WO2024049105A1 - 고순도 (메트)아크릴산의 제조방법 - Google Patents

고순도 (메트)아크릴산의 제조방법 Download PDF

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WO2024049105A1
WO2024049105A1 PCT/KR2023/012560 KR2023012560W WO2024049105A1 WO 2024049105 A1 WO2024049105 A1 WO 2024049105A1 KR 2023012560 W KR2023012560 W KR 2023012560W WO 2024049105 A1 WO2024049105 A1 WO 2024049105A1
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Prior art keywords
meth
acrylic acid
tower
water
supplied
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PCT/KR2023/012560
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English (en)
French (fr)
Korean (ko)
Inventor
유성진
장경수
이성규
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LG Chem Ltd
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LG Chem Ltd
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Priority claimed from KR1020230107030A external-priority patent/KR20240031053A/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to EP23860782.4A priority Critical patent/EP4491608A4/en
Priority to CN202380014288.5A priority patent/CN118201902A/zh
Priority to JP2024525179A priority patent/JP2025527381A/ja
Priority to US18/709,108 priority patent/US20250002439A1/en
Publication of WO2024049105A1 publication Critical patent/WO2024049105A1/ko
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
    • C07C51/445—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation by steam distillation

Definitions

  • the present invention relates to a method for producing high purity (meth)acrylic acid.
  • (meth)acrylic acid is generally produced by subjecting compounds such as propane, propylene, and (meth)acrolein to a gas phase oxidation reaction in the presence of a catalyst.
  • compounds such as propane, propylene, and (meth)acrolein
  • propane, propylene, etc. for example, in the presence of an appropriate catalyst in the reactor, propane, propylene, etc.
  • the (meth)acrylic acid-containing mixed gas is contacted with an absorption solvent such as water in an absorption tower and is recovered as an aqueous (meth)acrylic acid solution.
  • an absorption solvent such as water in an absorption tower
  • an aqueous (meth)acrylic acid solution is recovered as an aqueous (meth)acrylic acid solution.
  • processes such as extraction, distillation, and purification are generally involved.
  • various methods of adjusting process conditions or process sequence have been proposed.
  • the problem to be solved by the present invention is to secure a high (meth)acrylic acid recovery rate and further reduce energy usage in the purification process in order to solve the problems mentioned in the background technology of the above invention.
  • the purpose is to provide a method for producing meth)acrylic acid.
  • the step of contacting a mixed gas containing (meth)acrylic acid with water in an absorption tower to obtain an aqueous (meth)acrylic acid solution Supplying to a crystallizer and crystallizing to obtain purified (meth)acrylic acid and a mother liquor separated from the purified (meth)acrylic acid, supplying a portion of the mother liquor to an extraction tower, and supplying the remainder to a water separation tower, After contacting the extraction solvent and the mother liquor in an extraction tower, supplying the top discharge stream of the extraction tower to the water separation tower, the water separation tower top discharge stream containing water from the water separation tower, (meth)acrylic acid, and Separating the water separation tower bottom discharge stream containing high boiling point by-products into a water separation tower bottom discharge stream, supplying the water separation tower bottom discharge stream to the high boiling point by-product separation tower, and discharging the high boiling point by-product containing (meth)acrylic acid from the top of the separation tower.
  • the amount of water in the system is minimized in the process after the absorption tower, and the aqueous (meth)acrylic acid solution discharged from the absorption tower is supplied to a crystallizer, thereby producing high purity (meth)acrylic acid.
  • the aqueous (meth)acrylic acid solution discharged from the absorption tower is supplied to a crystallizer, thereby producing high purity (meth)acrylic acid.
  • acetic acid which is a by-product
  • the (meth)acrylic acid from the top of the absorption tower can be separated and removed. Losses can be reduced.
  • high-boiling by-products are separated after the water separation tower to prevent accumulation of high-boiling by-products in the system, and through this, high-purity purified (meth)acrylic acid can be obtained, and the upper discharge stream of high-boiling by-products is fed back to crystallization. By doing so, the loss of (meth)acrylic acid can be further reduced.
  • Figure 1 is a process flow diagram showing a method for producing (meth)acrylic acid according to an embodiment of the present invention.
  • Figures 2 and 3 are process flow charts showing a method for producing (meth)acrylic acid according to a comparative example of the present invention.
  • the term “stream” may refer to the flow of fluid within a process, or may also refer to the fluid itself flowing within a pipe. Specifically, the stream may refer to both the fluid itself and the flow of the fluid flowing within the pipes connecting each device.
  • the fluid may mean gas or liquid, and the case where the fluid contains a solid component is not excluded.
  • the "lower part” of the device refers to 95% of the device from the top to the bottom, unless otherwise specified. It means the point of height from 100% to 100%, and may specifically mean the lowest point (bottom of the tower).
  • the “top” of the device refers to a point 0% to 5% in height from the top of the device, unless otherwise specified, and may specifically mean the top (top). .
