WO2016082766A1 - 一种沸点接近的多元醇混合物的分离方法 - Google Patents

一种沸点接近的多元醇混合物的分离方法 Download PDF

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WO2016082766A1
WO2016082766A1 PCT/CN2015/095593 CN2015095593W WO2016082766A1 WO 2016082766 A1 WO2016082766 A1 WO 2016082766A1 CN 2015095593 W CN2015095593 W CN 2015095593W WO 2016082766 A1 WO2016082766 A1 WO 2016082766A1
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ethylene glycol
product
acetal
separated
acid catalyst
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French (fr)
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张涛
艾硕
郑明远
王爱琴
李为臻
王晓东
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中国科学院大连化学物理研究所
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Priority to US15/521,033 priority Critical patent/US9926251B2/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/88—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D1/00—Evaporating
    • B01D1/26—Multiple-effect evaporating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • 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
    • B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
    • 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
    • B01D3/06—Flash distillation
    • B01D3/065—Multiple-effect flash distillation (more than two traps)
    • 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
    • B01D3/10—Vacuum distillation
    • 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
    • B01D3/146—Multiple effect distillation
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/90—Regeneration or reactivation
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/02—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/18—Polyhydroxylic acyclic alcohols
    • 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
    • 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
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • 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
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the invention relates to a method for separating a mixture of polyols with similar boiling points, and belongs to the technical field of chemical separation.
  • glycol commonly known as glycol
  • glycol is a basic chemical raw material for bulk production. It can be used to produce polyester fiber (polyester), polyethylene terephthalate, explosives, solvents, antifreeze, plasticizer, Moisture absorber, etc. Due to technological monopoly and oil production restrictions, China's ethylene glycol supply has long relied on imports; since 2002, China's ethylene glycol imports accounted for more than 70% of demand. Among them, ethylene glycol consumed by the polyester industry accounts for more than 80%.
  • the traditional ethylene glycol synthesis route is based on the petrochemical industry, mainly using ethane as a raw material, ethylene glycol intermediate and water addition to form ethylene glycol, and by-product diethylene glycol, triethylene glycol, etc. Low value-added chemicals. Its key technologies are dominated by Shell (Hollywood), Halcon-SD (USA), Dow Chemical (USA), and UCC (USA). In addition, the hydration process and separation process consume large amounts of water, heat, oil and natural gas.
  • the ethylene carbonate process is a new process for the synthesis of ethylene glycol, which makes full use of the higher purity carbon dioxide emitted by the ethylene oxide plant, reduces carbon emissions, and consumes almost no water, thereby reducing the energy consumption for separation. A more significant advantage is the ability to co-produce dimethyl carbonate. However, this synthesis method also needs to consume ethylene oxide, still can not get rid of the dependence on oil, and its core technology is also monopolized by foreign companies.
  • the preparation of ethylene glycol from coal as raw materials mainly includes formaldehyde electrowinning dimerization method, methanol polymerization method and oxalate method.
  • formaldehyde electrowinning dimerization method methanol polymerization method
  • oxalate method the ethylene glycol yield of formaldehyde electro-hydrogenation dimerization method is higher, but the power consumption is more, and the purity of the produced ethylene glycol stock solution is very low, and the purification and purification cost is high.
  • the oxalate method is currently considered to be the most promising coal-based ethylene glycol synthesis route. It is based on CO in the synthesis gas as an intermediate medium, and the oxalate is formed by oxidative coupling reaction, and then subjected to catalytic hydrogenation of oxalate to finally form ethylene glycol.
  • 1,2-butanediol and ethylene glycol Due to excessive hydrogenation, the reaction system will produce methanol and ethanol, and ethylene glycol will react with methanol and ethanol to produce 1,2-propanediol and 1,2-butanediol.
  • 1,2-butanediol and ethylene glycol have the closest boiling point and can form azeotrope, so the energy consumption of the industrial distillation column is very large, which is also an important reason for the difficulty in industrialization of the coal-based ethylene glycol route.
  • the physical properties and chemical properties of the binary fusel and the ethylene glycol are close to each other, so it is difficult to separate them by conventional means such as rectification, extraction, and adsorption.
  • the polyol mixture at normal temperature and low temperature has a large viscosity, and in particular, a large flow resistance is generated in a space where the flow path is small, and the transportation energy is increased.
  • ethylene glycol is a bulk chemical, its yield is higher, and the liquid phase The adsorption amount of the adsorption method is small, so the adsorption separation method is also not suitable for the separation and purification of the polyol.
  • the present invention provides a novel process for the efficient separation of polyhydric alcohols from glycol mixtures and the purification of ethylene glycol.
  • the method has the advantages of short process flow and simple separation, and can convert the impurity polyol which is difficult to remove into an easily separated acetal or ketal compound with high added value.
  • the process has low energy consumption, low cost, high economy and less waste. It is a high-efficiency, energy-saving and environmentally-friendly separation route.
  • the ethylene glycol product of one or two or more of 2,3-butanediol, 1,4-butanediol, and glycerol is used as a raw material, and a crude ethylene glycol product containing a hetero alcohol is coal or raw
  • the substance is synthesized as a raw material, and the mass concentration of the ethylene glycol is 50% to 95%, and the mass content of the containing alcohol is between 5% and 50%.
  • the crude ethylene glycol product is mixed with the acid catalyst under normal pressure, and the dehydration reaction is started by heating in a dehydration reactor, and the dehydration reaction temperature is 150 to 198 ° C; the dehydration reaction of the above-mentioned fusel alcohol and the acetal reaction and the ketal reaction are converted into The light product is then removed by distillation or rectification to remove the above-mentioned fusel alcohol from the ethylene glycol.
  • the acid catalyst used includes one or a combination of two or more of a liquid protic acid, a solid protic acid, a Lewis acid, an acid center-containing oxide, or an acid center-containing mineral, wherein the more active catalyst is a hydrogen type molecular sieve.
  • the sulfonated activated carbon, the hydrogen type resin, the sulfuric acid, the hydrochloric acid, the nitric acid, and the acid catalyst account for 0.1% to 15% of the total mass of the dehydration reaction system.
  • the ethylene glycol product is purified again to remove the binary sterol contained therein, and a high-purity ethylene glycol product can be obtained; the purification method is any one or a combination of two or more of rectification, extraction, crystallization, adsorption, and chromatography.
  • the unvaporized material in the dehydration reactor contains a solid acid catalyst and ethylene glycol: the ethylene glycol product and the solid acid catalyst are separated by solid-liquid separation, distillation or rectification, and the solid-liquid separation device is press-filtered or Any of vacuum suction or sedimentation or centrifugal or vane solid-liquid separation equipment.
  • the solid acid catalyst can be recycled by calcination or solvent elution or drying; or, when the undistilled material contains a liquid acid catalyst and ethylene glycol: the ethylene glycol product and the liquid acid catalyst are separated by distillation or rectification, The liquid acid catalyst is recycled; or, after neutralization with a base, the ethylene glycol product and the neutralization reaction product of the liquid acid catalyst and the base are separated by distillation or crystallization; or the undistilled material contains a solid acid catalyst and a liquid acid catalyst.
  • the dehydration reaction of the fusel alcohol and the acetal reaction, the light product formed by the ketal reaction is condensed after evaporation, and collected, which is the substance to be removed, and the removed material includes the oil phase and the aqueous solution light product;
  • the aqueous solution in the substance is separated from the oil phase, and the acetal, ketal, dioxane product, aldehyde, ketone are separated from the oil phase; while the binary or polyhydric alcohol is removed, the byproduct acetal is removed.
  • the dehydration reactor itself can be used as a reactive distillation equipment to separate the above-mentioned by-products from ethylene glycol; the by-products can also be separated by reactive distillation;
  • the dehydration reaction with condensed reflux is carried out in the reaction vessel, and then the mixture is separated by liquid separation or extraction or adsorption or distillation.
  • Dehydration reaction the raw material used contains 50% to 95% of ethylene glycol, and contains 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2, One or more of binary or polyhydric alcohols such as 3-butanediol, 1,4-butanediol, and glycerin, and the content of the binary or polyhydric alcohol of non-ethylene glycol is between 5% and 50%.
