benzene is the best, with the lowest proportion of product carried out in the aqueous phase; however, the high toxicity of benzene limits its use.
而使用其他共沸剂时，产品单程收率降低，总能耗提高，不利于成本控制。When other azeotroping agents are used, the single-pass yield of the product is reduced, and the total energy consumption is increased, which is not conducive to cost control.
2、采用膜分离方式除水；由于2-甲基-3-丁炔-2-醇与水的分子量接近且相互之间的溶解性优良，这使得膜分离操作难度大，并且使用的聚乙烯醇膜和/或聚酰亚胺膜需定期更换，导致工业运行成本较采用溶剂共沸精馏法更高。2. Use membrane separation to remove water; because the molecular weight of 2-methyl-3-butyn-2-ol and water is close and the solubility between them is excellent, this makes the membrane separation operation difficult, and the polyethylene used The alcohol and/or polyimide membranes need to be replaced periodically, resulting in higher industrial operating costs than using solvent azeotropic distillation.
另外，现有2-甲基-3-丁炔-2-醇制备过程中，为达到较好的产物选择性， 需要提高乙炔用量；出于安全考虑，提高乙炔用量的同时也需要相应提高液氨用量，但这样就提高了反应器投资及能量损耗。出于成本考虑，部分厂家将乙炔与丙酮的摩尔比例降低至1左右，虽然这样的原料配比调整可使得能量损耗降低，但产物转化率及选择性也明显降低，产物中生成2,5-二甲基-3-己炔-2,5-二醇的含量甚至高于1％。In addition, in the existing 2-methyl-3-butyn-2-ol preparation process, in order to achieve better product selectivity, it is necessary to increase the amount of acetylene; for safety reasons, it is also necessary to increase the amount of liquid while increasing the amount of acetylene. Ammonia consumption, but this increases the reactor investment and energy consumption. Due to cost considerations, some manufacturers reduce the molar ratio of acetylene to acetone to about 1. Although such adjustment of raw material ratio can reduce energy loss, the conversion rate and selectivity of products are also significantly reduced, and 2,5- The content of dimethyl-3-hexyn-2,5-diol is even higher than 1%.
鉴于以上分析，如何有效地获得高纯度、高质量的2-甲基-3-丁炔-2-醇，就成为一个重要的探索课题。In view of the above analysis, how to effectively obtain high-purity and high-quality 2-methyl-3-butyn-2-ol has become an important exploration topic.
发明内容SUMMARY OF THE INVENTION
针对现有技术在2-甲基-3-丁炔-2-醇的制备和分离过程中会出现产物转化率及选择性降低、2,5-二甲基-3-己炔-2,5-二醇含量较高的问题，本发明的目的在于，提供一种高纯度的2-甲基-3-丁炔-2-醇的分离方法，该方法能够有效控制含有2-甲基-3-丁炔-2-醇的反应液中2,5-二甲基-3-己炔-2,5-二醇的含量，保证分离和纯化工序中膜分离处理的分离效果和膜使用寿命，进而可以实现有效地分离和纯化，获得高纯度的2-甲基-3-丁炔-2-醇产物，改善2-甲基-3-丁炔-2-醇产品的色号和折射率。In view of the prior art, in the process of preparation and separation of 2-methyl-3-butyn-2-ol, the product conversion rate and selectivity decrease, 2,5-dimethyl-3-hexyn-2,5 -The problem of high diol content, the purpose of the present invention is to provide a separation method of high-purity 2-methyl-3-butyn-2-ol, which can effectively control the content of 2-methyl-3-butyn-2-ol. - the content of 2,5-dimethyl-3-hexyn-2,5-diol in the reaction solution of butyn-2-ol, to ensure the separation effect and service life of the membrane separation treatment in the separation and purification process, Further, effective separation and purification can be achieved to obtain a high-purity 2-methyl-3-butyn-2-ol product, and the color number and refractive index of the 2-methyl-3-butyn-2-ol product can be improved.
为了实现上述目的，本发明提供的技术方案如下：In order to achieve the above object, the technical scheme provided by the present invention is as follows:
一种2-甲基-3-丁炔-2-醇的分离方法，包括：A separation method of 2-methyl-3-butyn-2-ol, comprising:
(1)预处理工序：将含有2-甲基-3-丁炔-2-醇的反应液进行预处理，除去其中未反应的丙酮和含有的盐，得到2-甲基-3-丁炔-2-醇粗品；所述含有2-甲基-3-丁炔-2-醇的反应液中，控制2,5-二甲基-3-己炔-2,5-二醇的含量≤0.1wt％，优选≤0.06wt％；(1) Pretreatment step: The reaction solution containing 2-methyl-3-butyn-2-ol is pretreated to remove unreacted acetone and salts contained therein to obtain 2-methyl-3-butyne -2-ol crude product; in the reaction solution containing 2-methyl-3-butyn-2-ol, control the content of 2,5-dimethyl-3-hexyn-2,5-diol≤ 0.1wt%, preferably ≤0.06wt%;
(2)分离和纯化工序：通过膜分离处理和减压精馏处理，对所述2-甲基-3-丁炔-2-醇粗品进行分离和纯化，得到2-甲基-3-丁炔-2-醇产品。(2) Separation and purification process: The crude 2-methyl-3-butyn-2-ol is separated and purified by membrane separation treatment and vacuum distillation treatment to obtain 2-methyl-3-butane Alkyn-2-ol products.
根据本发明提供的分离方法，一些示例中，所述分离方法包括如下步骤：According to the separation method provided by the present invention, in some examples, the separation method includes the following steps:
(1)预处理工序：将所述含有2-甲基-3-丁炔-2-醇的反应液通过精馏处理脱除丙酮以及通过蒸馏或精馏处理脱盐后，得到2-甲基-3-丁炔-2-醇粗品；(1) Pretreatment step: after the reaction solution containing 2-methyl-3-butyn-2-ol is subjected to rectification to remove acetone and to desalination through distillation or rectification, 2-methyl- 3-butyn-2-ol crude product;
所述2-甲基-3-丁炔-2-醇粗品中，水的含量在10wt％～40wt％，丙酮的 含量≤1wt％，2,5-二甲基-3-己炔-2,5-二醇的含量≤0.1wt％；In the crude 2-methyl-3-butyn-2-ol, the content of water is 10wt% to 40wt%, the content of acetone is less than or equal to 1wt%, 2,5-dimethyl-3-hexyn-2, The content of 5-diol≤0.1wt%;
(2)分离和纯化工序：将所述2-甲基-3-丁炔-2-醇粗品进行膜分离处理，得到含有2-甲基-3-丁炔-2-醇的混合物，其中，水的含量≤5％；再将所述含有2-甲基-3-丁炔-2-醇的混合物进行减压精馏处理，得到2-甲基-3-丁炔-2-醇产品，其中，水的含量≤1wt％。(2) Separation and purification process: subjecting the crude 2-methyl-3-butyn-2-ol to membrane separation to obtain a mixture containing 2-methyl-3-butyn-2-ol, wherein, The water content is less than or equal to 5%; then the mixture containing 2-methyl-3-butyn-2-ol is subjected to vacuum distillation to obtain a 2-methyl-3-butyn-2-ol product, Wherein, the content of water≤1wt%.
一些示例中，步骤(1)在预处理工序中进行的脱除丙酮以及脱盐的过程，两者没有先后顺序，即，可以先脱除丙酮后再脱盐，也可以先脱盐再脱除丙酮。In some examples, the process of removing acetone and desalting in step (1) in the pretreatment process is not sequential, that is, acetone can be removed first and then desalted, or acetone can be desalted first and then acetone removed.
例如，可以通过精馏的方式实现脱除丙酮。脱除丙酮可以选择使用精馏塔，其可选板式塔或填料塔，这是本领域技术人员所熟知的。一些示例中，使用精馏塔的过程中采用常压精馏方式对炔化反应所得反应液进行脱除丙酮处理。例如，精馏塔的塔釜操作温度为90-93℃，回流比为3:1，经脱除丙酮处理后的反应液中丙酮含量可低于0.5wt％。For example, the removal of acetone can be achieved by means of rectification. The removal of acetone can optionally use a rectification column, which can be a tray column or a packed column, which is well known to those skilled in the art. In some examples, in the process of using a rectifying column, atmospheric distillation is used to remove acetone from the reaction solution obtained from the acetylation reaction. For example, the operating temperature of the column still of the rectification tower is 90-93° C., the reflux ratio is 3:1, and the acetone content in the reaction solution after the acetone removal treatment can be lower than 0.5 wt%.
例如，可以通过蒸馏或精馏的方式实现脱盐，这是本领域技术人员所熟知的。一些示例中，脱盐过程的装置可选用薄膜蒸发器或短程蒸馏器，优选选用卧式薄膜蒸发器，金属刮板常压操作，配外循环的80-120℃油浴。For example, desalination can be accomplished by distillation or rectification, as is well known to those skilled in the art. In some examples, a thin-film evaporator or a short-path distiller can be used as the device for the desalination process, preferably a horizontal thin-film evaporator, metal scraper operating at atmospheric pressure, and an external circulation 80-120°C oil bath.
为提高膜分离过程中所用渗透膜寿命，需要严格限制2-甲基-3-丁炔-2-醇粗品中所含2,5-二甲基-3-己炔-2,5-二醇的含量低于0.1wt％。2,5-二甲基-3-己炔-2,5-二醇的含量对于渗透膜使用寿命有很不利影响，如果2,5-二甲基-3-己炔-2,5-二醇含量过高，将会堵塞渗透膜孔道，造成通量降低，影响膜使用寿命以及除水的效果。因此，为了保证膜分离过程中所用渗透膜寿命和分离除水效果，可以控制炔化反应所得反应液中的副产物2,5-二甲基-3-己炔-2,5-二醇含量。In order to improve the life of the permeable membrane used in the membrane separation process, it is necessary to strictly limit the 2,5-dimethyl-3-hexyn-2,5-diol contained in the crude 2-methyl-3-butyn-2-ol. content is less than 0.1 wt%. The content of 2,5-dimethyl-3-hexyn-2,5-diol has a very adverse effect on the service life of the permeable membrane, if 2,5-dimethyl-3-hexyn-2,5-diol If the alcohol content is too high, the pores of the permeable membrane will be blocked, resulting in a decrease in flux, affecting the service life of the membrane and the effect of water removal. Therefore, in order to ensure the life of the permeable membrane used in the membrane separation process and the effect of separation and water removal, the content of the by-product 2,5-dimethyl-3-hexyne-2,5-diol in the reaction solution obtained from the acetylation reaction can be controlled .
为保证产品质量，也可控制最终所得2-甲基-3-丁炔-2-醇产品中2,5-二甲基-3-己炔-2,5-二醇的含量。在一些优选实施方式中，步骤(2)所述2-甲基-3-丁炔-2-醇产品中，2,5-二甲基-3-己炔-2,5-二醇的含量≤0.01wt％。In order to ensure product quality, the content of 2,5-dimethyl-3-hexyn-2,5-diol in the final 2-methyl-3-butyn-2-ol product can also be controlled. In some preferred embodiments, in the 2-methyl-3-butyn-2-ol product of step (2), the content of 2,5-dimethyl-3-hexyn-2,5-diol ≤0.01wt%.
一些示例中，步骤(2)所述膜分离处理中，使用至少一个用于将水与2-甲基-3-丁炔-2-醇进行分离的膜分离器；所述膜分离器中设有亲水膜(或者渗透膜)。In some examples, in the membrane separation process of step (2), at least one membrane separator for separating water and 2-methyl-3-butyn-2-ol is used; There are hydrophilic membranes (or permeable membranes).
一些优选实施方式中，所述亲水膜选自聚乙烯醇膜、聚酰亚胺膜或陶 瓷膜，更优选为聚乙烯醇膜或聚酰亚胺膜。In some preferred embodiments, the hydrophilic film is selected from polyvinyl alcohol film, polyimide film or ceramic film, more preferably polyvinyl alcohol film or polyimide film.
一些示例中，使用所述亲水膜进行膜分离处理的操作温度大于等于0℃且小于等于100℃(例如，20℃、40℃、60℃、80℃)。In some examples, the operating temperature of the membrane separation process using the hydrophilic membrane is greater than or equal to 0°C and less than or equal to 100°C (eg, 20°C, 40°C, 60°C, 80°C).
可替代地，所述亲水膜也可以是，例如基于沸石A的陶瓷膜。用于渗透蒸发的陶瓷膜包括大孔载体上的纳米多孔层。该孔必须大到足以让水分子通过并小到足以截留2-甲基-3-丁炔-2-醇。该表面可以通过特定的涂层或处理进行修饰。这种膜已被用于从有机反应混合物中除去水，并且可以购自从FOLEX，瑞士。这里所述亲水膜的材质为本领域技术人员所熟知，这里不在赘述。Alternatively, the hydrophilic membrane may also be, for example, a zeolite A based ceramic membrane. Ceramic membranes for pervaporation include a nanoporous layer on a macroporous support. The pores must be large enough to pass water molecules and small enough to retain 2-methyl-3-butyn-2-ol. The surface can be modified with specific coatings or treatments. This membrane has been used to remove water from organic reaction mixtures and is available from FOLEX, Switzerland. The material of the hydrophilic membrane described here is well known to those skilled in the art, and will not be repeated here.
根据本发明提供的分离方法，一些优选实施方式中，步骤(2)的操作过程包括：According to the separation method provided by the present invention, in some preferred embodiments, the operation process of step (2) includes:
(i)将所述2-甲基-3-丁炔-2-醇粗品通过膜分离器进行处理，分离出含水的有机相流股和水相流股；其中，所述含水的有机相流股中(以所述含水的有机相流股中各组分总重量为100wt％计)，水的含量≤5wt％，2-甲基-3-丁炔-2-醇的含量≥90wt％；所述水相流股中，水的含量≥95wt％，2-甲基-3-丁炔-2-醇的含量≤1wt％(以所述水相流股中各组分总重量为100wt％计)；(i) processing the crude 2-methyl-3-butyn-2-ol through a membrane separator to separate an aqueous organic phase stream and an aqueous phase stream; wherein, the aqueous organic phase stream In the strand (based on the total weight of each component in the water-containing organic phase stream being 100wt%), the content of water is less than or equal to 5wt%, and the content of 2-methyl-3-butyn-2-ol is greater than or equal to 90wt%; In the water-phase stream, the content of water is greater than or equal to 95wt%, and the content of 2-methyl-3-butyn-2-ol is less than or equal to 1wt% (taking the total weight of each component in the water-phase stream as 100wt%) count);
(ii)将所述含水的有机相流股进入粗精馏塔进行处理，粗精馏塔的塔顶采出轻组分流股，所述轻组分流股中(以所述轻组分流股中各组分总重量为100wt％计)，水的含量为5wt％～30wt％；粗精馏塔的塔底采出待脱重组分流股，所述待脱重组分流股中，水的含量≤1wt％(以所述待脱重组分流股中各组分总重量为100wt％计)；(ii) entering the water-containing organic phase stream into the crude rectification column for processing, and extracting a light end stream from the top of the crude rectification column, in the light end stream (in the light end stream The total weight of each component is 100 wt %), and the water content is 5 wt % to 30 wt %; the fractional stream to be derecombined is extracted from the bottom of the crude rectification tower, and the content of water in the fractional stream to be removed is less than or equal to 1wt % (based on the total weight of each component in the to-be-recombined branch stream as 100wt%);
(iii)将所述待脱重组分流股进入产品分离塔进行处理，产品分离塔的塔顶采出产物流股；所述产物流股中(以所述产物流股中各组分总重量为100wt％计)，2-甲基-3-丁炔-2-醇的含量≥99wt％，水的含量≤1wt％，2,5-二甲基-3-己炔-2,5-二醇的含量≤0.01wt％；产品分离塔的塔底采出重组分流股，所述重组分流股中(以所述重组分流股中各组分总重量为100wt％计)，2-甲基-3-丁炔-2-醇的含量≤70wt％。(iii) enter the product separation tower into the product separation stream for processing, and extract the product stream from the top of the product separation tower; in the product stream (take the total weight of each component in the product stream as 100wt %), the content of 2-methyl-3-butyn-2-ol≥99wt%, the content of water≤1wt%, the content of 2,5-dimethyl-3-hexyn-2,5-diol Content ≤ 0.01wt%; a reorganized sub-stream is extracted from the bottom of the product separation tower, in the re-organized sub-stream (based on the total weight of each component in the re-organized sub-stream as 100 wt %), 2-methyl-3- The content of butyn-2-ol≤70wt%.
这里的重组分流股中，因含有的大分子量组分比例较高，黏度大，为保证流股的流动性，需要有一部分2-甲基-3-丁炔-2-醇产品的存在。The reconstituted stream here contains a high proportion of high molecular weight components and has a high viscosity. In order to ensure the fluidity of the stream, it is necessary to have a part of 2-methyl-3-butyn-2-ol product.
这里的粗精馏塔为可达到足够理想的分离状况。一些示例中，所述粗精馏塔的精馏段理论塔板数≥5块(例如，6块、8块、12块、14块、20块)，优选为10-15块。The crude distillation column here is a sufficiently ideal separation condition. In some examples, the number of theoretical plates in the rectification section of the crude rectification column is ≥5 (eg, 6, 8, 12, 14, 20), preferably 10-15.
