CN114849637A - Device and method capable of continuously reacting and purifying isosorbide - Google Patents

Device and method capable of continuously reacting and purifying isosorbide Download PDF

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Publication number
CN114849637A
CN114849637A CN202210685993.5A CN202210685993A CN114849637A CN 114849637 A CN114849637 A CN 114849637A CN 202210685993 A CN202210685993 A CN 202210685993A CN 114849637 A CN114849637 A CN 114849637A
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isosorbide
product
reaction
evaporator
unit
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张凯亮
聂毅
孟祥磊
余敏
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Zhengzhou Institute of Emerging Industrial Technology
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Zhengzhou Institute of Emerging Industrial Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2415—Tubular reactors
    • B01J19/242—Tubular reactors in series
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D1/00—Evaporating
    • B01D1/22—Evaporating by bringing a thin layer of the liquid into contact with a heated surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D1/00—Evaporating
    • B01D1/28—Evaporating with vapour compression
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/14—Fractional distillation or use of a fractionation or rectification column
    • B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D36/00—Filter circuits or combinations of filters with other separating devices
    • B01D36/04—Combinations of filters with settling tanks
    • B01D36/045—Combination of filters with centrifugal separation devices
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D9/00—Crystallisation
    • B01D9/0059—General arrangements of crystallisation plant, e.g. flow sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
    • B01J4/007—Feed or outlet devices as such, e.g. feeding tubes provided with moving parts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D9/00—Crystallisation
    • B01D2009/0086—Processes or apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00004—Scale aspects
    • B01J2219/00006—Large-scale industrial plants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00027—Process aspects
    • B01J2219/00033—Continuous processes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

The invention belongs to the field of chemistry and chemical engineering, relates to a device and a method for purifying isosorbide, and particularly relates to a device and a method for purifying isosorbide through continuous reaction. The device comprises a reaction unit, a dehydration unit, a product separation unit and a product refining unit. The method comprises the following steps: sorbitol and a solvent are mixed and then enter a tubular reactor, the solvent is recovered by an evaporator to prepare isosorbide, and the obtained product is refined, crystallized and separated to obtain high-purity isosorbide. The invention has the advantages that: the tubular reactor is adopted for reaction, the first-stage evaporator is used for dehydration, and the second-stage evaporator is used for extraction, so that continuous reaction and rapid separation of products are realized. The method has the advantages of low production cost, mild reaction conditions, short production time effect and simple operation process, and the yield of the isosorbide is more than or equal to 86 percent and can reach 90 percent at most, the purity is more than or equal to 95 percent and can reach 99.9 percent at most. Reaches the standard of pharmacopoeia WS1- (X-379) -2004Z and is suitable for industrial production.

Description

Device and method capable of continuously reacting and purifying isosorbide
Technical Field
The invention belongs to the field of chemistry and chemical engineering, relates to a device and a method for purifying isosorbide, and particularly relates to a device and a method for purifying isosorbide through continuous reaction.
Background
Isosorbide is a secondary dehydration product of sorbitol, is known as an important bio-based chemical raw material in the future, and is widely applied to the fields of food, cosmetics, plastics, medicines and the like. The isosorbide has obvious medicinal value, is an effective osmotic oral dehydration diuretic and is also a raw material for preparing the cardiovascular drug isosorbide mononitrate.
The research of people in the field of isosorbide preparation is influenced to a certain extent due to the relatively small medicine market. With the increasing exhaustion of world energy resources and the improvement of the quality requirements of people on artificial polymer substances, people find the unique effect of improving the polymer property of isosorbide in research, can be used for modifying polymers such as polyether, polyester, polyurethane, polycarbonate and the like, and the high-temperature performance and the impact resistance of the polymer can be obviously improved by the participation of isosorbide in polymerization, so that the material is endowed with optical transparency and biodegradability. The wide application of isosorbide further promotes the research of producing isosorbide by taking sorbitol as a raw material, and the raw material sorbitol is prepared by hydrogenating glucose, so that the source is rich and the price is low; isosorbide is the only bio-based diol which can be industrially produced, so that the future market prospect is wide.
CN201711269617.3 discloses a product preparation and separation system for by-product boiling point lower than that of the product and raw material, a processing method and application thereof, the system adopts liquid acid catalyst and sorbitol raw material to react in a membrane reactor, and finally isosorbide is obtained by purification in a rectifying tower. Although the method realizes continuous operation, the whole reaction process is carried out in a membrane reactor by utilizing the principle of liquid sedimentation, so that the reaction is carried out while water is evaporated in the reaction process, and manual intervention cannot be carried out, so that the reaction controllability is poor, the operation elasticity is small, and the sufficiency of the reaction cannot be ensured; although the high-purity refined isosorbide is obtained by adopting sectional type rectification, the energy consumption of a rectifying tower is high, and the yield of the isosorbide is to be improved. Therefore, the method has great difficulty in realizing industrialization.
CN143061A discloses a continuous method for preparing anhydrosugar alcohol and a reactor used by the same, wherein the method adopts 70% sorbitol aqueous solution and sulfuric acid, nitrogen is introduced into the reactor for reaction, and finally, the product isosorbide is obtained through distillation and melt recrystallization. The method has low raw material cost investment, but the whole process is intermittent operation, and the production efficiency is low.
CN108129488A discloses a method for catalyzing sorbitol to be hydrogenated and dehydrated, which adopts hydrogen as reaction gas, and sorbitol aqueous solution with the content of 50 percent is introduced into a fixed bed reactor to be hydrogenated and dehydrated to prepare isosorbide. Although the method adopts the heterogeneous catalyst to avoid the corrosion of the liquid acid catalyst to equipment, the content of the neutralized water in the raw materials is too high, so that the dehydration rate is slow, the conversion rate of the sorbitol is only 68.2 percent, the selectivity of the isosorbide is only 45 percent, the utilization rate of the raw materials in the whole process is low, the production efficiency is low, and the method is not suitable for industrial production.
CN109369666A discloses a method for synthesizing isosorbide by using solid acid, which takes sorbitol solution as raw material and composite solid acid as catalyst, and catalyzes sorbitol to synthesize isosorbide by two-step dehydration reaction. The method has the advantages that the molar yield of the isosorbide can reach 87.21%, but the process flow cannot continuously prepare the isosorbide, the production efficiency is low, and the economic benefit is not ideal.