  • the above crude ethylene glycol is added, heated to 150 to 198 ° C, and an acid catalyst is introduced, and the catalyst used accounts for 0.1% to 15% of the total mass of the dehydration reaction system.
  • the above dibasic or polyhydric alcohol is dehydrated and converted into an easily removable low boiling oil phase and an aqueous light product; wherein the 1,2-butanediol conversion is between 55% and 99.8%, 1, The conversion of 2-propanediol is between 50% and 99.6%;
  • the dehydration reactor itself can be used as a reactive distillation apparatus to separate the above-mentioned by-products from ethylene glycol; the by-products can also be separated by reactive distillation;
  • the dehydration reaction with condensed reflux may be carried out in the reaction vessel, and then the mixture may be separated by liquid separation or extraction or adsorption or distillation;
  • the liquid not distilled in the dehydration reactor contains an acid catalyst and an ethylene glycol intermediate product; the ethylene glycol intermediate product and the solid acid catalyst are separated by solid-liquid separation or distillation or rectification; , may be partially recycled, or may be completely neutralized with a base, and then removed by crystallization or distillation;
  • Vacuum distillation In the first step of dehydration, a small amount of high-boiling ethers such as diethylene glycol, triethylene glycol, tetraethylene glycol, and crown ether are generally produced.
  • the ethylene glycol intermediate product can be separated and purified by vacuum distillation.
  • the temperature of the column In order to avoid the polycondensation of ethylene glycol and ensure the yield of ethylene glycol, the temperature of the column is generally 116-135 ° C, and the pressure of the column is an absolute pressure of 3-17 kPa. ;
  • the impurities in the top product of the fourth step of vacuum distillation are mainly binary (such as 1,2-propanediol), which can be rectified and extracted. , crystallization, adsorption, chromatography, any one of them is removed, and high purity ethylene glycol is obtained;
  • the crude oil phase product obtained in the second step also contains a small amount of acetone, propionaldehyde and acetaldehyde.
  • the crude oil phase product can be initially separated into aldehyde, ketone light product and light by rectification.
  • the aldehyde and ketone mixture are mixed with the aldehyde and ketone concentrate obtained in the previous step, and different aldehyde or ketone products are separated by rectification;
  • acetal and ketal The main components of the acetal and ketal (very few) products obtained in the previous step are: propionaldehyde glycol acetal (light), propionaldehyde propylene glycol acetal (light weight) ), butyraldehyde glycol acetal (heavy), isobutyraldehyde propylene glycol acetal (heavy), etc., atmospheric boiling point between 100 ⁇ 138 ° C.
  • the light and heavy acetals are further separated by rectification or chromatography or gradient elution to obtain a relatively pure acetal product;
  • Catalyst regeneration the solid acid catalyst separated in the third step can be recycled by calcination or solvent elution or drying;
  • the dehydration reaction of the first step may be carried out by reactive distillation or reactive distillation;
  • the dehydration reaction of the first step is carried out at 180 to 186 ° C;
  • the HZSM5 acid molecular sieve having a ratio of 4% by mass of the reaction system of 25% or more of H ⁇ or a ratio of silica to alumina having a ratio of silica to alumina is used as a dehydration catalyst;
  • the reaction is carried out under normal pressure and liquid phase conditions
  • the high-temperature suspension containing the solid catalyst after the dehydration reaction is subjected to solid-liquid separation by heating.
  • the equipment required to carry out the invention mainly comprises: a catalytic dehydration reactor or a fixed bed reactor or a reactive rectification column, a solid-liquid separation device, a vacuum distillation device, a condenser, an oil separator, an atmospheric distillation device or Chromatography apparatus, etc.
  • Catalytic dehydration reaction ortho diol (ethylene glycol, 1,2-propanediol, 1,2-butanediol, 2,3-butanediol, etc.), under the action of an acid catalyst, the hydroxyl group is protonated, and then Remove one molecule of water to form carbon cations.
  • ortho diol ethylene glycol, 1,2-propanediol, 1,2-butanediol, 2,3-butanediol, etc.
  • the stability of the carbon cation determines the selectivity of the first dehydration reaction: the carbon cation (secondary carbon) formed by the ortho-butanediol has the highest stability, and the ortho-propylene glycol (secondary carbon), ethylene glycol. It is difficult to form carbon cations (primary carbon). Therefore, the conversion of 1,2-butanediol is the highest in the dehydration reaction, and 1,2-butanediol is the most difficult impurity to remove by conventional means. It is worth noting that a small amount of primary carbon atoms of propylene glycol also form carbon cations.
  • Pinacol rearrangement carbocation is transferred to a carbon atom to which another hydroxyl group is attached to form a relatively stable oxonium ion because the oxygen atom provides a conjugate of a lone pair of electrons and a carbon cation.
  • the coordination structure is relatively stable; at the same time as the carbon cation transfer, the transfer of alkyl or hydrogen occurs; and the primary carbon cation of the propylene glycol formed in the previous step also undergoes rearrangement reaction to form oxonium ions.
  • Both of the above oxonium ions are deprotonated to form stable aldehydes or ketones, of which the yield of aldehydes is higher.
  • aldehydes and ketones undergo acetal (ketone) reaction with ethylene glycol and propylene glycol under the action of high temperature and acid catalyst, mainly producing propionaldehyde glycol acetal, propionaldehyde propylene glycol acetal, butyraldehyde ethylene Alkenal, isobutyraldehyde propylene glycol acetal, four acetals.
  • isobutyraldehyde is a product of isomerization of n-butyraldehyde under the action of an acid catalyst.
  • the main reaction of dehydration can be carried out smoothly under the liquid phase system and normal pressure. Only the low-quality heat energy and the atmospheric pressure reaction kettle can be used to realize the main reaction. Under the premise of producing the same amount of 99% ethylene glycol, The total energy consumption of the invention is 50% to 75% of the conventional rectification method, and the process is energy-saving and environmentally friendly and low in cost.
  • the heavy product at the bottom of the vacuum distillation column associated with the refining of ethylene glycol is mainly a chain ether having a very low freezing point and can be used as a vehicle antifreeze.
  • acetaldehyde is 27 ° C lower than the boiling point of the other two carbonyl compounds, and acetaldehyde can be easily separated by rectification to obtain relatively pure acetaldehyde; the difference in boiling point between acetone and propionaldehyde At about 8.5 ° C, the two will not form azeotrope, and the boiling point is below 60 ° C. Only a lower temperature can be used to generate gas-liquid two phases, so only a low-quality heat can be used to rectify acetone and propionaldehyde. Separate.
  • Obtained dioxane crude product mainly oxygenated ethers (such as 1,4-dioxane), which can be used as raw materials for producing solvents, spray paints, varnishes, plasticizers and wetting agents. Potential market.
  • oxygenated ethers such as 1,4-dioxane
  • These materials generally have a flash point above 50 ° C and can be used as an oil additive to reduce the soot content of motor vehicle exhaust.
  • Acetal, ketal (very few) substances have a natural fruity or floral aroma, can be used as intermediates to synthesize higher value-added chemicals such as perfumes and fragrances.
  • acetal, shrinkage The economic value of ketones (very few) is far superior to that of ethylene glycol. Although its output is not high, it is dependent on its high production capacity. The diol industry has a considerable production. The acetal by-product enhances the industrial value of the entire separation process, giving the present invention a more significant economic advantage.
  • the invention can efficiently remove the polyhydric alcohol in the ethylene glycol, realize the recycling of the high value-added by-products, reduce the environmental pollution and energy consumption, and has significant economic advantages.
  • Figure 1 is a process flow diagram of the present invention.