一些示例中，所述粗精馏塔的操作压力为50hPa～300hPa(例如，60hPa、80hPa、150hPa、200hPa、250hPa)，优选为100hPa～200hPa；所述粗精馏塔的塔釜操作温度为100℃～130℃(例如，115℃、120℃)，优选为110℃～125℃。In some examples, the operating pressure of the crude rectification column is 50hPa～300hPa (for example, 60hPa, 80hPa, 150hPa, 200hPa, 250hPa), preferably 100hPa～200hPa; the operating temperature of the column bottom of the crude rectification column is 100 hPa °C to 130°C (for example, 115°C, 120°C), preferably 110°C to 125°C.
一些示例中，所述粗精馏塔的塔底釆出的待脱重组分流股从产品分离塔的塔中部进入，在产品分离塔中将2-甲基-3-丁炔-2-醇与其他组分进行分离。In some examples, the to-be-recombined fractions taken at the bottom of the crude rectification column enter from the middle of the column of the product separation column, and 2-methyl-3-butyn-2-ol is mixed with the product separation column in the product separation column. The other components are separated.
一些示例中，所述产品分离塔的理论塔板数≥5块(例如，6块、8块、12块、14块、20块)，优选为10-15块；In some examples, the number of theoretical plates of the product separation column is ≥5 (for example, 6, 8, 12, 14, 20), preferably 10-15;
一些示例中，所述产品分离塔的操作压力为50hPa～300hPa(例如，60hPa、80hPa、150hPa、200hPa、250hPa)，优选为100hPa～200hPa；所述产品分离塔的塔釜操作温度为100℃～130℃(例如，115℃、120℃)，优选为110℃～125℃。In some examples, the operating pressure of the product separation tower is 50hPa～300hPa (for example, 60hPa, 80hPa, 150hPa, 200hPa, 250hPa), preferably 100hPa～200hPa; the operating temperature of the column kettle of the product separation tower is 100℃～ 130°C (for example, 115°C, 120°C), preferably 110°C to 125°C.
产物中包含的副产物2,5-二甲基-3-己炔-2,5-二醇含量会影响产品2-甲基-3-丁炔-2-醇的品质，即，对2-甲基-3-丁炔-2-醇产品的色号、折射率均会产生不良影响；因此，在对其除水的过程中，也可以通过调节工艺条件的参数进一步有效控制该副产物的含量。一些示例中，经分离和纯化工序后，所得2-甲基-3-丁炔-2-醇产品中水的含量≤1wt％(例如，0.8wt％、0.5wt％、0.3wt％、0.1wt％)且2,5-二甲基-3-己炔-2,5-二醇的含量≤0.01wt％(例如，0.008wt％、0.005wt％、0.003wt％、0.001wt％)。The content of the by-product 2,5-dimethyl-3-hexyn-2,5-diol contained in the product affects the quality of the product 2-methyl-3-butyn-2-ol, i.e., for 2- The color number and refractive index of the methyl-3-butyn-2-ol product will have adverse effects; therefore, in the process of removing water, the by-product can be further effectively controlled by adjusting the parameters of the process conditions. content. In some examples, after the separation and purification process, the water content in the obtained 2-methyl-3-butyn-2-ol product is ≤ 1 wt % (eg, 0.8 wt %, 0.5 wt %, 0.3 wt %, 0.1 wt % %) and the content of 2,5-dimethyl-3-hexyne-2,5-diol≤0.01wt% (eg, 0.008wt%, 0.005wt%, 0.003wt%, 0.001wt%).
根据本发明提供的分离方法，一些优选实施方式中，所述含有2-甲基-3-丁炔-2-醇的反应液通过包含如下步骤的方法制得：According to the separation method provided by the present invention, in some preferred embodiments, the reaction solution containing 2-methyl-3-butyn-2-ol is prepared by a method comprising the following steps:
使用强碱作为催化剂，将丙酮、乙炔和二价金属盐在液氨中混合进行反应；反应结束后，加入弱酸性水溶液对体系中的催化剂进行中和，制备得到含有2-甲基-3-丁炔-2-醇的反应液；所述含有2-甲基-3-丁炔-2-醇的反应液中，2,5-二甲基-3-己炔-2,5-二醇的含量≤0.1wt％(例如，其含量为0.08wt％、0.06wt％、0.04wt％、0.02wt％)。Using a strong base as a catalyst, acetone, acetylene and a divalent metal salt are mixed in liquid ammonia for reaction; after the reaction is completed, a weakly acidic aqueous solution is added to neutralize the catalyst in the system to prepare a product containing 2-methyl-3- The reaction solution of butyn-2-ol; in the reaction solution containing 2-methyl-3-butyn-2-ol, 2,5-dimethyl-3-hexyn-2,5-diol The content of ≤0.1wt% (for example, its content is 0.08wt%, 0.06wt%, 0.04wt%, 0.02wt%).
这里的反应液制备过程中，反应的温度和时间为本领域技术人员熟知，这里不再赘述。In the preparation process of the reaction solution here, the temperature and time of the reaction are well known to those skilled in the art and will not be repeated here.
这里的强碱和弱酸性水溶液均可以为本领域的常规选择。例如，所述强碱可以选自氢氧化钠、氢氧化钾；所述弱酸性水溶液可选自硫酸铵水溶液。强碱在反应体系中的用量为本领域技术人员熟知，这里不再赘述。加入弱酸性水溶液的量，例如，能够将反应体系中存在的强碱刚好中和即可。Both the strong base and weakly acidic aqueous solutions here can be conventionally selected in the field. For example, the strong base can be selected from sodium hydroxide and potassium hydroxide; the weakly acidic aqueous solution can be selected from ammonium sulfate aqueous solution. The amount of the strong base in the reaction system is well known to those skilled in the art and will not be repeated here. The amount of adding the weakly acidic aqueous solution, for example, can just neutralize the strong base existing in the reaction system.
炔化反应制得的反应液中除了含有2-甲基-3-丁炔-2-醇，还包含多种其他组分，例如，副产物2,5-二甲基-3-己炔-2,5-二醇、水、未反应的原料丙酮、无机盐或其他杂质。一些示例中，所述含有2-甲基-3-丁炔-2-醇的反应液中(以反应液中各组分的总重量为100wt％计)，水的含量为10～40wt％，并且含有1～20wt％未反应的原料丙酮。这里的反应液中，所含无机盐的量与反应过程中加入的强碱与弱酸性水溶液的量有关。In addition to 2-methyl-3-butyn-2-ol, the reaction solution obtained from the alkylation reaction also contains various other components, such as the by-product 2,5-dimethyl-3-hexyn- 2,5-Diol, water, unreacted raw acetone, inorganic salts or other impurities. In some examples, in the reaction solution containing 2-methyl-3-butyn-2-ol (based on the total weight of the components in the reaction solution being 100 wt %), the water content is 10-40 wt %, And it contains 1-20 wt% of unreacted raw material acetone. In the reaction solution here, the amount of the inorganic salt contained is related to the amount of the strong base and the weakly acidic aqueous solution added in the reaction process.
根据本发明提供的分离方法，一些示例中，所述二价金属盐选自二价锌盐、二价镁盐和二价钴盐中的一种或多种，优选乙酸锌、硫酸镁和氯化钴中的一种或多种，进一步优选为乙酸锌和/或硫酸镁，更优选为乙酸锌。According to the separation method provided by the present invention, in some examples, the divalent metal salt is selected from one or more of divalent zinc salt, divalent magnesium salt and divalent cobalt salt, preferably zinc acetate, magnesium sulfate and chlorine One or more of the cobalt compounds, more preferably zinc acetate and/or magnesium sulfate, more preferably zinc acetate.
一些示例中，所述二价金属盐的用量为丙酮质量的0.01％～0.1％(例如，0.015％、0.03％、0.05％、0.08％、0.09％)，优选为0.02％～0.05％。In some examples, the amount of the divalent metal salt is 0.01%-0.1% (eg, 0.015%, 0.03%, 0.05%, 0.08%, 0.09%) of the mass of acetone, preferably 0.02%-0.05%.
一些示例中，在反应液的制备过程中，所述乙炔与丙酮的摩尔比大于等于1:1且小于等于3:1(例如，1.1:1、1.3:1、1.5:1、1.8:1、2.2:1、2.5:1、2.8:1)，优选为1.05:1～2:1。在乙炔与丙酮的摩尔比合适的条件下，通过在体系内添加二价金属盐，可以实现对制备所得含2-甲基-3-丁炔-2-醇的反应液中2,5-二甲基-3-己炔-2,5-二醇含量的有效控制，保证其处于较低含量范围(≤0.1wt％)。In some examples, during the preparation of the reaction solution, the molar ratio of acetylene to acetone is greater than or equal to 1:1 and less than or equal to 3:1 (for example, 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. Under the condition that the molar ratio of acetylene and acetone is suitable, by adding a divalent metal salt in the system, the 2,5-divalent metal salt in the prepared reaction solution containing 2-methyl-3-butyn-2-ol can be achieved. Effective control of methyl-3-hexyne-2,5-diol content ensures that it is in a lower content range (≤0.1 wt%).
反应过程中，将丙酮与乙炔的摩尔比控制在此范围内的作用在于：在保证一定乙炔含量的条件下，引入二价金属盐可抑制副产物生成，提高产物的选择性；同时在保证安全性的前提下，降低乙炔与丙酮的摩尔比能够降低能量损耗，节约成本。为综合产物的选择性及能耗的考虑，可优选乙炔与丙酮的摩尔比1.05:1～2:1。In the reaction process, the effect of controlling the molar ratio of acetone to acetylene within this range is: under the condition of ensuring a certain acetylene content, the introduction of divalent metal salt can inhibit the generation of by-products and improve the selectivity of the product; at the same time, it can ensure safety. Reducing the molar ratio of acetylene to acetone can reduce energy loss and save costs. For the consideration of the selectivity of the comprehensive product and the energy consumption, the molar ratio of acetylene to acetone may be preferably 1.05:1 to 2:1.
本发明一方面，通过在炔化反应中调节乙炔加入量以及在体系内添加 二价金属盐，可以提高炔化反应产物的选择性，有效控制制备所得反应液中副产物2,5-二甲基-3-己炔-2,5-二醇的含量。二价金属盐的加入量也会影响反应液中2,5-二甲基-3-己炔-2,5-二醇的含量。控制反应液中2,5-二甲基-3-己炔-2,5-二醇的含量≤0.1wt％，可以保证分离和纯化工序中膜分离的效果，以及延长渗透膜的使用寿命。另一方面，分离所得产品中2,5-二甲基-3-己炔-2,5-二醇的含量同样也可以在对含有2-甲基-3-丁炔-2-醇反应液进行分离的过程中实现控制，进一步降低其含量，保证所得产品的品质。In one aspect of the present invention, by adjusting the amount of acetylene added and adding a divalent metal salt in the system, the selectivity of the product of the acetylenic reaction can be improved, and the by-product 2,5-dimethylform in the reaction solution obtained can be effectively controlled. Content of yl-3-hexyn-2,5-diol. The amount of divalent metal salt added also affects the content of 2,5-dimethyl-3-hexyne-2,5-diol in the reaction solution. Controlling the content of 2,5-dimethyl-3-hexyne-2,5-diol in the reaction solution is less than or equal to 0.1 wt% can ensure the effect of membrane separation in the separation and purification process and prolong the service life of the permeable membrane. On the other hand, the content of 2,5-dimethyl-3-hexyn-2,5-diol in the product obtained by separation can also be the same as that of the reaction solution containing 2-methyl-3-butyn-2-ol. In the process of separation, control is achieved to further reduce its content and ensure the quality of the obtained product.
相对于现有技术，本发明技术方案的有益效果在于以下几个方面：Compared with the prior art, the beneficial effects of the technical solution of the present invention lie in the following aspects:
通过本发明的分离方法，可以在投资及能耗降低的情况下除去2-甲基-3-丁炔-2-醇产物中的水以及降低2,5-二甲基-3-己炔-2,5-二醇的含量，制备得到纯度和转化率均较高的2-甲基-3-丁炔-2-醇。Through the separation method of the present invention, the water in the 2-methyl-3-butyn-2-ol product can be removed and the 2,5-dimethyl-3-hexyne- 2,5-diol content, 2-methyl-3-butyn-2-ol with higher purity and higher conversion rate was prepared.
在乙炔与丙酮的摩尔比较低的工况下，通过在体系内添加二价金属盐，可以有效抑制反应过程中副产物的生成，从而控制所得含有2-甲基-3-丁炔-2-醇的反应液中2,5-二甲基-3-己炔-2,5-二醇含量在较低范围内(例如，小于等于0.1wt％)，提高了产物选择性；同时，还可降低能耗并且降低纯化难度。Under the condition that the molar ratio of acetylene and acetone is low, by adding a divalent metal salt in the system, the formation of by-products in the reaction process can be effectively suppressed, so as to control the resultant containing 2-methyl-3-butyne-2- The content of 2,5-dimethyl-3-hexyne-2,5-diol in the alcohol reaction solution is in a lower range (for example, less than or equal to 0.1 wt%), which improves the product selectivity; at the same time, it can also Reduce energy consumption and reduce purification difficulty.
通过严格控制所得含有2-甲基-3-丁炔-2-醇的反应液中关键组分2,5-二甲基-3-己炔-2,5-二醇含量，可提高膜分离过程中的除水效果和所用渗透膜寿命，渗透膜更换频次明显降低，例如，由每月更换变为每半年更换一次，降低了分离成本。By strictly controlling the content of the key component 2,5-dimethyl-3-hexyn-2,5-diol in the obtained reaction solution containing 2-methyl-3-butyn-2-ol, the membrane separation can be improved The water removal effect in the process and the life of the permeable membrane used are significantly reduced, and the replacement frequency of the permeable membrane is significantly reduced. For example, the replacement is changed from monthly to every six months, which reduces the cost of separation.
通过控制所得含有2-甲基-3-丁炔-2-醇的反应液中关键组分2,5-二甲基-3-己炔-2,5-二醇含量，为2-甲基-3-丁炔-2-醇粗品进一步进行膜分离处理和精馏处理提供了有力条件，使得产物中2-甲基-3-丁炔-2-醇与水分进行了充分分离，同时还进一步降低了2,5-二甲基-3-己炔-2,5-二醇含量(例如，小于等于0.01wt％)，也达到控制产品2-甲基-3-丁炔-2-醇品质的目的，可得到高质量、高纯度的合格产品。By controlling the content of the key component 2,5-dimethyl-3-hexyn-2,5-diol in the obtained reaction solution containing 2-methyl-3-butyn-2-ol, it is 2-methyl -3-Butyn-2-ol crude product is further subjected to membrane separation treatment and rectification treatment, which provides powerful conditions, so that 2-methyl-3-butyn-2-ol in the product can be fully separated from moisture, and further The content of 2,5-dimethyl-3-hexyn-2,5-diol is reduced (for example, less than or equal to 0.01wt%), and the quality of the product 2-methyl-3-butyn-2-ol is also controlled For the purpose of obtaining high-quality, high-purity qualified products.
采用膜分离工艺替代原有共沸精馏工艺，简化了操作工序，具有较好的工业可控性。The membrane separation process is used to replace the original azeotropic distillation process, which simplifies the operation process and has better industrial controllability.
附图说明Description of drawings
图1是本发明所述分离方法的一种实施方式中，分离和纯化工序的工艺流程图。FIG. 1 is a process flow diagram of the separation and purification steps in an embodiment of the separation method of the present invention.
图中的标号说明如下：The symbols in the figure are explained as follows:
1--2-甲基-3-丁炔-2-醇粗品，2--含水的有机相流股，3--水相流股，4--轻组分流股，5--待脱重组分流股，6--产物流股，7--重组分流股；1--2-methyl-3-butyn-2-ol crude product, 2--aqueous organic phase stream, 3--aqueous phase stream, 4--light component stream, 5--to be derecombined shunt, 6--product stream, 7--recombination shunt;
SEP-膜分离器，RAC1-粗精馏塔，COOLER1-塔顶冷凝器，REBOILER1-塔底再沸器；SEP-membrane separator, RAC1-coarse distillation column, COOLER1-column top condenser, REBOILER1-column bottom reboiler;
RAC2-产品分离塔，COOLER2-塔顶冷凝器，REBOILER2-塔底再沸器。RAC2-product separation column, COOLER2-column overhead condenser, REBOILER2-column bottom reboiler.
具体实施方式detailed description
为了能够详细地理解本发明的技术特征和内容，下面将更详细地描述本发明的优选实施方式。虽然实施例中描述了本发明的优选实施方式，然而应该理解，可以以各种形式实现本发明而不应被这里阐述的实施方式所限制。In order to be able to understand the technical features and contents of the present invention in detail, the preferred embodiments of the present invention will be described in more detail below. While 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.
