CN105693687B - High-efficiency reactive distillation method and device for glycol acetal/ketone reaction - Google Patents
High-efficiency reactive distillation method and device for glycol acetal/ketone reaction Download PDFInfo
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Abstract
The invention relates to a high-efficiency reactive distillation method and a device for glycol acetal/ketone reaction, wherein a reactive distillation tower consists of a distillation section and a reactive distillation section, a glycol raw material is one or a mixture of ethylene glycol, propylene glycol and butanediol, a feed inlet of the reactive distillation tower is arranged at the top of the reactive distillation section, an aldehyde/ketone feed inlet is arranged at the bottom of the reactive distillation tower, an acetal/ketone product is discharged from the top of the reactive distillation tower, and the acetal/ketone product is obtained after the aldehyde/ketone is recovered by an aldehyde/ketone recovery tower. The method and the device are characterized in that the lower half part of the tower is provided with a reaction rectifying section, the reaction heat of the acetal/ketone reaction can be well utilized, the method can obtain high conversion rate in the acetal/ketone reaction of the glycol, the flow is simple, and the method and the device can obtain remarkable economic benefit when being applied to the acetal/ketone reaction of the glycol in the coal-to-glycol or biomass catalytic method to prepare the glycol or other process flows.
Description
Technical Field
The invention belongs to the field of chemical rectification separation, and relates to a high-efficiency reaction rectification method and device for a glycol acetal/ketone reaction.
Background
The diol acetal/ketone reaction can be applied not only to the preparation of diol acetal/ketone products such as 1, 3-dioxolane, 2-methyl-1, 3-dioxolane, 4-ethyl-2-methyl-1, 3-dioxolane, meanwhile, due to the reaction reversibility, the method can be applied to the separation of mixed glycol, such as the separation of liquid phase mixture of glycol prepared by coal or glycol prepared by biomass catalysis, because the boiling points of the ethylene glycol, the propylene glycol and the butanediol are close and the relative volatility is small, particularly the ethylene glycol and the 1, 2-butanediol can form azeotropy, so that the separation of ethylene glycol requires a high energy consumption, while a certain amount of ethylene glycol has to be wasted, and the propylene glycol and butanediol products with high addition value cannot be well utilized, so that the economical efficiency of the process flow is reduced. By adopting reversible acetal/ketone reaction, the mixed diol is firstly converted into acetal/ketone products, and the acetal/ketone products are obtained by hydrolysis refining after separation, so that the pressure for removing propylene glycol and butanediol in the original process can be greatly reduced, higher yield of ethylene glycol products can be obtained, and byproducts such as propylene glycol and butanediol can be recovered.
Compared with the acetal/ketone reaction process flow with separate operation of reaction and separation, the reaction rectification process flow which organically couples the reaction and rectification unit operations in the same equipment and simultaneously carries out, can greatly simplify the process, the reaction rectification technology can continuously remove the product from the reaction zone through rectification separation, keep the concentration of reactants in the reaction zone at a higher degree, ensure the reaction rate, simultaneously promotes the forward progress of the reaction, breaks through the limit of chemical reaction balance, realizes high conversion rate, the heat of reaction is well utilized, the energy-saving effect is achieved, and better economic benefit is obtained by using the ethylene glycol as an important basic organic chemical raw material, and the ethylene glycol is mainly used for producing polyester fibers, antifreeze, unsaturated polyester resin, lubricant, plasticizer, nonionic surfactant, explosive and the like. China is a large ethylene glycol consuming country, the domestic ethylene glycol yield can not meet the self demand, in 2014, the domestic ethylene glycol yield is 350 ten thousand tons, and the apparent consumption reaches 1225 ten thousand tons, so the domestic ethylene glycol industry has a good development prospect.