  • (1) Dehydration reaction In the dehydration reactor, 100 mL of crude ethylene glycol is added, wherein the ethylene glycol mass fraction is 73%, the 1,2-propanediol mass fraction is 17%, and the 1,2-butanediol mass fraction is 10%; the material was heated to 180 ° C, 2 g of HZSM5 zeolite molecular sieve catalyst with an average particle size of 300 mesh and a silica-alumina ratio of 25 was added, and the mixture was thoroughly stirred, and the light product formed by dehydration of the binary fusel was distilled off, and ended after 4 hours;
  • the light product distilled in the first step contains low-boiling substances such as acetal, ketal (very few), water vapor, acetone, and propionaldehyde; in addition, part of the polyol vapor is also mixed into the light product. After condensing at 10 ° C condenser, liquefaction, collection, light products total about 20g;
  • the crude oil phase product obtained in the fifth step can be initially separated into ketone aldehyde light product (20-60 ° C) and light acetal (70-90 ° C) by atmospheric distillation. Mixtures of five different boiling ranges of dioxane crude product (90-100 ° C), heavy acetal (110-140 ° C), heavy oxygenated compound (140-190 ° C). Wherein, the aldehyde and ketone mixture is mixed with the aldehyde and ketone concentrate obtained in the seventh step, and is separated by common rectification;
  • the acetal and ketal (very few) products obtained in the previous step are The most abundant content of crude oil products is about 4g; among them, light acetals account for about 60%, the main components are propionaldehyde glycol acetal and propionaldehyde propylene glycol acetal; heavy acetals account for 40%, mainly butyraldehyde glycol acetal, isobutyraldehyde propylene glycol acetal. The light and heavy acetals can be further separated by two small atmospheric distillation columns to finally obtain four pure acetal products;
  • HZSM5 zeolite molecular sieve can be regenerated by calcination at a temperature of 550-580 ° C;
  • (1) Dehydration reaction In the dehydration reactor, 100 mL of crude ethylene glycol is added, wherein the ethylene glycol mass fraction is 73%, the 1,2-propanediol mass fraction is 17%, and the 1,2-butanediol mass fraction is 10%; The material was heated to 185 ° C, and 5 g of H ⁇ zeolite molecular sieve catalyst having an average particle diameter of 300 mesh and a silica-alumina ratio of 25 was charged, and the mixture was thoroughly stirred, and the light product formed by dehydration of the binary fusel was distilled off, and was finished after 4 hours;
  • the light product distilled in the first step contains low-boiling substances such as acetal, ketal (very few), water vapor, acetone, and propionaldehyde; in addition, part of the polyol vapor also enters the light product. After condensing at 10 ° C condenser, liquefaction, collection, light products total about 34g;
  • Liquid-liquid separation the distillate collected by condensation in the previous step enters the oil-water separator, and the oil-water two phases are separated, the oil phase is 24.9 g, and the aqueous phase is 9.1 g;
  • Extracting aldehydes and ketones from the crude phase of the aqueous phase separating the crude phase product obtained by the above step by atmospheric distillation, the distillate is mainly a mixture of acetaldehyde, propionaldehyde and acetone, and the tower is low in production.
  • the concentration of dioxane aqueous solution is separated by hot air stripping; the temperature of the overhead condenser is 8 ° C, and the temperature of the reboiler is about 92 ° C;
  • the crude oil phase product obtained in the fifth step can be initially separated into ketone aldehyde light product (20-60 ° C) and light acetal (70-90 ° C) by atmospheric distillation. Mixtures of five different boiling ranges of dioxane crude product (90-100 ° C), heavy acetal (110-140 ° C), heavy oxygenated compound (140-190 ° C). Wherein, the aldehyde and ketone mixture is mixed with the aldehyde and ketone concentrate obtained in the seventh step, and is separated by common rectification;
  • the acetal and ketal (very few) products obtained in the previous step are the most abundant substances in the crude oil phase, about 20 g; among them, light acetal About 60%, the main components are propionaldehyde glycol acetal and propionaldehyde propylene glycol acetal; heavy acetal accounted for about 40%, mainly butyraldehyde propylene glycol acetal, butyraldehyde glycol acetal.
  • the light and heavy acetals can be further separated by two small atmospheric distillation columns to finally obtain four pure acetal products;
  • H ⁇ zeolite molecular sieve can be regenerated by calcination at a temperature of 650-700 ° C;
  • Extracting aldehydes and ketones from the crude phase of the aqueous phase separating the crude phase product obtained by the above step by atmospheric distillation, the distillate is mainly a mixture of acetaldehyde, propionaldehyde and acetone, and the tower is low in production.
  • the concentration of dioxane aqueous solution is separated by steam stripping and is utilized; the temperature of the overhead condenser is 8 ° C, and the temperature of the reboiler is about 92 ° C;
  • the crude oil phase product obtained in the fifth step can be initially separated into ketone aldehyde light product (20-60 ° C) and light acetal (70-90 ° C) by atmospheric distillation. Mixtures of five different boiling ranges of dioxane crude product (90-100 ° C), heavy acetal (110-140 ° C), heavy oxygenated compound (140-190 ° C). Wherein, the aldehyde and ketone mixture is mixed with the aldehyde and ketone concentrate obtained in the fifth step, and is subjected to common rectification and separation;
  • HZSM5 zeolite molecular sieve can be regenerated by calcination at a temperature of 650-750 ° C;
  • (1) Dehydration reaction In the dehydration reactor, 100 mL of crude ethylene glycol is added, wherein the ethylene glycol mass fraction is 85%, the 1,2-propanediol mass fraction is 10%, and the 1,3-butanediol mass fraction is 5%; the material is heated to 185 ° C, adding 4% of concentrated sulfuric acid with a mass fraction of 98%, fully stirred, the light product formed by the dehydration of the binary sterol is distilled off, and ends after 4 hours;
  • the light product distilled in the first step contains low-boiling substances such as acetal, ketal (very few), water vapor, acetone, and propionaldehyde; in addition, part of the polyol vapor is also mixed into the light product. After condensing at 10 ° C condenser, liquefaction, collection, light products total about 13g;
  • liquid-liquid separation the distillate collected by condensation in the previous step enters the oil-water separator, and the oil-water two phases are separated, the oil phase is 9g, and the aqueous phase is 4g;
  • Extracting aldehydes and ketones from the crude phase of the aqueous phase separating the crude phase product obtained by the above step by atmospheric distillation, the distillate is mainly a mixture of acetaldehyde, propionaldehyde and acetone, and the tower is low in production.
  • the concentration of dioxane aqueous solution is separated by hot air stripping; the temperature of the overhead condenser is 8 ° C, and the temperature of the reboiler is about 92 ° C;
  • the crude oil phase product obtained in the fifth step can be initially separated into ketone aldehyde light product (20-60 ° C) and light acetal (70-90 ° C) by atmospheric distillation. , dioxane crude product (90 ⁇ 100 ° C), heavy acetal (110 ⁇ 140 ° C), heavy oxygen (140 ⁇ 190 ° C) five different boiling range mixture.
  • the aldehyde and ketone mixture is mixed with the aldehyde and ketone concentrate obtained in the seventh step, and is separated by common rectification;
  • Catalyst regeneration the residual liquid produced in the second step contains concentrated sulfuric acid and diethylene glycol, and the concentrated sulfuric acid can be separated and regenerated by vacuum distillation;
  • (1) Dehydration reaction In the dehydration reactor, 100 mL of crude ethylene glycol is added, wherein the ethylene glycol mass fraction is 60%, the 1,2-propanediol mass fraction is 25%, and the 2,3-butanediol mass fraction is 15%; the material was heated to 185 ° C, 3 g of HZSM5 zeolite molecular sieve catalyst with an average particle size of 300 mesh and a silica-alumina ratio of 25 was added, and the mixture was thoroughly stirred, and the light product formed by dehydration of the binary fusel was distilled off, and ended after 4 hours;
  • the light product distilled in the first step contains low-boiling substances such as acetal, ketal (very few), water vapor, acetone, and propionaldehyde; in addition, part of the polyol vapor is also mixed into the light product. After condensing at 10 ° C condenser, liquefaction, collection, light products total about 34g;
  • Extracting aldehydes and ketones from the crude phase of the aqueous phase separating the crude phase product obtained by the above step by atmospheric distillation, the distillate is mainly a mixture of acetaldehyde, propionaldehyde and acetone, and the tower is low in production.
