CN107915612B - Method for preparing purified MIBK from industrial byproduct waste liquid acetone - Google Patents
Method for preparing purified MIBK from industrial byproduct waste liquid acetone Download PDFInfo
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- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/73—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with hydrogenation
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- C07C45/78—Separation; Purification; Stabilisation; Use of additives
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- C07C45/80—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
- C07C45/83—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation by extractive distillation
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Abstract
The invention discloses a process for preparing high-purity MIBK by using industrial byproduct waste liquid acetone. The method comprises the steps that a reaction liquid for synthesizing MIBK from waste liquid acetone obtains a light component with a boiling point lower than that of acetone at the top of a light component removing tower, and unreacted acetone is obtained at the top of an acetone recovery tower; obtaining organic matters with boiling points lower than the MIBK/water azeotrope and the MIBK/water azeotrope at the top of the process water tower; low boiling point organic matters such as acetone, methanol and the like from raw materials are obtained at the top of the dehydrating tower; obtaining an alcohol/water distillate at the top of the dealcoholization tower and a crude MIBK distillate at the bottom of the dealcoholization tower; obtaining light components with the boiling point lower than that of the MIBK at the top of the MIBK refining tower and obtaining a MIBK product with the purity more than or equal to 99.5% at the lateral line. The method disclosed by the invention has the advantages of simple technical process, low energy consumption and low production cost, can obtain a high-purity MIBK product by using high-impurity waste liquid acetone, and has remarkable economic benefit.
Description
Technical Field
The invention relates to a method for producing purified MIBK, in particular to a method for producing purified MIBK from industrial byproduct waste liquid acetone.
Technical Field
The process for producing the propylene oxide by the co-oxidation method is a mainstream process for industrially producing the propylene oxide, and comprises a PO/TBA process and a PO/SM process, wherein the current global PO device capacity is about 1000 ten thousand tons/year, and the co-oxidation method process accounts for about 55 to 60 percent. Because the oxidation reaction of the co-oxidation method is a free radical reaction, the activity of the intermediate product is extremely high, and the product is relatively complex. The industrial co-oxidation method propylene oxide device produces a large amount of waste liquid as a byproduct, the waste liquid is complex in composition, main impurities except a large amount of acetone are epoxy isobutane, methanol, tert-butyl alcohol and the like, and due to the fact that the boiling point difference among the components is small, multiple groups of azeotropes of methanol/acetone, acetone/epoxy isobutane, tert-butyl alcohol/water and the like exist, and the satisfactory separation effect cannot be achieved through conventional separation. Therefore, the utilization of the material is severely limited, the material is generally used for burning organic waste materials in industry to recover partial heat, and the utilization value is very limited.
CN201410128345 discloses a method for preparing MIBK from waste liquid acetone, which realizes the high-efficiency conversion from acetone to MIBK by adopting advanced catalysis and hydrogenation technologies, and simultaneously skillfully avoids the influences on raw material purification caused by the close boiling points of the components, the existence of complex azeotropic phenomena and the like.
Methyl isobutyl ketone (MIBK) is a medium boiling point solvent with excellent comprehensive performance, is also an acetone downstream derivative product with wide application, is mainly applied to the fields of industrial solvents such as coatings, paints, lubricating oil dewaxing and the like, and is also an important raw material for synthesizing rubber anti-aging agents and other chemical products. At present, the main industrial preparation process of MIBK is an acetone one-step method, and the specification of acetone as a raw material is generally 99.5 percent of industrial first-grade products.
In the method disclosed in CN201410128345, the byproduct waste liquid acetone of the co-oxidation method propylene oxide device is used as a raw material to synthesize MIBK in one step, so that the difficult problem of complex purification of the raw material is avoided, the efficient utilization of the acetone is realized, and the economic benefit is remarkable. But simultaneously, the product composition is more complicated, and the separation difficulty is increased compared with the traditional process.
At present, the MIBK purification process aims at the MIBK product prepared by a pure acetone one-step method, and no literature report exists for the purification of MIBK prepared from industrial by-product waste liquid acetone, so that a new method for producing purified MIBK from industrial by-product waste liquid acetone is required to be found.