At present, the large-scale ethylene glycol production at home and abroad adopts a direct hydration method or a pressurized hydration method process line, and the process comprises the steps of mixing ethylene oxide and water according to the ratio of 1: 20-22 (molar ratio) to prepare a mixed aqueous solution, reacting in a fixed bed reactor at 130-180 ℃ and 1.0-2.5 MPa for 18-30 minutes, completely converting the ethylene oxide into mixed alcohol, and then performing dehydration concentration and reduced pressure rectification separation by using a multi-effect evaporator to obtain the ethylene glycol. The evaporation dehydration consumes a large amount of energy, and in order to reduce the cost, catalytic hydration methods are researched by major companies and scientific research institutes for producing ethylene glycol at home and abroad. Meanwhile, research is also directed to an ethylene carbonate method, in which ethylene carbonate is synthesized from ethylene oxide and carbon dioxide, and ethylene glycol is obtained by hydrolysis of the ethylene carbonate, and patents US 4508927, US 4500559 and JP 571006631 propose different process routes for the ethylene carbonate method. Along with the increasing shortage of petroleum resources, the world oil price fluctuation is large, and the method has very important significance in developing C1 chemical engineering in China by combining the resource conditions of lean oil, less gas and rich coal in China, so that the dependence on petroleum import can be reduced, and the environmental pressure is relieved. The process of preparing the synthesis gas by taking coal or natural gas as a raw material, preparing oxalate by coupling the synthesis gas and obtaining glycol by hydrogenating the oxalate is considered to be the line with the most industrial prospect, and more than 20 sets of devices for domestic on-line production and coal glycol preparation are currently built. The reaction product of the hydrogenation of oxalate to ethylene glycol contains substances with low boiling points such as methanol and glycolate, and also contains a small amount of substances which have close boiling points to ethylene glycol and are difficult to separate by ordinary rectification, such as 1, 2-propylene glycol, 1, 2-butanediol and the like, wherein the boiling points of the 1, 2-butanediol and the ethylene glycol are the closest, and the 1, 2-butanediol and the ethylene glycol form azeotropy, so that the separation is the most difficult. In addition, as a sustainable energy line, a route for producing glycol such as ethylene glycol from biomass has attracted much attention from various countries, such as the biomass catalytic process for producing ethylene glycol, which is studied by the institute of academicians, the institute of chemical and physical research, the institute of academy of the academy of sciences. The separation of ethylene glycol and 1, 2-butanediol is also a problem in obtaining high purity diol chemical products.
Aiming at the problem that butanediol and ethylene glycol are difficult to separate, glycol acetal/ketone products are obtained through a glycol mixture acetal/ketone reaction, then separation is carried out, and glycol products are obtained through glycol acetal/ketone products hydrolysis respectively, so that the mutual separation of the ethylene glycol and 1, 2-butanediol mixtures can be economically and effectively realized. The patent provides a reaction rectification method and a device which have high efficiency, energy conservation, simple flow and high reaction conversion rate for the acetal/ketone reaction.
The reactive distillation technology is a process strengthening technology which couples reaction and separation in the same equipment and simultaneously carries out the reaction and the separation. The reaction of the diol and the aldehyde/ketone is a heat-releasing reversible reaction, the reaction rectification technology can continuously remove products from a reaction zone through rectification separation, keep the concentration of reactants in the reaction zone at a high degree, ensure the reaction rate, promote the forward progress of the reaction, break through the limitation of chemical reaction balance, realize high conversion rate, well utilize the heat of the reaction and achieve the effect of energy conservation. Compared with a process in which the reaction and the separation are operated separately, the reactive distillation process used in the acetal/ketone reaction can realize better economic benefits for the whole separation process of the liquid phase mixture of the ethylene glycol prepared from coal or the ethylene glycol prepared by the biomass catalysis method.
Disclosure of Invention
The invention aims to provide a high-efficiency reactive distillation method and a device for glycol acetal/ketone reaction, and the reactive distillation method provided by the invention has the advantages of simple process flow, low equipment investment, high glycol conversion rate, low energy consumption and the like when being used for the acetal/ketone reaction of a glycol simple substance or a glycol mixture.
The invention also particularly provides a high-efficiency reactive distillation method for the acetal/ketone reaction of the mixture of the ethylene glycol and the butanediol.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a high-efficient reaction rectifier unit of glycol acetal/ketone reaction which characterized in that: the device comprises a reactive distillation column (T11), an aldehyde/ketone recovery column (T12), a condenser, a reboiler, a pump, related feed pipelines and pipelines for connecting the devices, and the specific connection mode is as follows:
the feed line of the diol raw material (S01) is connected to the top of the reactive distillation section of the reactive distillation column (T11), and the feed line of the aldehyde/ketone (S02) is connected to the bottom of the reactive distillation column (T11); the top extraction pipeline of the reactive distillation column (T11) is connected with the feed pipeline of the aldehyde/ketone recovery column (T12); feeding materials are extracted from the top of the aldehyde/ketone recovery tower (T12) and connected to the bottom of the reaction rectifying tower (T11) for recycling, glycol acetal/ketone products are extracted from the bottom of the aldehyde/ketone recovery tower (T12), and condensers and reboilers are arranged at the inlet and outlet positions of the reaction rectifying tower (T11) and the aldehyde/ketone recovery tower (T12) according to requirements.