  • the concentration of dioxane aqueous solution is separated by steam stripping and is utilized; the temperature of the overhead condenser is 8 ° C, and the temperature of the reboiler is about 92 ° C;
  • the crude oil phase product obtained in the fifth step can be initially separated into ketone aldehyde light product (20-60 ° C) and light acetal (70-90 ° C) by atmospheric distillation. Mixtures of five different boiling ranges of dioxane crude product (90-100 ° C), heavy acetal (110-140 ° C), heavy oxygenated compound (140-190 ° C). Wherein, the aldehyde and ketone mixture is mixed with the aldehyde and ketone concentrate obtained in the seventh step, and is separated by common rectification;
  • HZSM5 zeolite molecular sieve can be regenerated by calcination at a temperature of 700 to 750 ° C;
  • Continuous reactive distillation 1.2t of H ⁇ zeolite molecular sieve catalyst with a silicon to aluminum ratio of 160 is filled in the lower part of the continuous pressure distillation column at normal pressure as a reaction zone; 1t filler is charged in the upper part as a rectification zone; 1t/h of crude ethylene glycol, wherein the ethylene glycol mass fraction is 73% and the 1,2-propanediol mass fraction is 17%. 1,2-butanediol mass fraction is 10%; tower kettle is heated to 185 ° C, overhead condenser is set to 10 ° C; condensate production is about 200 kg / h;
  • the heavy component produced by the reaction distillation in the previous step is further separated by another vacuum distillation column, the absolute pressure at the top of the column is 10 kPa, and the temperature of the column is 140 °C.
  • the light component distilled is a crude ethylene glycol product with a yield of 630 kg/h, a purity of over 96%, a concentration of 1,2-butanediol of less than 0.4%, and a residue product as an antifreeze;
  • Extracting aldehydes and ketones from the crude phase of the aqueous phase separating the crude phase product obtained by the above step by atmospheric distillation, the distillate is mainly a mixture of acetaldehyde, propionaldehyde and acetone, and the tower is low in production.
  • the concentration of dioxane aqueous solution is separated by hot air stripping; the temperature of the overhead condenser is 8 ° C, and the temperature of the reboiler is about 92 ° C;
  • the crude oil phase product obtained in the fifth step can be initially separated into ketone aldehyde light product (20-60 ° C) and light acetal (70-90 ° C) by atmospheric distillation. Mixtures of five different boiling ranges of dioxane crude product (90-100 ° C), heavy acetal (110-140 ° C), heavy oxygenated compound (140-190 ° C). Wherein, the aldehyde and ketone mixture is mixed with the aldehyde and ketone concentrate obtained in the fifth step, and is subjected to rectification and separation;
  • acetal and ketal (very few) The acetal and ketal (very few) products obtained in the previous step are the most abundant substances in the crude oil phase, and the yield is 197 kg/h;
  • the acetal is about 60%, and the main components are propionaldehyde glycol acetal and propionaldehyde propylene glycol acetal;
  • heavy acetal accounts for about 40%, mainly butyraldehyde glycol acetal and isobutyraldehyde propylene glycol acetal.
  • the light and heavy acetals can be further separated by two small atmospheric distillation columns to finally obtain four pure acetal products;