CN107141301A discloses a method for preparing crystalline isosorbide, which comprises the steps of preparing an isosorbide reaction solution by a melting method, then diluting with pure water, filtering, treating an isosorbide mixed solution by a device for decoloring, deionizing and separating a mixture, crystallizing by a normal-temperature water phase method, and drying to obtain the isosorbide. The content of the isosorbide obtained by the method is more than 98 percent, the preparation process is free of acid-base catalysis, but the whole process is intermittent production, the production efficiency is low, the productivity is low, the requirement on the precision of the device is high, and the method is only suitable for small-batch production.
CN104788465A discloses a process for preparing isosorbide, which uses a plug flow reactor to prepare an isosorbide reaction solution, and uses a rectifying tower to purify the isosorbide reaction solution to obtain the product isosorbide.
Therefore, the method realizes industrial production on the basis of ensuring the purity of the isosorbide, solves the problems of high energy consumption, resource waste, environmental pollution and the like, and is a difficult problem to overcome urgently at present.
Disclosure of Invention
Aiming at the technical problems of low production efficiency, poor controllability and incapability of realizing continuous production in the prior art, the invention provides a device and a method for purifying isosorbide by continuous reaction. Through the continuous reaction purification device, the solvent is recycled in the production process, the problems that the production efficiency of the isosorbide is low, the raw materials cannot be fully utilized, the energy consumption is high, the environmental pollution in the production process is serious and the like in the prior art are practically solved, and the purpose of efficiently producing the isosorbide is realized.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a device capable of continuously reacting and purifying isosorbide comprises a reaction unit, a dehydration unit, a product separation unit and a product refining unit, wherein the reaction unit is connected with the dehydration unit, the dehydration unit is connected with the product separation unit, and the product separation unit is connected with the product refining unit; wherein the reaction unit comprises a stirring kettle and a tubular reactor; the dehydration unit comprises a primary evaporator, a dehydration condenser, a dehydration collection tank and an oil-water separator; the product separation unit comprises a secondary evaporator, a product condenser and a product collecting tank; the product refining unit includes a mixing tank and a centrifuge.
Further, the bottom of the stirring kettle of the reaction unit is connected with the bottom of the tubular reactor through a pipeline; the top of the first-stage evaporator is provided with a first-stage evaporator gas-phase discharge port, and the bottom of the first-stage evaporator is provided with a first-stage evaporator liquid-phase discharge port; the top of the tubular reactor is connected with a primary evaporator, a gas phase discharge port of the primary evaporator is connected with an inlet of a dehydration condenser, a liquid phase discharge port of the primary evaporator is connected with a secondary evaporator, and an outlet of the dehydration condenser is connected with an inlet of a dehydration collection tank; the oil-water separator is provided with an oil-water separator water phase discharge port and an oil-water separator oil phase discharge port, the outlet of the dehydration collection tank is connected with the inlet of the oil-water separator, the oil-water separator water phase discharge port is connected with the waste liquid pipeline, and the oil-water separator oil phase discharge port is connected with the inlet of the stirred tank; second grade evaporimeter top is equipped with second grade evaporimeter gaseous phase discharge gate, the bottom is equipped with second grade evaporimeter liquid phase discharge gate, second grade evaporimeter gaseous phase discharge gate links to each other with the import of product condenser, the export of product condenser links to each other with the product holding tank, the product holding tank links to each other with blending tank import I, blending tank bottom export links to each other with the centrifuge import, centrifuge bottom export I links to each other with the product collecting pipeline, centrifuge export II links to each other with blending tank import II through crystallization solvent ejection of compact pipeline, second grade evaporimeter liquid phase discharge gate links to each other with reaction unit stirred tank raw materials charge-in pipeline.
Further, a heating device is arranged in the stirring kettle.
Further, the first-stage evaporator and the second-stage evaporator are membrane evaporators.
Further, the membrane evaporator is any one or combination of two of a falling-film evaporator, a rising-film evaporator and a wiped-film evaporator.
Further, the centrifuge comprises any one of a filter centrifuge, a scraper centrifuge, a horizontal screw centrifuge or a three-leg centrifuge or a combination of two of the two.
Preferably, sorbitol is in a powder state, and needs to be heated in a stirring kettle to be heated to melt the sorbitol into a liquid state, and then enters the tubular reactor together with a specific solvent. In the present invention, the heating method is not particularly limited, and examples thereof include electric heating, heating with a heat transfer medium, and the like, and the heat transfer medium includes, but is not limited to, any one of heat transfer oil, steam, and molten salt.
Preferably, the isosorbide reaction is an endothermic reaction, and a heating device is arranged in the tubular reactor, and the heating method is not particularly limited in the invention, and any one or any combination of two of electric heating, steam heat exchange, molten salt heat exchange and heat transfer oil heat exchange can be listed.
Preferably, the first-stage evaporator is provided with a heating device, the heating mode is not particularly limited in the invention, and one or any two combination of electric heating, steam heat exchange, molten salt heat exchange and heat transfer oil heat exchange can be listed.
Preferably, the second-stage evaporator is provided with a heating device, the heating mode is not particularly limited in the invention, and one or any two combination of electric heating, steam heat exchange, molten salt heat exchange and heat transfer oil heat exchange can be listed.
Further, according to the continuous reaction purification method of the device capable of purifying isosorbide by continuous reaction, after sorbitol is mixed with a reaction solvent, isosorbide is prepared by the continuous reaction purification device, and the steps are as follows:
s1: tubular reaction: preheating a tubular reactor in advance, then feeding sorbitol, a catalyst and a reaction solvent into a stirring kettle according to a feeding ratio of a mass ratio, heating, discharging internal materials from the bottom of the stirring kettle in a molten state, feeding the internal materials into the tubular reactor for reaction, and after the reaction is finished, discharging the materials from the tubular reactor and feeding the materials into a dehydration unit;
s2: and (3) dehydrating: feeding the material obtained in the step S1 from the top of a primary evaporator of a dehydration unit, evaporating in the primary evaporator, wherein gas-phase materials mainly comprise solvent and water, condensing the gas-phase materials from a gas-phase discharge port of the primary evaporator through a dehydration condenser and then feeding the condensed gas-phase materials into a dehydration collection tank, discharging liquid-phase materials from the bottom of the dehydration collection tank and feeding the liquid-phase materials into an oil-water separator of a product separation unit, and realizing oil-water separation through interface control, wherein oil-phase solvent is circularly returned to a stirring kettle in a reaction unit through an oil-phase discharge port of the oil-water separator, and water-phase materials enter a waste liquid pipeline from a water-phase discharge port of the oil-water separator to be treated with waste liquid;
s3: product separation: discharging the liquid-phase material in the primary condenser obtained in the step S2 from a liquid-phase discharge port of the primary evaporator, feeding the liquid-phase material from the top of a secondary evaporator of the product separation unit, and evaporating the liquid-phase material in the secondary evaporator, wherein the gas-phase material mainly comprises crude isosorbide, the liquid-phase material is discharged from a gas-phase discharge port of the secondary evaporator, condensed into a liquid phase by the product condenser, enters a product collection tank, discharged from the bottom of the product collection tank and enters a product refining unit, and the liquid-phase material in the secondary evaporator is discharged from the bottom and enters a reaction unit stirring kettle to participate in production again;
s4: and (3) refining a product: discharging the liquid-phase material coarse isosorbide in the product collection tank obtained in the step S3 from the bottom, feeding the liquid-phase material coarse isosorbide into a mixing tank of a product refining unit, uniformly mixing the coarse isosorbide and a crystallization solvent through the mixing tank according to the mass ratio, feeding the mixture into a centrifuge from a bottom pipeline, filtering and drying crystals obtained by filtering in the centrifuge to obtain the pharmaceutical grade isosorbide, and circulating the solution obtained by filtering in the centrifuge through a crystallization solvent discharge pipeline to return to the mixing tank.