Moreover, the reactive distillation column (T11) is composed of a distillation section and a reactive distillation section, wherein the distillation section uses a packing or a tray, and the reactive distillation section uses a catalytic packing or a catalytic tray.
Further, a rectifying section for separating and recovering the unreacted aldehyde/ketone may be provided in the rectifying section of the reactive rectifying column (T11), and the acetal/ketone reaction product may be taken out from the side of the reactive rectifying column (T11) without using the aldehyde/ketone recovering column (T12).
A high-efficiency reactive distillation method for glycol acetal/ketone reaction comprises the steps of enabling a glycol stream (S01) and an aldehyde/ketone stream (S02) to respectively enter a reactive distillation column (T11) from the upper part of a reactive distillation section and the bottom of the column, and carrying out acetal/ketone reaction in the reactive distillation section in the column; a gas phase (S03) at the top of the reactive distillation column (T11) passes through an overhead condenser (E1) and a liquid phase (S04) passes through a reactive distillation column reflux extraction pump (P1) to obtain a liquid phase (S05), wherein one part of the liquid phase is used as reflux (S06), and the other part of the liquid phase is used as a feed (S07) of an aldehyde/ketone recovery column (T12); an aldehyde/ketone recovery tower (T12) overhead gas phase (S08) passes through an overhead condenser (E3) and a liquid phase (S09) passes through a reflux extraction pump (P2) to obtain a liquid phase (S10), one part of the liquid phase is taken as overhead reflux (S11), the other part of an extracted stream (S12) is recycled to a tower bottom feed of the reactive distillation tower (T11), and a glycol acetal/ketone product (S13) is extracted from the tower bottom.
And the gas phase (S03) at the top of the reactive distillation column (T11) passes through an overhead condenser (E1) and the liquid phase (S04) passes through a reflux extraction pump (P1) to obtain a liquid phase (S05), one part of the liquid phase is taken as reflux (S06), the other part of the liquid phase is taken as an extracted aldehyde/ketone stream and circulated to the feeding material (S07) at the bottom of the reactive distillation column, and the liquid phase extracted at a certain position of a rectifying section (S08) passes through a feeding pump (P2) to obtain a glycol acetal/ketone product (S09).
Moreover, the operating pressure of the reactive distillation tower is 0.05-10 atm in absolute pressure, the reflux ratio is 0.01-40, and the molar ratio of the aldehyde/ketone amount entering the tower kettle of the reactive distillation tower to the total amount of the glycol to be treated is controlled to be 1-15 by adopting a solid acid or solid base catalyst; the operation pressure of the aldehyde/ketone recovery tower is 0.1-10 atm in absolute pressure, the reflux ratio is 0.01-10, and the purity of the aldehyde/ketone obtained by separation is controlled at the tower top.
A high-efficient reaction rectification method for acetal/ketone reaction of ethylene glycol and butanediol mixture comprises the steps of enabling a mixed glycol stream (S01) of ethylene glycol and butanediol and an aldehyde/ketone stream (S02) to respectively enter a reaction rectification tower (T11) from the upper part of a reaction rectification section and a tower bottom, and carrying out acetal/ketone reaction in the reaction rectification section in the tower; a gas phase (S03) at the top of the reactive distillation column (T11) passes through an overhead condenser (E1) and a liquid phase (S04) passes through a reactive distillation column reflux extraction pump (P1) to obtain a liquid phase (S05), wherein one part of the liquid phase is used as reflux (S06), and the other part of the liquid phase is used as a feed (S07) of an aldehyde/ketone recovery column (T12); an aldehyde/ketone recovery tower (T12) overhead gas phase (S08) passes through an overhead condenser (E3) and a liquid phase (S09) passes through a reflux extraction pump (P2) to obtain a liquid phase (S10), one part of the liquid phase is taken as overhead reflux (S11), the other part of an extracted stream (S12) is recycled to a tower bottom feed of the reactive distillation tower (T11), and a glycol acetal/ketone product (S13) is extracted from the tower bottom.