  • Catalyst regeneration the H ⁇ zeolite molecular sieve is fully calcined and recycled at a temperature of 550 to 600 ° C using an industrial electric furnace, and recycled;

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Abstract

本发明公开了一种沸点接近的多元醇混合物的分离方法，以含有二元或多元杂醇(如1,2-丙二醇和1,2-丁二醇)的乙二醇为原料，在酸催化剂的作用下，二元或多元杂醇经过(1)脱水反应(2)频哪醇重排(3)缩醛或缩酮反应，生成醛类(少量)、缩醛、缩酮(极少)，并通过蒸馏收集；同时，反应液经过进一步分离，得到高纯乙二醇。本发明提供了一种通过液相脱水反应除去乙二醇中二元或多元杂醇的路线，反应条件温和，能耗较低；特别是对用常规手段难以除去的1,2-丁二醇具有较高的脱除率，最后得到纯度很高的乙二醇产品；同时副产附加值较高的缩醛类或缩酮类化合物，也能产出一定的乙醛、丙醛和丙酮等基础化工原料。本发明是将难以分离的乙二醇粗产品转化为高纯乙二醇及其他化工产品的绿色环保工艺。

Description

一种沸点接近的多元醇混合物的分离方法 技术领域
本发明涉及一种沸点接近的多元醇混合物的分离方法，属于化工分离技术领域。
背景技术
乙二醇俗名甘醇，是一种大宗生产的基础化工原料，可以用来生产聚酯纤维(涤纶)、聚对苯二甲酸乙二醇酯、炸药、溶剂、抗冻剂、增塑剂、吸湿剂等。由于技术垄断和石油产量的限制，我国的乙二醇供应长期依赖进口；自2002年来，中国的乙二醇进口量所占需求量的比例一直维持在70％以上。其中聚酯行业消耗的乙二醇占80％以上。
传统的乙二醇合成路线建立在石化工业的基础上，主要以乙烷为原料，经环氧乙烷中间体与水加成而生成乙二醇，同时副产二甘醇、三甘醇等低附加值产化学品。其关键技术主要被Shell(英荷)、Halcon-SD(美国)、Dow Chemical(美国)、以及UCC(美国)所垄断。另外，水合过程和分离流程需要消耗大量的水、热能、石油和天然气。碳酸乙烯酯法是乙二醇合成的新工艺，其充分利用了环氧乙烷装置所排放的纯度较高的二氧化碳，减少了碳排放，且几乎不消耗水，减少了分离能耗，此工艺更为显著的优点是能够联产碳酸二甲酯。但该合成方法也需要消耗环氧乙烷，仍然不能摆脱对石油的依赖，而且其核心技术同样被国外公司垄断。
随着科学技术的进步，以煤或生物质为原料生产乙二醇逐渐显现出了其巨大的优势，不但可以减少国家对石油的依赖，而且能够打破国外的技术壁垒。尤其是生物质基乙二醇生产工艺，其原料是富含纤维素的木材、草本植物等廉价、速生、零碳排放的材料，因此可以降低生产成本、有效地减少温室效应。是具有广阔前景的乙二醇生产工艺。
以煤为原料制备乙二醇，主要包括甲醛电化加氢二聚法、甲醇聚合法、草酸酯法。其中甲醛电化加氢二聚法的乙二醇收率较高，但耗电较多，且生成的乙二醇原液纯度很低，精制提纯成本较高。草酸酯法是目前被广泛认为最有前景的煤基乙二醇合成路线。它是以合成气中的CO为中间媒介，通过氧化偶联反应生成草酸酯，再经过草酸酯的催化加氢而最终生成乙二醇。由于过度加氢，反应体系会生成甲醇和乙醇，而乙二醇会和甲醇、乙醇发生Guerbet反应，分别生成1,2-丙二醇和1,2-丁二醇。其中1,2-丁二醇和乙二醇沸点最为接近，且能形成共沸物，因此工业精馏塔的能耗很大，这也是煤基乙二醇路线难以实现工业化的一个重要原因。
在以生物质为原料的合成路线中，由于催化剂的选择性有限，在纤维素长链的氢解过程中，除了生成乙二醇主产物以外，另有约30％～40％的二元杂醇和三元杂醇等生成，如1,2-丙二醇、1,2-丁二醇、1,3-丁二醇、2,3-丁二醇、甘油等。其中二元杂醇的沸点和乙二醇相差约10℃，且部分二醇和乙二醇能形成共沸物，导致精馏分离效率和能耗显著增加。二元杂醇和乙二醇的物理性质和化学性质均接近，因此精馏、萃取、吸附等常规手段难以将其分离。另外，常温和低温下的多元醇混合物粘度很大，特别是在流道狭小的空间会产生很大的流动阻力，增加了输送能耗。同时，由于乙二醇属大宗化学品，对其产率要求较高，而液相 吸附法的处理量较小，因此吸附分离法也不适用于多元醇的分离提纯。
发明内容
本发明提供了一种从多元醇混合物中有效分离多元杂醇、纯化乙二醇的新方法。此方法工艺流程短，分离简单，可以将难以除去的杂质多元醇转化为易分离的、具有高附加值的缩醛类或缩酮类化合物。过程能耗低，成本低，经济性高，三废量少，是一种高效节能环保的分离路线。具体说来，以含有1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,2-戊二醇、1,2-己二醇、1,3-丁二醇、2,3-丁二醇、1,4-丁二醇、甘油中的一种或二种以上杂醇的乙二醇粗产品为原料，含有杂醇的乙二醇粗产品是以煤或生物质为原料合成的，其中含有乙二醇的质量浓度为50％～95％，含有杂醇的质量含量在5％～50％之间。
在常压下将乙二醇粗产品与酸催化剂混合，在脱水反应器中加热开始脱水反应，脱水反应温度在150～198℃；上述杂醇发生脱水反应和缩醛反应、缩酮反应转化为轻产物，然后轻产物通过蒸馏或精馏得到移除，从而将上述杂醇从乙二醇中去除。所用的酸催化剂包括液体质子酸、固体质子酸、路易斯酸、含有酸性中心的氧化物、或含有酸性中心的矿物中的一种或二种以上的组合，其中活性较好的催化剂为氢型分子筛、磺酸化活性炭、氢型树脂、硫酸、盐酸、硝酸，酸催化剂占脱水反应体系总质量的0.1％～15％。乙二醇产物经再次纯化，去除其中含有的二元杂醇，可得到高纯乙二醇产品；纯化方式为精馏、萃取、结晶、吸附、层析中的任意一种或二种以上组合。脱水反应器中未蒸发的物料含有固体酸催化剂和乙二醇时：通过固液分离、蒸馏或精馏分离出乙二醇产物和固体酸催化剂，所述的固液分离设备是压滤式或真空吸滤式或沉降式或离心式或叶片式固液分离设备中的任意一种。固体酸催化剂可通过焙烧或溶剂洗脱或干燥再生，循环使用；或，未蒸出的物料含有液体酸催化剂和乙二醇时：通过蒸馏或精馏分离出乙二醇产物和液体酸催化剂，液体酸催化剂循环使用；或，加碱中和后通过蒸馏或结晶分离出乙二醇产物和液体酸催化剂与碱的中和反应产物；或，未蒸出的物料含有固体酸催化剂、液体酸催化剂和乙二醇时：通过固液分离去除固体酸催化剂、然后通过蒸馏或精馏将乙二醇产物和液体酸催化剂分离；或通过蒸馏或精馏直接分离出乙二醇产物。
杂醇发生脱水反应和缩醛反应、缩酮反应生成的轻产品蒸发后被冷凝、收集，其为被移除的物质，被移除的物质包括油相和水溶液轻产物；将被移除的物质中的水溶液与油相分离，并从油相中分离出缩醛、缩酮、二氧六环类产品、醛、酮；在脱除二元或多元杂醇的同时，有副产物缩醛、缩酮、环醚、链醚、醛、酮产生；脱水反应器本身可作为反应蒸馏设备将上述副产物从乙二醇中分离；也可采用反应精馏的方式分离上述副产物；也可以先在反应釜中进行带有冷凝回流的脱水反应，然后再通过分液或萃取或吸附或蒸馏对混合物加以分离
实现上述方法的具体步骤如下：
(1)脱水反应：所用原料含有乙二醇50％～95％，并含有1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、2,3-丁二醇、1,4-丁二醇、甘油等二元或多元杂醇中的一种以上，非乙二醇的二元或多元杂醇的含量在5％～50％之间。在脱水反应器中，加入上述乙二醇粗品，加热至150～198℃，投入酸催化剂，所用催化剂占脱水反应体系总质量的0.1％～15％。在充分搅拌下，上述二元或多元杂醇发生脱水反应转化为易去除的低沸点油相和水溶液轻产物；其中1,2-丁二醇转化率在55％～99.8％之间，1,2-丙二醇转化率在50％～99.6％之间；