Disclosure of Invention
The invention aims to provide a method for producing purified MIBK from industrial byproduct waste liquid acetone, which solves the problem of separation difficulty caused by introducing various impurities by using the waste liquid acetone as a raw material, and provides an optimized separation method and an optimized technological process so as to simplify the production flow of products, reduce the cost and obtain high-purity MIBK products.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a method for preparing purified MIBK from industrial byproduct waste liquid acetone comprises the following steps:
(i) in the reaction section, carrying out condensation, dehydration and hydrogenation catalytic reaction on industrial byproduct waste liquid acetone to generate MIBK and realize conversion of most impurities to obtain MIBK synthetic liquid;
(ii) separating hydrogen from the MIBK synthetic liquid, then feeding the hydrogen into a light component removal tower for extractive distillation, removing light components from the tower top, and feeding liquid phase material flow in the tower kettle into an acetone recovery tower;
(iii) (ii) the liquid phase material in the tower bottom in the step (ii) flows through an acetone recovery tower for extractive distillation, unreacted acetone is recovered at the tower top, and the liquid phase material in the tower bottom is subjected to phase separation to obtain a material flow rich in a water phase and a material flow rich in an organic phase;
(iv) the material flow rich in the water phase enters a process water tower, organic matters with the boiling point lower than the MIBK/water azeotrope and the MIBK/water azeotrope obtained at the tower top enter a dehydrating tower, and the tower bottom liquid part enters a light component removing tower or a light component removing tower and an acetone recovery tower;
(v) feeding the material flow rich in the organic phase and the material flow (organic matter with the boiling point lower than MIBK/water azeotrope and MIBK/water azeotrope) of the process water tower top into a dehydrating tower, wherein the dehydrating tower is a dividing wall tower, the material flow of the process water tower top enters from one side of the dehydrating tower, the material flow rich in the organic phase enters from a public rectifying section of the dehydrating tower, a liquid-liquid delayer is arranged on a tower plate at the other side of the dehydrating tower, a distillate which is nearly composed of azeotropic water/alcohol and does not contain water/alcohol basically containing MIBK (the MIBK content is less than 10 wt%) is obtained at the side line, removing acetone and methanol at the tower top, and obtaining a liquid phase material flow which does not contain water basically (;
(vi) and (3) feeding the liquid phase material flow at the bottom of the dehydrating tower into a dealcoholization tower, removing impurity alcohols at the top of the tower, feeding the crude MIBK distillate obtained at the bottom of the tower into a MIBK refining tower, removing light components at the top of the tower after refining, and collecting a MIBK product at the side line.
As a preferred embodiment, the method for preparing purified MIBK from the industrial byproduct waste liquid acetone comprises the following steps:
(i) in the reaction section, carrying out condensation, dehydration and hydrogenation catalytic reaction on industrial byproduct waste liquid acetone to generate MIBK and realize conversion of most impurities to obtain MIBK synthetic liquid;
(ii) the MIBK synthetic liquid is separated from hydrogen and then enters a light component removal tower, the hydrogen enters a reaction section for cyclic utilization, and the MIBK synthetic liquid contains MIBK, acetone, water, isopropanol, diacetone alcohol, DIBK (diisobutyl ketone), isobutane, 2-methylpentane, methanol, tert-butanol, isobutyraldehyde, isobutanol, Methyl Ethyl Ketone (MEK) from raw materials and ethers;
(iii) extracting and rectifying the MIBK synthetic liquid after hydrogen separation in a light component removal tower in the presence of an extracting agent, removing light components containing isobutane, 2-methylpentane, isobutyraldehyde, methyl ethyl ketone and ethers from the top of the tower, feeding heavy components into a tower kettle, and feeding the obtained tower kettle liquid phase material flow into an acetone recovery tower;
(iv) (iii) the liquid phase material in the tower bottom flows through an acetone recovery tower to be extracted and rectified in the presence of an extracting agent, unreacted acetone is recovered at the tower top, heavy components enter the tower bottom of the acetone recovery tower, and the obtained liquid phase material in the tower bottom enters a water separator;
(v) (iv) separating the liquid phase in the tower bottom in the step (iv) into a material flow rich in an organic phase and a material flow rich in a water phase through a water separator;
(vi) (v) the water-phase-rich material flow enters a process water tower to recover organic matters in the water-phase-rich material flow, meanwhile, the extraction agent is recycled, organic matters with boiling points lower than the MIBK/water azeotrope and the MIBK/water azeotrope obtained at the tower top enter a dehydration tower, 60-98 wt% of tower bottom liquid enters a light component removal tower as the extraction agent, 0-20 wt% of tower bottom liquid enters an acetone recovery tower as the extraction agent, and the rest is discharged as wastewater; the organic matter with the boiling point lower than the MIBK/water azeotrope comprises acetone, methanol, isopropanol, tert-butyl alcohol, the MIBK and water azeotrope and the like;
(vii) organic matter with a boiling point lower than MIBK/water azeotrope and MIBK/water azeotrope separated from the water separator and the process water tower enter a dehydrating tower, the dehydrating tower is a dividing wall tower, the organic matter with the boiling point lower than MIBK/water azeotrope and MIBK/water azeotrope separated from the process water tower enter from one side of the dehydrating tower, the organic matter with the boiling point lower than MIBK/water azeotrope separated from the water separator enters from a common stripping section of the dehydrating tower, a liquid-liquid delayer is arranged on a tower plate on the other side of the dividing wall tower, filler is filled in the liquid-liquid delayer, a water/alcohol distillate with the MIBK content lower than 10 wt% is obtained at a lateral line, acetone, methanol and the like are removed from the tower top, and a liquid phase material flow with the water content lower than 0.2 wt% is;
(viii) liquid phase material flow at the bottom of the dehydrating tower enters a dealcoholization tower, impurity alcohols are removed at the top of the tower, and crude MIBK distillate obtained at the bottom of the tower enters a MIBK refining tower; wherein the impurity alcohols comprise isopropanol, tert-butanol, isobutanol and the like;
(ix) light components are removed from the top of the MIBK refining tower, partial heavy components such as diacetone alcohol (DAA) and the like can be decomposed, light components such as DAA decomposition products acetone and the like are obtained in a fractionation section, the MIBK product is collected from the side line, and a high-boiling-point material flow containing DIBK is obtained from the bottom of the tower.