  • a method for producing (meth)acrylic acid includes the steps of contacting a mixed gas containing (meth)acrylic acid with water in an absorption tower to obtain an aqueous (meth)acrylic acid solution, the aqueous (meth)acrylic acid solution Supplying to a crystallizer and crystallizing to obtain purified (meth)acrylic acid and a mother liquor separated from the purified (meth)acrylic acid, supplying a portion of the mother liquor to an extraction tower, and supplying the remainder to a water separation tower, After contacting the extraction solvent and the mother liquor in the extraction tower, supplying the top discharge stream of the extraction tower to the water separation tower, the water separation tower top discharge stream containing water and (meth)acrylic acid from the water separation tower and separating the water separation tower bottom discharge stream containing high boiling point by-products, and supplying the water separation tower bottom discharge stream to the high boiling point by-product separation tower, and the high boiling point by-product separation tower top containing (meth)acrylic
  • the method for producing (meth)acrylic acid may include the step of contacting a mixed gas containing (meth)acrylic acid with water in an absorption tower to obtain an aqueous (meth)acrylic acid solution.
  • the mixed gas containing (meth)acrylic acid is a general term for gaseous components discharged from the reactor 10 that produces (meth)acrylic acid through a gaseous oxidation reaction.
  • the mixed gas may include (meth)acrylic acid, unreacted raw material compounds, (meth)acrolein, inert gas, carbon monoxide, carbon dioxide, water vapor, and various organic by-products (acetic acid, low-boiling by-products, high-boiling by-products, etc.).
  • organic by-products acetic acid, low-boiling by-products, high-boiling by-products, etc.
  • 'low boiling point by-products' (light ends) or 'high boiling point by-products' (heavies) are a type of by-product that can be produced in the production and recovery process of the desired (meth)acrylic acid, and have a molecular weight higher than (meth)acrylic acid. It can be a small or large compound.
  • the mixed gas containing (meth)acrylic acid can be prepared as follows.
  • a reaction gas containing an oxygen-containing gas and a raw material compound is supplied to a reactor 10 equipped with a catalyst through the reaction gas supply line 1, and a gas phase oxidation reaction occurs in the presence of the catalyst within the reactor 10.
  • a mixed gas containing the (meth)acrylic acid can be obtained.
  • the gas containing oxygen may be air.
  • the raw material compound may be one or more compounds selected from the group consisting of propane, propylene, butane, i-butylene, t-butylene, and (meth)acrolein. Specifically, the raw material compound may include propylene.
  • the reaction gas supplied to the reactor 10 may further include recycle gas recovered from the upper part of the absorption tower 100 and recycled. Therefore, the mixed gas containing (meth)acrylic acid may be a reaction product of a gas phase oxidation reaction of a reactant containing air, raw material compounds, and recycle gas within the reactor 10.
  • the recycle gas may originate from the top of the absorption tower 100, which will be described later. That is, the mixed gas is in contact with water, which is an absorption solvent, in the absorption tower 100, and the non-condensable gas that is not dissolved in the water can be discharged to the upper discharge stream 110 of the absorption tower 100. there is.
  • the non-condensable gas may include impurities such as acetic acid, inert gas, unreacted raw material compounds, and a minimal amount of (meth)acrylic acid.
  • a portion 3 of the absorption tower top discharge stream 110 may be supplied to the cooling tower 20, and the remainder may be supplied to a waste gas incinerator for disposal.
  • the cooling tower 20 has a water supply line 5 at the top, and water used as an absorption solvent in the absorption tower can be supplied into the cooling tower 20 from the water supply line 5.
  • water may come into contact with non-condensable gases contained in a portion 3 of the absorption tower overhead stream 110.
  • the non-condensable gas may include acetic acid and a minimal amount of (meth)acrylic acid, and these components may be dissolved in the water, which may be discharged as a bottom discharge stream of the cooling tower 20 in the form of an aqueous solution. .
  • a portion 6 of the bottom discharge stream of the cooling tower 20 may be supplied to the absorption tower 100, and the remainder may be cooled through a heat exchanger and then circulated to the cooling tower.
  • the water needed for the absorption tower 100 can be supplied through the water supply line 5 provided at the top of the cooling tower 20.
  • the water may specifically include water such as tap water or deionized water, and may include recycled process water introduced from another process (e.g., aqueous phase recycled from an extraction process and/or a distillation process).
  • the absorption solvent may contain trace amounts of organic by-products (for example, acetic acid) introduced from other processes.
  • the recycle gas can be supplied to the reactor 10 so that it can be used in a gas phase oxidation reaction for producing (meth)acrylic acid that proceeds in the reactor.
  • the recycle gas may be mixed with the reaction gas and supplied to the reactor, and may be supplied to the reactor through a line (4) separate from the line (1) through which the reaction gas is supplied.
  • the water content in the recycle gas circulated from the cooling tower 20 to the reactor can be reduced. That is, by reducing the moisture content in the recycle gas, the moisture content in the stream supplied from the reactor 10 to the absorption tower 100 can be lowered, and through this, the moisture content in the absorption tower 100 can also be lowered.
  • the water discharged from the reactor may contain dissolved various by-products that are unsuitable for introduction into the crystallizer, and if water is present in excess in the absorption tower (100), it is difficult to obtain a high concentration of (meth)acrylic acid aqueous solution, so it is difficult to obtain a high concentration of (meth)acrylic acid aqueous solution in the recycle gas.