(2)低沸点产物的移除：在脱水反应器的高温下，上一步所生成的低沸点产物蒸发、冷凝、收集、油水分液；油状轻产品包括乙醛乙二醇缩醛、丙醛乙二醇缩醛、丙醛丙二醇缩醛、丁醛乙二醇缩醛、正丁醛丙二醇缩醛、异丁醛丙二醇缩醛、丁酮乙二醇缩酮、1,4-二氧六环等；同时有少量丙酮、丙醛、丁醛、丁酮等产生；脱水反应器本身可作为反应蒸馏设备将上述副产物从乙二醇中分离；也可采用反应精馏的方式分离上述副产物；也可以先在反应釜中进行带有冷凝回流的脱水反应，然后再通过分液或萃取或吸附或蒸馏对混合物加以分离；
(3)催化剂分离：脱水反应器中未蒸出的液体含有酸催化剂和乙二醇中间产品；通过固液分离或蒸馏或精馏将乙二醇中间产品和固体酸催化剂分离；如果用液体酸，可部分循环使用，也可全部用碱中和，然后通过结晶或蒸馏除去；
(4)减压精馏：在第一步脱水反应中，一般会生成少量的二甘醇、三甘醇、四甘醇、冠醚等高沸点醚类。可以通过减压精馏将乙二醇中间产品分离纯化，为了避免乙二醇的缩聚、保证乙二醇的收率，塔釜温度一般在116～135℃，塔釜压力为绝对压力3～17kPa；
(5)极少量二元或多元杂醇的脱除：第四步减压精馏的塔顶产品所含杂质主要是二元杂醇(如1,2-丙二醇)，可通过精馏、萃取、结晶、吸附、层析中的任意一种除去，并得到高纯乙二醇；
(6)提取水相粗产品中的醛、酮：第二步所得水相粗产品的主要成分是水，其次含有一定量的丙酮、丙醛、乙醛等，其沸点与水-二氧六环的共沸物相差30℃左右，可以通过气提或蒸馏将醛和酮加以浓缩，得到这三种醛、酮的混合物，然后通过精馏分离；
(7)油相粗产品的初步分离：第二步所得的油相粗产品也含有少量丙酮、丙醛、乙醛，通过精馏可将油相粗产品初步分离为醛、酮轻产品、轻质缩醛、二氧六环粗产品、重质缩醛、重质含氧化合物五种不同沸程的混合物。其中，醛、酮混合物与上一步所得的醛、酮浓缩液混合，通过精馏分离出不同的醛或酮产品；
(8)缩醛、缩酮的提纯：上一步所得缩醛、缩酮(极少)产品的主要组分为：丙醛乙二醇缩醛(轻质)、丙醛丙二醇缩醛(轻质)、丁醛乙二醇缩醛(重质)、异丁醛丙二醇缩醛(重质)等，常压沸点在100～138℃之间。通过精馏技术或层析法或梯度洗脱法将轻质、重质缩醛进一步分离，最终得到较为纯净的缩醛产品；
(9)催化剂再生：第三步分离出的固体酸催化剂可通过焙烧或溶剂洗脱或干燥再生，循环使用；
作为优选，第一步的脱水反应可以采用反应蒸馏或反应精馏的方式；
作为优选，第一步的脱水反应在180～186℃下进行；
作为优选，占反应体系质量分数4％的硅铝比为25或160的Hβ或硅铝比为25的HZSM5酸分子筛用作脱水催化剂；
作为优选，反应在常压、液相条件下进行；
作为优选，可将脱水反应后含有固体催化剂的高温悬浊液趁热进行固液分离。
实现本发明所需的设备主要有：催化脱水反应器或固定床反应器或反应精馏塔、固-液分离设备、减压精馏设备、冷凝器、分油器、常压精馏设备或层析装置等。
本发明分离多元醇以及制备缩醛、缩酮(极少)产品的原理是：
催化脱水反应：邻位二醇(乙二醇、1,2-丙二醇、1,2-丁二醇、2,3-丁二醇等)，在酸催化剂的作用下，羟基发生质子化，然后脱去一分子水生成碳正离子。
其中碳正离子的稳定性决定了第一步脱水反应的选择性：邻位丁二醇所形成的碳正离子(仲碳)稳定性最高，邻位丙二醇次之(仲碳)，乙二醇难以形成碳正离子(伯碳)。因此，脱水反应中1,2-丁二醇的转化率最高，而1,2-丁二醇正是常规手段最难除去的杂质。值得注意的是，少量丙丁二醇的伯碳原子也会形成碳正离子。
频哪醇(pinacol)重排：碳正离子转移至另一个羟基所连接的碳原子上，形成比较稳定的氧鎓离子，原因是氧原子提供孤对电子和碳正离子发生共轭，所形成的配位结构较为稳定；在碳正离子转移的同时，发生烷基或氢的转移；而上一步形成的丙丁二醇的伯碳正离子也会发生重排反应生成氧鎓离子。
以上两种氧鎓离子都发生去质子化，分别形成稳定的醛类或酮类，其中醛类的收率更高。
二次脱水反应：醛、酮类在高温和酸催化剂的作用下与乙二醇、丙二醇发生缩醛(酮)化反应，主要生成丙醛乙二醇缩醛、丙醛丙二醇缩醛、丁醛乙二醇缩醛、异丁醛丙二醇缩醛四种缩醛。其中异丁醛是正丁醛在酸催化剂的作用下发生异构化的产物。由于酮类的羰基被两侧的烷基阻挡而难以反应，绝大部分丙酮直接蒸发，所以最终产物中缩酮的量极少，在缩醛产品中不必分离。因此酮醛类产品中的丙酮最多，其次为丙醛和乙醛。而丁醛和丁酮(极少)则全部发生了缩醛反应。
与现有技术相比，本发明的优势在于：
对1，2-丁二醇和1,2-丙二醇有很高的选择性，能够除去55％～99.8％的1，2-丁二醇、50％～99.6％的1,2-丙二醇，乙二醇终产品能够满足下游聚酯工业的要求。
脱水主反应在液相体系、常压下即可顺利进行，只需要较少的低品质的热能和常压反应釜即可实现主反应，在生产等量99％乙二醇的前提下，本发明的总能耗为常规精馏方法的50％～75％，过程节能环保且成本低廉。
与乙二醇精制有关的减压精馏塔底的重质产品主要是凝固点很低的链醚，可以用作机动车抗冻剂。
在煤基草酸二甲酯制乙二醇工艺及生物质基乙二醇生产工艺中，某些副反应会导致含羰基杂质的生成，如醛、酮、二酮，这些杂质含量较少，但有强烈的紫外吸收，对乙二醇品质影响很大；本工艺可将含羰基的杂质转化为缩醛或缩酮等没有强紫外吸收的产物，从而提高了乙二醇的品质；另外，本脱水反应所产生的醛或酮沸点很低，在操作过程中与乙二醇完全分离，通过气相色谱没有检测出乙二醇终产品中含有因脱水而生成的羰基化合物。
可获得三种醛、酮类产品：乙醛比另外两种羰基化合物的沸点低27℃，可以通过精馏较为容易地将乙醛分离，得到较纯的乙醛；丙酮、丙醛的沸点差约8.5℃，二者不会形成共沸，且沸点在60℃以下，只需较低温度即可生成气液两相，因此只需消耗低品质的热量即可通过精馏将丙酮、丙醛加以分离。
可获得二氧六环粗产品：主要是含氧的醚类(如1,4-二氧六环)，可用作生产溶剂、喷漆、清漆、增塑剂、润湿剂的原料，具有一定的潜在市场。
可获得重质含氧化合物产品：此类物质闪点一般高于50℃，可作为油品添加剂，能够降低机动车废气的烟尘含量。
缩醛、缩酮(极少)类物质具有天然的果香或花香味，可以用作中间体合成香料和香精等附加值更高的化学品，就相同质量的产品而言，缩醛、缩酮(极少)类的经济价值远超乙二醇主产品。虽然其产量不高，但由于其依托高生产量的乙 二醇产业，其产量也较为可观。缩醛副产品能提升整个分离工艺的工业价值，使本发明具有更显著的经济优势。
基于上述原因，本发明能够高效脱除乙二醇中的多元杂醇，且实现了高附加值副产品的回收利用，减少了环境污染和能量消耗，具有显著的经济优势。
附图说明
图1为本发明的工艺流程图。
图中：1、多元醇原料 2、催化剂 3、脱水反应釜 4、催化剂分离 5、催化剂再生器 6、气液分离 7、液相 8、气相 9、真空蒸馏 10、二甘醇、三甘醇、甘油等重组分 11、减压精馏 12、1,2-丙二醇等二(多)元杂醇 13、乙二醇主产品 14、冷凝器 15、油水分离器 16、水相粗产品 17、油相粗产品 18、精馏装置 19、水 20、醛和酮 21、精馏装置 22、乙醛 23、丙醛 24、丙酮 25、精馏装置 26、轻质缩醛 27、二氧六环粗产品 28、重质含氧化合物 29、精馏或层析 30、丙醛乙二醇缩醛 31、丙醛丙二醇缩醛 32、重质缩醛 33、精馏或层析 34、异丁醛丙二醇缩醛 35、丁醛乙二醇缩醛。
具体实施方式
下面结合附图和实例对本发明进行详细说明。
实施例一
(1)脱水反应：在脱水反应器中，加入乙二醇粗品100mL，其中乙二醇质量分数为73％，1,2-丙二醇质量分数为17％，1,2-丁二醇质量分数为10％；将物料加热至180℃，投入平均粒径为300目、硅铝比为25的HZSM5沸石分子筛催化剂2g，充分搅拌，二元杂醇脱水生成的轻产物被蒸出，4h后结束；
(2)催化剂分离：脱水反应结束后，将沸石分子筛与液相产品用离心法分离，离心机转速为6000rpm；
(3)精馏纯化：上一步脱水反应结束后，将反应器内的液体混合物通过减压精馏加以分离，塔顶绝压10kPa，塔釜温度为135～150℃。蒸馏出约65g乙二醇粗产品，纯度在90％以上，1,2-丁二醇的浓度低于1％；釜残液产品作为抗冻剂；