Moreover, the operating pressure of the reactive distillation tower is 0.1-5 atm in absolute pressure, the reflux ratio is 0.01-30, and the molar ratio of the aldehyde/ketone amount entering the tower kettle of the reactive distillation tower to the total amount of the glycol to be treated is controlled to be 1-10 by adopting a solid acid or solid alkali resin catalyst; the operation pressure of the aldehyde/ketone recovery tower is 0.2-10 atm in absolute pressure, and the reflux ratio is 0.01-10.
Moreover, the high-efficiency reactive distillation method for the acetal/ketone reaction of the ethylene glycol and butanediol mixture is characterized in that aldehyde is C1-C8 aldehyde, and ketone is C3-C8 ketone.
A high-efficiency reactive distillation method for acetal/ketone reaction of a mixture of ethylene glycol and butanediol is characterized in that a gas phase (S03) at the top of a reactive distillation column (T11) passes through an overhead condenser (E1) and a liquid phase (S04) and then passes through a reflux extraction pump (P1) to obtain a liquid phase (S05), one part of the liquid phase is used as reflux (S06), the other part of the liquid phase is used as an extracted aldehyde/ketone stream and circulated to a column bottom feeding (S07) of the reactive distillation column, and a liquid phase extraction (S08) at a certain position of a distillation section is used as a diol acetal/ketone product (S09) after passing through a feeding pump (P2).
The invention has the following advantages and beneficial effects:
the high-efficiency reactive distillation method and the device for the glycol acetal/ketone reaction have the advantages that the exothermic reversible acetal/ketone reaction is arranged at the lower section of the reactive distillation tower, the rectification is well utilized to promote the reaction, the high conversion rate is realized, the equipment and heat are well integrated, the method and the device have the advantages of simple process flow, low equipment investment, high glycol conversion rate, low energy consumption and the like, and the glycol acetal/ketone reaction can obtain good economic benefit.
The method is applied to the acetal/ketone reaction of the mixture of ethylene glycol and butanediol, can obtain high conversion rate, has simple process, is applied to the acetal/ketone reaction separation of the mixture of ethylene glycol and butanediol in the process flow of preparing ethylene glycol by coal or preparing ethylene glycol by a biomass catalytic method or in other process flows, and can obtain remarkable economic benefit.
Drawings
FIG. 1 is a schematic diagram of a high efficiency reactive distillation process for a glycol acetal/ketone reaction.
FIG. 2 is a schematic diagram of a high efficiency reactive distillation process for the glycol acetal/ketone reaction without the aldehyde/ketone recovery column.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments, which are illustrative only and not limiting, and the scope of the present invention is not limited thereby.
The first part
The technical scheme of the invention is as follows:
the invention provides a high-efficiency reactive distillation device for glycol acetal/ketone reaction, which comprises a reactive distillation column (T11), an aldehyde/ketone recovery column (T12), a condenser, a reboiler, a pump, related feed pipelines and pipelines for connecting the above devices, as shown in figure 1. The feed line of the diol raw material (S01) is connected to the top of the reactive distillation section of the reactive distillation column (T11), and the feed line of the aldehyde/ketone (S02) is connected to the bottom of the reactive distillation column (T11); the top extraction pipeline of the reactive distillation column (T11) is connected with the feed pipeline of the aldehyde/ketone recovery column (T12); feeding materials from the tower bottom of the aldehyde/ketone recovery tower (T12) connected to the reactive distillation tower (T11) are extracted from the tower top of the aldehyde/ketone recovery tower (T12) and recycled, and glycol acetal/ketone products are extracted from the tower bottom of the aldehyde/ketone recovery tower (T11).
The reaction rectifying tower (T11) is composed of a rectifying section and a reaction rectifying section, wherein the rectifying section uses a filler or a tray, the reaction rectifying section uses a catalytic filler or a catalytic tray, and the catalyst adopts a solid acid or solid base resin catalyst.
The high-efficiency reactive distillation device for the glycol acetal/ketone reaction can be provided with a rectifying section for separating and recovering unreacted aldehyde/ketone in the rectifying section of the reactive distillation column (T11), thereby saving an aldehyde/ketone recovery column (T12), as shown in figure 2.