Further, in S1, the catalyst is a sulfuric acid ionic liquid or a benzenesulfonic acid ionic liquid, where the sulfuric acid ionic liquid includes 1-ethyl-3-methylimidazolium ethyl sulfate ionic liquid or 1-ethyl-3-methyltetrafluoroborate onium salt, the benzenesulfonic acid ionic liquid includes 1-methyl-3- [ α -methyl-4- (sulfonic acid benzyl) imidazole p-toluenesulfonate ] or 1-methyl-3- [ α -methyl- (4-sulfonic acid benzyl) ] imidazolium chloride, and the mass ratio of sorbitol to catalyst is (50-1500): 1.
further, both the sulfuric acid-based ionic liquid and the benzenesulfonic acid-based ionic liquid can be purchased from the market.
Further, the reaction solvent in S1 is a nonpolar system, and includes one or a combination of at least two of benzene, toluene, xylene, ethylbenzene, p-xylene, m-xylene, cumene, styrene, or diethyl ether, and the mass ratio of sorbitol to the reaction solvent is 1: (20-100).
Further, the preheating temperature of the tubular reactor in S1 is 110-200 ℃, and the stirring temperature of the stirring kettle is 60-100 ℃; the reaction temperature of the tubular reactor is 110-.
Preferably, the preheating temperature of the tubular reactor in S1 is 130-180 ℃, and the reaction temperature is 130-180 ℃.
Further, the operation temperature of the evaporation in the S2 primary evaporator is 70-200 ℃, and the operation pressure during evaporation is 1-100 kPa.
Preferably, the operation temperature of the evaporation in the S2 primary evaporator is 70-160 ℃.
Further, the operation temperature in the dehydration condenser in the S2 is 0-20 ℃, and the operation pressure is 1-100 kPa.
Further, the operation temperature of evaporation in the S3 secondary evaporator is 80-200 ℃, and the operation pressure is 1-100 kPa.
Further, the operation temperature in the product condenser in the S3 is 0-60 ℃, and the operation pressure is 1-100 kPa.
Further, the product refining unit in S4 comprises any one or a combination of at least two of distillation, crystallization, separation and drying; the crystallization solvent is any one or the combination of two of methanol, ethanol, isopropanol, acetone, ethyl acetate, chloroform, glacial acetic acid, dioxane, carbon tetrachloride, benzene, petroleum ether, toluene, nitromethane, diethyl ether, dimethylformamide, dimethyl sulfoxide or acetone; the mass ratio of the crude sorbitol to the crystallization solvent is 1: (2-5).
Further, the centrifuge in S4 is a filter centrifuge.
Further, the operation temperature of the centrifuge in the S4 is-20-10 ℃.
Further, the crystallization solvent of the product refining unit in S4 is ethyl acetate.
The invention has the following beneficial effects:
1. the invention adopts a tubular reactor for reaction, sorbitol and a reaction solvent are mixed and fed, the tubular reactor is filled with a liquid acid catalyst, and the product is dehydrated by a first-stage evaporator, separated by a second-stage evaporator, finally recrystallized and purified, thereby realizing continuous chemical reaction and rapid separation of the product. In the process of continuously purifying the isosorbide, firstly, solid sorbitol is converted into liquid by the stirring kettle and then enters the tubular reactor for reaction, the reaction progress degree is controlled by controlling factors such as reaction temperature, reaction time and the like, the controllable space is large, and the full progress of the reaction can be ensured to the greatest extent. On the basis, a first-stage evaporator is arranged to carry out primary separation on a tubular reactor reaction system, so that light components and heavy components which are easy to separate are separated, mutual interference caused when the easily-separated components and the difficultly-separated components are separated in the primary separation process is avoided, the heavy components (products and byproducts) enter a second-stage evaporator, and the light components (solvents and water) return to the stirring kettle through a condenser and a collection tank to be recycled; and the heavy component is separated again by a secondary evaporator, in the process, a relatively lighter component (crude isosorbide) in the heavy component flows out from a gas phase discharge port, refined isosorbide is obtained by condensation, collection, recrystallization and centrifugation, and the relatively heavier component (by-product) is recycled in the stirring kettle. In the process flow, the advantages of the tubular reactor and the membrane evaporator are fully utilized, the isosorbide can be purified only in 4 hours from the beginning of stirring to the end of centrifugal drying, continuous purification of the isosorbide can be continuously carried out, the yield of the prepared isosorbide is more than or equal to 86 percent, the purity of the prepared isosorbide is more than or equal to 95 percent, the prepared isosorbide reaches the standard of pharmacopoeia WS1- (X-379) -2004Z, and the process flow is suitable for industrial production.
2. The invention prepares the isosorbide by the continuous reaction purification device, solves the defect of the current intermittent operation, saves energy consumption compared with the traditional process, and has simple flow and high production efficiency. Compared with a fixed bed reactor, the tubular reactor used in the invention is convenient to process and manufacture, is convenient to debug before being put into production formally, has short test period and low operation difficulty, and is suitable for industrial production.
3. The evaporator used in the invention is a film evaporator which leads the material liquid to flow in a film shape along the wall of the heating pipe for heat transfer and evaporation, the heat transfer efficiency is high, the evaporation speed is high, and the retention time of the material is short, so the evaporator is particularly suitable for the evaporation of the heat-sensitive material in the invention, and simultaneously, the evaporator has the characteristics of large production capacity, high efficiency, short material heating time and the like. The traditional evaporator has small liquid contact heat transfer area, so that the evaporation efficiency is low, the traditional evaporator can complete the work within one hour, the thin film evaporator can be realized within 20 minutes, the purity of the separated product is high, the continuous separation can be realized, the carbonization of isosorbide can be reduced in the separation process, and the yield of the obtained product is high. In the dehydration separation unit, the solution moves linearly in a membrane shape in the tube nest during the dehydration process of the first-stage evaporator, so that high-efficiency separation can be realized, the aim of quickly recovering the solvent is fulfilled, and the purity of the main product after separation is more than or equal to 95 percent, which is improved by 80 percent compared with the traditional separation method.