<原料来源><Source of raw materials>
丙酮，99wt％，山东立维化工；Acetone, 99wt%, Shandong Liwei Chemical;
乙炔，98wt％，青岛乙炔气有限公司；Acetylene, 98wt%, Qingdao Acetylene Gas Co., Ltd.;
液氨，99wt％，东营恒昇化工有限公司；Liquid ammonia, 99wt%, Dongying Hengsheng Chemical Co., Ltd.;
硫酸镁，99wt％，百灵威科技有限公司；Magnesium sulfate, 99wt%, Bailingwei Technology Co., Ltd.;
乙酸锌，99wt％，百灵威科技有限公司；Zinc acetate, 99wt%, Bailingwei Technology Co., Ltd.;
氢氧化钾，济南金昊化工有限公司；Potassium hydroxide, Jinan Jinhao Chemical Co., Ltd.;
硫酸铵，99wt％，百灵威科技有限公司。Ammonium sulfate, 99wt%, Bailingwei Technology Co., Ltd.
<分析方法><Analysis method>
各实施例和对比例的测试方法如下：The test method of each embodiment and comparative example is as follows:
1、流股中各组分的组成，采用气相色谱仪：Agilent7820A，色谱柱HP-5(30m×320μm×0.25μm)，进样口温度：150℃；分流比50:1；载气流量：1.5ml/min；1. The composition of each component in the stream, using gas chromatograph: Agilent7820A, chromatographic column HP-5 (30m×320μm×0.25μm), inlet temperature: 150°C; split ratio 50:1; carrier gas flow rate: 1.5ml/min;
升温程序：40℃保持1min，以10℃/min升温至90℃，保持0min，然 后以5℃/min升温至160℃，保持0min，然后以30℃/min升温至280℃，保持6min。检测器温度：280℃。Heating program: hold 40°C for 1min, heat up to 90°C at 10°C/min, hold for 0min, then heat up to 160°C at 5°C/min, hold for 0min, then heat up to 280°C at 30°C/min, hold for 6min. Detector temperature: 280°C.
2、产品的折射率测试：采用METTLER TOLEDO折光率仪Easy R40。2. Refractive index test of the product: METTLER TOLEDO refractometer Easy R40 is used.
3、产品的色号测试：采用HANNA铂钴(Pt-Co)色度测定仪。3. The color number test of the product: HANNA platinum cobalt (Pt-Co) colorimeter is used.
实施例1：1#反应液的制备Example 1: Preparation of 1# reaction solution
首先将500L高压釜用氨气置换3次，将反应釜内温度降至-20℃，加入液氨(144.5Kg，8500mol)，开启搅拌，通入乙炔(16800L，750mol)，加入浓度为20wt％的硫酸镁水溶液43.5g及浓度为50wt％的氢氧化钾水溶液(1008g，作为溶质的氢氧化钾用量为丙酮的3mol％)，升温至10℃并加入丙酮(17.4Kg，300mol)，控制丙酮加入速率在1h左右进料完毕；反应温度为10℃，反应2h后加入5Kg浓度为10wt％的硫酸铵水溶液进行中和，得到含有2-甲基-3-丁炔-2-醇的1#反应液，并取样通过GC检测反应液。First, the 500L autoclave was replaced with ammonia gas three times, the temperature in the reactor was lowered to -20°C, liquid ammonia (144.5Kg, 8500mol) was added, stirring was started, acetylene (16800L, 750mol) was introduced, and the concentration was 20wt% The magnesium sulfate aqueous solution 43.5g and the potassium hydroxide aqueous solution (1008g, the potassium hydroxide consumption as the solute is 3mol% of acetone) with a concentration of 50wt% are warming up to 10 ° C and add acetone (17.4Kg, 300mol), control acetone to add The rate of feeding is completed in about 1h; the reaction temperature is 10°C, and after 2h of reaction, 5Kg of ammonium sulfate aqueous solution with a concentration of 10wt% is added for neutralization, and the 1# reaction containing 2-methyl-3-butyn-2-ol is obtained The solution was sampled and the reaction solution was detected by GC.
1#反应液的组成：无机盐的含量为2.16wt％，水的含量为16.61wt％、2-甲基-3-丁炔-2-醇的含量为77.30wt％、丙酮的含量为3.56wt％、2,5-二甲基-3-己炔-2,5-二醇的含量为0.05wt％、其他组分的含量为0.32wt％，以1#反应液各组分的总重量为100wt％计。The composition of the 1# reaction solution: the content of inorganic salt is 2.16wt%, the content of water is 16.61wt%, the content of 2-methyl-3-butyn-2-ol is 77.30wt%, and the content of acetone is 3.56wt% %, the content of 2,5-dimethyl-3-hexyne-2,5-diol is 0.05wt%, the content of other components is 0.32wt%, and the total weight of each component of the 1# reaction solution is 100wt%.
实施例2：2#反应液的制备Example 2: Preparation of 2# reaction solution
首先将500L高压釜用氨气置换3次，将反应釜内温度降至-20℃，加入液氨(144.5Kg，8500mol)，开启搅拌，通入乙炔(16800L，750mol)，加入浓度为20wt％的乙酸锌水溶液17.5g，再加入浓度为50wt％的氢氧化钾水溶液(1008g，作为溶质的氢氧化钾用量为丙酮的3mol％)，升温至10℃并加入丙酮(17.4Kg，300mol)，控制丙酮加入速率在1h左右进料完毕；反应温度为10℃，反应2h后加入5Kg浓度为10wt％的硫酸铵水溶液进行中和，得到含有2-甲基-3-丁炔-2-醇的2#反应液，并取样通过GC检测反应液。First, the 500L autoclave was replaced with ammonia gas three times, the temperature in the reactor was lowered to -20°C, liquid ammonia (144.5Kg, 8500mol) was added, stirring was started, acetylene (16800L, 750mol) was introduced, and the concentration was 20wt% Zinc acetate aqueous solution 17.5g, then add the potassium hydroxide aqueous solution (1008g, the potassium hydroxide consumption as solute is 3mol% of acetone) that concentration is 50wt%, be warming up to 10 ℃ and add acetone (17.4Kg, 300mol), control The addition rate of acetone is completed in about 1h; the reaction temperature is 10 ° C, and 5Kg of ammonium sulfate aqueous solution with a concentration of 10wt% is added after the reaction for 2h for neutralization to obtain 2-methyl-3-butyn-2-ol. #Reaction solution, and sample the reaction solution by GC.
2#反应液的组成：无机盐的含量为2.17wt％，水的含量为16.62wt％、2-甲基-3-丁炔-2-醇的含量为77.27wt％、丙酮的含量为3.52wt％、2,5-二甲 基-3-己炔-2,5-二醇的含量为0.02wt％、其他组分的含量为0.40wt％，以2#反应液各组分的总重量为100wt％计。The composition of the 2# reaction solution: the content of inorganic salt is 2.17wt%, the content of water is 16.62wt%, the content of 2-methyl-3-butyn-2-ol is 77.27wt%, and the content of acetone is 3.52wt% %, the content of 2,5-dimethyl-3-hexyne-2,5-diol is 0.02wt%, the content of other components is 0.40wt%, and the total weight of each component of the 2# reaction solution is 100wt%.
实施例3：3#反应液的制备Example 3: Preparation of 3# reaction solution
首先将500L高压釜用氨气置换3次，将反应釜内温度降至-20℃，加入液氨(144.5Kg，8500mol)，开启搅拌，通入乙炔(16800L，750mol)，加入浓度为20wt％的乙酸锌水溶液8.7g，再加入浓度为50wt％的氢氧化钾水溶液(1008g，作为溶质的氢氧化钾用量为丙酮的3mol％)，升温至10℃并加入丙酮(17.4Kg，300mol)，控制丙酮加入速率在1h左右进料完毕；反应温度为10℃，反应2h后加入5Kg浓度为10wt％的硫酸铵水溶液进行中和，得到含有2-甲基-3-丁炔-2-醇的3#反应液，并取样通过GC检测反应液。First, the 500L autoclave was replaced with ammonia gas three times, the temperature in the reactor was lowered to -20°C, liquid ammonia (144.5Kg, 8500mol) was added, stirring was started, acetylene (16800L, 750mol) was introduced, and the concentration was 20wt% Zinc acetate aqueous solution 8.7g, then add the potassium hydroxide aqueous solution (1008g, the potassium hydroxide consumption as solute is 3mol% of acetone) that concentration is 50wt%, be warming up to 10 ℃ and add acetone (17.4Kg, 300mol), control The addition rate of acetone is completed in about 1h; the reaction temperature is 10 ° C, and after 2h of reaction, 5Kg of ammonium sulfate aqueous solution with a concentration of 10wt% is added for neutralization to obtain 3-methyl-3-butyn-2-ol. #Reaction solution, and sample the reaction solution by GC.
3#反应液的组成：无机盐的含量为2.17wt％，水的含量为16.62wt％、2-甲基-3-丁炔-2-醇的含量为77.41wt％、丙酮的含量为3.32wt％、2,5-二甲基-3-己炔-2,5-二醇的含量为0.06wt％、其他组分的含量为0.42wt％，以3#反应液各组分的总重量为100wt％计。The composition of the 3# reaction solution: the content of inorganic salt is 2.17wt%, the content of water is 16.62wt%, the content of 2-methyl-3-butyn-2-ol is 77.41wt%, and the content of acetone is 3.32wt% %, the content of 2,5-dimethyl-3-hexyne-2,5-diol is 0.06wt%, the content of other components is 0.42wt%, and the total weight of each component of the 3# reaction solution is 100wt%.
实施例4：4#反应液的制备Example 4: Preparation of 4# reaction solution
首先将500L高压釜用氨气置换3次，将反应釜内温度降至-20℃，加入液氨(30.35Kg，1785mol)，开启搅拌，通入乙炔(7056L，315mol)，加入浓度为20wt％的氯化钴水溶液87g，再加入浓度为50wt％的氢氧化钾水溶液(840g，作为溶质的氢氧化钾用量为丙酮的2.5mol％)，升温至10℃并加入丙酮(17.4Kg，300mol)，控制丙酮加入速率在1h左右进料完毕；反应温度为10℃，反应2h后加入4.5Kg浓度为10wt％的硫酸铵水溶液进行中和，得到含有2-甲基-3-丁炔-2-醇的4#反应液，并取样通过GC检测反应液。First, the 500L autoclave was replaced with ammonia gas for 3 times, the temperature in the reactor was lowered to -20°C, liquefied ammonia (30.35Kg, 1785mol) was added, stirring was started, acetylene (7056L, 315mol) was introduced, and the concentration was 20wt% 87g of cobalt chloride aqueous solution, then add the potassium hydroxide aqueous solution that concentration is 50wt% (840g, the potassium hydroxide consumption as solute is 2.5mol% of acetone), be warming up to 10 ℃ and add acetone (17.4Kg, 300mol), The acetone addition rate was controlled to complete the feeding in about 1 hour; the reaction temperature was 10 ° C, and after the reaction for 2 hours, 4.5 Kg of ammonium sulfate aqueous solution with a concentration of 10 wt % was added for neutralization to obtain 2-methyl-3-butyn-2-ol containing 2-methyl-3-butyn-2-ol The 4# reaction solution was sampled and detected by GC.
4#反应液的组成：无机盐的含量为1.81wt％，水的含量为15.30wt％、2-甲基-3-丁炔-2-醇的含量为76.57wt％、丙酮的含量为5.75wt％、2,5-二甲基-3-己炔-2,5-二醇的含量为0.08wt％、其他组分的含量为0.49wt％，以4#反应液各组分的总重量为100wt％计。The composition of the 4# reaction solution: the content of inorganic salt is 1.81wt%, the content of water is 15.30wt%, the content of 2-methyl-3-butyn-2-ol is 76.57wt%, and the content of acetone is 5.75wt% %, the content of 2,5-dimethyl-3-hexyne-2,5-diol is 0.08wt%, the content of other components is 0.49wt%, and the total weight of each component in the 4# reaction solution is 100wt%.
实施例5：1#反应液的预处理Example 5: Pretreatment of 1# reaction solution
1)采用薄膜蒸发器对炔化反应制得的1#反应液进行脱盐处理，该薄膜蒸发器的外循环油浴温度为80℃，其操作压力为800hPa。1#反应液的组成：无机盐的含量为2.16wt％，水的含量为16.61wt％、2-甲基-3-丁炔-2-醇的含量为77.30wt％、丙酮的含量为3.56wt％、2,5-二甲基-3-己炔-2,5-二醇的含量为0.05wt％、其他组分的含量为0.32wt％。1) The 1# reaction solution obtained by the acetylation reaction was desalted by a thin film evaporator. The temperature of the external circulating oil bath of the thin film evaporator was 80°C, and the operating pressure was 800hPa. The composition of the 1# reaction solution: the content of inorganic salt is 2.16wt%, the content of water is 16.61wt%, the content of 2-methyl-3-butyn-2-ol is 77.30wt%, and the content of acetone is 3.56wt% %, the content of 2,5-dimethyl-3-hexyne-2,5-diol is 0.05wt%, and the content of other components is 0.32wt%.
将1#反应液通入薄膜蒸发器。1#反应液的进料速率为0.950kg/h，薄膜蒸发器上出口的采出速率为0.902kg/h，采出液相组成：水的含量为16.98wt％、2-甲基-3-丁炔-2-醇的含量为79.01wt％、丙酮的含量为3.64wt％、2,5-二甲基-3-己炔-2,5-二醇的含量为0.05wt％、其他组分的含量为0.32wt％，以上出口的采出液相各组分的总重量为100wt％计。薄膜蒸发器下出口的采出速率为0.048kg/h。The 1# reaction solution was passed into a thin film evaporator. The feed rate of the 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: the content of water is 16.98wt%, 2-methyl-3- The content of butyn-2-ol is 79.01wt%, the content of acetone is 3.64wt%, the content of 2,5-dimethyl-3-hexyn-2,5-diol is 0.05wt%, other components Its content is 0.32wt%, and the total weight of each component of the produced liquid phase at the above outlet is calculated as 100wt%. The extraction rate of the lower outlet of the thin film evaporator is 0.048kg/h.
2)采用板网波纹填料塔对薄膜蒸发器上出口的采出液相进行脱丙酮处理，精馏塔(或填料塔)塔径100mm，填料层高0.5m，理论板数5块，采出液相组成：水的含量为16.98wt％、2-甲基-3-丁炔-2-醇的含量为79.01wt％、丙酮的含量为3.64wt％、2,5-二甲基-3-己炔-2,5-二醇的含量为0.05wt％、其他组分的含量为0.32wt％。2) Deacetone treatment of the produced liquid phase from the upper outlet of the thin film evaporator by using a corrugated packing tower with a plate mesh. The diameter of the rectification tower (or packed tower) is 100 mm, the height of the packing layer is 0.5 m, and the number of theoretical plates is 5. Liquid phase composition: the content of water is 16.98wt%, the content of 2-methyl-3-butyn-2-ol is 79.01wt%, the content of acetone is 3.64wt%, the content of 2,5-dimethyl-3- The content of hexyne-2,5-diol was 0.05 wt %, and the content of other components was 0.32 wt %.
将该采出液相由塔下部第4块理论板处的进料管线进入精馏塔。精馏塔的操作压力为1Kpa。塔顶冷凝器使用10℃冷却水为冷媒，塔底的操作温度92-93℃。精馏塔塔顶冷凝器流出冷凝液回流与采出比例为3:1。The produced liquid phase enters the rectification column from the feed line at the fourth theoretical plate in the lower part of the column. The operating pressure of the distillation column is 1Kpa. The top condenser uses 10°C cooling water as the refrigerant, and the operating temperature at the bottom of the tower is 92-93°C. The ratio of reflux and production of the condensate flowing out of the top condenser of the rectification tower is 3:1.
精馏塔塔顶采出液相的组成：水的含量为19.35wt％、2-甲基-3-丁炔-2-醇的含量为48.27wt％、丙酮的含量为32.15wt％、其他组分的含量为0.23wt％，以塔顶采出液相中各组分的总重量为100wt％计。The composition of the liquid phase produced at the top of the distillation column: the content of water is 19.35wt%, the content of 2-methyl-3-butyn-2-ol is 48.27wt%, the content of acetone is 32.15wt%, and the other groups The content of the components is 0.23 wt %, and the total weight of each component in the liquid phase drawn from the top of the tower is 100 wt %.
精馏塔塔底采出液相的组成：水的含量为16.72wt％、2-甲基-3-丁炔-2-醇的含量为82.37wt％、丙酮的含量为0.52wt％、2,5-二甲基-3-己炔-2,5-二醇的含量为0.06wt％、其他组分的含量为0.33wt％，以塔底采出液相中各组分的总重量为100wt％计；即，得到2-甲基-3-丁炔-2-醇粗品。The composition of the liquid phase produced at the bottom of the distillation column: the content of water is 16.72wt%, the content of 2-methyl-3-butyn-2-ol is 82.37wt%, the content of acetone is 0.52wt%, 2, The content of 5-dimethyl-3-hexyne-2,5-diol is 0.06wt%, the content of other components is 0.33wt%, and the total weight of each component in the liquid phase extracted from the column bottom is 100wt% %; that is, crude 2-methyl-3-butyn-2-ol was obtained.