The invention relates to a high-efficiency reactive distillation method for glycol acetal/ketone reaction, which comprises the following steps: feeding the glycol stream (S01) and the aldehyde/ketone stream (S02) into a reactive distillation column (T11) from the upper part and the bottom of the reactive distillation section respectively, and carrying out an acetal/ketone reaction in the reactive distillation section in the column; a gas phase (S03) at the top of the reactive distillation column (T11) passes through an overhead condenser (E1) and a liquid phase (S04) passes through a reactive distillation column reflux extraction pump (P1) to obtain a liquid phase (S05), wherein one part of the liquid phase is used as reflux (S06), and the other part of the liquid phase is used as a feed (S07) of an aldehyde/ketone recovery column (T12); an aldehyde/ketone recovery tower (T12) overhead gas phase (S08) passes through an overhead condenser (E3) and a liquid phase (S09) passes through a reflux extraction pump (P2) to obtain a liquid phase (S10), one part of the liquid phase is taken as overhead reflux (S11), the other part of an extracted stream (S12) is recycled to a tower bottom feed of the reactive distillation tower (T11), and a glycol acetal/ketone product (S13) is extracted from the tower bottom.
The high-efficiency reactive distillation method for the glycol acetal/ketone reaction comprises the following steps of preparing a mixture of glycol, ethylene glycol, propylene glycol and butylene glycol, wherein the aldehyde can be C1-C8 aldehyde such as formaldehyde, acetaldehyde, propionaldehyde and butyraldehyde, the ketone can be C3-C8 ketone such as acetone, butanone and cyclohexanone, and the mixture of the glycol, the propylene glycol and the butylene glycol can be obtained.
If the separation and recovery of aldehyde/ketone are realized on a reactive distillation tower, the method comprises the following steps: gas phase (S03) at the top of a reactive rectifying tower (T11) passes through an overhead condenser (E1) and liquid phase (S04) passes through a reflux extraction pump (P1) to obtain liquid phase (S05), one part of the liquid phase is used as reflux (S06), the other part of the liquid phase is used as an extracted aldehyde/ketone stream and circulated to a tower bottom feeding material (S07) of the reactive rectifying tower, and liquid phase extraction (S08) at a certain position of a rectifying section passes through a feeding pump (P2) to obtain a glycol acetal/ketone product (S09).
In the technical scheme of the high-efficiency reactive distillation of the glycol acetal/ketone reaction, the operating pressure of a reactive distillation tower is 0.05-10 atm in absolute pressure, the reflux ratio is 0.01-40, a solid acid or solid base resin catalyst is adopted, and the molar ratio of the amount of aldehyde/ketone entering the tower kettle of the reactive distillation tower to the total amount of glycol to be treated is controlled to be 1-15; the operation pressure of the aldehyde/ketone recovery tower is 0.1-10 atm in absolute pressure, the reflux ratio is 0.01-10, and the purity of the aldehyde/ketone obtained by separation is controlled at the tower top.
In order to fully illustrate the advantages of the above aspects, the present invention provides the following embodiments.
Example 1
Adopting the flow shown in figure 1, the glycol is 1, 2-butanediol, the treatment capacity is 450kg/hr, the aldehyde/ketone is acetaldehyde, the total plate number of the reactive distillation column is 20, the 7 th to 20 th stages are reactive distillation sections, macroporous acidic cationic resin is used as a catalyst, and the molar ratio of the acetaldehyde amount entering the reactive distillation column to the total glycol amount is 1.2: 1, operating the pressure of the reactive distillation tower at absolute pressure of 0.5atm, and the reflux ratio of 0.17; the total theoretical plate number of the aldehyde/ketone recovery column was 19, the operating pressure was 2atm absolute, and the operating reflux ratio was 1.8.
After the process, butanediol is basically and completely converted, and the conversion rate reaches over 99.8 percent.
Example 2
By adopting the flow shown in fig. 1, the diol is a mixture of ethylene glycol and 1, 2-butanediol, wherein the content of ethylene glycol is 61.6 w%, the treatment capacity is 1000kg/hr, the used aldehyde/ketone is propionaldehyde, the total plate number of the reactive distillation column is 21, stages 7 to 21 are reactive distillation sections, a strongly acidic molecular sieve (NKC-9) is used as a catalyst, and the molar ratio of the total amount of propionaldehyde entering the reactive distillation column to the total amount of diol is 1.3: 1, operating the pressure of the reactive distillation tower at absolute pressure of 0.5atm, and the reflux ratio of 0.14; the total theoretical plate number of the aldehyde/ketone recovery tower is 22, the operation pressure is normal pressure, and the operation reflux ratio is 1.8.