In the invention, the industrial byproduct acetone is from a propylene oxide/tert-butyl alcohol co-production device, more specifically from a propylene oxide/tert-butyl alcohol co-oxidation method device, based on the weight of waste liquid acetone, the industrial byproduct acetone comprises 0.1-5 wt% of water, 0.5-6 wt% of methanol, 1-20 wt% of epoxy isobutane, 60-95 wt% of acetone, 0.01-0.5 wt% of isopropanol, 0.01-0.2 wt% of methyl ethyl ketone, 1-15 wt% of tert-butyl alcohol, 0.01-2 wt% of aldehydes (iso-butyl aldehyde and the like), and 0.01-5 wt% of ethers (methyl tert-butyl ether, isopropyl tert-butyl ether, n-propyl tert-butyl ether, isobutyl tert-butyl ether and the like).
In the present invention, the catalyst used in the reaction stage of step (i) may be any solid catalyst capable of catalyzing condensation, dehydration and hydrogenation of acetone to produce MIBKAn oxidizing agent. The hydrogenation reaction may be carried out in the gas phase or in the liquid phase, and is preferably carried out under liquid phase conditions. The catalyst includes but is not limited to Pd-resin composite catalyst, Pd-ZSM-5 composite catalyst, Pd/Al2O3Catalyst or Ni/Al2O3A catalyst. Preferably, a catalyst such as a Pd-ion exchange resin composite catalyst is used in liquid phase conditions, typically including temperatures of about 80-160 ℃ and pressures of 25 Bar-75 Bar, preferably pressures in the range of 25 Bar-45 Bar.
The crude reaction product separated from the reaction section contains MIBK as a product, unreacted acetone, impurity water, isopropanol, diacetone alcohol, DIBK and 2-methyl pentane produced by the reaction, methanol, tertiary butanol, methyl ethyl ketone, ether and the like brought by the acetone raw material of the waste liquid as impurities, and isobutane, isobutyraldehyde and the like produced by the reaction of the impurities in the raw material through the reaction section under the action of a catalyst. In fact, the MIBK synthetic fluid contains 45-75 wt% of acetone, 18-35 wt% of MIBK, 4-10 wt% of water, 0.01-2 wt% of isopropanol, 0-1 wt% of diacetone alcohol, 0.1-2 wt% of DIBK, 0.01-2 wt% of isobutane, 0.001-0.5 wt% of 2-methyl pentane, 0.01-6 wt% of methanol, 0-8 wt% of tert-butyl alcohol, 0.1-15 wt% of isobutyraldehyde, 0.01-15 wt% of isobutanol, and 0.01-0.2 wt% of methyl ethyl ketone and 0.01-5 wt% of ethers from raw materials.
It is not possible to separate such mixtures satisfactorily by conventional fractional distillation methods, since the components of such mixtures form binary or multicomponent azeotropes with one another. Meanwhile, the composition of the azeotropic mixture of the system is mostly independent of the pressure, or a suitable pressure variation range cannot be found to be effective for all azeotropic mixtures, and therefore, the separation of the azeotropic mixture cannot be achieved by changing the pressure. However, in the separation process performed by extractive distillation of the light components and the unreacted raw material acetone using the extractant in the dehydrogenation component column and the acetone recovery column, a satisfactory fractionation effect can be obtained. When the dosage of the extractant in the light component removal tower is larger, the proportion of the extractant in the acetone recovery tower can be properly reduced, even the extractant is not added.
In the invention, the light component removing tower is an extraction and rectification tower, and the extracting agent and the reaction liquid from the reactor are simultaneously added into the tower. The extractant is selected from one or more of monoethanolamine, ethylene glycol, hexanediol and water, and water is preferably used as the extractant. The light component removal tower is operated under the pressure of 80-300 KPaA, preferably 100-200 KPaA; the theoretical plate number is 15-60, preferably 25-50; the feeding position is 10 th to 30 th plates, preferably 15 th to 25 th plates; the reflux ratio is 2 to 50, preferably 5 to 25. The adding position of the extracting agent is the same as or higher than the adding position of the feeding liquid, and 2-20 th theoretical plates (counted from top to bottom, the same below) are preferred. The ratio of the extracting agent to the feeding liquid is 0.05-5: 1, preferably 0.1-3: 1. In particular, when water is used as an extractant for light components such as 2-methylpentane, it is possible to allow a mixture containing light components such as 2-methylpentane and acetone to be separated into a stream containing light components such as 2-methylpentane and having an acetone proportion of less than 30 wt%, preferably less than 10 wt%, more preferably less than 5 wt% and a stream containing acetone and having a 2-methylpentane content of less than 0.02 wt%, preferably less than 0.01 wt%, more preferably less than 50 PPm.
In the invention, the acetone recovery tower is operated under the pressure of 50-100 KPaA so as to better give consideration to relative volatility and cooling water consumption; the acetone recovery tower is an extractive distillation tower, and the extracting agent can be one or more of monoethanolamine, ethylene glycol, hexanediol and water, preferably water. The mass ratio of the dosage of the extracting agent to the feeding liquid is 0-5: 1, and preferably 0-3: 1. The temperature of the top of the tower is 40-60 ℃, and the temperature of the bottom of the tower is 70-90 ℃; the theoretical plate number is 10-100, preferably 30-60; the feeding position is 5 th to 60 th plates, preferably 15 th to 40 th plates; the reflux ratio is 0.5-5, preferably 0.5-3; the adding position of the extracting agent is the same as or higher than the adding position of the feeding liquid, and the 2 nd to 20 th theoretical plates are preferred. The acetone at the top of the acetone recovery tower can be purified to 85-99%, and the acetone content at the bottom of the tower is less than 1 wt%, preferably less than 0.5 wt%, and more preferably less than 0.2 wt%.