4. According to the invention, the oil phase material separated from the oil-water separator is recycled from the oil phase material port and returned to the stirring kettle, the heavy component separated from the liquid phase discharge port of the secondary evaporator is recycled and returned to the stirring kettle, and the crystallization solvent obtained by centrifugation from the centrifuge is recycled and returned to the mixing tank for recrystallization of the crude isosorbide in the next process. The non-aqueous solution in the whole process flow is recycled, so that the energy consumption is saved, the pollution is reduced, the production cost is low, the reaction condition is mild, the production aging is short, and the operation process is simple.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic view of an apparatus for continuous reaction purification of isosorbide according to example 1 of the present invention.
Wherein, 1, a stirring kettle; 2. a tubular reactor; 3. a first-stage evaporator; 301. a gas phase material outlet of the first-stage evaporator; 302. a liquid-phase material outlet of the first-stage evaporator; 4. a dehydration condenser; 5. a dewatering collection tank; 6. an oil-water separator; 601. a water phase discharge port of the oil-water separator; 602. an oil phase discharge port of the oil-water separator; 7. a secondary evaporator; 701. a gas phase discharge port of the secondary evaporator; 702. a liquid phase discharge port of the secondary evaporator; 8. a product condenser; 9. a product collection tank; 10. a mixing tank; 11. a centrifuge; 12. and a crystallization solvent discharge pipeline. The arrows shown in the figure represent the direction of material flow.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
A device capable of continuously reacting and purifying isosorbide is shown in figure 1 and comprises a reaction unit, a dehydration unit, a product separation unit and a product refining unit, wherein the reaction unit is connected with the dehydration unit, the dehydration unit is connected with the product separation unit, and the product separation unit is connected with the product refining unit; wherein the reaction unit comprises a stirring kettle 1 and a tubular reactor 2; the dehydration unit comprises a primary evaporator 3, a dehydration condenser 4, a dehydration collection tank 5 and an oil-water separator 6; the product separation unit comprises a secondary evaporator 7, a product condenser 8 and a product collection tank 9; the product finishing unit comprises a mixing tank 10 and a centrifuge 11, the evaporator comprising any one or a combination of two of a falling film evaporator, a rising film evaporator or a wiped film evaporator.
The bottom of a stirring kettle 1 of the reaction unit is connected with a feed inlet of a tubular reactor 2, and sorbitol is powdered, so that the heating and the temperature rise are needed to be carried out in the stirring kettle 1 firstly, and the sorbitol is melted into liquid and then enters the tubular reactor 2 together with a reaction solvent for tubular reaction.
The top of the first-stage evaporator 3 is provided with a first-stage evaporator gas-phase discharge hole 301, and the bottom is provided with a first-stage evaporator liquid-phase discharge hole 302; a discharge port of the tubular reactor 2 is connected with a primary evaporator 3, a gas phase discharge port 301 of the primary evaporator is connected with an inlet of a dehydration condenser 4, a liquid phase discharge port 302 of the primary evaporator is connected with a secondary evaporator 7, and an outlet of the dehydration condenser 4 is connected with an inlet of a dehydration collection tank 5; an oil-water separator water phase discharge port 601 and an oil-water separator oil phase discharge port 602 are arranged on the oil-water separator 6, the outlet of the dehydration condenser 5 is connected with the inlet of the oil-water separator 6, the oil-water separator water phase discharge port 601 is connected with a waste liquid pipeline, and the oil-water separator oil phase discharge port 602 is connected with the inlet of the stirring kettle 1. The main components flowing out of the gas phase discharge port 301 of the primary evaporator are solvent and water, the solvent and the water are changed from gas state to liquid state through the dehydration condenser 4 and then enter the dehydration collection tank 5, and then enter the oil-water separation tank 6 from the dehydration collection tank 5, and the oil phase solvent is recycled through the connection of the oil phase discharge port 602 of the oil-water separator in the oil-water separator 6 and the stirring kettle 1, so that the cost and the energy consumption are saved.
The main component who flows from one-level evaporator liquid phase discharge gate 302 is the heavy component, one-level evaporator liquid phase discharge gate 302 links to each other with second grade evaporator 7, 7 tops of second grade evaporator are equipped with second grade evaporator gas phase discharge gate 701, the bottom is equipped with second grade evaporator liquid phase discharge gate 702, second grade evaporator gas phase discharge gate 701 links to each other with the import of product condenser 8, the export of product condenser 8 links to each other with product collection tank 9, product collection tank 9 links to each other with mixing tank 10 import I, mixing tank 10 bottom export links to each other with centrifuge 11 import, centrifuge 11 bottom export I links to each other with the product collecting pipe, centrifuge 11 export II links to each other with mixing tank 10 import II through crystallization solvent ejection of compact pipeline 12, second grade evaporator liquid phase discharge gate 702 links to each other with reaction unit stirred tank 1 raw materials feed pipeline.
The heavy components flow out through a liquid phase discharge port 302 of the primary evaporator and enter a secondary evaporator, relatively lighter components in the heavy components are evaporated and flow out through a gas phase discharge port 701 of the secondary evaporator through evaporation, the heavy components are condensed by a product condenser 8 to form liquid substances, the liquid substances enter a product collecting tank 9 and then enter a mixing tank to realize recrystallization of isosorbide through a crystallization solvent and certain crystallization conditions, and the recrystallized materials are subjected to suction filtration and drying by a centrifuge 11 to obtain pure isosorbide. And the relatively heavier components in the secondary evaporator 7 are connected with the feed pipeline of the reaction unit stirred tank 1 through the liquid phase discharge port 702 of the secondary evaporator to participate in the production again. The crystallization solvent pumped and filtered out from the centrifuge 11 is recycled and returned to the mixing tank 10 through a crystallization solvent discharging pipeline 12, so that the recycling of the crystallization solvent is realized.