实施例6：2#反应液的预处理Example 6: Pretreatment of 2# reaction solution
1)采用薄膜蒸发器对炔化反应制得的2#反应液进行脱盐处理，该薄膜蒸发器的外循环油浴温度为80℃，其操作压力为800hPa。2#反应液的组成：无机盐的含量为2.17wt％，水的含量为16.62wt％、2-甲基-3-丁炔-2-醇的含量为77.27wt％、丙酮的含量为3.52wt％、2,5-二甲基-3-己炔-2,5-二醇的含量为0.02wt％、其他组分的含量为0.40wt％。1) The 2# reaction solution obtained by the acetylenic reaction is desalted by a thin film evaporator, the temperature of the external circulating oil bath of the thin film evaporator is 80°C, and the operating pressure is 800hPa. The composition of the 2# reaction solution: the content of inorganic salt is 2.17wt%, the content of water is 16.62wt%, the content of 2-methyl-3-butyn-2-ol is 77.27wt%, and the content of acetone is 3.52wt% %, the content of 2,5-dimethyl-3-hexyne-2,5-diol is 0.02wt%, and the content of other components is 0.40wt%.
将2#反应液通入薄膜蒸发器。2#反应液的进料速率为0.950kg/h，薄膜蒸发器上出口的采出速率为0.902kg/h，采出液相组成：水的含量为16.99wt％、2-甲基-3-丁炔-2-醇的含量为78.98wt％、丙酮的含量为3.60wt％、2,5-二甲基-3-己炔-2,5-二醇的含量为0.02wt％、其他组分的含量为0.41wt％，以上出口的采出液相各组分的总重量为100wt％计。薄膜蒸发器下出口的采出速率为0.048kg/h。The 2# reaction solution was passed into a thin film evaporator. The feed rate of the 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: the content of water is 16.99wt%, 2-methyl-3- The content of butyn-2-ol is 78.98wt%, the content of acetone is 3.60wt%, the content of 2,5-dimethyl-3-hexyn-2,5-diol is 0.02wt%, other components Its content is 0.41wt%, and the total weight of each component of the produced liquid phase at the above outlet is calculated as 100wt%. The extraction rate of the lower outlet of the thin film evaporator is 0.048kg/h.
2)采用板网波纹填料塔对薄膜蒸发器上出口的采出液进行脱丙酮处理，精馏塔(或填料塔)塔径100mm，填料层高0.5m，理论板数5块，采出液相组成：水的含量为16.99wt％、2-甲基-3-丁炔-2-醇的含量为78.98wt％、丙酮的含量为3.60wt％、2,5-二甲基-3-己炔-2,5-二醇的含量为0.02wt％、其他组分的含量为0.41wt％。2) Deacetone treatment is carried out on the produced liquid at the outlet of the thin-film evaporator by using a corrugated packed tower of plate mesh. The diameter of the rectification tower (or packed tower) is 100 mm, the height of the packing layer is 0.5 m, the number of theoretical plates is 5, and the produced liquid is 100 mm in diameter. Phase composition: the content of water is 16.99wt%, the content of 2-methyl-3-butyn-2-ol is 78.98wt%, the content of acetone is 3.60wt%, the content of 2,5-dimethyl-3-hexyl The content of alkyne-2,5-diol was 0.02 wt %, and the content of other components was 0.41 wt %.
将该采出液从由塔下部第4块理论板处的进料管线进入精馏塔。精馏塔的操作压力为1Kpa。塔顶冷凝器使用10℃冷却水为冷媒，塔底的操作温度92-93℃。精馏塔塔顶冷凝器流出冷凝液回流与采出比例为3:1。The produced liquid enters the rectification column from the feed line at the fourth theoretical plate in the lower part of the column. The operating pressure of the distillation column is 1Kpa. The top condenser uses 10°C cooling water as the refrigerant, and the operating temperature at the bottom of the tower is 92-93°C. The ratio of reflux and production of the condensate flowing out of the top condenser of the rectification tower is 3:1.
精馏塔塔顶采出液相的组成：水的含量为19.38wt％、2-甲基-3-丁炔-2-醇的含量为48.15wt％、丙酮的含量为32.12wt％、其他组分的含量为0.35wt％，以塔顶采出液相中各组分的总重量为100wt％计。The composition of the liquid phase produced at the top of the rectification tower: the content of water is 19.38wt%, the content of 2-methyl-3-butyn-2-ol is 48.15wt%, the content of acetone is 32.12wt%, and the other groups The content of the components is 0.35 wt %, and the total weight of each component in the liquid phase drawn from the top of the tower is 100 wt %.
精馏塔塔底采出液相的组成：水的含量为16.73wt％、2-甲基-3-丁炔-2-醇的含量为82.35wt％、丙酮的含量为0.48wt％、2,5-二甲基-3-己炔-2,5-二醇的含量为0.02wt％、其他组分的含量为0.42wt％，以塔底采出液相中各组分的总重量为100wt％计；即，得到2-甲基-3-丁炔-2-醇粗品。The composition of the liquid phase produced at the bottom of the rectifying tower: the content of water is 16.73wt%, the content of 2-methyl-3-butyn-2-ol is 82.35wt%, the content of acetone is 0.48wt%, 2, The content of 5-dimethyl-3-hexyne-2,5-diol is 0.02wt%, the content of other components is 0.42wt%, and the total weight of each component in the liquid phase extracted from the column bottom is 100wt% %; that is, crude 2-methyl-3-butyn-2-ol was obtained.
实施例7：3#反应液的预处理Example 7: Pretreatment of 3# reaction solution
1)采用板网波纹填料塔对反应制得的3#反应液进行脱丙酮处理，精馏塔(填料塔)塔径100mm，填料层高0.5m，理论板数5块；3#反应液 的组成：无机盐含量为2.17wt％、水的含量为16.62wt％、2-甲基-3-丁炔-2-醇的含量为77.41wt％、丙酮的含量为3.32wt％、2,5-二甲基-3-己炔-2,5-二醇的含量为0.06wt％、其他组分的含量为0.42wt％。1) The 3# reaction solution obtained by the reaction is subjected to deacetone treatment by using a corrugated packing column of plate mesh, the diameter of the rectifying column (packing column) is 100mm, the height of the packing layer is 0.5m, and the number of theoretical plates is 5; Composition: the content of inorganic salt is 2.17wt%, the content of water is 16.62wt%, the content of 2-methyl-3-butyn-2-ol is 77.41wt%, the content of acetone is 3.32wt%, the content of 2,5- The content of dimethyl-3-hexyne-2,5-diol was 0.06 wt %, and the content of other components was 0.42 wt %.
将3#反应液由塔下部第4块理论板处的进料管线进入精馏塔。精馏塔的操作压力为1Kpa。塔顶冷凝器使用10℃冷却水为冷媒，塔底的操作温度92-93℃。精馏塔塔顶冷凝器流出冷凝液回流与采出比例为3:1。The 3# reaction liquid is fed into the rectification tower from the feed line at the fourth theoretical plate in the lower part of the tower. The operating pressure of the distillation column is 1Kpa. The top condenser uses 10°C cooling water as the refrigerant, and the operating temperature at the bottom of the tower is 92-93°C. The ratio of reflux and production of the condensate flowing out of the top condenser of the rectification tower is 3:1.
精馏塔塔顶采出液相的组成：水的含量为19.37wt％、2-甲基-3-丁炔-2-醇的含量为48.05wt％、丙酮的含量为32.19wt％、其他组分的含量为0.39wt％，以塔顶采出液相中各组分的总重量为100wt％计。The composition of the liquid phase produced at the top of the rectification tower: the content of water is 19.37wt%, the content of 2-methyl-3-butyn-2-ol is 48.05wt%, the content of acetone is 32.19wt%, and the other groups The content of the components is 0.39 wt %, and the total weight of each component in the liquid phase drawn from the top of the tower is 100 wt %.
精馏塔塔底采出液相的组成：无机盐的含量为2.40wt％、水的含量为16.33wt％、2-甲基-3-丁炔-2-醇的含量为80.46wt％、丙酮的含量为0.32wt％、2,5-二甲基-3-己炔-2,5-二醇的含量为0.07wt％、其他组分的含量为0.42wt％，以塔底采出液相中各组分的总重量为100wt％计。The composition of the liquid phase produced at the bottom of the distillation column: the content of inorganic salts is 2.40wt%, the content of water is 16.33wt%, the content of 2-methyl-3-butyn-2-ol is 80.46wt%, the content of acetone The content of 0.32wt%, the content of 2,5-dimethyl-3-hexyne-2,5-diol is 0.07wt%, and the content of other components is 0.42wt%, and the liquid phase is extracted from the bottom of the tower The total weight of each component is calculated as 100 wt%.
2)采用薄膜蒸发器对精馏塔塔底采出液进行脱盐处理，该薄膜蒸发器的外循环油浴温度为80℃，操作压力为800hPa。精馏塔塔底采出液组成：无机盐含量为2.40wt％、水的含量为16.33wt％、2-甲基-3-丁炔-2-醇的含量为80.46wt％、丙酮的含量为0.32wt％、2,5-二甲基-3-己炔-2,5-二醇的含量为0.07wt％、其他组分的含量为0.42wt％。2) A thin film evaporator is used to desalt the produced liquid at the bottom of the rectification tower. The temperature of the external circulating oil bath of the thin film evaporator is 80°C and the operating pressure is 800hPa. The composition of the produced liquid at the bottom of the distillation column: the content of inorganic salts is 2.40wt%, the content of water is 16.33wt%, the content of 2-methyl-3-butyn-2-ol is 80.46wt%, and the content of acetone is 0.32wt%, the content of 2,5-dimethyl-3-hexyne-2,5-diol is 0.07wt%, and the content of other components is 0.42wt%.
将精馏塔塔底采出液通入薄膜蒸发器，其进料速率为0.861kg/h，薄膜蒸发器上出口的采出速率为0.817kg/h，采出液相组成：水的含量为16.74wt％、2-甲基-3-丁炔-2-醇的含量为82.44wt％、丙酮的含量为0.32wt％、2,5-二甲基-3-己炔-2,5-二醇的含量为0.07wt％、其他组分的含量为0.43wt％，以上出口的采出液相各组分的总重量为100wt％计；即，得到2-甲基-3-丁炔-2-醇粗品。薄膜蒸发器下出口的采出速率为0.044kg/h。The produced liquid from the bottom of the rectifying tower is passed into the thin film evaporator, the feed rate is 0.861kg/h, the production rate of the upper outlet of the thin film evaporator is 0.817kg/h, and the composition of the produced liquid phase: the content of water is 16.74wt%, the content of 2-methyl-3-butyn-2-ol is 82.44wt%, the content of acetone is 0.32wt%, 2,5-dimethyl-3-hexyn-2,5-di The content of alcohol is 0.07 wt %, the content of other components is 0.43 wt %, and the total weight of each component of the produced liquid phase at the above outlet is 100 wt %; that is, 2-methyl-3-butyne-2 is obtained - Crude alcohol. The extraction rate of the lower outlet of the thin film evaporator is 0.044kg/h.
实施例8：4#反应液的预处理Example 8: Pretreatment of 4# reaction solution
1)采用板网波纹填料塔对反应制得的4#反应液进行脱丙酮处理，精馏塔(填料塔)塔径100mm，填料层高0.5m，理论板数5块，4#反应液的组成：无机盐的含量为1.81wt％，水的含量为15.30wt％、2-甲基-3-丁炔-2-醇的含量为76.57wt％、丙酮的含量为5.75wt％、2,5-二甲基-3-己炔-2,5- 二醇的含量为0.08wt％、其他组分的含量为0.49wt％。1) The 4# reaction solution obtained by the reaction is subjected to deacetone treatment by using a corrugated packing column of plate mesh. Composition: The content of inorganic salt is 1.81wt%, the content of water is 15.30wt%, the content of 2-methyl-3-butyn-2-ol is 76.57wt%, the content of acetone is 5.75wt%, the content of 2,5 - The content of dimethyl-3-hexyn-2,5-diol was 0.08 wt %, and the content of other components was 0.49 wt %.
将4#反应液由塔下部第4块理论板处的进料管线进入精馏塔。精馏塔的操作压力为1Kpa。塔顶冷凝器使用10℃冷却水为冷媒，塔底的操作温度92-93℃。精馏塔塔顶冷凝器流出冷凝液回流与采出比例为3:1。The 4# reaction liquid is fed into the rectification tower from the feed line at the 4th theoretical plate in the lower part of the tower. The operating pressure of the distillation column is 1Kpa. The top condenser uses 10°C cooling water as the refrigerant, and the operating temperature at the bottom of the tower is 92-93°C. The ratio of reflux and production of the condensate flowing out of the top condenser of the rectification tower is 3:1.
精馏塔塔顶采出液相的组成：水的含量为19.38wt％、2-甲基-3-丁炔-2-醇的含量为47.89wt％、丙酮的含量为32.21wt％、其他组分的含量为0.52wt％，以塔顶采出液相中各组分的总重量为100wt％计。The composition of the liquid phase produced at the top of the rectification tower: the content of water is 19.38wt%, the content of 2-methyl-3-butyn-2-ol is 47.89wt%, the content of acetone is 32.21wt%, and the other groups The content of the components is 0.52 wt %, and the total weight of each component in the liquid phase drawn from the top of the tower is 100 wt %.
精馏塔塔底采出液相的组成：无机盐的含量为2.14wt％、水的含量为14.56wt％、2-甲基-3-丁炔-2-醇的含量为81.79wt％、丙酮的含量为0.93wt％、2,5-二甲基-3-己炔-2,5-二醇的含量为0.09wt％、其他组分的含量为0.49wt％，以塔底采出液相中各组分的总重量为100wt％计。The composition of the liquid phase produced at the bottom of the distillation column: the content of inorganic salts is 2.14wt%, the content of water is 14.56wt%, the content of 2-methyl-3-butyn-2-ol is 81.79wt%, the content of acetone The content of 0.93wt%, the content of 2,5-dimethyl-3-hexyne-2,5-diol is 0.09wt%, and the content of other components is 0.49wt%, and the liquid phase is extracted from the bottom of the tower The total weight of each component is calculated as 100 wt%.
2)采用薄膜蒸发器对精馏塔塔底采出液进行脱盐处理，该薄膜蒸发器上午外循环油浴温度为80℃，操作压力为800hPa。精馏塔塔底采出液组成：无机盐含量为2.14wt％、水的含量为14.56wt％、2-甲基-3-丁炔-2-醇的含量为81.79wt％、丙酮的含量为0.93wt％、2,5-二甲基-3-己炔-2,5-二醇的含量为0.09wt％、其他组分的含量为0.49wt％。2) A thin film evaporator is used to desalt the produced liquid at the bottom of the rectification tower. The temperature of the external circulating oil bath of the thin film evaporator in the morning is 80°C and the operating pressure is 800hPa. The composition of the produced liquid at the bottom of the distillation column: the content of inorganic salts is 2.14wt%, the content of water is 14.56wt%, the content of 2-methyl-3-butyn-2-ol is 81.79wt%, and the content of acetone is 0.93wt%, the content of 2,5-dimethyl-3-hexyne-2,5-diol is 0.09wt%, and the content of other components is 0.49wt%.
将精馏塔塔底采出液通入薄膜蒸发器，其进料速率为0.794kg/h，薄膜蒸发器上出口的采出速率为0.763kg/h，采出液相组成：水的含量为14.87wt％、2-甲基-3-丁炔-2-醇的含量为83.58wt％、丙酮的含量为0.95wt％、2,5-二甲基-3-己炔-2,5-二醇的含量为0.10wt％、其他组分的含量为0.50wt％，以上出口的采出液相各组分的总重量为100wt％计；即，得到2-甲基-3-丁炔-2-醇粗品。薄膜蒸发器下出口的采出速率为0.031kg/h。The produced liquid from the bottom of the rectifying tower is passed into the thin film evaporator, the feed rate is 0.794kg/h, the production rate of the upper outlet of the thin film evaporator is 0.763kg/h, the composition of the produced liquid phase: the content of water is 14.87wt%, the content of 2-methyl-3-butyn-2-ol is 83.58wt%, the content of acetone is 0.95wt%, 2,5-dimethyl-3-hexyn-2,5-di The content of alcohol is 0.10 wt %, the content of other components is 0.50 wt %, and the total weight of each component of the produced liquid phase at the above outlet is 100 wt %; that is, 2-methyl-3-butyne-2 is obtained - Crude alcohol. The extraction rate of the lower outlet of the thin film evaporator was 0.031 kg/h.
实施例9Example 9
如图1所示，该分离和纯化工序包括如下步骤：As shown in Figure 1, the separation and purification process includes the following steps:
(i)将实施例5所得2-甲基-3-丁炔-2-醇粗品1(水16.72wt％、2-甲基-3-丁炔-2-醇82.37wt％、丙酮0.52wt％、2,5-二甲基-3-己炔-2,5-二醇0.06wt％、其他组分0.33wt％)以0.813kg/h的进料流量通入膜分离器SEP，进行膜分离操作，操作温度为95℃。(i) 2-methyl-3-butyn-2-ol crude product 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 0.06wt%, other components 0.33wt%) into the membrane separator SEP at a feed flow rate of 0.813kg/h for membrane separation Operation, the operating temperature is 95 ℃.