In the invention, the water separator separates the tower bottom liquid of the acetone recovery tower into a material flow rich in an organic phase and a material flow rich in a water phase. Wherein the stream rich in aqueous phase enters a process water tower to recover MIBK dissolved therein and organics lighter than MIBK, while achieving the recovery of extractant water. The organic phase-rich stream and the process water tower overhead stream enter the dehydration tower respectively.
In the invention, the process water tower is operated under the condition that the pressure is 50-200 KPaA, preferably 80-160 KPaA; the theoretical plate number is 5-30, preferably 10-25; the feeding position is 2-20 plates, preferably 2-15 plates; the reflux ratio is 0.1 to 10, preferably 1 to 5.
In the invention, the dehydration tower is a side line extraction tower, and a liquid-liquid delayer is arranged in the tower, so that the water/alcohol distillate with the MIBK content of less than 10 wt% is obtained through side line extraction. The organic phase-rich material flow separated from the water separator contains more alcohol such as isopropanol, isobutanol, tert-butanol and the like, so that the layering effect of side line extraction can be influenced.
In the invention, the dehydration tower is operated under the condition of pressure of 50-500 KPaA, preferably 100-260 KPaA; the reflux ratio is 1-30, preferably 5-15; the theoretical plate number is 20-80, preferably 20-60. The upper part of the dehydration tower is a public rectification section, the lower part of the dehydration tower is a public stripping section, one side of the dehydration tower is a next door tower section for feeding, the other side of the dehydration tower is a next door tower section for lateral line extraction, wherein the next door tower section for feeding is divided into a tower section between the upper part of a feeding part of the MIBK/water azeotrope and the public rectification section and a tower section between the lower part of the feeding part and the upper end of the public stripping section, wherein the boiling point of the organic matter is lower than that of the MIBK/water azeotrope, and the. The next door tower section of the side line extraction is divided into a tower section between the upper part of the side line extraction and the lower end of the public rectification section and a tower section between the lower part of the side line extraction and the upper end of the public stripping section.
Preferably, the theoretical plate number of the public rectification section accounts for 5-50%, preferably 10-30% of the total theoretical plate number of the dehydration tower; the organic matter with the boiling point lower than that of the MIBK/water azeotrope and the theoretical plate number between the upper part of the feeding part of the MIBK/water azeotrope and the lower end of the public rectification section account for 5-30%, preferably 10-25% of the total theoretical plate number of the dehydration tower; the organic matter with the boiling point lower than that of the MIBK/water azeotrope, and the theoretical plate number between the lower part of the feeding part of the MIBK/water azeotrope and the upper end of the common stripping section account for 10-50% of the total number of the theoretical plates of the dehydrating tower, and are preferably 10-35%; the theoretical plate number between the upper part of the lateral line extraction part and the upper end of the public rectification section accounts for 10-50%, preferably 10-35% of the total number of the theoretical plates of the dehydration tower; the theoretical plate number between the lower part of the side line extraction part and the upper end of the public stripping section accounts for 5-30%, preferably 10-25% of the total number of the theoretical plates of the dehydration tower; the theoretical plate number of the public stripping section accounts for 5-50%, preferably 20-40% of the total number of the theoretical plates of the dehydrating tower. The organic phase rich stream is fed to a common stripping section of the dehydration column at a feed location selected from any one of the theoretical plates of the common stripping section.
In the present invention, the packing filled in the liquid-liquid separator on the tray on one side of the dehydration column contains packing A and packing B. The filler A is a modified super-hydrophilic metal filler, the filler B is a modified super-lipophilic metal filler, the filler A is filled in the lower layer, the filler B is filled in the upper layer, and the filling height ratio of the filler A to the filler B is 1: 8-4: 1, preferably 1: 4-2: 1.
In the invention, the filler A is obtained by placing a metal filler (such as stainless steel, carbon steel and the like) into a strong oxidizing solution for treatment for 12-18 h, and then washing the treated filler with deionized water to be neutral, wherein the strong oxidizing solution is preferably a potassium dichromate sulfuric acid and/or potassium permanganate sulfuric acid solution. Spraying a surface modifier and an auxiliary agent on the surface of the filler A, and heating at 200-300 ℃ for 30-60 min to obtain a filler B, wherein the surface modifier is preferably polytetrafluoroethylene emulsion, and the auxiliary agent is preferably sulfonated polyimide emulsion, the adding mass ratio of the polytetrafluoroethylene emulsion to the sulfonated polyimide emulsion is 1: 1-20: 1, preferably 5: 1-10: 1, and the mass sum of the surface modifier and the auxiliary agent accounts for 0.001-1%, preferably 0.01-0.1% of the mass of the filler A.
The surface of the metal filler is oxidized, so that the roughness of the surface of the filler is improved, the wettability of the filler to water is enhanced, and the filler is modified into the super-hydrophilic filler. The surface modifier on the surface of the filler B can be adsorbed on the rough surface of the filler, and can form a tiny sphere or block in the groove on the surface of the filler after being dried, so that the super-oleophylic and super-hydrophobic effect is achieved. The filler A and the filler B are filled in the delayer in an up-down layered manner, so that the separation of oil phase and water phase is better promoted, and the heat transfer capacity of the mass transfer on the tower plate is improved. And the addition of the auxiliary agent in the filler B leads sulfonic acid groups to be introduced into the filler, the introduction of the sulfonic acid groups leads the tert-butyl alcohol dissolved in the oil phase to carry out dehydration reaction on the surface of the filler to generate isobutene and water, the generated water quickly separates from the super-oleophilic and super-hydrophobic filler to enter a water phase, isobutene is gas and is discharged from the top of the tower, and the reaction is reversible, so that the reaction is promoted to develop towards the positive reaction direction. Meanwhile, the conversion of tertiary butanol in the oil phase promotes the stratification of the oil phase and the water phase.