Example 2
This example is a method for continuous reaction purification of isosorbide using the apparatus for continuous reaction purification of isosorbide of example 1, comprising the steps of:
(1) a tubular reaction unit: sorbitol, a catalyst and toluene are added into a stirring kettle 1 according to the mass ratio of 1:0.02:40, the mixture is heated to 80 ℃, internal materials are discharged from the bottom of the stirring kettle 1 and enter a tubular reactor 2 in a molten state, the tubular reactor 2 is preheated to 140 ℃ in advance, the materials enter the tubular reactor 2 and stay for 2 hours at the reaction temperature of 140 ℃, the operation pressure is 10kPa, and after the reaction is finished, the materials are discharged from a discharge hole of the tubular reactor 2 and enter a dehydration unit; the catalyst is 1-ethyl-3-methylimidazolium ethyl sulfate ionic liquid.
(2) A dehydration unit: feeding materials from the top of a primary evaporator (falling film evaporator) 3, wherein the operating temperature in the primary evaporator (falling film evaporator) 3 is 110 ℃, and the absolute pressure is 10kPa, wherein the gas-phase materials in the primary evaporator (falling film evaporator) 3 mainly comprise solvents and water, the gas-phase materials are condensed from a gas-phase discharge port 301 of the primary evaporator at 5 ℃ and the absolute pressure of 10kPa into a dehydration collection tank 5, the materials in the dehydration collection tank 5 are discharged from the bottom and enter an oil-water separator 6, oil-water separation is realized through interface control, the oil-phase solvents are circularly returned to a reaction unit stirring kettle 1 from an oil-phase discharge port 602 of the oil-water separator, and the water-phase materials flow out from a water-phase discharge port 601 of the oil-water separator to be treated by waste liquid; the liquid phase material in the first-stage evaporator (falling film evaporator) 3 is discharged from the bottom and enters a product separation unit.
(3) A product separation unit: the material is fed from the top of a secondary evaporator (falling film evaporator) 7, the operating temperature of the secondary evaporator (falling film evaporator) 7 is 120 ℃, the absolute pressure is 10kPa, wherein in the secondary evaporator (falling film evaporator) 7, the gas-phase material is mainly crude isosorbide, the material is discharged from a gas-phase discharge port 701 of the secondary evaporator at the top and then condensed into a liquid phase by a product condenser 8 at 50 ℃ under the absolute pressure of 10kPa and then enters a product collecting tank 9, the material is discharged from the bottom of the product collecting tank 9 and enters a product refining unit, and the liquid-phase material in the secondary evaporator (falling film evaporator) 7 is connected with a raw material feeding pipeline of a reaction unit stirring kettle 1 from a liquid-phase discharge port 702 of the secondary evaporator at the bottom to participate in the reaction again.
(4) A product refining unit: liquid phase materials in the product collecting tank 9 are mainly coarse isosorbide, the liquid phase materials are discharged from the bottom and enter a mixing tank 10, the coarse isosorbide and ethyl acetate are uniformly mixed through the mixing tank according to the mass ratio of 1:3 and then enter a centrifuge 11 through a bottom pipeline, the operation temperature of the centrifuge is 5 ℃, crystals are filtered and dried to obtain medical-grade isosorbide, and the solution filtered in the centrifuge is circulated and returned to the mixing tank 10 through a crystallization solvent discharging pipeline 12.
In the embodiment, sorbitol, a catalyst and toluene are mixed and heated according to a certain proportion and then enter a tubular reactor for reaction, wherein the catalyst is a sulfuric acid ionic liquid catalyst, isosorbide is prepared through continuous reaction, the purity of the obtained isosorbide reaches 99.9 percent of the pharmaceutical grade, the yield is 90 percent, the purification of isosorbide can be completed only 4 hours from the beginning of stirring to the final centrifugal drying, and the continuous purification of isosorbide can be continuously and continuously performed, so that the problem of low production efficiency caused by intermittent operation of the traditional process is solved, the energy consumption is saved, and the utilization rate of raw materials is improved. Is the best scheme of the invention.
Example 3
This example is a method for continuous reaction purification of isosorbide using the apparatus for continuous reaction purification of isosorbide of example 1, comprising the steps of:
(1) a tubular reaction unit: sorbitol, a catalyst and xylene are fed into a stirring kettle 1 according to a mass ratio of 1:0.02:40, the mixture is heated to 80 ℃, internal materials are discharged from the bottom of the stirring kettle 1 and fed into a tubular reactor 2 in a molten state, the tubular reactor 2 is preheated to 140 ℃ in advance, the materials are fed into the tubular reactor 2 from the bottom, the retention time is 2 hours, the reaction temperature is 140 ℃, the operation pressure is 10kPa, the reaction is finished, and the materials are discharged from a discharge hole of the tubular reactor 2 and fed into a dehydration unit; the catalyst is 1-methyl-3- [ alpha-methyl-4- (sulfonic acid benzyl) imidazole p-toluenesulfonate ].
(2) A dehydration unit: feeding materials from the top of a primary evaporator (wiped film evaporator) 3, wherein the operating temperature in the primary evaporator (wiped film evaporator) 3 is 180 ℃ and the absolute pressure is 10kPa, gas-phase materials in the primary evaporator (wiped film evaporator) 3 mainly comprise solvent and water, the gas-phase materials are condensed from a gas-phase discharge port 301 of the wiped film evaporator at 5 ℃ and the absolute pressure of 10kPa into a dehydration collection tank 5, the materials in the dehydration collection tank 5 are discharged from the bottom and enter an oil-water separator 6, oil-water separation is realized through interface control, the oil-phase solvent is circularly returned to a reaction unit stirring kettle 1 from an oil-phase discharge port 602 of the oil-water separator, and the water-phase materials flow out from a water-phase discharge port 601 of the oil-water separator to be treated by waste liquid; the liquid phase material in the first-stage evaporator (wiped film evaporator) 3 is discharged from the bottom and enters a product separation unit.
(3) A product separation unit: the material is fed from the top of a secondary evaporator (wiped film evaporator) 7, the operating temperature of the secondary evaporator (wiped film evaporator) 7 is 120 ℃, the absolute pressure is 10kPa, wherein in the secondary evaporator (wiped film evaporator) 7, gas-phase material mainly comprises crude isosorbide discharged from the top 701 and condensed into liquid phase through a product condenser 8 at 50 ℃ under the absolute pressure of 10kPa and enters a product collecting tank 9, the material is discharged from the bottom of the product collecting tank 9 and enters a product refining unit, and the liquid-phase material discharged from the bottom 702 in the secondary evaporator (wiped film evaporator) 7 is connected with a raw material feeding pipeline of a reaction unit stirring kettle 1.