After the process, the ethylene glycol and the butanediol are basically and completely converted, the conversion rate of the ethylene glycol is over 99.5 percent, and the conversion rate of the butanediol is over 99.8 percent.
Example 3
Adopting the flow shown in figure 1, the diols are the mixture of ethylene glycol, 1, 2-propylene glycol and 1, 2-butanediol, the compositions are 61.6 w% of ethylene glycol, 16.5 w% of 1, 2-propylene glycol and 21.9 w% of 1, 2-butanediol, the treatment capacity is 1500kg/hr, the used aldehyde/ketone is acetaldehyde, the total plate number of the reactive distillation tower is 21, the 7 th to 21 th stages are reactive distillation sections, the metal heteropolyacid is used as a catalyst, the molar ratio of the total amount of propionaldehyde entering the reactive distillation tower to the total amount of diol is 1.25: 1, operating the pressure of the reactive distillation tower at absolute pressure of 0.5atm, and the reflux ratio of 0.16; the total theoretical plate number of the aldehyde/ketone recovery column was 22, the operating pressure was 2atm in terms of absolute pressure, and the operating reflux ratio was 1.8.
After the process, the conversion rate of the ethylene glycol reaches over 99.4 percent, the conversion rate of the 1, 2-propylene glycol reaches over 99.5 percent, and the conversion rate of the 1, 2-butylene glycol reaches over 99.8 percent. The above catalyst can be used (macroporous acidic cationic resin NCK-9).
Example 4
The raw material situation of the embodiment 2 is processed by adopting the process flow shown in fig. 2, the total plate number of the reactive distillation tower is 29, the 16 th to 29 th stages are reactive distillation sections, macroporous basic anion resin is used as a catalyst, and the molar ratio of the total amount of propionaldehyde entering the reactive distillation tower to the total amount of glycol is 1.18: 1, the operating pressure of the reactive distillation column is normal pressure, the reflux ratio is 16, the glycol stream is fed from a 15 th-stage theoretical plate, reaction products are extracted from the lateral line of an 11 th theoretical plate, and the purity of propionaldehyde is controlled at the top of the reactive distillation column for recycling.
After the process, the conversion rate of the ethylene glycol reaches 99.2 percent, and the conversion rate of the 1, 2-butanediol reaches 99.6 percent.
The second part
The invention is embodied to a high-efficiency reaction rectification device for the acetal/ketone reaction of the mixture of the ethylene glycol and the butanediol according to the device, which comprises a reaction rectification tower (T11), an aldehyde/ketone recovery tower (T12), a condenser, a reboiler, a pump, related feeding pipelines and pipelines for connecting the devices. A feed line of the mixture raw material (S01) of the ethylene glycol and the butanediol is connected to the top of a reaction rectifying section of the reaction rectifying tower (T11), and a feed line of the aldehyde/ketone (S02) is connected to the bottom of the reaction rectifying tower (T11); the top extraction pipeline of the reactive distillation column (T11) is connected with the feed pipeline of the aldehyde/ketone recovery column (T12); feeding materials from the tower bottom of the aldehyde/ketone recovery tower (T12) connected to the reactive distillation tower (T11) are extracted from the tower top of the aldehyde/ketone recovery tower (T12) and recycled, and glycol acetal/ketone products are extracted from the tower bottom of the aldehyde/ketone recovery tower (T11). The reaction rectifying tower (T11) is composed of a rectifying section and a reaction rectifying section, wherein the rectifying section uses a filler or a tray, the reaction rectifying section uses a catalytic filler or a catalytic tray, and the catalyst adopts a solid acid or solid base resin catalyst.