In the present invention, isopropanol, a small amount of tert-butanol, an azeotrope of MIBK and isobutanol, and other alcoholic components lighter than MIBK are removed from the top of the dealcoholization column. The dealcoholization tower is operated under the condition of the pressure of 80-300 KPaA, preferably 100-200 KPaA; the theoretical plate number is 15-55, and preferably 20-40 plates; the feeding position is 5 th to 35 th plates, preferably 15 th to 25 th plates; the reflux ratio is 5 to 50, preferably 5 to 30.
In the invention, the MIBK refining tower is operated under the condition that the pressure is 50-300 KPaA, preferably 100-200 KPaA; the theoretical plate number is 20-60, preferably 30-50; the feeding position is 10 th to 40 th plates, preferably 15 th to 20 th plates; the reflux ratio is 20 to 150, preferably 50 to 120.
The separation method for preparing high-purity MIBK by using the industrial waste liquid acetone disclosed by the invention solves the problem of separation difficulty caused by introducing impurities into raw materials, and simultaneously improves the problems in the prior art. The loss of acetone and MIBK products is greatly reduced through extractive distillation and a divided wall tower technology, the process is simpler, the investment is reduced, the energy consumption is saved, a high-purity product can be obtained, and the method has remarkable technical and economic advantages. Finally, the efficient utilization of the waste liquid acetone can be realized, and the economic benefit is obvious.
All pressures recited in the present invention are absolute pressures.
Description of the drawings: FIG. 1 is a process flow diagram of the present invention for the preparation of purified MIBK from acetone, an industrial by-product waste stream.
The specific implementation mode is as follows:
in order to more clearly explain the process disclosed in the present invention and to easily implement and operate a preferred process and apparatus for producing high purity MIBK using acetone, which is a by-product of a propylene oxide plant using an co-oxidation process, the process of the present invention will be further described below.
Those skilled in the art will recognize that, since the drawings are schematic, some other equipment is also required on a suite of industrial plants, such as condensers, heat exchangers, reflux drums, column reboilers, pumps, vacuum pumps, temperature sensors, pressure relief valves, control valves, flow controllers, level controllers, receiving drums, storage tanks, and the like. The specification requirements for these ancillary equipment are not within the scope of the present discussion and may be considered in accordance with conventional chemical engineering techniques.
The invention is further described with reference to the accompanying drawings:
as shown in figure 1, wherein C-100 is a light component removal tower, C-101 is an acetone recovery tower, C-102 is a dehydration tower, C-103 is a dealcoholization tower, C-104 is a MIBK refining tower, and C-105 is a process water tower. Waste acetone (stream 1) (the main components of which are acetone, methanol, water, epoxy isobutane, isopropanol, methyl ethyl ketone, tert-butyl alcohol, aldehydes, ethers and the like) and acetone (stream 9) recovered from an acetone recovery column C-101 are mixed and enter a reactor R-100 together with hydrogen (stream 2), condensation dehydration hydrogenation reaction is carried out in the reactor R-100, and unreacted hydrogen (stream 4) and MIBK synthetic liquid (stream 5) are separated from generated substances and unreacted hydrogen (stream 3) through a hydrogen separator D-100. The MIBK synthesis solution (mainly comprising MIBK, acetone, water, isopropanol, diacetone alcohol, DIBK, isobutane, 2-methylpentane, methanol, tert-butanol, isobutyraldehyde, isobutanol, and methyl ethyl ketone, ethers and the like from raw materials) firstly enters a light component removal column C-100. The light component removing tower is an extraction tower, an extracting agent 6 enters from a position above the feeding material, the light component removing tower mainly plays a role in removing light components in the synthetic liquid, including light components such as 2-methylpentane, isobutane and ethers, a stream 7 is extracted from the top of the tower, and tower bottom liquid (a stream 8) enters an acetone recovery tower C-101. The acetone recovery tower mainly functions to recover the unreacted acetone, the acetone (stream 9) with the purity far higher than that of the raw material (stream 1) is obtained at the tower top through the separation of the acetone recovery tower, and the tower bottom liquid (stream 10) enters the water separator D-101. In the water separator D-101, the oil phase is separated into oil phase and water phase based on the interphase liquid-liquid equilibrium, the oil phase (stream 11) enters the dehydration column C-102, and the water phase (stream 12) enters the process water column. The organics with boiling point lower than MIBK/water azeotrope are recovered at the top of the process water column (stream 13) into the dehydration column and the bottoms (stream 14) is recycled as extractant with only a small amount of water being discharged (stream 15). Acetone, methanol, isobutylene, etc. are removed at the top of the dehydration column C-102 (stream 16), water and a small amount of alcohols are taken off at the side (stream 17), and the bottoms (stream 18) enter the dealcoholization column C-103. Alcohols such as isopropanol and the like are removed at the top of the dealcoholization tower (stream 19), and the tower bottom liquid (stream 20) enters the MIBK refining tower C-104. And obtaining a small amount of light components (stream 21) such as acetone and the like generated by DAA decomposition at the top of the MIBK refining tower, collecting MIBK products (stream 22) with the purity of more than 99.5% at the side line, and taking tower bottom liquid (stream 23) as heavy components.