  • By lowering the water content it becomes possible to introduce the discharge stream from the absorption tower 100 into the crystallizer without a separate water distillation process, as described later.
  • the moisture content in the recycle gas may be 1% by weight to 10% by weight, specifically 3% by weight to 5% by weight. If the moisture content in the recirculated gas is less than 1% by weight, operating costs, especially costs related to the installation and operation of the cooler, may increase. On the other hand, when the moisture content in the recycle gas exceeds 10% by weight, the moisture content supplied into the absorption tower 100 via the reactor 10 increases, making it impossible to obtain high purity (meth)acrylic acid. In addition, it may be difficult to simply obtain high purity (meth)acrylic acid through a crystallizer without a water distillation process for the (meth)acrylic acid aqueous solution discharged from the absorption tower. In addition, due to the increased amount of moisture (water) in the subsequent process, energy usage may increase when separating and distilling it.
  • the upper temperature of the cooling tower 20 for this purpose may be 35°C to 55°C, specifically 35°C to 45°C. If the upper temperature of the cooling tower 20 is lower than at least 35°C, excessive refrigerant may be consumed compared to the effect of reducing the moisture content contained in the recirculating gas, or a lower temperature refrigerant may be required, so there may not be a significant benefit from the viewpoint of efficient energy use. there is. Meanwhile, when the upper temperature of the cooling tower 20 exceeds 55°C, the content of the absorption solvent (moisture) contained in the recirculating gas transfer line 4 increases excessively, and thus the high concentration discharged from the absorption tower 100 It may be difficult to obtain a (meth)acrylic acid solution.
  • Control of the temperature of the upper part of the cooling tower 20 is performed by a heat exchanger provided at the bottom of the cooling tower 20, and specifically, a portion of the lower stream of the cooling tower 20 is transferred to the heat exchanger and the cooling tower ( 20) can be performed by cycling. Meanwhile, the upper part of the cooling tower 20 may be operated under normal pressure operating conditions.
  • the mixed gas containing the (meth)acrylic acid is supplied to the absorption tower (100) through the reactor discharge line (2), and is brought into contact with water in the absorption tower (100) to obtain an aqueous (meth)acrylic acid solution.
  • a mixed gas containing (meth)acrylic acid, organic by-products, and water vapor generated by the synthesis reaction of (meth)acrylic acid is brought into contact with water, which is an absorption solvent, in the absorption tower 100 to obtain an aqueous (meth)acrylic acid solution. You can.
  • the type of the absorption tower 100 may be determined considering the contact efficiency of the mixed gas and the absorption solvent, for example, a packed column type absorption tower, a multistage tray type, etc. type) of absorption tower.
  • the packed column type absorption tower may have fillers such as rashing ring, pall ring, saddle, gauze, structured packing, etc. applied inside.
  • the mixed gas 2 may be supplied to the lower part of the absorption tower 100, and water, which is an absorption solvent, may be supplied to the upper part of the absorption tower 100.
  • the absorption tower 100 has an internal pressure of 1 to 1.5 bar or 1 to 1.3 bar, 50 to 120 °C or 50 to 100 °C, considering the condensation conditions of (meth)acrylic acid and the moisture content according to the saturated vapor pressure. Can be operated under internal temperature.
  • the (meth)acrylic acid aqueous solution is obtained through an absorption process performed in the absorption tower 100, and the (meth)acrylic acid aqueous solution is discharged from the bottom of the absorption tower 100. It may be discharged to stream 120.
  • the upper discharge stream of the absorption tower 100 may contain non-condensable gases that are not dissolved in water, which is an absorption solvent in the absorption tower 100, and the non-condensable gases include acetic acid and inert gas. , unreacted raw materials and a minimal amount of (meth)acrylic acid may be included.
  • the acetic acid content in the discharge stream from the top of the absorption tower can be controlled so that the content of (meth)acrylic acid lost to the top of the absorption tower can be minimized.
  • acetic acid can be additionally separated and removed by the water separation tower and layer separator after the absorption tower, which will be described later, the problem of acetic acid accumulating in the system and acting as an impurity can be solved.
  • the flow rate of acetic acid discharged to the top of the absorption tower may be 20% by weight to 80% by weight, and specifically, 30% by weight to 60% by weight. It can be. Meanwhile, the content of (meth)acrylic acid contained in the upper discharge stream of the absorption tower may be 0.1% by weight to 0.5% by weight, and specifically 0.2% by weight to 0.3% by weight.
  • the aqueous solution of (meth)acrylic acid is supplied to a crystallizer 300, crystallized, and purified (meth)acrylic acid is separated from the purified (meth)acrylic acid. It may include obtaining a mother liquor.
  • the (meth)acrylic acid aqueous solution may be supplied to the crystallizer 300 through the absorption tower discharge line 120 as a discharge stream from the bottom of the absorption tower 100.
  • the aqueous (meth)acrylic acid solution is supplied to the degassing tower (150). ) to remove low-boiling by-products including acrolein and then supply to the crystallizer (300).
  • the acrolein may be a raw material for the production of (meth)acrylic acid, and may also be generated as a by-product during the gas phase oxidation reaction for the production of (meth)acrylic acid.