The high-efficiency reactive distillation method for the acetal/ketone reaction of the corresponding ethylene glycol and butanediol mixture comprises the following steps: respectively feeding a mixed glycol stream (S01) of ethylene glycol and butanediol and an aldehyde/ketone stream (S02) into a reactive distillation column (T11) from the upper part and the bottom of the reactive distillation section, and carrying out an acetal/ketone reaction in the reactive distillation section in the column; a gas phase (S03) at the top of the reactive distillation column (T11) passes through an overhead condenser (E1) and a liquid phase (S04) passes through a reactive distillation column reflux extraction pump (P1) to obtain a liquid phase (S05), wherein one part of the liquid phase is used as reflux (S06), and the other part of the liquid phase is used as a feed (S07) of an aldehyde/ketone recovery column (T12); an aldehyde/ketone recovery tower (T12) overhead gas phase (S08) passes through an overhead condenser (E3) and a liquid phase (S09) passes through a reflux extraction pump (P2) to obtain a liquid phase (S10), one part of the liquid phase is taken as overhead reflux (S11), the other part of an extracted stream (S12) is recycled to a tower bottom feed of the reactive distillation tower (T11), and a glycol acetal/ketone product (S13) is extracted from the tower bottom.
If the separation and recovery of aldehyde/ketone are realized on a reactive distillation tower, the method comprises the following steps: gas phase (S03) at the top of a reactive rectifying tower (T11) passes through an overhead condenser (E1) and liquid phase (S04) passes through a reflux extraction pump (P1) to obtain liquid phase (S05), one part of the liquid phase is used as reflux (S06), the other part of the liquid phase is used as an extracted aldehyde/ketone stream and circulated to a tower bottom feeding material (S07) of the reactive rectifying tower, and liquid phase extraction (S08) at a certain position of a rectifying section passes through a feeding pump (P2) to obtain a glycol acetal/ketone product (S09).
The invention relates to a high-efficiency reaction rectification method for acetal/ketone reaction of a mixture of ethylene glycol and butanediol, wherein aldehyde can be C1-C8 aldehyde such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde and the like, and ketone can be C3-C8 ketone such as acetone, butanone, cyclohexanone and the like.
In the technical scheme of the high-efficiency reactive distillation for the acetal/ketone reaction of the ethylene glycol and butanediol mixture, the operating pressure of a reactive distillation tower is 0.1-5 atm in absolute pressure, the reflux ratio is 0.01-30, a solid acid or solid base resin catalyst is adopted, and the molar ratio of the amount of aldehyde/ketone entering the tower kettle of the reactive distillation tower to the total amount of the processed glycol is controlled to be 1-10; the operation pressure of the aldehyde/ketone recovery tower is 0.2-10 atm in absolute pressure, the reflux ratio is 0.01-10, and the purity of the aldehyde/ketone obtained by separation is controlled at the tower top.
Detailed description of the preferred embodiments example 1
By adopting the flow shown in FIG. 1, the mixture of ethylene glycol and butanediol contains 50.8 w% of ethylene glycol, the treatment capacity is 10kg/hr, the aldehyde/ketone is acetaldehyde, the total plate number of the reactive distillation tower is 21, stages 7 to 21 are reactive distillation sections, macroporous acidic cationic resin is used as a catalyst, and the molar ratio of the acetaldehyde amount entering the reactive distillation tower to the total glycol amount is 1.2: 1, operating the pressure of the reactive distillation tower at absolute pressure of 0.5atm, and the reflux ratio of 0.16; the total theoretical plate number of the aldehyde/ketone recovery column was 20, the operating pressure was 2atm absolute, and the operating reflux ratio was 1.7.
After the above process, both ethylene glycol and butanediol are substantially completely converted.
Detailed description of the preferred embodiments example 2
By adopting the flow shown in fig. 1, the mixture of ethylene glycol and butanediol contains 61.6 w% of ethylene glycol, the treatment capacity is 1000kg/hr, the used aldehyde/ketone is propionaldehyde, the total plate number of the reaction rectifying tower is 20, the 7 th to 20 th stages are reaction rectifying sections, the metal heteropolyacid is used as a catalyst, and the molar ratio of the total amount of the propionaldehyde entering the reaction rectifying tower to the total amount of the glycol is 1.3: 1, operating the pressure of the reactive distillation tower at absolute pressure of 0.5atm, and the reflux ratio of 0.14; the total theoretical plate number of the aldehyde/ketone recovery tower is 20, the operation pressure is normal pressure, and the operation reflux ratio is 2.
After the above process, both ethylene glycol and butanediol are substantially completely converted.