(4) A product refining unit: liquid phase materials in the product collecting tank 9 are mainly coarse isosorbide, the liquid phase materials are discharged from the bottom and enter a mixing tank 10, the coarse isosorbide and ethyl acetate are uniformly mixed through the mixing tank according to the mass ratio of 1:3 and then enter a centrifuge 11 through a bottom pipeline, the operation temperature of the centrifuge is 5 ℃, crystals are filtered and dried to obtain medical-grade isosorbide, and the solution filtered in the centrifuge is circulated and returned to the mixing tank 10 through a crystallization solvent discharging pipeline 12.
In this embodiment, the mixed solvent of raw solid sorbitol, the catalyst and the operation temperature and type of the first-stage evaporator 3 are adjusted, and the mixed solvent can be selected and purchased preferentially according to market price on the premise of ensuring that the purity of isosorbide is not affected. The purity of the produced isosorbide is 95%, the yield of the isosorbide is 86%, and the purification of the isosorbide can be completed in 5 hours from the beginning of stirring to the final completion of centrifugal drying.
Example 4
This example is a method for continuous reaction purification of isosorbide using the apparatus for continuous reaction purification of isosorbide of example 1, comprising the steps of:
(1) a tubular reaction unit: sorbitol, a catalyst and xylene are added into a stirring kettle 1 according to the mass ratio of 1:0.02:40, the mixture is heated to 80 ℃, internal materials are discharged from the bottom of the stirring kettle 1 and enter a tubular reactor 2 in a molten state, the tubular reactor 2 is preheated to 140 ℃ in advance, the materials enter the tubular reactor 2 from the bottom, the residence time is 2 hours, the reaction temperature is 140 ℃, the operation pressure is 10kPa, and after the reaction is finished, the materials enter a dehydration unit from a discharge hole of the tubular reactor 2; the catalyst is chlorinated 1-methyl-3- [ alpha-methyl- (4-sulfonic acid benzyl) ] imidazole salt.
(2) A dehydration unit: feeding materials from the top of a primary evaporator (falling film evaporator) 3, wherein the operating temperature in the primary evaporator (falling film evaporator) 3 is 180 ℃ and the absolute pressure is 10kPa, wherein gas-phase materials in the primary evaporator (falling film evaporator) 3 mainly comprise solvent and water, the gas-phase materials are condensed from a gas-phase discharge port 301 of the falling film evaporator at 5 ℃ and the absolute pressure of 10kPa into a dehydration collection tank 5, the materials in the dehydration collection tank 5 are discharged from the bottom and enter an oil-water separator 6, oil-water separation is realized through interface control, an oil-phase solvent is circularly returned to a reaction unit stirring kettle 1 from an oil-phase discharge port 602 of the oil-water separator, and water-phase materials flow out from a water-phase discharge port 601 of the oil-water separator to be treated by waste liquid; the liquid phase material in the first-stage evaporator (falling film evaporator) 3 is discharged from the bottom and enters a product separation unit.
(3) A product separation unit: the material is fed from the top of a secondary evaporator (falling film evaporator) 7, the operating temperature of the secondary evaporator (falling film evaporator) 7 is 120 ℃, the absolute pressure is 10kPa, wherein in the secondary evaporator (falling film evaporator) 7, gas-phase material mainly comprises crude isosorbide discharged from the top 701 and condensed into liquid phase through a product condenser 8 at 50 ℃ under the absolute pressure of 10kPa and enters a product collecting tank 9, the material is discharged from the bottom of the product collecting tank 9 and enters a product refining unit, and the liquid-phase material discharged from the bottom 702 in the secondary evaporator (scraping film evaporator) 7 is connected with a raw material feeding pipeline of a reaction unit stirring kettle 1.
(4) A product refining unit: liquid phase materials in the product collecting tank 9 are mainly coarse isosorbide, the liquid phase materials are discharged from the bottom and enter a mixing tank 10, the coarse isosorbide and ethyl acetate are uniformly mixed through the mixing tank according to the mass ratio of 1:3 and then enter a centrifuge 11 through a bottom pipeline, the operation temperature of the centrifuge is 5 ℃, crystals are filtered and dried to obtain medical-grade isosorbide, and the solution filtered in the centrifuge is circulated and returned to the mixing tank 10 through a crystallization solvent discharging pipeline 12.
The difference from the example 2 is that the benzenesulfonic acid ionic liquid is selected as the catalyst to participate in the reaction, the mixed solvent of the solid sorbitol is adjusted, and other process conditions are the same as those in the example 2.
In the embodiment, the catalyst is adjusted, and the catalyst can be purchased preferentially according to market price on the premise of ensuring that the purity of the isosorbide is not influenced. The purity of the produced isosorbide reaches 99.9 percent of the pharmaceutical grade, the yield is 90 percent, and the purification of the isosorbide can be completed in 4 hours from the beginning of stirring to the final centrifugal drying.
Example 5
This example is a method for continuous reaction purification of isosorbide using the apparatus for continuous reaction purification of isosorbide of example 1, comprising the steps of:
(1) a tubular reaction unit: sorbitol, a catalyst and m-xylene in a mass ratio of 1: 0.002: 20, heating the mixture to 60 ℃, discharging the internal materials from the bottom of the stirring kettle 1 to enter a tubular reactor 2 in a molten state, preheating the tubular reactor 2 to 110 ℃ in advance, allowing the materials to enter the tubular reactor 2 from the bottom, staying for 2 hours at the reaction temperature of 110 ℃, keeping the operation pressure of 1kPa at the absolute pressure, and discharging the materials from a discharge hole of the tubular reactor 2 to enter a dehydration unit after the reaction is finished; the catalyst is 1-ethyl-3-methyl tetrafluoroborate onium salt.
(2) A dehydration unit: feeding materials from the top of a primary evaporator (climbing-film evaporator) 3, wherein the operating temperature in the primary evaporator (climbing-film evaporator) 3 is 200 ℃, and the absolute pressure is 1kPa, wherein gas-phase materials in the primary evaporator (climbing-film evaporator) 3 mainly comprise solvents and water, the gas-phase materials are condensed from a gas-phase discharge port 301 of the primary evaporator at 0 ℃ under the absolute pressure of 1kPa by a dehydration condenser 4 and then enter a dehydration collection tank 5, the materials in the dehydration collection tank 5 are discharged from the bottom and enter an oil-water separator 6, oil-water separation is realized by interface control, oil-phase solvents are circularly returned to a reaction unit stirring kettle 1 from an oil-phase discharge port 602 of the oil-water separator, and water-phase materials flow out from a water-phase discharge port 601 of the oil-water separator to be treated as waste liquid; the liquid phase material in the first-stage evaporator (climbing film evaporator) 3 is discharged from the bottom and enters a product separation unit.