膜分离器SEP包括以下部件(图中未画出)：具有循环泵的进料容器、 具有亲水膜((CMC-E,Celfa AG，瑞士)的膜渗透单元，通过亲水膜以气态形式除去富含水的渗透物。通过膜分离器分离出含水的有机相流股2(即，渗余物)和水相流股3(即，渗透物)：渗余物流量为0.695kg/h，其包含约96.31wt％的2-甲基-3-丁炔-2-醇、2.89wt％的水、0.38wt％的丙酮、0.06wt％的2,5-二甲基-3-己炔-2,5-二醇以及0.36wt％的其他杂质，以渗余物各组分的总重量为100wt％计；渗透物流量为0.118kg/h，其包含约0.31wt％的2-甲基-3-丁炔-2-醇、1.34wt％的丙酮、0.14wt％的其他杂质以及剩余的为水，以渗透物各组分的总重量为100wt％计。The membrane separator SEP consists of the following components (not shown in the figure): a feed vessel with a circulating pump, a membrane permeation unit with a hydrophilic membrane ((CMC-E, Celfa AG, Switzerland), which is passed through the hydrophilic membrane in gaseous form Water rich permeate is removed. Aqueous organic phase stream 2 (ie, retentate) and aqueous phase stream 3 (ie, permeate) are separated by membrane separator: retentate flow rate 0.695 kg/h , which contains 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 of 100 wt%; the permeate flow rate was 0.118 kg/h, which contained about 0.31 wt% of 2-methyl -3-butyn-2-ol, 1.34 wt % acetone, 0.14 wt % other impurities and the remainder water, based on the total weight of the permeate components as 100 wt %.
(ii)将所得含水的有机相流股2(即，渗余物)以0.695kg/h的流速从由塔下部第10块理论板处的进料管线进入粗精馏塔RAC1，该粗精馏塔采用板网波纹填料塔，塔径100mm，填料层高2m，理论板数15块。粗精馏塔的操作压力为100hPa。塔顶冷凝器COOLER1使用10℃冷却水为冷媒，塔底再沸器REBOILER1实现对塔底温度的调控，塔底的操作温度为119-120℃。粗精馏塔塔顶冷凝器流出冷凝液回流与采出比例为1:1，塔顶的操作温度为42-43℃，塔顶釆出轻组分流股4，采出流速为0.0725kg/h。粗精馏塔塔顶采出液相的组成：水的含量为25.35wt％、丙酮的含量为3.64wt％、2-甲基-3-丁炔-2-醇的含量为71.01wt％，以塔顶釆出液相各组分的总重量为100wt％计。(ii) The resulting aqueous organic phase stream 2 (ie, retentate) was fed into the crude rectification column RAC1 from the feed line at the 10th theoretical plate in the lower part of the column at a flow rate of 0.695 kg/h. The distillation column adopts the corrugated packing column of plate mesh, the diameter of the column is 100mm, the height of the packing layer is 2m, and the number of theoretical plates is 15. The operating pressure of the crude distillation column was 100 hPa. The column top condenser COOLER1 uses 10 ℃ cooling water as the refrigerant, and the column bottom reboiler REBOILER1 realizes the regulation of the column bottom temperature, and the operating temperature of the column bottom is 119-120 ℃. The ratio of condensate reflux and extraction from the top condenser of the crude rectification tower is 1:1, the operating temperature at the top of the column is 42-43 ° C, and the top of the column is drawn with a light component stream 4, and the extraction flow rate is 0.0725kg/h . The composition of the liquid phase produced at the top of the crude distillation column: the content of water is 25.35wt%, the content of acetone is 3.64wt%, and the content of 2-methyl-3-butyn-2-ol is 71.01wt%, with The total weight of each component in the liquid phase extracted from the top of the column is calculated as 100 wt %.
粗精馏塔塔底以0.6225kg/h的流速采出待脱重组分流股5，并进入产品分离塔。粗精馏塔塔底釆出液相的组成：水的含量为0.27wt％、2-甲基-3-丁炔-2-醇的含量为99.25wt％、2,5-二甲基-3-己炔-2,5-二醇的含量为0.07wt％、其他组分的含量为0.41wt％，以塔底釆出液相各组分的总重量为100wt％计。At the bottom of the crude rectification tower, a flow rate of 0.6225kg/h is taken out of the sub-stream 5 to be removed and entered into the product separation tower. The composition of the liquid phase at the bottom of the crude distillation column: the content of water is 0.27wt%, the content of 2-methyl-3-butyn-2-ol is 99.25wt%, the content of 2,5-dimethyl-3 The content of -hexyne-2,5-diol is 0.07 wt %, and the content of other components is 0.41 wt %, and the total weight of each component in the liquid phase extracted from the bottom of the tower is 100 wt %.
(iii)粗精馏塔的塔底釆出的待脱重组分流股，从产品分离塔RAC2的塔中部进入；产品分离塔采用板网波纹填料塔，塔径100mm，填料层高1m，理论板数7块，粗精馏塔塔底液由第4块理论板处的进料管线进入产品分离塔。产品分离塔的操作压力为100hPa。塔顶冷凝器COOLER2使用10℃冷却水为冷媒，塔底再沸器REBOILER2实现对塔底温度的调控，塔底的操作温度119-120℃。塔顶冷凝器流出冷凝液回流与采出比例为1:1，塔顶的操作温度53-54℃，塔顶采出产物流股6，其采出流速为0.6127kg/h。 产品分离塔塔顶的采出液相组成：水的含量为0.27wt％、2-甲基-3-丁炔-2-醇的含量为99.73wt％，以塔顶釆出液相各组分的总重量为100wt％计。(iii) the fractional stream to be de-weighted that is taken at the bottom of the crude rectification tower, enters from the middle of the tower of the product separation tower RAC2; the product separation tower adopts a plate mesh corrugated packing tower, the tower diameter is 100mm, the packing layer height is 1m, and the theoretical plate Number 7, the crude distillation column bottom liquid enters the product separation column from the feed line at the fourth theoretical plate. The operating pressure of the product separation column was 100 hPa. The column top condenser COOLER2 uses 10℃ cooling water as the refrigerant, and the column bottom reboiler REBOILER2 realizes the regulation of the column bottom temperature, and the column bottom operating temperature is 119-120℃. The ratio of reflux and production of condensate flowing out of the tower top condenser is 1:1, the operating temperature of the tower top is 53-54°C, and the product stream 6 is produced from the top of the tower, and its production flow rate is 0.6127kg/h. The composition of the produced liquid phase at the top of the product separation tower: the content of water is 0.27% by weight, the content of 2-methyl-3-butyn-2-ol is 99.73% by weight, and the components of the liquid phase are taken from the top of the tower. The total weight is 100wt%.
产品分离塔的塔底以0.0098kg/h的流速采出重组分流股7，产品分离塔塔底的釆出液相组成：2-甲基-3-丁炔-2-醇的含量为69.72wt％、2,5-二甲基-3-己炔-2,5-二醇的含量为4.6wt％、其他组分的含量为25.68wt％，以塔底釆出液相各组分的总重量为100wt％计。The bottom of the product separation tower draws out the reorganization branch 7 with the flow velocity of 0.0098kg/h, and the liquid phase composition at the bottom of the product separation tower: the content of 2-methyl-3-butyn-2-ol is 69.72wt %, the content of 2,5-dimethyl-3-hexyne-2,5-diol is 4.6wt%, and the content of other components is 25.68wt%. The weight is based on 100 wt%.
包含膜分离器的膜渗透单元持续进料3000小时，未见明显异常。产品分离塔的塔顶采出液，即所得产品2-甲基-3-丁炔-2-醇，测得其折射率：n20/D 1.4215，色号：16(Pt-Co)。The membrane permeation unit including the membrane separator was continuously fed for 3000 hours, and no obvious abnormality was observed. The produced liquid at the top of the product separation tower, namely the obtained product 2-methyl-3-butyn-2-ol, measured its refractive index: n20/D 1.4215, color number: 16 (Pt-Co).
实施例10Example 10
如图1所示，该分离和纯化工序包括如下步骤：As shown in Figure 1, the separation and purification process includes the following steps:
(i)将实施例6所得2-甲基-3-丁炔-2-醇粗品1(水16.73wt％、2-甲基-3-丁炔-2-醇82.35wt％、丙酮0.48wt％、2,5-二甲基-3-己炔-2,5-二醇0.02wt％、其他组分0.42wt％)以0.813kg/h的进料流量通入膜分离器SEP，进行膜分离操作，操作温度为95℃。(i) 2-methyl-3-butyn-2-ol crude product 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 0.02wt%, other components 0.42wt%) into the membrane separator SEP at a feed flow rate of 0.813kg/h for membrane separation Operation, the operating temperature is 95 ℃.
膜分离器SEP包括以下部件(图中未画出)：具有循环泵的进料容器、具有亲水膜(CMC-E,Celfa AG，瑞士)的膜渗透单元，通过亲水膜以气态形式除去富含水的渗透物。通过膜分离器分离出含水的有机相流股2(即，渗余物)和水相流股3(即，渗透物)：渗余物流量为0.692kg/h，其包含约96.69wt％的2-甲基-3-丁炔-2-醇、2.46wt％的水、0.37wt％的丙酮、0.03wt％的2,5-二甲基-3-己炔-2,5-二醇以及0.45wt％的其他杂质，以渗余物各组分的总重量为100wt％计；渗透物流量为0.121kg/h，包含约0.35wt％的2-甲基-3-丁炔-2-醇、1.12wt％的丙酮、0.18wt％的其他杂质以及剩余的为水，以渗透物各组分的总重量为100wt％计。The membrane separator SEP consists of the following components (not shown in the figure): a feed vessel with a circulating pump, a membrane permeation unit with a hydrophilic membrane (CMC-E, Celfa AG, Switzerland), which is removed in gaseous form by a hydrophilic membrane Water-rich permeate. Aqueous organic phase stream 2 (ie, retentate) and aqueous phase stream 3 (ie, permeate) were separated by a membrane separator: the retentate flow rate was 0.692 kg/h, which contained 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-hexyn-2,5-diol and 0.45wt% of other impurities, based on the total weight of the retentate components as 100wt%; the permeate flow rate is 0.121kg/h, containing about 0.35wt% of 2-methyl-3-butyn-2-ol , 1.12 wt % of acetone, 0.18 wt % of other impurities and the remainder being water, based on the total weight of the permeate components as 100 wt %.
(ii)将所得含水的有机相流股2(即，渗余物)以0.695kg/h的流速从由塔下部第10块理论板处的进料管线进入粗精馏塔RAC1，该粗精馏塔采用板网波纹填料塔，塔径100mm，填料层高2m，理论板数15块。粗精馏塔的操作压力为100hPa。塔顶冷凝器COOLER1使用10℃冷却水为冷媒，塔底再沸器REBOILER1实现对塔底温度的调控，塔底的操作温度为 119-120℃。粗精馏塔塔顶冷凝器流出冷凝液回流与采出比例为1:1，塔顶的操作温度为42-43℃，塔顶釆出轻组分流股4，采出流速为0.0519kg/h。粗精馏塔塔顶采出液相的组成：水的含量为25.35wt％、丙酮的含量为4.87wt％、2-甲基-3-丁炔-2-醇的含量为69.78wt％，以塔顶釆出液相各组分的总重量为100wt％计。(ii) The resulting aqueous organic phase stream 2 (ie, retentate) was fed into the crude rectification column RAC1 from the feed line at the 10th theoretical plate in the lower part of the column at a flow rate of 0.695 kg/h. The distillation column adopts the corrugated packing column of plate mesh, the diameter of the column is 100mm, the height of the packing layer is 2m, and the number of theoretical plates is 15. The operating pressure of the crude distillation column was 100 hPa. The column top condenser COOLER1 uses 10 ℃ cooling water as the refrigerant, and the column bottom reboiler REBOILER1 realizes the regulation of the column bottom temperature, and the operating temperature of the column bottom is 119-120 ℃. The ratio of condensate reflux and extraction from the top condenser of the crude rectification tower is 1:1, the operating temperature at the top of the column is 42-43 ° C, and the top of the column draws a light component stream 4, and the extraction flow rate is 0.0519kg/h . The composition of the liquid phase produced at the top of the crude distillation column: the content of water is 25.35wt%, the content of acetone is 4.87wt%, and the content of 2-methyl-3-butyn-2-ol is 69.78wt%, with The total weight of each component in the liquid phase extracted from the top of the column is calculated as 100 wt %.
粗精馏塔塔底以0.6401kg/h的流速采出待脱重组分流股5，并进入产品分离塔。粗精馏塔塔底釆出液相的组成：水的含量为0.60wt％、2-甲基-3-丁炔-2-醇的含量为98.87wt％、2,5-二甲基-3-己炔-2,5-二醇的含量为0.03wt％、其他组分的含量为0.50wt％，以塔底釆出液相各组分的总重量为100wt％计。At the bottom of the crude rectification tower, a flow rate of 0.6401kg/h is taken out of the fractional stream 5 to be deweighted, and enters the product separation tower. The composition of the liquid phase at the bottom of the crude distillation column: the content of water is 0.60wt%, the content of 2-methyl-3-butyn-2-ol is 98.87wt%, the content of 2,5-dimethyl-3 The content of -hexyne-2,5-diol is 0.03 wt %, and the content of other components is 0.50 wt %, and the total weight of each component in the liquid phase extracted from the bottom of the tower is 100 wt %.
(iii)粗精馏塔的塔底釆出的待脱重组分流股5，从产品分离塔RAC2的塔中部进入；产品分离塔采用板网波纹填料塔，塔径100mm，填料层高1m，理论板数7块，粗精馏塔塔底液由第4块理论板处的进料管线进入产品分离塔。产品分离塔的操作压力为100hPa。塔顶冷凝器COOLER2使用10℃冷却水为冷媒，塔底再沸器REBOILER2实现对塔底温度的调控，塔底的操作温度为119-120℃。塔顶冷凝器流出冷凝液回流与采出比例为1:1，塔顶的操作温度为53-54℃，塔顶采出产物流股6，其采出流速为0.6316kg/h。产品分离塔塔顶的采出液相组成：水的含量为0.61wt％、2-甲基-3-丁炔-2-醇的含量为99.39wt％，以塔顶釆出液相各组分的总重量为100wt％计。(iii) the fractional stream 5 to be taken off at the bottom of the crude rectifying tower, enters from the middle of the tower of the product separation tower RAC2; The number of plates is 7, and the crude distillation column bottom liquid enters the product separation column from the feed line at the fourth theoretical plate. The operating pressure of the product separation column was 100 hPa. The column top condenser COOLER2 uses 10 ℃ cooling water as the refrigerant, and the column bottom reboiler REBOILER2 realizes the regulation of the column bottom temperature, and the operating temperature of the column bottom is 119-120 ℃. The ratio of reflux and production of the condensate flowing out of the tower top condenser is 1:1, the operating temperature of the tower top is 53-54°C, and the product stream 6 is produced from the top of the tower, and its production flow rate is 0.6316kg/h. The composition of the produced liquid phase at the top of the product separation tower: the content of water is 0.61 wt%, the content of 2-methyl-3-butyn-2-ol is 99.39 wt%, and the components of the liquid phase are taken from the top of the tower. The total weight is 100wt%.
产品分离塔塔底以0.0085kg/h的流速采出重组分流股7，产品分离塔塔底的釆出液相组成：2-甲基-3-丁炔-2-醇的含量为60.60wt％、2,5-二甲基-3-己炔-2,5-二醇的含量为2.12wt％、其他组分的含量为37.28wt％，以塔底釆出液相各组分的总重量为100wt％计。At the bottom of the product separation tower, the reorganization branch 7 is extracted at a flow rate of 0.0085kg/h, and the liquid phase composition at the bottom of the product separation tower is: the content of 2-methyl-3-butyn-2-ol is 60.60wt% , the content of 2,5-dimethyl-3-hexyne-2,5-diol is 2.12wt%, the content of other components is 37.28wt%, and the total weight of each component in the liquid phase is obtained from the bottom of the tower 100% by weight.
包含膜分离器的膜渗透单元持续进料4000小时，未见明显异常。产品分离塔的塔顶采出液，即所得产品2-甲基-3-丁炔-2-醇，测得其折射率：n20/D 1.4215，色号：15(Pt-Co)。The membrane permeation unit including the membrane separator was continuously fed for 4000 hours, and no obvious abnormality was observed. The produced liquid at the top of the product separation tower, namely the obtained product 2-methyl-3-butyn-2-ol, was measured with refractive index: n20/D 1.4215, color number: 15 (Pt-Co).
实施例11Example 11
如图1所示，该分离和纯化工序包括如下步骤：As shown in Figure 1, the separation and purification process includes the following steps:
(i)将实施例7所得2-甲基-3-丁炔-2-醇粗品1(水16.74wt％、2-甲基-3-丁炔-2-醇82.44wt％、丙酮0.32wt％、2,5-二甲基-3-己炔-2,5-二醇0.07wt％、其他组分0.43wt％)以0.817kg/h的进料流量通入膜分离器SEP，进行膜分离操作，操作温度为95℃。(i) 2-methyl-3-butyn-2-ol crude product 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 0.07wt%, other components 0.43wt%) into the membrane separator SEP at a feed flow rate of 0.817kg/h for membrane separation Operation, the operating temperature is 95 ℃.