  • it may be desirable to separate and remove low-boiling by-products such as acrolein before crystallization.
  • the gaseous fraction containing the low-boiling by-products in the degassing tower 150 may be circulated to the absorption tower 100, and the (meth)acrylic acid aqueous solution from which the low-boiling by-products have been degassed is the lower discharge stream of the degassing tower 150 ( 160) may be introduced into the crystallizer 300.
  • the content of (meth)acrylic acid in the bottom discharge stream 160 of the degassing tower may be 85% by weight to 99% by weight, specifically 85% by weight to 95% by weight. This is a higher level than the content of (meth)acrylic acid in the (meth)acrylic acid aqueous solution discharged from the existing absorption tower.
  • the aqueous (meth)acrylic acid solution can be produced in the crystallizer (300) without undergoing a separate purification process or separation process for the aqueous (meth)acrylic acid solution. ), through which overall process energy can be reduced, and at the same time, high purity (meth)acrylic acid can be obtained in the crystallizer 300.
  • the (meth)acrylic acid aqueous solution having such a high (meth)acrylic acid content is, for example, optimally controlled by controlling the operating conditions of the cooling tower 20 and the absorption tower 100 according to the material components and their contents in the system, so that the absorption tower ( 100) can be achieved by minimizing the moisture content within. That is, the absorption solvent component in the recirculating gas circulated from the cooling tower 20 to the reactor 10 is minimized, and the input and usage amount of water supplied to the cooling tower 20 and the absorption tower 100 is minimized, thereby producing a high level of (meth)acrylic acid.
  • a (meth)acrylic acid aqueous solution having a high concentration can be implemented.
  • (meth)acrylic acid contained in the (meth)acrylic acid aqueous solution supplied to the crystallizer 300 can be recrystallized through a crystallization process to obtain high purity crystallized (meth)acrylic acid.
  • (meth)acrylic acid crystallized in the crystallizer may be referred to as purified (meth)acrylic acid. This crystallization process can be performed under conventional conditions.
  • the crystallization method for obtaining the product through crystallization may be a suspension crystallization or a layer crystallization method without limitation, may be continuous or batch, and may be performed in one or two or more stages.
  • the (meth)acrylic acid may be dynamically crystallized to provide purified (meth)acrylic acid.
  • the aqueous (meth)acrylic acid solution may first flow in the form of a falling film on the inner wall of the pipe.
  • crystals can be formed on the inner wall of the tube by adjusting the temperature of the tube below the freezing point of (meth)acrylic acid. Subsequently, the temperature of the tube can be raised to near the solidification point of (meth)acrylic acid to cause sweating of about 5% by weight of (meth)acrylic acid. Then, high purity purified (meth)acrylic acid can be obtained by removing the perspired mother liquid from the tube and recovering the crystals formed on the inner wall of the tube.
  • the mother liquid may refer to a solution from which purified (meth)acrylic acid has been removed from the (meth)acrylic acid aqueous solution introduced into the crystallizer 300. Therefore, the mother liquid may include (meth)acrylic acid, water, acetic acid, and high boiling point by-products, where (meth)acrylic acid is residual (meth)acrylic acid that has not been crystallized in the crystallizer 300, and the high boiling point to be described later.
  • the point by-product may be separated in the separation tower (600) and circulated back to the crystallizer (300).
  • Separation of the mother liquor and crystallized (meth)acrylic acid can be performed using a solid-liquid separation device, for example, a belt filter, a centrifuge, etc.
  • the purified (meth)acrylic acid can be recovered as a (meth)acrylic acid recovery stream 320, and the mother liquor is discharged from the crystallizer 300 through the mother liquor recovery line 310, and a portion of the discharged mother liquor is extracted. It may be supplied to the tower 400, and the remainder may be supplied to the water separation tower 500.
  • the mother liquor recovery line 310 branches into a first crystallizer discharge line 330 and a second crystallizer discharge line 340, and the crystallizer first discharge line 330 is connected to the extraction tower 400. and the second discharge line 340 of the crystallizer may be connected to the water separation tower 500.
  • the mother liquor is discharged from the crystallizer 300 through the mother liquor recovery line 310, and can then be divided and supplied to the extraction tower 400 and the water separation tower 500, respectively.
  • the mother liquid discharged from the crystallizer 300 may contain 50% to 80% by weight of (meth)acrylic acid, specifically 60% to 70% by weight. Additionally, the mother liquid may contain 20% to 50% by weight of water, specifically 30% to 40% by weight.
  • the processing burden and energy consumption of the (meth)acrylic acid aqueous solution in the water separation tower 500 can be greatly reduced. Furthermore, the method according to the present invention divides and supplies the (meth)acrylic acid aqueous solution obtained from the absorption tower (100) to the extraction tower (400) and the water separation tower (500), thereby reducing the overall equipment burden and reducing the overall equipment burden on the water separation tower. Energy usage can be reduced by reducing the amount of water that needs to be distilled at (500) through extraction.
  • the ratio of supplying the mother liquor to the extraction tower 400 and the water separation tower 500 takes into account the capacity ratio of the extraction tower 400 and the water separation tower 500, processing capacity, and the effect of increasing energy efficiency of the entire process. can be decided.