(3) A product separation unit: the material is fed from the top of a secondary evaporator (wiped film evaporator) 7, the operating temperature of the secondary evaporator (wiped film evaporator) 7 is 200 ℃, and the absolute pressure is 1kPa, wherein in the secondary evaporator (wiped film evaporator) 7, the gas-phase material is mainly crude isosorbide, the material is discharged from a gas-phase discharge port 701 of the secondary evaporator at the top, then the material is condensed into a liquid phase by a product condenser 8 at 60 ℃ under the absolute pressure of 1kPa and then enters a product collecting tank 9, the material is discharged from the bottom of the product collecting tank 9 and enters a product refining unit, and the liquid-phase material in the secondary evaporator (wiped film evaporator) 7 is discharged from the bottom 702 and is connected with a raw material feeding pipeline of a reaction unit stirring kettle 1.
(4) A product refining unit: liquid phase materials in the product collecting tank 9 are mainly crude isosorbide, the liquid phase materials are discharged from the bottom and enter a mixing tank 10, the crude isosorbide and chloroform are uniformly mixed through the mixing tank according to the mass ratio of 1:2 and then enter a centrifuge 11 through a bottom pipeline, the operation temperature of the centrifuge is 10 ℃, crystals are filtered and dried to obtain medical-grade isosorbide, and the solution filtered in the centrifuge is circulated and returned to the mixing tank 10 through a crystallization solvent discharging pipeline 12.
In this example, the operation conditions of the tubular reaction unit, the dehydration unit, the product separation unit, and the product purification unit were adjusted.
Example 6
This example is a method for purifying isosorbide by continuous reaction using the apparatus for purifying isosorbide by continuous reaction of example 1, comprising the steps of:
(1) a tubular reaction unit: sorbitol, a catalyst, styrene and cumene according to a mass ratio of 1: 0.000666: 100 of the materials enter a stirring kettle 1, the materials are heated to 100 ℃, the internal materials are discharged from the bottom of the stirring kettle 1 and enter a tubular reactor 2 in a molten state, the tubular reactor 2 is preheated to 200 ℃ in advance, the materials enter the tubular reactor 2 from the bottom, the residence time is 8 hours, the reaction temperature is 180 ℃, the operation pressure is 1000kPa, and the materials are discharged from a discharge hole of the tubular reactor 2 and enter a dehydration unit after the reaction is finished; the catalyst is 1-ethyl-3-methylimidazolium ethyl sulfate ionic liquid and 1-methyl-3- [ alpha-methyl-4- (sulfonic acid benzyl) imidazole p-toluenesulfonate ].
(2) A dehydration unit: feeding materials from the top of a primary evaporator (climbing-film evaporator) 3, wherein the operating temperature in the primary evaporator (climbing-film evaporator) 3 is 70 ℃ and the absolute pressure is 100kPa, wherein gas-phase materials in the primary evaporator (climbing-film evaporator) 3 mainly comprise solvents and water, the gas-phase materials are condensed from a gas-phase discharge hole 301 of the primary evaporator at 20 ℃ and the absolute pressure of 100kPa into a dehydration collection tank 5, the materials in the dehydration collection tank 5 are discharged from the bottom and enter an oil-water separator 6, oil-water separation is realized through interface control, oil-phase solvents are circularly returned to a reaction unit stirring kettle 1 from an oil-phase discharge hole 602 of the oil-water separator, and water-phase materials flow out from a water-phase discharge hole 601 of the oil-water separator to be treated by waste liquid; the liquid phase material in the first-stage evaporator (climbing film evaporator) 3 is discharged from the bottom and enters a product separation unit.
(3) A product separation unit: the material is fed from the top of a secondary evaporator (climbing-film evaporator) 7, the operating temperature of the secondary evaporator (climbing-film evaporator) 7 is 80 ℃, and the absolute pressure is 1kPa, wherein in the secondary evaporator (climbing-film evaporator) 7, the gas-phase material is mainly crude isosorbide, the material is discharged from a gas-phase discharge port 701 of the secondary evaporator at the top, then is condensed into a liquid phase by a product condenser 8 at 0 ℃ under the absolute pressure of 100kPa and then enters a product collecting tank 9, the material is discharged from the bottom of the product collecting tank 9 and enters a product refining unit, and the liquid-phase material in the secondary evaporator (climbing-film evaporator) 7 is discharged from the bottom 702 and is connected with a raw material feeding pipeline of a reaction unit stirring kettle 1.
(4) A product refining unit: liquid phase materials in the product collecting tank 9 are mainly coarse isosorbide, the liquid phase materials are discharged from the bottom and enter a mixing tank 10, the coarse isosorbide and acetone are uniformly mixed through the mixing tank according to the mass ratio of 1:5 and then enter a centrifuge 11 through a bottom pipeline, the operation temperature of the centrifuge is minus 20 ℃, crystals are filtered and dried to obtain medical-grade isosorbide, and the solution filtered in the centrifuge is circulated and returned to the mixing tank 10 through a crystallization solvent discharging pipeline 12.
In this example, the operation conditions of the tubular reaction unit, the dehydration unit, the product separation unit and the product purification unit were adjusted.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. The device capable of continuously reacting and purifying the isosorbide is characterized in that: the continuous reaction purification device comprises a reaction unit, a dehydration unit, a product separation unit and a product refining unit which are connected in sequence; wherein the reaction unit comprises a stirring kettle (1) and a tubular reactor (2); the dehydration unit comprises a primary evaporator (3), a dehydration condenser (4), a dehydration collection tank (5) and an oil-water separator (6); the product separation unit comprises a secondary evaporator (7), a product condenser (8) and a product collection tank (9); the product refining unit comprises a mixing tank (10) and a centrifuge (11).
2. The apparatus for continuous reactive purification of isosorbide according to claim 1, wherein: the stirring kettle (1) of the reaction unit is connected with a tubular reactor (2), the tubular reactor (2) is connected with a primary evaporator (3), a gas phase discharge port (301) of the primary evaporator is connected with a dehydration condenser (4), a liquid phase discharge port (302) of the primary evaporator is connected with a secondary evaporator (7), and the dehydration condenser (4) is connected with a dehydration collection tank (5); the dehydration collection tank (5) is connected with an oil-water separator (6), a water phase discharge port (601) of the oil-water separator is connected with a waste liquid pipeline, and an oil phase discharge port (602) of the oil-water separator is connected with the stirring kettle (1); a gas phase discharge hole (701) of a secondary evaporator (7) is connected with a product condenser (8), the product condenser (8) is connected with a product collecting tank (9), the product collecting tank (9) is connected with a mixing tank (10), the mixing tank (10) is connected with an inlet of a centrifugal machine (11), the centrifugal machine (11) is connected with the mixing tank (10), and a liquid phase discharge hole (702) of the secondary evaporator (7) is connected with a feed pipeline of a reaction unit stirring kettle (1).