Comparative example
The waste liquid acetone mixed solution is rectified and separated at normal pressure in a rectifying column with the diameter of 26mm, a filler adopts a triangular spiral with the diameter of 3 x 3, the height of the column is 1.5m, the temperature of condensed water at the top of the column is 25 ℃, the temperature of extracted water at the top of the column is 52-57 ℃, the reflux ratio is 10:1, and the compositions of samples extracted at the top of the column are shown in table 1.
TABLE 1 recovery of acetone by distillation of acetone mixture as by-product
From the above table, it can be seen that: when the acetone is rectified and purified under the conditions of large theoretical plate number and large reflux ratio, methanol, epoxy isobutane, acetone, isopropanol, methyl ethyl ketone, aldehydes and ethers are hardly separated. Therefore, it is difficult to directly recycle acetone in the mixed solution, and other acetone application routes must be designed.
The composition of the raw material waste liquid acetone used in each example is shown in table 2:
TABLE 2 composition of raw material waste liquid acetone
The reactor R-100 conditions for each example are shown in Table 3:
TABLE 3 reactor conditions in the examples
| Reaction conditions | Example one | Example two | EXAMPLE III |
| Reaction temperature C | 80 | 100 | 160 |
| Reaction pressure/bar | 45 | 30 | 25 |
| Catalyst and process for preparing same | Pd-resin catalyst | Pd-resin catalyst | Pd-Al2O3 |
Pd-resin catalyst: amberlyst CH-28, Dow chemical Co., Ltd, wherein the Pd content was 0.7 wt%.
Example 1
As shown in the flow chart of the attached drawing, after the reaction synthesis solution was dehydrogenated, the reaction synthesis solution was rectified under the rectification conditions shown in tables 4 and 5, wherein the extractant of the light component removal column was water, the mass ratio of the amount of water to the feed solution was 3:1, and the extractant was added to the 2 nd theoretical plate, and wherein the height ratio of the filler A to the filler B in the liquid-liquid demixer on the tray on the side of the dehydration column was 1:4, and the results obtained are shown in Table 6. From table 6, it can be seen that: and finally, the mass fraction of the MIBK product is 99.56 percent through the rectification of each rectifying tower.
The preparation method of the filler A and the filler B is as follows: and (3) putting the stainless steel filler into a potassium permanganate sulfuric acid solution for treatment for 18h, and then washing the stainless steel filler with deionized water until the stainless steel filler is neutral to obtain the filler A. Spraying polytetrafluoroethylene emulsion and sulfonated polyimide emulsion on the surface of the filler A, and heating for 30min at 250 ℃ to obtain a filler B, wherein the mass ratio of the polytetrafluoroethylene emulsion to the sulfonated polyimide emulsion is 5:1, and the mass sum of the surface modifier and the auxiliary agent accounts for 0.02% of the mass of the filler A.
TABLE 4 rectification conditions of the rectification column
| Rectifying tower | C-100 | C-101 | C-103 | C-104 | C-105 |
| Number of |
15 | 50 | 30 | 60 | 30 |
| |
10 | 30 | 15 | 40 | 20 |
| pressure/ |
100 | 100 | 300 | 50 | 50 |
| Reflux ratio | 50 | 0.5 | 5 | 100 | 4 |
TABLE 5 rectification conditions for the dehydration column C-102
TABLE 6 rectification results
Example 2
As shown in the flow chart of the attached drawing, after dehydrogenation, the reaction synthesis solution was rectified under the rectification conditions shown in tables 7 and 8, wherein the extractant of the light component removal column was water, the mass ratio of the amount of the extractant to the feed solution was 2:1, and the extractant was added to the 5 th theoretical plate, and wherein the height ratio of the filler A to the filler B in the liquid-liquid demixer on the tray on the side of the dehydration column was 1:1, and the results were shown in Table 9. From table 9, it can be seen that: and finally, the mass fraction of the MIBK product is 99.67 percent through the rectification of each rectifying tower. The preparation of filler a and filler B is shown in example one.
TABLE 7 rectification conditions of the rectification column
| Rectifying tower | C-100 | C-101 | C-103 | C-104 | C-105 |
| Number of theoretical plates | 30 | 100 | 55 | 20 | 5 |
| |
20 | 40 | 35 | 10 | 2 |
| pressure/KPaA | 300 | 50 | 80 | 200 | 100 |
| |
2 | 2 | 30 | 150 | 10 |
TABLE 8 rectification conditions for dehydration column C-102
TABLE 9 rectification results
Example 3
As shown in the flow chart of the drawing, after dehydrogenation of the reaction synthesis solution, the distillation was carried out under the distillation conditions shown in tables 10 and 11, wherein the extractant of the light component removal column was water in an amount of 0.1 by mass based on the feed liquid, and was fed to the 20 th theoretical plate, and the extractant of the acetone recovery column was water in an amount of 0.3 by mass based on the feed liquid, and was fed to the 2 nd theoretical plate, and wherein the height ratio of the filler A to the filler B in the liquid-liquid demixer on the tray on the side of the dehydration column was 1:4, and the results shown in Table 12 were obtained. From table 12, it can be seen that: and finally obtaining the MIBK product with the mass fraction of 99.72 percent through the rectification of each rectifying tower.