  • the flow rate of the mother liquor supplied to the extraction tower 400 relative to the total flow rate of the mother liquor discharged through the mother liquor recovery line 310 is 20% by weight to 60% by weight, specifically 30% by weight. It may be from 50% by weight, and in this case, it is advantageous in terms of developing the above-mentioned effects.
  • the remainder may be supplied to the water separation tower 500 as described above.
  • the processing sharing efficiency of the water separation tower 500 can be improved, and thus the energy efficiency of the entire process can be improved.
  • a larger capacity extraction tower (400) is required, and the operating conditions of the downstream water separation tower (500) become poor, resulting in increased loss of (meth)acrylic acid. Since the process efficiency may actually decrease, it is advantageous to adjust the supply ratio of the mother liquor within the above-mentioned range.
  • the amount of mother liquor supplied to the water separation tower 500 increases, the amount of water that must be removed by azeotropic distillation from the water separation tower 500 increases, so the energy use reduction effect according to the present invention may decrease. It is advantageous that the feed rate of the mother liquor is adjusted within the above-mentioned range.
  • an extraction liquid and a raffinate liquid are obtained by contacting the extraction solvent and the mother liquid in the extraction tower 400, and the extract liquid stream 410 containing the extract liquid is sent to the water separation tower 500. It may include a supply extraction process step.
  • the extraction tower 400 receives a portion of the mother liquor discharged from the crystallizer 300, removes most of the water contained in the mother liquor without using a lot of energy, and supplies it to the water separation tower 500, thereby performing water separation, which will be described later. It is possible to save energy used for azeotropic distillation in the tower 500. In this respect, it is preferable to use a liquid-liquid contact method for extraction in the extraction tower 400 in terms of improving energy efficiency of the entire process.
  • the extraction solvent may be a hydrocarbon solvent that can form an azeotrope with water and organic by-products (acetic acid, etc.), but does not form an azeotrope with (meth)acrylic acid, but can sufficiently extract it, and also has a boiling point of 10 to 120 ° C. Having it is advantageous in the extraction process.
  • the extraction solvent is benzene, toluene, xylene, n-heptane, cycloheptane, cycloheptene, 1-heptene (1- heptene), ethyl-benzene, methyl-cyclohexane, n-butyl acetate, isobutyl acetate, isobutyl acrylate, n-propyl acetate, isopropyl acetate, methyl isobutyl ketone, 2-methyl-1-heptene, 6-methyl- 1-Heptene (6-methyl-1-heptene), 4-methyl-1-heptene, 2-ethyl-1-hexene, ethylcyclopentane (ethylcyclopentane), 2-methyl-1-hexene, 2,3-dimethylpentane, 5-methyl-1-hexene ) and isopropyl-butyl-ether (isopropyl-but
  • the mother liquid in the extraction process, it is advantageous for the mother liquid to have a temperature of 10 to 70°C.
  • the extraction tower 400 may be an extraction device based on a liquid-liquid contact method.
  • the extraction device may include a Karr reciprocating plate column, a rotary-disk contactor, a Scheibel column, a Kuhni column, or a spray extraction tower. , a packed extraction tower, a pulsed packed column, a bank of mixer-settlers, a mixer, and a centrifugal counter current extractor.
  • the extract may include (meth)acrylic acid, acetic acid, extraction solvent, and high boiling point by-products.
  • water contained in the mother liquid can be recovered as a raffinate liquid.
  • the recovered raffinate liquid may be discharged as a raffinate stream 420 and introduced into a layer separator 550, which will be described later.
  • energy consumption can be greatly reduced by reducing the operating burden of the distillation process described later.
  • the stream supplied to the water separation tower 500 is the mother liquor supplied along the second crystallizer discharge line 340, and the extract liquid supplied along the extract liquid stream 410. may include.
  • the flow rate of water in the stream supplied to the water separation tower 500 may be 20% by weight to 50% by weight, specifically 25% by weight to 40% by weight, based on the flow rate of water introduced into the absorption tower 100. .
  • the distillation process within the water separation tower 500 for the stream supplied to the water separation tower 500 is an upper fraction containing water and acetic acid and (meth)acrylic acid and high boiling point by-products by azeotropic distillation. It may be a process of separating the lower fraction.
  • distillation in the water separation tower 500 is performed in the presence of a hydrophobic azeotropic solvent, and the hydrophobic azeotropic solvent, water, and organic by-products (acetic acid, etc.) can be recovered simultaneously, which is advantageous in the process.
  • the hydrophobic azeotropic solvent is a hydrophobic solvent that can form an azeotrope with water and acetic acid, but does not form an azeotrope with (meth)acrylic acid, and any hydrocarbon-based solvent that satisfies the above physical properties can be applied without limitation.
  • the hydrophobic azeotropic solvent may have a boiling point lower than (meth)acrylic acid, and may preferably have a boiling point of 10 to 120°C.
  • hydrophobic azeotropic solvents satisfying the above physical properties include benzene, toluene, xylene, n-heptane, cycloheptane, and cycloheptene.