3. The apparatus for continuous reactive purification of isosorbide according to claim 2, characterized in that: the primary evaporator (3) and the secondary evaporator (7) are membrane evaporators; the centrifuge (11) includes any one or a combination of two of a filter centrifuge, a scraper centrifuge, a horizontal screw centrifuge, and a three-leg centrifuge.
4. A method for continuous reaction purification using the apparatus for continuous reaction purification of isosorbide according to any one of claims 1 to 3, wherein isosorbide is produced by mixing sorbitol with a reaction solvent and passing the mixture through the continuous reaction purification apparatus, characterized by comprising the steps of:
s1: tubular reaction: preheating a tubular reactor (2) in advance, then feeding sorbitol, a catalyst and a reaction solvent into a stirring kettle (1) according to a feeding ratio of a mass ratio, heating, discharging internal materials from the bottom of the stirring kettle (1) in a molten state, feeding the internal materials into the tubular reactor (2) for reaction, and after the reaction is finished, discharging the materials from the tubular reactor (2) and feeding the materials into a dehydration unit;
s2: and (3) dehydrating: feeding the material obtained in the step S1 from the top of a primary evaporator of a dehydration unit, evaporating in a primary evaporator (3), wherein gas-phase materials mainly comprise solvent and water, condensing from a gas-phase discharge port (301) of the primary evaporator through a dehydration condenser (4) and then entering a dehydration collection tank (5), discharging a liquid-phase material from the bottom of the dehydration collection tank (5) and entering an oil-water separator (6) of a product separation unit, realizing oil-water separation through interface control, wherein the oil-phase solvent circularly returns to a stirring kettle (1) in a reaction unit through an oil-phase discharge port (602) of the oil-water separator, and the water-phase material enters a waste liquid pipeline from a water-phase discharge port (601) of the oil-water separator to be subjected to waste liquid treatment;
s3: product separation: discharging liquid-phase materials in the primary condenser (3) obtained in the step S2 from a liquid-phase discharge port (302) of the primary evaporator, feeding the materials from the top of a secondary evaporator (7) of a product separation unit, and evaporating the materials in the secondary evaporator (7), wherein the gas-phase materials are mainly crude isosorbide, are discharged from a gas-phase discharge port (701) of the secondary evaporator, are condensed into liquid phases through a product condenser (8), enter a product collection tank (9), are discharged from the bottom of the product collection tank (9), enter a product refining unit, and are discharged from the bottom of the secondary evaporator (7) and enter a reaction unit stirring kettle (1);
s4: and (3) refining a product: discharging the liquid-phase material crude isosorbide in the product collection tank (9) obtained in the step S3 from the bottom, feeding the liquid-phase material crude isosorbide into a mixing tank (10) of a product refining unit, uniformly mixing the crude isosorbide and a crystallization solvent through the mixing tank (10) according to the mass ratio, feeding the mixture into a centrifuge (11) from a bottom pipeline, filtering and drying crystals obtained by filtering in the centrifuge (11) to obtain medical-grade isosorbide, and circulating the solution filtered in the centrifuge (11) back to the mixing tank (10).
5. The method for purifying isosorbide by continuous reaction according to claim 4, characterized in that: the reaction solvent in the S1 is a nonpolar system and comprises any one or combination of at least two of benzene, toluene, xylene, ethylbenzene, paraxylene, metaxylene, cumene, styrene or diethyl ether, and the mass ratio of sorbitol to the reaction solvent is 1: (20-100).
6. The method for purifying isosorbide by continuous reaction according to claim 5, characterized in that: the catalyst in the S1 is a sulfuric acid ionic liquid or a benzenesulfonic acid ionic liquid, wherein the sulfuric acid ionic liquid comprises 1-ethyl-3-methylimidazolium ethyl sulfate ionic liquid or 1-ethyl-3-methyltetrafluoroborate onium salt, the benzenesulfonic acid ionic liquid comprises 1-methyl-3- [ alpha-methyl-4- (sulfonic acid benzyl) imidazole p-toluenesulfonate ] or 1-methyl-3- [ alpha-methyl- (4-sulfonic acid benzyl) ] imidazolium chloride, and the mass ratio of sorbitol to the catalyst is (50-1500): 1.
7. the method for continuous reactive purification of isosorbide according to claim 6, characterized in that: the preheating temperature of the tubular reactor in the S1 is 110-200 ℃, and the stirring temperature of the stirring kettle is 60-100 ℃; the reaction temperature of the tubular reactor is 110-.
8. The method for purifying isosorbide by continuous reaction according to claim 7, characterized in that: the operation temperature of evaporation in the S2 primary evaporator (3) is 70-200 ℃, and the operation pressure of evaporation is 1-100 kPa.
9. The method for purifying isosorbide by continuous reaction according to claim 8, characterized in that: the operation temperature of evaporation in the S3 secondary evaporator (7) is 80-200 ℃, and the operation pressure is 1-100 kPa.
10. The method for purifying isosorbide by continuous reaction according to claim 9, characterized in that: the product refining unit in S4 comprises any one or combination of at least two of distillation, crystallization, separation and drying; the crystallization solvent comprises one or two of methanol, ethanol, isopropanol, acetone, ethyl acetate, chloroform, glacial acetic acid, dioxane, carbon tetrachloride, benzene, petroleum ether, toluene, nitromethane, diethyl ether, dimethylformamide, dimethyl sulfoxide or acetone; the mass ratio of the crude sorbitol to the crystallization solvent is 1: (2-5).
CN202210685993.5A 2022-06-17 2022-06-17 Device and method capable of continuously reacting and purifying isosorbide Pending CN114849637A (en)

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CN110372716A (en) * 2019-08-14 2019-10-25 中国科学院过程工程研究所 A kind of method that sorbierite successive reaction prepares isobide

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040110994A1 (en) * 2002-04-17 2004-06-10 Bhatia Kamlesh Kumar Integrated continuous process for anhydro sugar alcohol manufacture
CN107417539A (en) * 2017-05-16 2017-12-01 天津大学 A kind of method of tank reactor series connection tubular reactor synthesis tetramethyl ammonium hydrogen carbonate
CN107955012A (en) * 2017-12-05 2018-04-24 中国科学院过程工程研究所 A kind of product preparative separation system and its processing method and purposes for being less than product and raw material for accessory substance boiling point
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