TABLE 10 rectification conditions of the rectification column
| Rectifying tower | C-100 | C-101 | C-103 | C-104 | C-105 |
| Number of theoretical plates | 60 | 10 | 15 | 40 | 15 |
| Feed position | 30 | 5 | 5 | 20 | 10 |
| pressure/KPaA | 80 | 70 | 140 | 300 | 200 |
| |
20 | 5 | 50 | 20 | 0.1 |
TABLE 11 rectification conditions for dehydration column C-102
TABLE 12 rectification results
Claims (20)
1. A method for preparing purified MIBK from industrial byproduct waste liquid acetone comprises the following steps:
(i) in the reaction section, carrying out condensation, dehydration and hydrogenation catalytic reaction on industrial byproduct waste liquid acetone to generate MIBK and realize conversion of most impurities to obtain MIBK synthetic liquid;
(ii) separating hydrogen from the MIBK synthetic liquid, then feeding the hydrogen into a light component removal tower for extractive distillation, removing light components from the tower top, and feeding liquid phase material flow in the tower kettle into an acetone recovery tower;
(iii) (ii) the liquid phase material in the tower bottom in the step (ii) flows through an acetone recovery tower for extractive distillation, unreacted acetone is recovered at the tower top, and the liquid phase material in the tower bottom is subjected to phase separation to obtain a material flow rich in a water phase and a material flow rich in an organic phase;
(iv) the material flow rich in the water phase enters a process water tower, organic matters with the boiling point lower than the MIBK/water azeotrope and the MIBK/water azeotrope obtained at the tower top enter a dehydrating tower, and the tower bottom liquid part enters a light component removing tower or a light component removing tower and an acetone recovery tower;
(v) the method comprises the following steps that a material flow rich in an organic phase and a material flow at the top of a process water tower enter a dehydrating tower, the dehydrating tower is a dividing wall tower, the material flow at the top of the process water tower enters from one side of the dehydrating tower, the material flow rich in the organic phase enters from a public stripping section of the dehydrating tower, a liquid-liquid delayer is arranged on a tower plate at the other side of the dehydrating tower, a water/alcohol distillate which is close to a water/alcohol azeotropic composition and basically does not contain MIBK is obtained at a lateral line, acetone and methanol are removed from the top of the dehydrating tower;
(vi) and (3) feeding the liquid phase material flow at the bottom of the dehydrating tower into a dealcoholization tower, removing impurity alcohols at the top of the tower, feeding the crude MIBK distillate obtained at the bottom of the tower into a MIBK refining tower, removing light components at the top of the tower after refining, and collecting a MIBK product at the side line.
2. The method according to claim 1, wherein the industrial byproduct, namely the waste liquid acetone, is acetone byproduct from a co-oxidation method propylene oxide/tert-butyl alcohol co-production device, and comprises 0.1-5 wt% of water, 0.5-6 wt% of methanol, 1-20 wt% of epoxy isobutane, 60-95 wt% of acetone, 0.01-0.5 wt% of isopropanol, 0.01-0.2 wt% of methyl ethyl ketone, 1-15 wt% of tert-butyl alcohol, 0.01-2 wt% of aldehydes, and 0.01-5 wt% of ethers, based on the weight of the waste liquid acetone.
3. The method according to claim 1 or 2, wherein the MIBK synthetic fluid comprises 45-75 wt% of acetone, 18-35 wt% of MIBK, 4-10 wt% of water, 0.01-2 wt% of isopropanol, 0-1 wt% of diacetone alcohol, 0.1-2 wt% of diisobutyl ketone, 0.01-2 wt% of isobutane, 0.001-0.5 wt% of 2-methylpentane, 0.01-6 wt% of methanol, 0-8 wt% of tert-butanol, 0.1-15 wt% of isobutyraldehyde, 0.01-15 wt% of isobutanol, and 0.01-0.2 wt% of methyl ethyl ketone and 0.01-5 wt% of ethers.
4. The method according to claim 1, wherein the light component removal tower and the acetone recovery tower are extractive distillation towers, the extracting agent is one or more selected from monoethanolamine, ethylene glycol, hexanediol and water, the mass ratio of the using amount of the extracting agent in the light component removal tower to the waste liquid acetone is 0.05-5: 1, and the mass ratio of the using amount of the extracting agent in the acetone recovery tower to the feed liquid is 0-5: 1.
5. The method according to claim 1, wherein the light component removal tower and the acetone recovery tower are extractive distillation towers, the extracting agent is water, the mass ratio of the using amount of the extracting agent in the light component removal tower to the waste liquid acetone is 0.1-3: 1, and the mass ratio of the using amount of the extracting agent in the acetone recovery tower to the feed liquid is 0-3: 1.