  • the hydrophobic azeotropic solvent may be the same as or different from the extraction solvent applied to the extraction tower 400. However, in consideration of production efficiency according to the continuous process, it is preferable that the hydrophobic azeotropic solvent is the same as the extraction solvent. In this way, when the same compound is used as the hydrophobic azeotropic solvent and the extraction solvent, at least a portion of the hydrophobic azeotropic solvent distilled and recovered in the water separation tower 500 is supplied to the lower part of the extraction tower 400 and can be used as part of the extraction solvent. .
  • the upper fraction of the water separation tower recovered in this way can be supplied to the layer separator 550 through the water separation tower upper discharge stream 510, and the lower fraction of the water separation tower is supplied to the water separation tower lower discharge stream 520. It can be supplied to the high boiling point by-product separation tower (600).
  • the layer separator 550 is a liquid-liquid layer separator, and is a device for separating immiscible fluids using gravity or centrifugal force due to density differences, and the relatively light liquid is moved to the top of the layer separator 550. , the relatively heavy liquid can be separated into the lower part of the layer separator 550.
  • the water separation tower top discharge stream 510 supplied to the layer separator 550 may be separated into an organic layer containing a hydrophobic azeotropic solvent and an aqueous layer containing water and acetic acid.
  • the organic layer separated in the layer separator 550 is supplied to the top of the water separation tower 500 and can be reused as a hydrophobic azeotropic solvent, and the remainder is supplied to the extraction tower 400 and used as an extraction solvent. can be reused
  • the water layer separated in the layer separator 550 can be supplied to the top of the absorption tower 100 and used as an absorption solvent, and the remainder can be discharged as wastewater.
  • the aqueous layer may contain acetic acid, and the concentration of acetic acid contained in the aqueous layer may vary depending on the type of hydrophobic azeotropic solvent and the reflux ratio of the column installed in the water separation tower 500. According to the present invention, the concentration of acetic acid contained in the water layer may be 1 to 30% by weight, preferably 2 to 20% by weight, and more preferably 3 to 10% by weight.
  • acetic acid is discharged through the upper discharge stream of the absorption tower 100, and at the same time is discharged through azeotropic distillation performed through the water separation tower 500 and the layer separator 550.
  • the total flow rate of acetic acid introduced into the absorption tower 100 is the flow rate of acetic acid in the upper discharge stream of the absorption tower 100 and the flow rate of acetic acid in the stream contained in the water layer of the layer separator 550 and discharged. It may be equal to the sum of the flow rates.
  • the discharge stream from the bottom of the water separation tower (500) is supplied to the high boiling point by-product separation tower (600), and the high boiling point by-product containing the (meth)acrylic acid is supplied. It may include supplying the top discharge stream of the point by-product separation tower (600) to the crystallizer (300).
  • the discharge stream from the bottom of the water separation tower 500 is distilled to form a lower fraction containing high boiling point by-products, and the high boiling point by-products are removed to contain a high content of (meth)acrylic acid. It can be separated into an upper fraction.
  • the upper fraction may be supplied to the crystallizer 300 through the high boiling point by-product separation tower top discharge stream 610, and the content of the (meth)acrylic acid contained in the high boiling point by-product separation tower top discharge stream 510 It may be 90% to 99% by weight, specifically 95% to 99% by weight.
  • the amount of water contained in each stream has already been reduced in the process after the absorption tower 100, and a significant amount of water is removed through the extraction tower 400 and the water separation tower 500, so high boiling point by-products
  • the water content in the separation tower top discharge stream 610 is controlled to be low, which makes it possible to create a concentrated stream with a high concentration of (meth)acrylic acid that can be directly introduced into the crystallizer 300.
  • the loss of (meth)acrylic acid can be reduced to the maximum.
  • a reaction gas containing air and a raw material compound (propylene) was supplied to the reactor 10 equipped with a catalyst through the reaction gas supply line 1, and the recycle gas derived from the cooling tower 20 was transferred to the reactor 10. It was supplied to the reactor (10) through line (4).
  • the composition includes (meth)acrylic acid (7.0 mol%), water (11.8 mol%), high boiling point material (0.09 mol%), and inert gas (80.6 mol%).
  • a mixed gas (2) was obtained.
  • the mixed gas (2) was introduced into the 22nd stage from the top of the absorption tower (100) at a temperature of 164°C.
  • the mixed gas was contacted with an absorption solvent (water) in the absorption tower 100 to obtain an aqueous (meth)acrylic acid solution.
  • the water introduced into the absorption tower 100 was supplied through the lower discharge stream 6 of the cooling tower and the water layer from the layer separator 550, which will be described later, and the water was supplied at 5.8% by weight compared to the flow rate of the mixed gas 2. It was supplied to the top of the absorption tower (100) at a mass flow rate of .
  • the mass flow rate of acetic acid discharged to the outside of the system through the upper discharge stream 110 of the absorption tower was 40.8% by weight.
  • the pressure at the top of the absorption tower 100 was 1.1 bar and the temperature at the bottom of the absorption tower 100 was 84.1°C.
  • non-condensable gas containing components not dissolved in water was separated as the absorption tower top discharge stream (110), and a portion (3) of the absorption tower top discharge stream was supplied to the cooling tower (20). And the rest were discharged outside the system.