膜分离器SEP包括以下部件(图中未画出)：具有循环泵的进料容器、具有亲水膜(CMC-E,Celfa AG，瑞士)的膜渗透单元，通过亲水膜以气态形式除去富含水的渗透物。通过膜分离器分离出含水的有机相流股2(即，渗余物)和水相流股3(即，渗透物)：渗余物流量为0.714kg/h，其包含约94.29wt％的2-甲基-3-丁炔-2-醇、4.93wt％的水、0.24wt％的丙酮、0.08wt％的2,5-二甲基-3-己炔-2,5-二醇以及0.46wt％的其他杂质，以渗余物各组分的总重量为100wt％计；渗透物流量为0.103kg/h，包含约0.34wt％的2-甲基-3-丁炔-2-醇、0.86wt％的丙酮、0.19wt％的其他杂质以及剩余的为水，以渗透物各组分的总重量为100wt％计。The membrane separator SEP consists of the following components (not shown in the figure): a feed vessel with a circulating pump, a membrane permeation unit with a hydrophilic membrane (CMC-E, Celfa AG, Switzerland), which is removed in gaseous form by a hydrophilic membrane Water-rich permeate. Aqueous organic phase stream 2 (ie, retentate) and aqueous phase stream 3 (ie, permeate) were separated by a membrane separator: the retentate flow rate was 0.714 kg/h, which contained about 94.29 wt% of 2-methyl-3-butyn-2-ol, 4.93 wt % water, 0.24 wt % acetone, 0.08 wt % 2,5-dimethyl-3-hexyn-2,5-diol and 0.46 wt% of other impurities, based on the total weight of the retentate components as 100 wt%; the permeate flow rate was 0.103 kg/h, containing 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 is water, based on the total weight of the permeate components as 100 wt %.
(ii)将所得含水的有机相流股2(即，渗余物)以0.714kg/h的流速从由塔下部第10块理论板处的进料管线进入粗精馏塔RAC1，该粗精馏塔采用板网波纹填料塔，塔径100mm，填料层高2m，理论板数15块。粗精馏塔的操作压力为100hPa。塔顶冷凝器COOLER1使用10℃冷却水为冷媒，塔底再沸器REBOILER1实现对塔底温度的调控，塔底的操作温度为119-120℃。粗精馏塔塔顶冷凝器流出冷凝液回流与采出比例为1:1，塔顶的操作温度为42-43℃，塔顶釆出轻组分流股4，采出流速为0.1225kg/h。粗精馏塔塔顶采出液相的组成：水的含量为25.69wt％、丙酮的含量为1.41wt％、2-甲基-3-丁炔-2-醇的含量为72.90wt％，以塔顶釆出液相各组分的总重量为100wt％计。(ii) The resulting aqueous organic phase stream 2 (ie, retentate) was fed into the crude rectification column RAC1 from the feed line at the 10th theoretical plate in the lower part of the column at a flow rate of 0.714 kg/h. The distillation column adopts the corrugated packing column of plate mesh, the diameter of the column is 100mm, the height of the packing layer is 2m, and the number of theoretical plates is 15. The operating pressure of the crude distillation column was 100 hPa. The column top condenser COOLER1 uses 10 ℃ cooling water as the refrigerant, and the column bottom reboiler REBOILER1 realizes the regulation of the column bottom temperature, and the operating temperature of the column bottom is 119-120 ℃. The ratio of reflux and extraction of the condensate flowing out of the top condenser of the crude rectification tower is 1:1, the operating temperature at the top of the column is 42-43 ° C, and the top of the column is drawn with a light component stream 4, and the extraction flow rate is 0.1225kg/h . The composition of the liquid phase produced at the top of the crude distillation column: the content of water is 25.69wt%, the content of acetone is 1.41wt%, and the content of 2-methyl-3-butyn-2-ol is 72.90wt%, with The total weight of each component in the liquid phase extracted from the top of the column is calculated as 100 wt %.
粗精馏塔塔底以0.5915kg/h的流速采出待脱重组分流股5，并进入产品分离塔。粗精馏塔塔底釆出液相的组成：水的含量为0.64wt％、2-甲基-3-丁炔-2-醇的含量为98.71wt％、2,5-二甲基-3-己炔-2,5-二醇的含量为0.09wt％、其他组分的含量为0.56wt％，以塔底釆出液相各组分的总重量为100wt％计。At the bottom of the crude rectification tower, a flow rate of 0.5915kg/h is taken out of the fractional stream 5 to be deweighted, and enters the product separation tower. The composition of the liquid phase at the bottom of the crude distillation column: the content of water is 0.64wt%, the content of 2-methyl-3-butyn-2-ol is 98.71wt%, the content of 2,5-dimethyl-3 The content of -hexyne-2,5-diol is 0.09wt%, the content of other components is 0.56wt%, and the total weight of each component in the liquid phase extracted from the bottom of the tower is 100wt%.
(iii)粗精馏塔的塔底釆出的待脱重组分流股5，从产品分离塔RAC2的塔中部进入；产品分离塔采用板网波纹填料塔，塔径100mm，填料层高 1m，理论板数7块，粗精馏塔塔底液由第4块理论板处的进料管线进入产品分离塔。产品分离塔的操作压力为100hPa。塔顶冷凝器COOLER2使用10℃冷却水为冷媒，塔底再沸器REBOILER2实现对塔底温度的调控，塔底的操作温度为119-120℃。塔顶冷凝器流出冷凝液回流与采出比例为1:1，塔顶的操作温度为53-54℃，塔顶采出产物流股6，其采出流速为0.5819kg/h。产品分离塔塔顶的采出液相组成：水的含量为0.64wt％、2-甲基-3-丁炔-2-醇的含量为99.36wt％，以塔顶釆出液相各组分的总重量为100wt％计。(iii) the fractional stream 5 to be taken off at the bottom of the crude rectifying tower, enters from the middle of the tower of the product separation tower RAC2; The number of plates is 7, and the crude distillation column bottom liquid enters the product separation column from the feed line at the fourth theoretical plate. The operating pressure of the product separation column was 100 hPa. The column top condenser COOLER2 uses 10 ℃ cooling water as the refrigerant, and the column bottom reboiler REBOILER2 realizes the regulation of the column bottom temperature, and the operating temperature of the column bottom is 119-120 ℃. The ratio of reflux and production of condensate flowing out of the tower top condenser is 1:1, the operating temperature of the tower top is 53-54°C, and the product stream 6 is produced from the top of the tower, and its production flow rate is 0.5819kg/h. The composition of the produced liquid phase at the top of the product separation tower: the content of water is 0.64% by weight, the content of 2-methyl-3-butyn-2-ol is 99.36% by weight, and the components of the liquid phase are taken from the top of the tower. The total weight is 100wt%.
产品分离塔的塔底以0.096kg/h的流速采出重组分流股7，产品分离塔塔底的釆出液相组成：2-甲基-3-丁炔-2-醇的含量为59.48wt％、2,5-二甲基-3-己炔-2,5-二醇的含量为5.96wt％、其他组分的含量为34.56wt％，以塔底釆出液相各组分的总重量为100wt％计。The bottom of the product separation tower draws out the reorganization branch 7 with the flow velocity of 0.096kg/h, and the liquid phase composition at the bottom of the product separation tower: the content of 2-methyl-3-butyn-2-ol is 59.48wt %, the content of 2,5-dimethyl-3-hexyne-2,5-diol is 5.96wt%, and the content of other components is 34.56wt%. The weight is based on 100 wt%.
包含膜分离器的膜渗透单元持续进料3500小时，未见明显异常。产品分离塔的塔顶采出液，即所得产品2-甲基-3-丁炔-2-醇，测得其折射率：n20/D 1.4215，色号：16(Pt-Co)。The membrane permeation unit including the membrane separator was continuously fed for 3500 hours without any obvious abnormality. The produced liquid at the top of the product separation tower, namely the obtained product 2-methyl-3-butyn-2-ol, measured its refractive index: n20/D 1.4215, color number: 16 (Pt-Co).
实施例12Example 12
如图1所示，该分离和纯化工序包括如下步骤：As shown in Figure 1, the separation and purification process includes the following steps:
(i)将实施例8所得2-甲基-3-丁炔-2-醇粗品1(水14.87wt％、2-甲基-3-丁炔-2-醇83.58wt％、丙酮0.95wt％、2,5-二甲基-3-己炔-2,5-二醇0.10wt％、其他组分0.50wt％)以0.763kg/h的进料流量通入膜分离器SEP，进行膜分离操作，操作温度为95℃。(i) 2-methyl-3-butyn-2-ol crude product 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 0.10wt%, other components 0.50wt%) into the membrane separator SEP at a feed flow rate of 0.763kg/h for membrane separation Operation, the operating temperature is 95 ℃.
膜分离器SEP包括以下部件(图中未画出)：具有循环泵的进料容器、具有亲水膜((CMC-E,Celfa AG，瑞士)的膜渗透单元，通过亲水膜以气态形式除去富含水的渗透物。通过膜分离器分离出含水的有机相流股2(即，渗余物)和水相流股3(即，渗透物)：渗余物流量为0.658kg/h，其包含约96.86wt％的2-甲基-3-丁炔-2-醇、1.61wt％的水、0.87wt％的丙酮、0.11wt％的2,5-二甲基-3-己炔-2,5-二醇以及0.55wt％的其他杂质，以渗余物各组分的总重量为100wt％计；渗透物流量为0.105kg/h，其包含约0.36wt％的2-甲基-3-丁炔-2-醇、1.45wt％的丙酮、0.22wt％的其他杂质以及剩余的为水， 以渗透物各组分的总重量为100wt％计。The membrane separator SEP consists of the following components (not shown in the figure): a feed vessel with a circulating pump, a membrane permeation unit with a hydrophilic membrane ((CMC-E, Celfa AG, Switzerland), passing through the hydrophilic membrane in gaseous form Water-rich permeate was removed. Aqueous organic phase stream 2 (ie, retentate) and aqueous phase stream 3 (ie, permeate) were separated by a membrane separator: retentate flow rate was 0.658 kg/h , which contains about 96.86 wt% 2-methyl-3-butyn-2-ol, 1.61 wt% water, 0.87 wt% acetone, 0.11 wt% 2,5-dimethyl-3-hexyne -2,5-diol and 0.55 wt% of other impurities, based on the total weight of the retentate components of 100 wt%; the permeate flow rate was 0.105 kg/h, which contained about 0.36 wt% of 2-methyl -3-butyn-2-ol, 1.45 wt % acetone, 0.22 wt % other impurities and the remainder water, based on the total weight of the permeate components as 100 wt %.
(ii)将所得含水的有机相流股2(即，渗余物)以0.658kg/h的流速从由塔下部第10块理论板处的进料管线进入粗精馏塔RAC1，该粗精馏塔采用板网波纹填料塔，塔径100mm，填料层高2m，理论板数15块。粗精馏塔的操作压力为100hPa。塔顶冷凝器COOLER1使用10℃冷却水为冷媒，塔底再沸器REBOILER1实现对塔底温度的调控，塔底的操作温度为119-120℃。粗精馏塔塔顶冷凝器流出冷凝液回流与采出比例为1:1，塔顶的操作温度为42-43℃，塔顶釆出轻组分流股4，采出流速为0.0725kg/h。粗精馏塔塔顶采出液相的组成：水的含量为19.59wt％、丙酮的含量为17.62wt％、2-甲基-3-丁炔-2-醇的含量为62.79wt％，以塔顶釆出液相各组分的总重量为100wt％计。(ii) The resulting aqueous organic phase stream 2 (ie, retentate) was fed into the crude distillation column RAC1 from the feed line at the 10th theoretical plate in the lower part of the column at a flow rate of 0.658 kg/h. The distillation column adopts the corrugated packing column of plate mesh, the diameter of the column is 100mm, the height of the packing layer is 2m, and the number of theoretical plates is 15. The operating pressure of the crude distillation column was 100 hPa. The column top condenser COOLER1 uses 10 ℃ cooling water as the refrigerant, and the column bottom reboiler REBOILER1 realizes the regulation of the column bottom temperature, and the operating temperature of the column bottom is 119-120 ℃. The ratio of condensate reflux and extraction from the top condenser of the crude rectification tower is 1:1, the operating temperature at the top of the column is 42-43 ° C, and the top of the column is drawn with a light component stream 4, and the extraction flow rate is 0.0725kg/h . The composition of the liquid phase produced at the top of the crude distillation column: the content of water is 19.59wt%, the content of acetone is 17.62wt%, and the content of 2-methyl-3-butyn-2-ol is 62.79wt%, with The total weight of each component in the liquid phase extracted from the top of the column is calculated as 100 wt %.
粗精馏塔塔底以0.6255kg/h的流速采出待脱重组分流股5，并进入产品分离塔。粗精馏塔塔底釆出液相的组成：水的含量为0.68wt％、2-甲基-3-丁炔-2-醇的含量为98.63wt％、2,5-二甲基-3-己炔-2,5-二醇的含量为0.12wt％、其他组分的含量为0.57wt％，以塔底釆出液相各组分的总重量为100wt％计。At the bottom of the crude rectification tower, a flow rate of 0.6255kg/h is taken out of the sub-stream 5 to be deweighted, and enters the product separation tower. The composition of the liquid phase at the bottom of the crude distillation column: the content of water is 0.68wt%, the content of 2-methyl-3-butyn-2-ol is 98.63wt%, the content of 2,5-dimethyl-3 The content of -hexyne-2,5-diol is 0.12 wt %, and the content of other components is 0.57 wt %, and the total weight of each component in the liquid phase extracted from the bottom of the tower is 100 wt %.
(iii)粗精馏塔的塔底釆出的待脱重组分流股5，从产品分离塔RAC2的塔中部进入；产品分离塔采用板网波纹填料塔，塔径100mm，填料层高1m，理论板数7块，粗精馏塔塔底液由第4块理论板处的进料管线进入产品分离塔。产品分离塔的操作压力为100hPa。塔顶冷凝器COOLER2使用10℃冷却水为冷媒，塔底再沸器REBOILER2实现对塔底温度的调控，塔底的操作温度为119-120℃。塔顶冷凝器流出冷凝液回流与采出比例为1:1，塔顶的操作温度为53-54℃，塔顶采出产物流股6，其采出流速为0.6134kg/h。产品分离塔的塔顶采出液组成：水的含量为0.69wt％、2-甲基-3-丁炔-2-醇的含量为99.31wt％，以塔顶釆出液相各组分的总重量为100wt％计。(iii) the fractional stream 5 to be taken off at the bottom of the crude rectifying tower, enters from the middle of the tower of the product separation tower RAC2; The number of plates is 7, and the crude distillation column bottom liquid enters the product separation column from the feed line at the fourth theoretical plate. The operating pressure of the product separation column was 100 hPa. The column top condenser COOLER2 uses 10 ℃ cooling water as the refrigerant, and the column bottom reboiler REBOILER2 realizes the regulation of the column bottom temperature, and the operating temperature of the column bottom is 119-120 ℃. The ratio of reflux and production of the condensate flowing out of the tower top condenser is 1:1, the operating temperature of the tower top is 53-54°C, and the product stream 6 is produced from the top of the tower, and its production flow rate is 0.6134kg/h. The composition of the produced liquid at the top of the product separation tower: the content of water is 0.69 wt %, the content of 2-methyl-3-butyn-2-ol is 99.31 wt %, and the liquid phase components are extracted from the top of the tower. The total weight is based on 100 wt%.
产品分离塔塔底以0.121kg/h的流速采出重组分流股7，产品分离塔塔底的釆出液相组成：2-甲基-3-丁炔-2-醇的含量为64.07wt％、2,5-二甲基-3-己炔-2,5-二醇的含量为6.31wt％、其他组分的含量为29.62wt％，以塔底釆出液相各组分的总重量为100wt％计。At the bottom of the product separation tower, the reorganization branch 7 is extracted at a flow rate of 0.121 kg/h, and the liquid phase composition at the bottom of the product separation tower is: the content of 2-methyl-3-butyn-2-ol is 64.07wt% , the content of 2,5-dimethyl-3-hexyne-2,5-diol is 6.31wt%, the content of other components is 29.62wt%, and the total weight of each component in the liquid phase is obtained from the bottom of the tower 100% by weight.
包含膜分离器的膜渗透单元持续进料2000小时，未见明显异常。产品分离塔的塔顶采出液，即所得产品2-甲基-3-丁炔-2-醇，测得其折射率：n20/D 1.4216，色号：18(Pt-Co)。The membrane permeation unit including the membrane separator was continuously fed for 2000 hours, and no obvious abnormality was observed. The produced liquid at the top of the product separation tower, namely the obtained product 2-methyl-3-butyn-2-ol, measured its refractive index: n20/D 1.4216, color number: 18 (Pt-Co).