(4)精馏除杂醇：通过减压精馏除去杂质1,2-丙二醇和极少量的1,2-丁二醇，塔釜温度为115～130℃，塔顶绝压10kPa，所得乙二醇纯度在98％以上；
(5)气液分离：第一步被蒸出的轻产物含有缩醛、缩酮(极少)、水蒸气、丙酮、丙醛等低沸点物质；另外，部分多元醇蒸汽也混入轻产品。经过10℃的冷凝器冷凝后液化、收集，轻产品共约20g；
(6)液液分离：上一步通过冷凝收集得到的馏出物进入油-水分离器，将油水两相加以分离，油相12g，水相8g；
(7)提取水相粗产品中的醛、酮：通过常压精馏分离上一步得到的水相粗产品，馏出物主要是乙醛、丙醛、丙酮的混合物，塔釜采出的低浓度二氧六环水溶液经过水蒸气气提分离后加以利用；塔顶冷凝器温度为8℃，再沸器温度约为92℃；
(8)油相粗产品的初步分离：通过常压精馏可将第5步所得油相粗产品初步分离为酮醛轻产品(20～60℃)、轻质缩醛(70～90℃)、二氧六环粗产品(90～100℃)、重质缩醛(110～140℃)、重质含氧化合物(140～190℃)五类不同沸程的混合物。其中，醛酮混合物与第7步所得的醛酮浓缩液混合，共同精馏分离；
(9)缩醛、缩酮(极少)的提纯：上一步所得缩醛、缩酮(极少)产品是 油相粗产品中含量最多的一类物质，约有4g；其中轻质缩醛约占60％，主要组分为丙醛乙二醇缩醛和丙醛丙二醇缩醛；重质缩醛约占40％，主要为丁醛乙二醇缩醛、异丁醛丙二醇缩醛。通过两个小型常压精馏塔即可分别将轻质和重质缩醛进一步分离，最终得到四种纯净的缩醛产品；
(10)催化剂再生：HZSM5沸石分子筛可以在550～580℃的温度下通过焙烧再生；
实施例二
(1)脱水反应：在脱水反应器中，加入乙二醇粗品100mL，其中乙二醇质量分数为73％，1,2-丙二醇质量分数为17％，1,2-丁二醇质量分数为10％；将物料加热至185℃，投入平均粒径为300目、硅铝比为25的Hβ沸石分子筛催化剂5g，充分搅拌，二元杂醇脱水生成的轻产物被蒸出，4h后结束；
(2)催化剂分离：脱水反应结束后，将Hβ沸石分子筛与液相产品用真空吸滤机分离；
(3)精馏纯化：上一步脱水反应结束后，将反应器内的混合物通过减压精馏加以分离，收集绝压10kPa下沸点低于150℃的轻馏分，约65g，产品的乙二醇浓度在97.5％以上，1,2-丁二醇的浓度低于0.5％，1,2-丙二醇的浓度低于2％；釜残液产品作为抗冻剂；
(4)精馏除杂醇：通过减压精馏除去杂质1,2-丙二醇，塔顶绝压10kPa，塔釜温度为115～130℃，所得乙二醇纯度为99.5％；
(5)气液分离：第一步被蒸出的轻产物含有缩醛、缩酮(极少)、水蒸气、丙酮、丙醛等低沸点物质；另外，部分多元醇蒸汽也进入轻产品。经过10℃的冷凝器冷凝后液化、收集，轻产品共约34g；
(6)液液分离：上一步通过冷凝收集得到的馏出物进入油-水分离器，将油水两相加以分离，油相24.9g，水相9.1g；
(7)提取水相粗产品中的醛、酮：通过常压精馏分离上步所得的水相粗产品，馏出物主要是乙醛、丙醛、丙酮的混合物，塔釜采出的低浓度二氧六环水溶液经过热空气气提分离后加以利用；塔顶冷凝器温度为8℃，再沸器温度约为92℃；
(8)油相粗产品的初步分离：通过常压精馏可将第5步所得油相粗产品初步分离为酮醛轻产品(20～60℃)、轻质缩醛(70～90℃)、二氧六环粗产品(90～100℃)、重质缩醛(110～140℃)、重质含氧化合物(140～190℃)五类不同沸程的混合物。其中，醛酮混合物与第7步所得的醛酮浓缩液混合，共同精馏分离；
(9)缩醛、缩酮(极少)的提纯：上一步所得缩醛、缩酮(极少)产品是油相粗产品中含量最多的一类物质，约有20g；其中轻质缩醛约占60％，主要组分为丙醛乙二醇缩醛和丙醛丙二醇缩醛；重质缩醛约占40％，主要为丁醛丙二醇缩醛、丁醛乙二醇缩醛。通过两个小型常压精馏塔即可分别将轻质和重质缩醛进一步分离，最终得到四种纯净的缩醛产品；
(10)催化剂再生：Hβ沸石分子筛可以在650～700℃的温度下通过焙烧再生；
实施例三
(1)间歇式反应精馏：在常压间歇式反应精馏柱下部填充硅铝比为25的HZSM5沸石分子筛催化剂100g，作为反应区；上部装入100g填料，作为精馏区；塔釜加入乙二醇粗品100mL，其中乙二醇质量分数为73％，1,2-丙二醇质量分数为17％，1,4-丁二醇质量分数为10％；塔釜加热至180～190℃，塔顶冷凝器设为 10℃；收集冷凝液，约22g，3h后结束；
(2)精馏纯化：上一步反应精馏所产生的重组分再通过另一个减压精馏柱加以分离，塔顶绝压10kPa，塔釜温度为135～150℃。蒸馏出的轻组分为乙二醇粗产品，约67g，纯度在93％以上，1,4-丁二醇的浓度低于0.4％；釜残液产品作为抗冻剂；
(3)精馏除杂醇：通过减压精馏除去杂质1,2-丙二醇，塔顶绝压10kPa，塔釜温度为115～130℃，所得乙二醇产品纯度在99.3％以上；
(4)液液分离：将第1步收集得到的馏出物用油-水分离器加以分离，得到油相13g，水相9g；
(5)提取水相粗产品中的醛、酮：通过常压精馏分离上步所得的水相粗产品，馏出物主要是乙醛、丙醛、丙酮的混合物，塔釜采出的低浓度二氧六环水溶液经过水蒸气气提分离后加以利用；塔顶冷凝器温度为8℃，再沸器温度约为92℃；
(6)油相粗产品的初步分离：通过常压精馏可将第5步所得油相粗产品初步分离为酮醛轻产品(20～60℃)、轻质缩醛(70～90℃)、二氧六环粗产品(90～100℃)、重质缩醛(110～140℃)、重质含氧化合物(140～190℃)五类不同沸程的混合物。其中，醛酮混合物与第5步所得的醛酮浓缩液混合，共同精馏分离；
(7)缩醛、缩酮(极少)的提纯：上一步所得缩醛、缩酮(极少)产品是油相粗产品中含量最多的一类物质，约有4g；其中轻质缩醛约占60％，重质缩醛约占40％。通过两个小型常压精馏塔即可分别将轻质和重质缩醛进一步分离，最终得到四种纯净的缩醛产品；
(8)催化剂再生：HZSM5沸石分子筛可以在650～750℃的温度下通过焙烧再生；
实施例四
(1)脱水反应：在脱水反应器中，加入乙二醇粗品100mL，其中乙二醇质量分数为85％，1,2-丙二醇质量分数为10％，1,3-丁二醇质量分数为5％；将物料加热至185℃，加入质量分数98％的浓硫酸4g，充分搅拌，二元杂醇脱水生成的轻产物被蒸出，4h后结束；
(2)浓硫酸分离与精馏纯化：上一步脱水反应结束后，将反应器内的重组分通过减压精馏加以分离，塔顶绝压10kPa，塔釜温度为135～150℃。蒸馏出的轻组分为乙二醇产品，约67g，纯度在96％以上，1,3-丁二醇的浓度低于0.5％；
(3)精馏除杂醇：通过减压精馏除去杂质1,2-丙二醇，塔顶绝压10kPa，塔釜温度为115～130℃，所得乙二醇产品纯度在99.2％以上；
(4)气液分离：第一步被蒸出的轻产物含有缩醛、缩酮(极少)、水蒸气、丙酮、丙醛等低沸点物质；另外，部分多元醇蒸汽也混入轻产品。经过10℃的冷凝器冷凝后液化、收集，轻产品共约13g；
(5)液液分离：上一步通过冷凝收集得到的馏出物进入油-水分离器，将油水两相加以分离，油相9g，水相4g；
(6)提取水相粗产品中的醛、酮：通过常压精馏分离上步所得的水相粗产品，馏出物主要是乙醛、丙醛、丙酮的混合物，塔釜采出的低浓度二氧六环水溶液经过热空气气提分离后加以利用；塔顶冷凝器温度为8℃，再沸器温度约为92℃；
(7)油相粗产品的初步分离：通过常压精馏可将第5步所得油相粗产品初步分离为酮醛轻产品(20～60℃)、轻质缩醛(70～90℃)、二氧六环粗产品(90～ 100℃)、重质缩醛(110～140℃)、重质含氧化合物(140～190℃)五类不同沸程的混合物。其中，醛酮混合物与第7步所得的醛酮浓缩液混合，共同精馏分离；
(8)缩醛、缩酮(极少)的提纯：上一步所得缩醛、缩酮(极少)产品是油相粗产品中含量最多的一类物质，约有4g；其中轻质缩醛约占60％，重质缩醛约占40％。通过两个小型常压精馏塔即可分别将轻质和重质缩醛进一步分离，最终得到四种纯净的缩醛产品；
(9)催化剂再生：第2步所产生的釜残液含有浓硫酸和二甘醇等物质，可通过减压精馏将浓硫酸分离再生；