Concrete application example 3
By using the scheme shown in FIG. 2, the mixture of ethylene glycol and butanediol contained 63.6 w% of ethylene glycol, the throughput was 100kg/hr, and the aldehyde/ketone used was acetaldehyde. The total plate number of the reactive distillation column is 29, the 16 th to 29 th stages are reactive distillation sections, a strong acid molecular sieve is used as a catalyst, and the molar ratio of the total amount of propionaldehyde entering the reactive distillation column to the total amount of glycol is 1.18: 1, the operating pressure of the reactive distillation column is normal pressure, the reflux ratio is 16, the glycol stream is fed at a 15 th-level theoretical plate, reaction products are collected at the lateral line of an 11 th theoretical plate, and the purity of acetaldehyde is controlled at the top of the column for recycling.
After the process, the conversion rate of the ethylene glycol reaches 99.7 percent, and the conversion rate of the butylene glycol reaches 99.8 percent.
The present invention provides a high efficiency reactive distillation apparatus and method for the acetal/ketone reaction of ethylene glycol and butanediol mixture, which has been described with reference to the preferred embodiments, but is not limited to the specific apparatus described above, and it will be apparent to those skilled in the art that the present technology can be practiced by modifying or appropriately changing the apparatus and process flow described herein without departing from the spirit, scope and spirit of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention.
Claims (1)
1. Process for the aldolisation/ketonization of mixtures of ethylene glycol and butanediol, characterized in that: the reactive distillation device adopted by the method comprises a reactive distillation column (T11), an aldehyde/ketone recovery column (T12), a condenser, a reboiler, a pump, related feed pipelines and pipelines for connecting the above devices, wherein the feed pipeline of the raw material (S01) of the mixture of ethylene glycol and butanediol is connected to the top of the reactive distillation section of the reactive distillation column (T11), and the feed pipeline of the aldehyde/ketone (S02) is connected to the bottom of the reactive distillation column (T11); the top extraction pipeline of the reactive distillation column (T11) is connected with the feed pipeline of the aldehyde/ketone recovery column (T12); feeding materials are extracted from the top of an aldehyde/ketone recovery tower (T12) and connected to the bottom of a reaction rectifying tower (T11) and are recycled, glycol acetal/ketone products are extracted from the bottom of the aldehyde/ketone recovery tower (T12), a condenser and a reboiler are installed at the inlet and outlet positions of the reaction rectifying tower (T11) and the aldehyde/ketone recovery tower (T12) according to needs, wherein the reaction rectifying tower (T11) consists of a rectifying section and a reaction rectifying section, the rectifying section uses a filler or a tray, the reaction rectifying section uses a catalytic filler or a catalytic tray, and the catalyst is macroporous acidic cationic resin NKC-9;
the reaction rectification method comprises the following steps: respectively feeding a mixed glycol stream (S01) of ethylene glycol and butanediol and an aldehyde/ketone stream (S02) into a reactive distillation column (T11) from the upper part and the bottom of the reactive distillation section, and carrying out an acetal/ketone reaction in the reactive distillation section in the column; the gas phase (S03) at the top of the reactive distillation column (T11) passes through an overhead condenser (E1), the liquid phase (S04) passes through a reactive distillation column reflux extraction pump (P1) to obtain a liquid phase (S05), one part of the liquid phase is used as reflux (S06), and the other part of the liquid phase is used as a feed (S07) of an aldehyde/ketone recovery column (T12); an aldehyde/ketone recovery tower (T12) passes through an overhead condenser (E3) from an overhead gas phase (S08), a liquid phase (S09) passes through a reflux extraction pump (P2) to obtain a liquid phase (S10), one part of the liquid phase is taken as overhead reflux (S11), the other part of an extracted stream (S12) is recycled to a tower bottom of a reactive distillation tower (T11) for feeding, and a glycol acetal/ketone product (S13) is extracted from the tower bottom;
the aldehyde is formaldehyde, acetaldehyde, propionaldehyde or butyraldehyde, and the ketone is acetone, butanone or cyclohexanone;
the operating pressure of the reactive distillation tower is 0.1-5 atm in absolute pressure, the reflux ratio is 0.01-30, macroporous acidic cationic resin NKC-9 is used as a catalyst, and the molar ratio of the aldehyde/ketone amount entering the tower kettle of the reactive distillation tower to the total amount of the glycol to be treated is controlled to be 1-10; the operation pressure of the aldehyde/ketone recovery tower is 0.2-10 atm in absolute pressure, the reflux ratio is 0.01-10, and the purity of the aldehyde/ketone obtained by separation is controlled at the tower top.
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