  • the cooling tower (20) the non-condensable gas contained in a portion (3) of the absorption tower top discharge stream was dissolved in water. At this time, the water was supplied through the water supply line (5).
  • the gas that was not dissolved in water in the cooling tower (20) was supplied to the reactor (10) through the recirculation gas transfer line (4), and water and components dissolved in the water (acetic acid and components that were not dissolved in water in the absorption tower) were supplied to the reactor (10) through the recirculation gas transfer line (4).
  • a portion (6) of the cooling tower bottom discharge stream containing (meth)acrylic acid) was fed to the top of the absorption tower (100).
  • the above-described (meth)acrylic acid aqueous solution is supplied to the degassing tower 150 as the absorption tower bottom discharge stream 120 and degassed, and the low boiling point by-product is supplied to the absorption tower 100 as the degassing tower top discharge stream.
  • This degassed aqueous (meth)acrylic acid solution was supplied to the crystallizer 300 as a discharge stream 160 from the bottom of the degassing tower.
  • the upper exhaust stream of the degassing tower was supplied to the absorption tower (100) at a flow rate of 25% by weight compared to the mass flow rate of water introduced into the absorption tower (100).
  • composition of the stripping tower bottom discharge stream 160 is (meth)acrylic acid (89.5% by weight), acetic acid (1.8% by weight), water (7% by weight), furfural (0.8% by weight), and maleic acid (0.8% by weight). % by weight) was included.
  • the degassing tower bottom discharge stream 160 was mixed with the high boiling point by-product separation tower top discharge stream 610 described later and supplied to the crystallizer 300, and the mixed stream contained (meth)acrylic acid (90.9% by weight), It included acetic acid (1.6% by weight), water (5.9% by weight), furfural (0.8% by weight) and maleic acid (0.7% by weight).
  • a (meth)acrylic acid recovery stream 320 containing (meth)acrylic acid was obtained through the crystallization process performed in the crystallizer 300, and through this, (meth)acrylic acid was obtained.
  • the content of (meth)acrylic acid in the (meth)acrylic acid recovery stream 320 was 99.5% by weight or more.
  • the mother liquid separated from the (meth)acrylic acid was obtained in the crystallizer 300.
  • the mother liquid contained (meth)acrylic acid (64% by weight), water (23.7% by weight), acetic acid (6.5% by weight), and high boiling point by-product (6.0% by weight).
  • the mother liquor discharged through the mother liquor recovery line 310 is branched, and 40% by weight of the total weight of the mother liquor is supplied to the extraction tower 400 through the first discharge line 330 of the crystallizer, and the remaining 60% of the mother liquor is supplied to the extraction tower 400. Weight percent was fed through the crystallizer second discharge line (340) and to the water separation tower (500). Meanwhile, the second discharge line 340 of the crystallizer mixed the extract stream 410, which will be described later, and supplied it to the water separation tower 500.
  • a raffinate stream 420 containing water and an extract liquid stream 410 containing toluene and (meth)acrylic acid were obtained.
  • toluene supplied to the lower part of the extraction tower (400) was supplied at a mass flow rate of 4.5 times the flow rate of water in the mother liquid supplied to the extraction tower (400).
  • the raffinate stream 420 was supplied to a layer separator 550, which will be described later, and the extract liquid stream 410 was supplied to the water separation tower 500.
  • the water separation tower top discharge stream 510 containing toluene, water and acetic acid, and (meth)acrylic acid and high boiling point by-products A water separation tower bottom discharge stream 520 containing was obtained.
  • the toluene supplied to the water separation tower (500) was supplied at a mass flow rate twice that of the toluene supplied to the extraction tower (400).
  • the water separation tower top discharge stream 510 was supplied to a layer separator 550 and separated into an aqueous layer containing water and acetic acid and an organic layer containing toluene. Part of the water layer was supplied to the absorption tower (100), and the remainder was discharged to the outside of the system as wastewater. Meanwhile, the organic layer was supplied to the extraction tower (400) and the water separation tower (500).
  • the above-described water separation tower bottom discharge stream 520 is supplied to the high boiling point by-product separation tower 600, and the high boiling point by-product separation tower top discharge stream 610 and high boiling point by-products including (meth)acrylic acid are supplied to the water separation tower bottom discharge stream 520.
  • a discharge stream (620) from the bottom of the separation tower containing high boiling point by-products was obtained.
  • the high boiling point by-product separation tower top discharge stream 610 was mixed with the degassing tower bottom discharge stream 160 as described above and supplied to the crystallizer 300. At this time, the content of (meth)acrylic acid in the upper discharge stream 610 of the high boiling point by-product separation tower was 98.6% by weight.
  • the energy used in the water separation tower (500) was 89.1 kcal/kg AA
  • the energy used in the high boiling point by-product separation tower (600) was 35.9 kcal/kg AA, for a total of 125 kcal/kg AA. Energy was used.
  • the amount of (meth)acrylic acid lost through the absorption tower top discharge stream 110 was 0.92% by weight compared to the (meth)acrylic acid production (the amount of (meth)acrylic acid obtained from the crystallizer), and The amount of (meth)acrylic acid lost through the derived wastewater was 0.13% by weight compared to the (meth)acrylic acid production, resulting in a total loss of 1.05% by weight of (meth)acrylic acid.