实施例五
(1)脱水反应：在脱水反应器中，加入乙二醇粗品100mL，其中乙二醇质量分数为60％，1,2-丙二醇质量分数为25％，2,3-丁二醇质量分数为15％；将物料加热至185℃，投入平均粒径为300目、硅铝比为25的HZSM5沸石分子筛催化剂3g，充分搅拌，二元杂醇脱水生成的轻产物被蒸出，4h后结束；
(2)催化剂分离：脱水反应结束后，将沸石分子筛与液相产品用叶片式固液分离设备分离；
(3)精馏纯化：上一步脱水反应结束后，将反应器内的重组分通过减压精馏加以分离，塔顶绝压10kPa，塔釜温度为135～150℃。蒸馏出的轻组分为乙二醇产品，约53g，纯度在84％以上，2,3-丁二醇的浓度低于1％；残液产品作为抗冻剂；
(4)精馏除杂醇：通过减压精馏除去杂质1,2-丙二醇，塔顶绝压10kPa，塔釜温度为115～130℃，所得乙二醇产品纯度在99％以上；
(5)气液分离：第一步被蒸出的轻产物含有缩醛、缩酮(极少)、水蒸气、丙酮、丙醛等低沸点物质；另外，部分多元醇蒸汽也混入轻产品。经过10℃的冷凝器冷凝后液化、收集，轻产品共约34g；
(6)液液分离：上一步通过冷凝收集得到的馏出物进入油-水分离器，将油水两相加以分离，油相20g，水相14g；
(7)提取水相粗产品中的醛、酮：通过常压精馏分离上步所得的水相粗产品，馏出物主要是乙醛、丙醛、丙酮的混合物，塔釜采出的低浓度二氧六环水溶液经过水蒸气气提分离后加以利用；塔顶冷凝器温度为8℃，再沸器温度约为92℃；
(8)油相粗产品的初步分离：通过常压精馏可将第五步所得油相粗产品初步分离为酮醛轻产品(20～60℃)、轻质缩醛(70～90℃)、二氧六环粗产品(90～100℃)、重质缩醛(110～140℃)、重质含氧化合物(140～190℃)五类不同沸程的混合物。其中，醛酮混合物与第7步所得的醛酮浓缩液混合，共同精馏分离；
(9)缩醛、缩酮(极少)的提纯：上一步所得缩醛、缩酮(极少)产品是油相粗产品中含量最多的一类物质，约有8.5g；其中轻质缩醛约占60％。通过两个小型常压精馏塔即可分别将轻质和重质缩醛进一步分离，最终得到四种纯净的缩醛产品；
(10)催化剂再生：HZSM5沸石分子筛可以在700～750℃的温度下通过焙烧再生；
实施例六
(1)连续式反应精馏：在常压连续式反应精馏柱下部填充硅铝比为160的Hβ沸石分子筛催化剂1.2t，作为反应区；上部装入1t填料，作为精馏区；塔中部进乙二醇粗品1t/h，其中乙二醇质量分数为73％，1,2-丙二醇质量分数为17％， 1,2-丁二醇质量分数为10％；塔釜加热至185℃，塔顶冷凝器设为10℃；冷凝液产量约为200kg/h；
(2)精馏纯化：上一步反应精馏所产生的重组分再通过另一个减压精馏塔加以分离，塔顶绝压10kPa，塔釜温度为140℃。蒸馏出的轻组分为乙二醇粗产品，产量为630kg/h，纯度在96％以上，1,2-丁二醇的浓度低于0.4％；釜残液产品作为抗冻剂；
(3)精馏除杂醇：通过减压精馏除去杂质1,2-丙二醇，塔顶绝压10kPa，塔釜温度为115～130℃，所得乙二醇产品纯度为99.7％，产量为610kg/h；
(4)液液分离：将第1步收集得到的馏出物用斜板分油器加以分离，其中油相产率为230kg/h，水相产率为110kg/h；
(5)提取水相粗产品中的醛、酮：通过常压精馏分离上步所得的水相粗产品，馏出物主要是乙醛、丙醛、丙酮的混合物，塔釜采出的低浓度二氧六环水溶液经过热空气气提分离后加以利用；塔顶冷凝器温度为8℃，再沸器温度约为92℃；
(6)油相粗产品的初步分离：通过常压精馏可将第5步所得油相粗产品初步分离为酮醛轻产品(20～60℃)、轻质缩醛(70～90℃)、二氧六环粗产品(90～100℃)、重质缩醛(110～140℃)、重质含氧化合物(140～190℃)五类不同沸程的混合物。其中，醛酮混合物与第5步所得的醛酮浓缩液混合，精馏分离；
(7)缩醛、缩酮(极少)的提纯：上一步所得缩醛、缩酮(极少)产品是油相粗产品中含量最多的一类物质，产率为197kg/h；其中轻质缩醛约占60％，主要组分为丙醛乙二醇缩醛和丙醛丙二醇缩醛；重质缩醛约占40％，主要为丁醛乙二醇缩醛、异丁醛丙二醇缩醛。通过两个小型常压精馏塔即可分别将轻质和重质缩醛进一步分离，最终得到四种纯净的缩醛产品；
(8)催化剂再生：使用工业电炉在550～600℃的温度下将Hβ沸石分子筛进行充分焙烧再生，循环使用；
上述各实施例仅为效果较好的实现方式，除此之外，仍有许多类似方法可实现本发明，凡采用等同或等效替换的技术方案，均在本发明的保护范围之内。

Claims (10)

  1. 一种沸点接近的多元醇混合物的分离方法，其特征在于：以含有1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,2-戊二醇、1,2-己二醇、1,3-丁二醇、2,3-丁二醇、1,4-丁二醇、甘油中的一种或二种以上杂醇的乙二醇粗产品为原料，在高于150℃的温度下与酸催化剂混合，在脱水反应器中加热开始脱水反应；上述杂醇发生脱水反应和缩醛反应、缩酮反应转化为轻产物，然后轻产物通过蒸馏或精馏得到移除，从而将上述杂醇从乙二醇中去除。
  2. 根据权利要求1所述的方法，其特征在于：所用的酸催化剂包括液体质子酸、固体质子酸、路易斯酸、含有酸性中心的氧化物、或含有酸性中心的矿物中的一种或二种以上的组合。
  3. 根据权利要求1所述的方法，其特征在于：乙二醇产物经再次纯化，去除其中含有的二元杂醇，可得到高纯乙二醇产品；纯化方式为精馏、萃取、结晶、吸附、层析中的任意一种或二种以上组合。
  4. 根据权利要求1所述的方法，其特征在于：脱水反应器中未蒸发的物料含有固体酸催化剂和乙二醇时：通过固液分离、蒸馏或精馏分离出乙二醇产物和固体酸催化剂，固体酸催化剂可通过焙烧或溶剂洗脱或干燥再生，循环使用；或，未蒸出的物料含有液体酸催化剂和乙二醇时：通过蒸馏或精馏分离出乙二醇产物和液体酸催化剂，液体酸催化剂循环使用；或，加碱中和后通过蒸馏或结晶分离出乙二醇产物和液体酸催化剂与碱的中和反应产物；或，未蒸出的物料含有固体酸催化剂、液体酸催化剂和乙二醇时：通过固液分离去除固体酸催化剂、然后通过蒸馏或精馏将乙二醇产物和液体酸催化剂分离；或通过蒸馏或精馏直接分离出乙二醇产物。
  5. 根据权利要求1所述的方法，其特征在于：杂醇发生脱水反应和缩醛反应、缩酮反应生成的轻产品蒸发后被冷凝、收集，其为被移除的物质，被移除的物质包括油相和水溶液轻产物；将被移除的物质中的水溶液与油相分离，并从油相中分离出缩醛、缩酮、二氧六环类产品、醛、酮；在脱除二元或多元杂醇的同时，有副产物缩醛、缩酮、环醚、链醚、醛、酮产生；脱水反应器本身可作为反应蒸馏设备将上述副产物从乙二醇中分离；也可采用反应精馏的方式分离上述副产物；也可以先在反应釜中进行带有冷凝回流的脱水反应，然后再通过分液或萃取或吸附或蒸馏对混合物加以分离。
  6. 根据权利要求1所述的方法，其特征在于：所用原料含有乙二醇质量浓度为50％～95％，并含有1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,2-戊二醇、1,2-己二醇、1,3-丁二醇、2,3-丁二醇、1,4-丁二醇、甘油中的一种以上的杂醇，杂醇的质量含量在5％～50％之间。
  7. 根据权利要求1或2所述的方法，其特征在于：所用酸催化剂为氢型分子筛、磺酸化活性炭、氢型树脂、硫酸、盐酸、硝酸，酸催化剂占脱水反应体系总质量的0.1％～15％。
  8. 根据权利要求1所述的方法，其特征在于：常压下，脱水反应温度在150～198℃。
  9. 根据权利要求1所述的方法，其特征在于：含有杂醇的乙二醇粗产品是以煤或生物质为原料合成的。
  10. 根据权利要求1所述的方法，其特征在于：所述的固液分离设备是压滤式或真空吸滤式或沉降式或离心式或叶片式固液分离设备中的任意一种。
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