6. The method according to claim 1, wherein the number of theoretical plates of the dehydration column is 20 to 80; the theoretical plate number of the public rectification section accounts for 5-50% of the total number of the theoretical plates of the dehydration tower; the organic matter with the boiling point lower than that of the MIBK/water azeotrope and the theoretical plate number between the upper part of the feeding part of the MIBK/water azeotrope and the lower end of the public rectification section account for 5-30% of the total number of the theoretical plates of the dehydration tower; the organic matter with the boiling point lower than that of the MIBK/water azeotrope and the theoretical plate number between the lower part of the feeding part of the MIBK/water azeotrope and the upper end of the common stripping section account for 10-50% of the total number of the theoretical plates of the dehydrating tower; the theoretical plate number between the upper part of the side line extraction part and the lower end of the public rectification section accounts for 10-50% of the total number of the theoretical plates of the dehydration tower; the theoretical plate number between the lower part of the side line extraction part and the upper end of the public stripping section accounts for 5-30% of the total number of the theoretical plates of the dehydration tower; the theoretical plate number of the public stripping section accounts for 5-50% of the total number of the theoretical plates of the dehydrating tower.
7. The method according to claim 1, wherein the number of theoretical plates of the dehydration column is 20 to 60; the theoretical plate number of the public rectification section accounts for 10-30% of the total number of the theoretical plates of the dehydration tower; the organic matter with the boiling point lower than that of the MIBK/water azeotrope and the theoretical plate number between the upper part of the feeding part of the MIBK/water azeotrope and the lower end of the public rectification section account for 10-25% of the total number of the theoretical plates of the dehydration tower; organic matters with boiling points lower than that of the MIBK/water azeotrope, and theoretical plate numbers between the lower part of the feeding part of the MIBK/water azeotrope and the upper end of the common stripping section account for 11-35% of the total number of the theoretical plates of the dehydration tower; the theoretical plate number between the upper part of the side line extraction part and the lower end of the public rectification section accounts for 11-35% of the total number of the theoretical plates of the dehydration tower; the theoretical plate number between the lower part of the side line extraction part and the upper end of the public stripping section accounts for 10-25% of the total number of the theoretical plates of the dehydration tower; the theoretical plate number of the public stripping section accounts for 20-40% of the total number of the theoretical plates of the dehydrating tower.
8. The method according to any one of claims 1, 6 and 7, characterized in that the liquid-liquid delayer on the tower plate at one side of the dehydrating tower is filled with a filler, the filler comprises a filler A and a filler B, wherein the filler A is a modified super-hydrophilic metal filler, the filler B is a modified super-oleophilic metal filler, the filler A is filled at the lower layer, the filler B is filled at the upper layer, and the filling height ratio of the filler A to the filler B is 1: 8-4: 1.
9. The method according to claim 8, wherein the packing A and the packing B are packed at a height ratio of 1:4 to 2: 1.
10. The method according to claim 8, wherein the filler A is obtained by placing the metal filler into a strong oxidizing solution for treatment for 12-18 h, and then washing the metal filler with water until the metal filler is neutral, wherein the strong oxidizing solution is a potassium dichromate sulfuric acid solution and/or a potassium permanganate sulfuric acid solution.
11. The method according to claim 10, wherein the filler B is obtained by spraying a surface modifier and an auxiliary agent on the surface of the filler A, and heating the mixture at 200-300 ℃ for 30-60 min, wherein the surface modifier is polytetrafluoroethylene emulsion, the auxiliary agent is sulfonated polyimide emulsion, the mass ratio of the polytetrafluoroethylene emulsion to the sulfonated polyimide emulsion is 1: 1-20: 1, and the total mass of the surface modifier and the auxiliary agent accounts for 0.001-1% of the mass of the filler A.
12. The method according to claim 11, wherein the polytetrafluoroethylene emulsion and the sulfonated polyimide emulsion are added in a mass ratio of 5:1 to 10:1, and the total mass of the surface modifier and the auxiliary agent accounts for 0.01 to 0.1% of the mass of the filler A.
13. The method according to claim 1 or 4, wherein the light component removal tower is operated under the condition of pressure of 80-300 KPaA; the number of theoretical plates is 15-60; the feeding position is 10 th to 30 th plates; the reflux ratio is 2-50, and the adding position of the extracting agent is the same as or higher than that of the feeding liquid.
14. The method according to claim 13, wherein the light component removal tower is operated under the pressure of 100-200 KPaA; the theoretical plate number is 25-50; the feeding position is 15 th to 25 th plates; the reflux ratio is 5-25, the adding position of the extracting agent is the same as or higher than that of the feeding liquid, and the theoretical plate is 2-20.
15. The method according to claim 1 or 6, wherein the dehydration column is operated at a pressure of 50 to 500 KPaA; the reflux ratio is 1 to 30.
16. The method according to claim 1 or 6, wherein the dehydration column is operated at a pressure of 100 to 260 KPaA; the reflux ratio is 5-15.
17. The method according to claim 1, wherein the dealcoholization column is operated at a pressure of 80 to 300 KPaA; the theoretical plate number is 15-55 plates; the feeding position is 5 th to 35 th plates; the reflux ratio is 5 to 50.
18. The method according to claim 1, wherein the dealcoholization column is operated at a pressure of 100 to 200 KPaA; the theoretical plate number is 20-40 plates; the feeding position is 15 th to 25 th plates; the reflux ratio is 5-30.
19. The process of claim 1, wherein the process water column is operated at a pressure of from 50 to 200 KPaA; the number of theoretical plates is 5-30; the feeding position is 2 nd to 20 th plates; the reflux ratio is 0.1 to 10.
20. The process of claim 1, wherein the process water column is operated at a pressure of from 80 to 160 kpa; the theoretical plate number is 10-25; the feeding position is 2 nd to 15 th plates; the reflux ratio is 1-5.
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