对比例1：Comparative Example 1:
5#反应液的制备：Preparation of 5# reaction solution:
首先将500L高压釜用氨气置换3次，将反应釜内温度降至-20℃，加入液氨(144.5Kg，8500mol)，开启搅拌，通入乙炔(16800L，750mol)，加入浓度为50wt％的氢氧化钾水溶液(1008g，作为溶质的氢氧化钾用量为丙酮的3mol％)，升温至10℃并加入丙酮(17.4Kg，300mol)，控制丙酮加入速率在1h左右进料完毕；反应温度为10℃，反应2h后加入5Kg浓度为10wt％的硫酸铵水溶液进行中和，得到含有2-甲基-3-丁炔-2-醇的5#反应液，并取样通过GC检测反应液。First, the 500L autoclave was replaced with ammonia gas three times, the temperature in the reactor was lowered to -20°C, liquefied ammonia (144.5Kg, 8500mol) was added, stirring was started, acetylene (16800L, 750mol) was introduced, and the concentration was 50wt% The potassium hydroxide aqueous solution (1008g, as the potassium hydroxide consumption of solute is 3mol% of acetone), be warming up to 10 DEG C and add acetone (17.4Kg, 300mol), control the acetone addition rate to complete the feeding at about 1h; the reaction temperature is At 10°C, after 2 hours of reaction, 5Kg of ammonium sulfate aqueous solution with a concentration of 10wt% was added for neutralization to obtain a 5# reaction solution containing 2-methyl-3-butyn-2-ol, and the reaction solution was sampled and detected by GC.
5#反应液的组成：无机盐的含量为2.17wt％，水的含量为16.62wt％、2-甲基-3-丁炔-2-醇的含量为75.31wt％、丙酮的含量为4.68wt％、2,5-二甲基-3-己炔-2,5-二醇的含量为0.59wt％、其他组分的含量为0.63wt％，以5#反应液各组分的总重量为100wt％计。The composition of the 5# reaction solution: the content of inorganic salt is 2.17wt%, the content of water is 16.62wt%, the content of 2-methyl-3-butyn-2-ol is 75.31wt%, and the content of acetone is 4.68wt% %, the content of 2,5-dimethyl-3-hexyne-2,5-diol is 0.59wt%, the content of other components is 0.63wt%, and the total weight of each component of the 5# reaction solution is 100wt%.
5#反应液的预处理：Pretreatment of 5# reaction solution:
1)采用薄膜蒸发器对炔化反应制得的5#反应液进行脱盐处理，该薄膜蒸发器的外循环油浴温度为80℃，操作压力为800hPa。5#反应液的组成：无机盐的含量为2.17wt％，水的含量为16.62wt％、2-甲基-3-丁炔-2-醇的含量为75.31wt％、丙酮的含量为4.68wt％、2,5-二甲基-3-己炔-2,5-二醇的含量为0.59wt％、其他组分的含量为0.63wt％。1) The 5# reaction solution obtained by the acetylation reaction was desalted by a thin film evaporator, the temperature of the external circulating oil bath of the thin film evaporator was 80°C, and the operating pressure was 800hPa. The composition of the 5# reaction solution: the content of inorganic salt is 2.17wt%, the content of water is 16.62wt%, the content of 2-methyl-3-butyn-2-ol is 75.31wt%, and the content of acetone is 4.68wt% %, the content of 2,5-dimethyl-3-hexyne-2,5-diol is 0.59wt%, and the content of other components is 0.63wt%.
将5#反应液通入薄膜蒸发器。5#反应液的进料速率为0.950kg/h，薄膜蒸发器上出口的采出速率为0.902kg/h，采出液相组成：水的含量为16.99wt％、2-甲基-3-丁炔-2-醇的含量为76.98wt％、丙酮的含量为4.79wt％、2,5-二甲基-3-己炔-2,5-二醇的含量为0.60wt％、其他组分的含量为0.64wt％，以采出液相各组分的总重量为100wt％计。薄膜蒸发器下出口的采出速率为0.048kg/h。Pass the 5# reaction solution into a thin film evaporator. The feed rate of the 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: the content of water is 16.99wt%, 2-methyl-3- The content of butyn-2-ol is 76.98wt%, the content of acetone is 4.79wt%, the content of 2,5-dimethyl-3-hexyn-2,5-diol is 0.60wt%, other components Its content is 0.64 wt %, calculated on the basis of the total weight of each component of the produced liquid phase as 100 wt %. The extraction rate of the lower outlet of the thin film evaporator is 0.048kg/h.
2)采用板网波纹填料塔对薄膜蒸发器上出口的采出液进行脱丙酮处 理，精馏塔(或填料塔)塔径100mm，填料层高0.5m，理论板数5块，采出液相组成：水的含量为16.99wt％、2-甲基-3-丁炔-2-醇的含量为76.98wt％、丙酮的含量为4.79wt％、2,5-二甲基-3-己炔-2,5-二醇的含量为0.60wt％、其他组分的含量为0.64wt％。2) Deacetone treatment is carried out on the produced liquid at the outlet of the thin-film evaporator by using a corrugated packed tower of plate mesh. The diameter of the rectification tower (or packed tower) is 100 mm, the height of the packing layer is 0.5 m, the number of theoretical plates is 5, and the produced liquid is 100 mm in diameter. Phase composition: the content of water is 16.99wt%, the content of 2-methyl-3-butyn-2-ol is 76.98wt%, the content of acetone is 4.79wt%, 2,5-dimethyl-3-hexyl The content of alkyne-2,5-diol was 0.60 wt %, and the content of other components was 0.64 wt %.
将该采出液从由塔下部第4块理论板处的进料管线进入精馏塔。精馏塔的操作压力为1Kpa。塔顶冷凝器使用10℃冷却水为冷媒，塔底的操作温度为92-93℃。精馏塔塔顶冷凝器流出冷凝液回流与采出比例为3:1。The produced liquid enters the rectification column from the feed line at the fourth theoretical plate in the lower part of the column. The operating pressure of the distillation column is 1Kpa. The top condenser uses 10°C cooling water as the refrigerant, and the operating temperature at the bottom of the tower is 92-93°C. The ratio of reflux and production of the condensate flowing out of the top condenser of the rectification tower is 3:1.
精馏塔塔顶采出液相的组成：水的含量为19.36wt％、2-甲基-3-丁炔-2-醇的含量为46.58wt％、丙酮的含量为33.72wt％、其他组分的含量为0.34wt％，以塔顶采出液相各组分的总重量为100wt％计。The composition of the liquid phase produced at the top of the distillation column: the content of water is 19.36wt%, the content of 2-methyl-3-butyn-2-ol is 46.58wt%, the content of acetone is 33.72wt%, and the other groups The content of the fractions is 0.34 wt %, and the total weight of each component of the liquid phase produced at the top of the tower is 100 wt %.
精馏塔塔底采出液相的组成：水的含量为16.68wt％、2-甲基-3-丁炔-2-醇的含量为80.99wt％、丙酮的含量为0.98wt％、2,5-二甲基-3-己炔-2,5-二醇的含量为0.67wt％、其他组分的含量为0.68wt％，以塔底采出液相各组分的总重量为100wt％计；即，得到2-甲基-3-丁炔-2-醇粗品。The composition of the liquid phase produced at the bottom of the distillation column: the content of water is 16.68wt%, the content of 2-methyl-3-butyn-2-ol is 80.99wt%, the content of acetone is 0.98wt%, 2, The content of 5-dimethyl-3-hexyne-2,5-diol is 0.67wt%, the content of other components is 0.68wt%, and the total weight of each component in the liquid phase extracted from the column bottom is 100wt% Calculation; that is, crude 2-methyl-3-butyn-2-ol was obtained.
对比例2：Comparative Example 2:
如图1所示，该分离和纯化工序包括如下步骤：As shown in Figure 1, the separation and purification process includes the following steps:
(i)将对比例1所得2-甲基-3-丁炔-2-醇粗品1(水16.68wt％、2-甲基-3-丁炔-2-醇80.99wt％、丙酮0.98wt％、2,5-二甲基-3-己炔-2,5-二醇0.67wt％、其他组分0.68wt％)以0.797kg/h的进料流量通入膜分离器SEP，进行膜分离操作，操作温度为95℃。(i) 2-methyl-3-butyn-2-ol crude product 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 0.67wt%, other components 0.68wt%) into the membrane separator SEP at a feed flow rate of 0.797kg/h for membrane separation Operation, the operating temperature is 95 ℃.
膜分离器SEP包括以下部件(图中未画出)：具有循环泵的进料容器、具有亲水膜(CMC-E,Celfa AG，瑞士)的膜渗透单元，通过亲水膜以气态形式除去富含水的渗透物。通过膜分离器分离出含水的有机相流股2(即，渗余物)和水相流股3(即，渗透物)：渗余物流量为0.689kg/h，其包含约93.63wt％的2-甲基-3-丁炔-2-醇、3.90wt％的水、0.92wt％的丙酮、0.79wt％的2,5-二甲基-3-己炔-2,5-二醇以及0.76wt％的其他杂质，以渗余物各组分的总重量为100wt％计；渗透物流量为0.108kg/h，其包含约0.31wt％的2-甲基-3-丁炔-2-醇、1.34wt％的丙酮、0.18wt％的其他杂质以及剩余的为水，以渗透物各组分的总重量为100wt％计。The membrane separator SEP consists of the following components (not shown in the figure): a feed vessel with a circulating pump, a membrane permeation unit with a hydrophilic membrane (CMC-E, Celfa AG, Switzerland), which is removed in gaseous form by a hydrophilic membrane Water-rich permeate. Aqueous organic phase stream 2 (ie, retentate) and aqueous phase stream 3 (ie, permeate) were separated by a membrane separator: the retentate flow rate was 0.689 kg/h, which contained 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-hexyn-2,5-diol and 0.76 wt% of other impurities, based on the total weight of the retentate components as 100 wt%; the permeate flow was 0.108 kg/h, which contained about 0.31 wt% of 2-methyl-3-butyne-2- Alcohol, 1.34 wt% acetone, 0.18 wt% other impurities and the remainder water, based on the total weight of the permeate components as 100 wt%.
(ii)将所得含水的有机相流股2(即，渗余物)以0.689kg/h的流速从由塔下部第10块理论板处的进料管线进入粗精馏塔RAC1，该粗精馏塔采用板网波纹填料塔，塔径100mm，填料层高2m，理论板数15块。粗精馏塔的操作压力为100hPa。塔顶冷凝器COOLER1使用10℃冷却水为冷媒，塔底再沸器REBOILER1实现对塔底温度的调控，塔底的操作温度为119-120℃。粗精馏塔塔顶冷凝器流出冷凝液回流与采出比例为1:1，塔顶的操作温度为42-43℃，塔顶釆出轻组分流股4，采出流速为0.0878kg/h。粗精馏塔塔顶采出液相的组成：水的含量为25.35wt％、丙酮的含量为7.24wt％、2-甲基-3-丁炔-2-醇的含量为67.41wt％，以塔顶釆出液相各组分的总重量为100wt％计。(ii) The resulting aqueous organic phase stream 2 (ie, retentate) was fed into the crude rectification column RAC1 from the feed line at the 10th theoretical plate in the lower part of the column at a flow rate of 0.689 kg/h. The distillation column adopts the corrugated packing column of plate mesh, the diameter of the column is 100mm, the height of the packing layer is 2m, and the number of theoretical plates is 15. The operating pressure of the crude distillation column was 100 hPa. The column top condenser COOLER1 uses 10 ℃ cooling water as the refrigerant, and the column bottom reboiler REBOILER1 realizes the regulation of the column bottom temperature, and the operating temperature of the column bottom is 119-120 ℃. The ratio of reflux and extraction of the condensate flowing out of the top condenser of the crude rectification tower is 1:1, the operating temperature at the top of the column is 42-43 ° C, and the top of the column is drawn with a light component stream 4, and the extraction flow rate is 0.0878kg/h . The composition of the liquid phase produced at the top of the crude distillation tower: the content of water is 25.35wt%, the content of acetone is 7.24wt%, and the content of 2-methyl-3-butyn-2-ol is 67.41wt%, with The total weight of each component in the liquid phase extracted from the top of the column is calculated as 100 wt %.
粗精馏塔塔底以0.6012kg/h的流速采出待脱重组分流股5，并进入产品分离塔。粗精馏塔塔底釆出液相的组成：水的含量为0.76wt％、2-甲基-3-丁炔-2-醇的含量为97.46wt％、2,5-二甲基-3-己炔-2,5-二醇的含量为0.91wt％、其他组分的含量为0.87wt％，以塔底釆出液相各组分的总重量为100wt％计。At the bottom of the crude rectification tower, a flow rate of 0.6012kg/h is taken out of the fractional stream 5 to be removed and entered into the product separation tower. The composition of the liquid phase at the bottom of the crude distillation column: the content of water is 0.76wt%, the content of 2-methyl-3-butyn-2-ol is 97.46wt%, the content of 2,5-dimethyl-3 The content of -hexyne-2,5-diol is 0.91 wt %, and the content of other components is 0.87 wt %, and the total weight of each component in the liquid phase extracted from the bottom of the tower is 100 wt %.
(iii)粗精馏塔的塔底釆出的待脱重组分流股5，从产品分离塔RAC2的塔中部进入；产品分离塔采用板网波纹填料塔，塔径100mm，填料层高1m，理论板数7块，粗精馏塔塔底液由第4块理论板处的进料管线进入产品分离塔。产品分离塔的操作压力为100hPa。塔顶冷凝器COOLER2使用10℃冷却水为冷媒，塔底再沸器REBOILER2实现对塔底温度的调控，塔底的操作温度为119-120℃。塔顶冷凝器流出冷凝液回流与采出比例为1:1，塔顶的操作温度为53-54℃，塔顶采出产物流股6，其采出流速为0.5736kg/h。产品分离塔塔顶的采出液相组成：水的含量为0.80％、2-甲基-3-丁炔-2-醇的含量为99.18wt％、2,5-二甲基-3-己炔-2,5-二醇的含量为0.01wt％、其他组分的含量为0.01wt％，以塔顶釆出液相各组分的总重量为100wt％计。(iii) the fractional stream 5 to be taken off at the bottom of the crude rectifying tower, enters from the middle of the tower of the product separation tower RAC2; The number of plates is 7, and the crude distillation column bottom liquid enters the product separation column from the feed line at the fourth theoretical plate. The operating pressure of the product separation column was 100 hPa. The column top condenser COOLER2 uses 10 ℃ cooling water as the refrigerant, and the column bottom reboiler REBOILER2 realizes the regulation of the column bottom temperature, and the operating temperature of the column bottom is 119-120 ℃. The ratio of reflux and production of the condensate flowing out of the tower top condenser is 1:1, the operating temperature of the tower top is 53-54°C, and the product stream 6 is produced from the top of the tower, and its production flow rate is 0.5736kg/h. Composition of the produced liquid phase at the top of the product separation tower: the content of water is 0.80%, the content of 2-methyl-3-butyn-2-ol is 99.18wt%, 2,5-dimethyl-3-hexanol The content of alkyne-2,5-diol is 0.01wt%, the content of other components is 0.01wt%, and the total weight of each component in the liquid phase extracted from the top of the column is 100wt%.
产品分离塔塔底以0.0276kg/h的流速采出重组分流股7，产品分离塔塔底的釆出液相组成：2-甲基-3-丁炔-2-醇的含量为61.32wt％、2,5-二甲基-3-己炔-2,5-二醇的含量为19.61wt％、其他组分的含量为19.07wt％，以塔底釆出液相各组分的总重量为100wt％计。At the bottom of the product separation tower, the reorganization branch 7 is extracted at a flow rate of 0.0276kg/h, and the liquid phase composition at the bottom of the product separation tower is: 2-methyl-3-butyn-2-ol is 61.32wt% , the content of 2,5-dimethyl-3-hexyne-2,5-diol is 19.61wt%, the content of other components is 19.07wt%, and the total weight of each component in the liquid phase is obtained from the bottom of the tower 100% by weight.
产品分离塔的塔顶采出液，即所得产品2-甲基-3-丁炔-2-醇，测得其折射率：n20/D 1.4500，色号：35(Pt-Co)。The produced liquid at the top of the product separation tower, namely the obtained product 2-methyl-3-butyn-2-ol, measured its refractive index: n20/D 1.4500, color number: 35 (Pt-Co).
包含膜分离器的膜渗透单元持续进料710小时后，压力波动异常，有堵塞现象。堵塞的出现会影响分离所得产品2-甲基-3-丁炔-2-醇的纯度及其折射率和色号。After the membrane permeation unit including the membrane separator was continuously fed for 710 hours, the pressure fluctuated abnormally, and there was clogging. The presence of clogging will affect the purity of the isolated product 2-methyl-3-butyn-2-ol, as well as its refractive index and color number.
从实施例1与对比例1的实验结果可知，通过在制备过程的体系内添加二价金属盐，可以有效抑制反应过程中副产物2,5-二甲基-3-己炔-2,5-二醇的生成，进而控制所得反应液中2,5-二甲基-3-己炔-2,5-二醇的含量在较低范围内(≤0.1wt％)，提高了产物选择性。From the experimental results of Example 1 and Comparative Example 1, it can be seen that by adding a divalent metal salt in the system of the preparation process, the by-product 2,5-dimethyl-3-hexyne-2,5 in the reaction process can be effectively suppressed - the formation of diol, and then control the content of 2,5-dimethyl-3-hexyne-2,5-diol in the obtained reaction solution to a lower range (≤0.1wt%), which improves the product selectivity .