  • a (meth)acrylic acid solution was obtained from the bottom of the absorption tower (100), and the (meth)acrylic acid solution was introduced into the crystallizer (300) through the degassing tower (150) to obtain (meth)acrylic acid ( 320) was obtained.
  • the water introduced into the absorption tower (100) was supplied by mixing the stream (6) directly supplied to the absorption tower and a portion of the discharge stream from the bottom of the cooling tower, and the water was supplied at 6.6% by weight compared to the flow rate of the mixed gas (2). It was supplied to the top of the absorption tower at a mass flow rate of .
  • the mother liquor 310 after crystallization in the crystallizer 300 is input into the high boiling point by-product separation tower 600, and the discharge stream 620 from the bottom of the high boiling point by-product separation tower containing high boiling point by-products and the high boiling point by-products are removed.
  • a high-boiling by-product separation tower top discharge stream (610) containing the mother liquor was obtained.
  • the high boiling point by-product separation tower top discharge stream (610) was recycled to the absorption tower (100). Except for this, (meth)acrylic acid was prepared in the same manner as in Example 1.
  • the degassing tower bottom discharge stream 160 introduced into the crystallizer 300 contains (meth)acrylic acid (90.5% by weight), acetic acid (1.8% by weight), water (5.9% by weight), furfural (0.7% by weight), and maleic acid. Iksan (0.7% by weight) was included. As a result, more than 99.5% by weight of (meth)acrylic acid was obtained from the (meth)acrylic acid recovery stream 320 of the crystallizer 300.
  • the energy used to remove high boiling point by-products in the high boiling point by-product separation tower 600 was 154.5 kcal/kg AA. Meanwhile, the amount of (meth)acrylic acid lost through the absorption tower top discharge stream 110 was 1.56% by weight compared to the (meth)acrylic acid produced.
  • Comparative Example 1 is a case where the mother liquor (310) was supplied to the high boiling point by-product separation tower (600), and the total energy consumption increased compared to Example 1, and the amount of (meth)acrylic acid loss also increased by approximately 1.5 times.
  • Comparative Example 1 does not supply the stripping tower bottom discharge stream 160 of the same composition as Example 1 to the crystallizer, but branches the stripping tower bottom discharge stream 160 to produce the stripping tower bottom discharge stream ( 40% by weight of the total weight of 160) was supplied to the extraction tower (400), and the remaining 60% by weight was supplied to the water separation tower (500).

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
PCT/KR2023/012560 2022-08-30 2023-08-24 고순도 (메트)아크릴산의 제조방법 Ceased WO2024049105A1 (ko)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP23860782.4A EP4491608A4 (en) 2022-08-30 2023-08-24 PROCESS FOR PREPARING HIGH-PURITY (METH)ACRYLIC ACID
CN202380014288.5A CN118201902A (zh) 2022-08-30 2023-08-24 高纯度(甲基)丙烯酸的制备方法
JP2024525179A JP2025527381A (ja) 2022-08-30 2023-08-24 高純度（メタ）アクリル酸の製造方法
US18/709,108 US20250002439A1 (en) 2022-08-30 2023-08-24 Method for preparation of high purity (meth)acrylic acid

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KR10-2022-0109483 2022-08-30
KR20220109483 2022-08-30
KR1020230107030A KR20240031053A (ko) 2022-08-30 2023-08-16 고순도 아크릴산의 제조방법
KR10-2023-0107030 2023-08-16

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20040108610A (ko) * 2003-06-05 2004-12-24 니폰 쇼쿠바이 컴파니 리미티드 아크릴산의 제조 방법
JP2007182437A (ja) * 2005-12-06 2007-07-19 Nippon Shokubai Co Ltd アクリル酸の製造方法
KR20070077053A (ko) * 2006-01-20 2007-07-25 니폰 쇼쿠바이 컴파니 리미티드 (메타)아크릴산의 제조 방법
KR20140060528A (ko) * 2011-09-16 2014-05-20 에보니크 룀 게엠베하 메타크릴산 및 메타크릴산 에스테르의 제조 방법
KR20160030715A (ko) * 2014-09-11 2016-03-21 주식회사 엘지화학 고순도 아크릴산의 제조방법

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Publication number Priority date Publication date Assignee Title
KR20040108610A (ko) * 2003-06-05 2004-12-24 니폰 쇼쿠바이 컴파니 리미티드 아크릴산의 제조 방법
JP2007182437A (ja) * 2005-12-06 2007-07-19 Nippon Shokubai Co Ltd アクリル酸の製造方法
KR20070077053A (ko) * 2006-01-20 2007-07-25 니폰 쇼쿠바이 컴파니 리미티드 (메타)아크릴산의 제조 방법
KR20140060528A (ko) * 2011-09-16 2014-05-20 에보니크 룀 게엠베하 메타크릴산 및 메타크릴산 에스테르의 제조 방법
KR20160030715A (ko) * 2014-09-11 2016-03-21 주식회사 엘지화학 고순도 아크릴산의 제조방법

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EP4491608A4 (en) 2025-11-19

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