从实施例2与实施例3的实验结果可知，在同等的丙酮与乙炔摩尔比条件下，随着添加的二价金属盐用量降低，副产物2,5-二甲基-3-己炔-2,5-二醇的含量上升，说明体系中二价金属盐的加入量可以调控所得反应液中2,5-二甲基-3-己炔-2,5-二醇的含量。另外，实施例2-3选用的二价金属盐为乙酸锌，作为优选的二价金属盐种类，其在降低副产物2,5-二甲基-3-己炔-2,5-二醇含量的效果上更明显。It can be seen from the experimental results of Example 2 and Example 3 that under the same molar ratio of acetone and acetylene, as the amount of added divalent metal salt decreases, the by-product 2,5-dimethyl-3-hexyne- The content of 2,5-diol increased, indicating that the addition amount of divalent metal salt in the system could regulate the content of 2,5-dimethyl-3-hexyne-2,5-diol in the obtained reaction solution. In addition, the divalent metal salt selected in Example 2-3 is zinc acetate, and as the preferred divalent metal salt species, it reduces the by-product 2,5-dimethyl-3-hexyne-2,5-diol The effect of content is more obvious.
从实施例1～3与实施例4的实验结果可知，炔化反应过程中较低的乙炔比例不利于控制2,5-二甲基-3-己炔-2,5-二醇的含量，就需要添加更大剂量的二价金属盐。From the experimental results of Examples 1 to 3 and Example 4, it can be seen that the lower acetylene ratio during the alkylation reaction is not conducive to controlling the content of 2,5-dimethyl-3-hexyne-2,5-diol, It is necessary to add larger doses of divalent metal salts.
从实施例9～12的实验结果可知，分离过程中，通过控制含有2-甲基-3-丁炔-2-醇的反应液中关键组分2,5-二甲基-3-己炔-2,5-二醇含量，可提高膜分离处理中所用渗透膜寿命；例如，2-甲基-3-丁炔-2-醇粗品中2,5-二甲基-3-己炔-2,5-二醇的含量低于0.10wt％，则膜分离器运行2000h以上都无需更换渗透膜。From the experimental results of Examples 9 to 12, it can be seen that during the separation process, by controlling the key component 2,5-dimethyl-3-hexyne in the reaction solution containing 2-methyl-3-butyn-2-ol -2,5-diol content, which increases the lifetime of permeable membranes used in membrane separation processes; for example, 2,5-dimethyl-3-hexyn- If the content of 2,5-diol is lower than 0.10 wt %, the membrane separator does not need to replace the permeable membrane when it runs for more than 2000 hours.
而从对比例2中可看出，当反应液中副产物含量较高，即，2-甲基-3-丁炔-2-醇粗品中2,5-二甲基-3-己炔-2,5-二醇的含量提高至0.67wt％，膜分离处理中所用渗透膜的寿命缩短到710h，运行成本提高。说明含有2-甲基-3-丁炔-2-醇的反应液中关键组分2,5-二甲基-3-己炔-2,5-二醇含量大于0.10wt％时，会对膜分离处理产生不利影响。It can be seen from Comparative Example 2 that when the content of by-products in the reaction solution is high, that is, 2,5-dimethyl-3-hexyn-2-ol in the crude 2-methyl-3-butyn-2-ol The content of 2,5-diol is increased to 0.67wt%, the lifespan of the permeable membrane used in the membrane separation treatment is shortened to 710h, and the operating cost is increased. Explain that when the content of the key component 2,5-dimethyl-3-hexyn-2,5-diol in the reaction solution containing 2-methyl-3-butyn-2-ol is greater than 0.10wt%, it will affect the Membrane separation treatment adversely affects.
以上已经描述了本发明的各实施例，上述说明是示例性的，并非穷尽性的，并且也不限于所披露的各实施例。在不偏离所说明的各实施例的范围和精神的情况下，对于本技术领域的普通技术人员来说许多修改和变更都是显而易见的。Various embodiments of the present invention have been described above, and the foregoing descriptions are exemplary, not exhaustive, and not limiting of the disclosed embodiments. Numerous modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.

Claims (11)

  1. 一种2-甲基-3-丁炔-2-醇的分离方法，其特征在于，包括：A kind of separation method of 2-methyl-3-butyn-2-ol, is characterized in that, comprises:
    (1)预处理工序：将含有2-甲基-3-丁炔-2-醇的反应液进行预处理，除去其中未反应的丙酮和含有的盐，得到2-甲基-3-丁炔-2-醇粗品；所述含有2-甲基-3-丁炔-2-醇的反应液中，控制2,5-二甲基-3-己炔-2,5-二醇的含量≤0.1wt％，优选≤0.06wt％；(1) Pretreatment step: The reaction solution containing 2-methyl-3-butyn-2-ol is pretreated to remove unreacted acetone and salts contained therein to obtain 2-methyl-3-butyne -2-ol crude product; in the reaction solution containing 2-methyl-3-butyn-2-ol, control the content of 2,5-dimethyl-3-hexyn-2,5-diol≤ 0.1wt%, preferably ≤0.06wt%;
    (2)分离和纯化工序：通过膜分离处理和减压精馏处理，对所述2-甲基-3-丁炔-2-醇粗品进行分离和纯化，得到2-甲基-3-丁炔-2-醇产品。(2) Separation and purification process: The crude 2-methyl-3-butyn-2-ol is separated and purified by membrane separation treatment and vacuum distillation treatment to obtain 2-methyl-3-butane Alkyn-2-ol products.
  2. 根据权利要求1所述的分离方法，其特征在于，所述分离方法包括如下步骤：The separation method according to claim 1, wherein the separation method comprises the steps of:
    (1)预处理工序：将所述含有2-甲基-3-丁炔-2-醇的反应液通过精馏处理脱除丙酮以及通过蒸馏或精馏处理脱盐后，得到2-甲基-3-丁炔-2-醇粗品；(1) Pretreatment step: after the reaction solution containing 2-methyl-3-butyn-2-ol is subjected to rectification to remove acetone and to desalination through distillation or rectification, 2-methyl- 3-butyn-2-ol crude product;
    所述2-甲基-3-丁炔-2-醇粗品中，水的含量在10wt％～40wt％，丙酮的含量≤1wt％，2,5-二甲基-3-己炔-2,5-二醇的含量≤0.1wt％；In the crude 2-methyl-3-butyn-2-ol, the content of water is 10wt% to 40wt%, the content of acetone is less than or equal to 1wt%, 2,5-dimethyl-3-hexyn-2, The content of 5-diol≤0.1wt%;
    (2)分离和纯化工序：将所述2-甲基-3-丁炔-2-醇粗品进行膜分离处理，得到含有2-甲基-3-丁炔-2-醇的混合物，其中，水的含量≤5％；再将所述含有2-甲基-3-丁炔-2-醇的混合物进行减压精馏处理，得到2-甲基-3-丁炔-2-醇产品，其中，水的含量≤1wt％；(2) Separation and purification process: subjecting the crude 2-methyl-3-butyn-2-ol to membrane separation to obtain a mixture containing 2-methyl-3-butyn-2-ol, wherein, The water content is less than or equal to 5%; then the mixture containing 2-methyl-3-butyn-2-ol is subjected to vacuum distillation to obtain a 2-methyl-3-butyn-2-ol product, Wherein, the content of water is less than or equal to 1wt%;
    优选地，步骤(2)所述2-甲基-3-丁炔-2-醇产品中，2,5-二甲基-3-己炔-2,5-二醇的含量≤0.01wt％。Preferably, in the 2-methyl-3-butyn-2-ol product of step (2), the content of 2,5-dimethyl-3-hexyn-2,5-diol is less than or equal to 0.01wt% .
  3. 根据权利要求1或2所述的分离方法，其特征在于，步骤(2)所述膜分离处理中，使用至少一个用于将水与2-甲基-3-丁炔-2-醇进行分离的膜分离器；所述膜分离器中设有亲水膜；The separation method according to claim 1 or 2, characterized in that, in the membrane separation treatment of step (2), at least one membrane for separating water and 2-methyl-3-butyn-2-ol is used. The membrane separator; the membrane separator is provided with a hydrophilic membrane;
    优选地，所述亲水膜选自聚乙烯醇膜、聚酰亚胺膜或陶瓷膜，更优选为聚乙烯醇膜或聚酰亚胺膜；Preferably, the hydrophilic film is selected from polyvinyl alcohol film, polyimide film or ceramic film, more preferably polyvinyl alcohol film or polyimide film;
    优选地，使用所述亲水膜进行膜分离处理的操作温度大于等于0℃ 且小于等于100℃。Preferably, the operating temperature of the membrane separation treatment using the hydrophilic membrane is greater than or equal to 0°C and less than or equal to 100°C.
  4. 根据权利要求1-3中任一项所述的分离方法，其特征在于，步骤(2)的操作过程包括：The separation method according to any one of claims 1-3, wherein the operation process of step (2) comprises:
    (i)将所述2-甲基-3-丁炔-2-醇粗品通过膜分离器进行处理，分离出含水的有机相流股和水相流股；其中，所述含水的有机相流股中，水的含量≤5wt％，2-甲基-3-丁炔-2-醇的含量≥90wt％；所述水相流股中，水的含量≥95wt％，2-甲基-3-丁炔-2-醇的含量≤1wt％；(i) processing the crude 2-methyl-3-butyn-2-ol through a membrane separator to separate an aqueous organic phase stream and an aqueous phase stream; wherein, the aqueous organic phase stream In the strand, the content of water is ≤5wt%, and the content of 2-methyl-3-butyn-2-ol is ≥90wt%; in the water-phase stream, the content of water is ≥95wt%, and the content of 2-methyl-3 -The content of butyn-2-ol≤1wt%;
    (ii)将所述含水的有机相流股进入粗精馏塔进行处理，粗精馏塔的塔顶采出轻组分流股，所述轻组分流股中，水的含量为5wt％～30wt％；粗精馏塔的塔底采出待脱重组分流股，所述待脱重组分流股中，水的含量≤1wt％；(ii) entering the water-containing organic phase stream into a crude rectification tower for processing, and extracting a light component stream from the top of the crude rectification tower, and in the light component stream, the content of water is 5wt%～30wt% %; the sub-stream to be de-recombined is extracted from the bottom of the crude rectification tower, and the water content in the sub-stream to be de-recombined is less than or equal to 1wt%;
    (iii)将所述待脱重组分流股进入产品分离塔进行处理，产品分离塔的塔顶采出产物流股；所述产物流股中，2-甲基-3-丁炔-2-醇的含量≥99wt％，水的含量≤1wt％，2,5-二甲基-3-己炔-2,5-二醇的含量≤0.01wt％；产品分离塔的塔底采出重组分流股，所述重组分流股中，2-甲基-3-丁炔-2-醇的含量≤70wt％；(iii) entering the product separation tower into the product separation column for processing, and extracting the product stream from the top of the product separation column; in the product stream, the 2-methyl-3-butyn-2-ol Content ≥ 99wt%, water content≤1wt%, 2,5-dimethyl-3-hexyne-2,5-diol content≤0.01wt%; the reorganized stream is extracted from the bottom of the product separation tower, In the reconstituted stream, the content of 2-methyl-3-butyn-2-ol≤70wt%;
    优选地，所述待脱重组分流股从产品分离塔的塔中部进入。Preferably, the to-be-recombined split stream enters from the middle of the product separation column.
  5. 根据权利要求4所述的分离方法，其特征在于，所述粗精馏塔的精馏段理论塔板数≥5块，优选为10-15块；The separation method according to claim 4, wherein the number of theoretical plates in the rectifying section of the crude rectifying column is ≥ 5, preferably 10-15;
    优选地，所述粗精馏塔的操作压力为50hPa～300hPa，更优选为100hPa～200hPa；所述粗精馏塔的塔釜操作温度为100℃～130℃，更优选为110℃～125℃。Preferably, the operating pressure of the crude rectification tower is 50hPa～300hPa, more preferably 100hPa～200hPa; the operating temperature of the tower kettle of the crude rectification tower is 100℃～130℃, more preferably 110℃～125℃ .
  6. 根据权利要求4所述的分离方法，其特征在于，所述产品分离塔的理论塔板数≥5块，优选为10-15块；The separation method according to claim 4, wherein the number of theoretical plates of the product separation tower is ≥ 5, preferably 10-15;
    优选地，所述产品分离塔的操作压力为50hPa～300hPa，更优选为100hPa～200hPa；所述产品分离塔的塔釜操作温度为100℃～130℃，更优选为110℃～125℃。Preferably, the operating pressure of the product separation tower is 50hPa～300hPa, more preferably 100hPa～200hPa; the operating temperature of the tower kettle of the product separation tower is 100°C～130°C, more preferably 110°C～125°C.
  7. 根据权利要求1-6中任一项所述的分离方法，其特征在于，经分离和纯化工序后，所得2-甲基-3-丁炔-2-醇产品中水的含量≤1wt％且2,5-二甲基-3-己炔-2,5-二醇的含量≤0.01wt％。The separation method according to any one of claims 1-6, characterized in that, after the separation and purification process, the water content in the obtained 2-methyl-3-butyn-2-ol product is less than or equal to 1wt% and The content of 2,5-dimethyl-3-hexyne-2,5-diol≤0.01wt%.
  8. 根据权利要求1-7中任一项所述的分离方法，其特征在于，所述含有2-甲基-3-丁炔-2-醇的反应液通过包含如下步骤的方法制得：The separation method according to any one of claims 1-7, wherein the reaction solution containing 2-methyl-3-butyn-2-ol is prepared by a method comprising the following steps:
    使用强碱作为催化剂，将丙酮、乙炔和二价金属盐在液氨中混合进行反应；反应结束后，加入弱酸性水溶液对体系中的催化剂进行中和，制备得到含有2-甲基-3-丁炔-2-醇的反应液；所述含有2-甲基-3-丁炔-2-醇的反应液中，2,5-二甲基-3-己炔-2,5-二醇的含量≤0.1wt％。Using a strong base as a catalyst, acetone, acetylene and a divalent metal salt are mixed in liquid ammonia for reaction; after the reaction is completed, a weakly acidic aqueous solution is added to neutralize the catalyst in the system to prepare a product containing 2-methyl-3- The reaction solution of butyn-2-ol; in the reaction solution containing 2-methyl-3-butyn-2-ol, 2,5-dimethyl-3-hexyn-2,5-diol The content of ≤0.1wt%.
  9. 根据权利要求8所述的分离方法，其特征在于，所述二价金属盐选自二价锌盐、二价镁盐和二价钴盐中的一种或多种，优选为乙酸锌、硫酸镁和氯化钴中的一种或多种，进一步优选为乙酸锌和/或硫酸镁，更优选为乙酸锌。The separation method according to claim 8, wherein the divalent metal salt is selected from one or more of divalent zinc salt, divalent magnesium salt and divalent cobalt salt, preferably zinc acetate, sulfuric acid One or more of magnesium and cobalt chloride, more preferably zinc acetate and/or magnesium sulfate, more preferably zinc acetate.
  10. 根据权利要求8或9所述的分离方法，其特征在于，所述二价金属盐的用量为丙酮质量的0.01％～0.1％，优选为0.02％～0.05％。The separation method according to claim 8 or 9, wherein the amount of the divalent metal salt is 0.01%-0.1% of the mass of acetone, preferably 0.02%-0.05%.
  11. 根据权利要求8-10中任一项所述的分离方法，其特征在于，所述乙炔与丙酮的摩尔比大于等于1:1且小于等于3:1，优选为1.05:1～2:1。The separation method according to any one of claims 8-10, 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 1.05:1 to 2:1.
PCT/CN2020/103014 2020-07-20 2020-07-20 Separation method for 2-methyl-3-butyne-2-ol WO2022016317A1 (en)

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GB705670A (en) * 1949-12-30 1954-03-17 Gen Aniline & Film Corp Dehydrating aqueous propynol by azeotropic distillation
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CN104045518A (en) * 2014-05-15 2014-09-17 四川泸州巨宏化工有限责任公司 Preparation method of 2-methyl-3-butyne-2-ol
CN104470879A (en) * 2012-07-11 2015-03-25 隆萨有限公司 Process for the production of methylbutinol
CN106117010A (en) * 2016-06-29 2016-11-16 西南化工研究设计院有限公司 A kind of acetylene synthesizes the new technology of alkynol with ketone compounds
CN207418630U (en) * 2017-10-31 2018-05-29 西南化工研究设计院有限公司 A kind of system of coproducing methyl butynol and dimethylhexyne glycol

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB705670A (en) * 1949-12-30 1954-03-17 Gen Aniline & Film Corp Dehydrating aqueous propynol by azeotropic distillation
CN102701911A (en) * 2011-03-28 2012-10-03 河北百灵威超精细材料有限公司 A method for purification and enhanced stability of alkynol compounds
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