WO2024049106A1 - 고순도 (메트)아크릴산의 제조방법 - Google Patents

고순도 (메트)아크릴산의 제조방법 Download PDF

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WO2024049106A1
WO2024049106A1 PCT/KR2023/012563 KR2023012563W WO2024049106A1 WO 2024049106 A1 WO2024049106 A1 WO 2024049106A1 KR 2023012563 W KR2023012563 W KR 2023012563W WO 2024049106 A1 WO2024049106 A1 WO 2024049106A1
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meth
acrylic acid
tower
water
aqueous
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PCT/KR2023/012563
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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 KR1020230107059A external-priority patent/KR20240031054A/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to CN202380014325.2A priority Critical patent/CN118201903A/zh
Priority to US18/710,686 priority patent/US20250019337A1/en
Priority to EP23860783.2A priority patent/EP4491609A4/en
Priority to JP2024525180A priority patent/JP2025527382A/ja
Publication of WO2024049106A1 publication Critical patent/WO2024049106A1/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
    • 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
    • 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

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 high purity (meth)acrylic acid with a high recovery rate in order to solve the problems mentioned in the background technology of the above invention, while further reducing energy usage in the purification process.
  • the purpose is to provide a method for recovering (meth)acrylic acid.
  • first and second aqueous (meth)acrylic acid solutions by contacting a mixed gas containing (meth)acrylic acid with water in an absorption tower, 1 Discharging the aqueous (meth)acrylic acid solution from the bottom of the absorption tower and supplying it to a crystallizer, discharging the second aqueous (meth)acrylic acid solution from the side of the absorption tower, discharging the second aqueous (meth)acrylic acid solution into water
  • Obtaining a distillate containing (meth)acrylic acid and high boiling point by-products by supplying the distillate to a separation tower, supplying the distillate to a high boiling point by-product separation tower, and discharging the high boiling point by-products containing (meth)acrylic acid from the top of the separation tower.
  • a method for producing (meth)acrylic acid comprising:
  • the amount of water introduced into the absorption tower for purifying (meth)acrylic acid is minimized, and a portion of the aqueous (meth)acrylic acid solution discharged from the absorption tower is not subjected to a distillation process.
  • the crystallizer directly to the crystallizer, the amount of energy consumed throughout the process can be reduced.
  • the loss of (meth)acrylic acid can be further reduced by separating the high boiling point by-products after the water separation tower to prevent accumulation of the high boiling point by-products in the system, and by supplying the upper discharge stream of the high boiling point by-products back to crystallization.
  • 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 to 4 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 first and second aqueous (meth)acrylic acid solutions, 1 Discharging the aqueous (meth)acrylic acid solution from the bottom of the absorption tower and supplying it to a crystallizer, discharging the second aqueous (meth)acrylic acid solution from the side of the absorption tower, discharging the second aqueous (meth)acrylic acid solution into water Obtaining a distillate containing (meth)acrylic acid and high boiling point by-products by supplying the distillate to a separation tower, supplying the distillate to a high boiling point by-product separation tower, and discharging the high boiling point by-products containing (meth)acrylic acid from the top of the separation tower. supplying a stream to the crystallizer, obtaining purified (meth)acrylic acid from the crystallizer, and
  • the method for producing (meth)acrylic acid includes the step of contacting a mixed gas containing (meth)acrylic acid with water in an absorption tower to obtain first and second aqueous (meth)acrylic acid solutions. It can be included.
  • 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.
  • 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.
  • 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.
  • 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. . Thereafter, the bottom discharge stream 6 of the cooling tower 20 may be supplied to the absorption tower 100.
  • 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 mixed gas containing (meth)acrylic acid which is a product of the gas phase oxidation reaction, is supplied to the absorption tower 100 through the reactor discharge line 2, and is brought into contact with water, which is an absorption solvent, in the absorption tower 100.
  • a process to obtain an aqueous (meth)acrylic acid solution can be performed.
  • the mixed gas may include organic by-products such as (meth)acrylic acid, acetic acid, and acrolein, and water vapor.
  • 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 100 °C or 50 to 90 °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 first aqueous (meth)acrylic acid solution discharged from the bottom of the absorption tower 100 and the absorption tower 100 through an absorption process performed in the absorption tower 100 can be obtained.
  • the lower part of the absorption tower 100 from which the first aqueous (meth)acrylic acid solution is discharged may be a point at a height of 95% to 100% downward from the top of the absorption tower 100, Specifically, it may be the bottom of the absorption tower.
  • the side of the absorption tower 100 where the second aqueous (meth)acrylic acid solution is discharged may be a side with a height of 40% to 80% downward from the top of the absorption tower 100.
  • the content of (meth)acrylic acid in the first aqueous (meth)acrylic acid solution may be 75% by weight to 95% by weight, specifically 80% by weight to 90% by weight. Additionally, the water content in the first (meth)acrylic acid aqueous solution may be 5% by weight to 20% by weight, specifically 10% by weight to 15% by weight.
  • the first aqueous (meth)acrylic acid solution may include a residual amount of organic by-products in addition to the (meth)acrylic acid and water.
  • the content of (meth)acrylic acid in the first aqueous (meth)acrylic acid solution is higher than the content of (meth)acrylic acid in the aqueous (meth)acrylic acid solution discharged from the existing absorption tower.
  • the first (meth)acrylic acid can be obtained without undergoing a separate purification or separation process for the first aqueous (meth)acrylic acid solution.
  • the aqueous acrylic acid solution can be supplied directly to the crystallizer 300, thereby reducing overall process energy, and at the same time, high purity (meth)acrylic acid can be obtained from the crystallizer 300.
  • the content of (meth)acrylic acid in the second aqueous (meth)acrylic acid solution may be 30% by weight to 60% by weight, specifically 40% by weight to 55% by weight. Additionally, the water content in the second (meth)acrylic acid aqueous solution may be 40% by weight to 60% by weight.
  • the second aqueous (meth)acrylic acid solution may include a residual amount of organic by-products in addition to the (meth)acrylic acid and water. To this end, the second aqueous (meth)acrylic acid solution may be discharged from the side at a height of 40% to 80% downward from the top of the absorption tower 100.
  • 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 present invention can minimize the content of (meth)acrylic acid lost in the absorption tower by controlling the amount of acetic acid contained in the upper discharge stream of the absorption tower 100.
  • 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, 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 first aqueous (meth)acrylic acid solution may be supplied to the crystallizer 300 through the absorption tower bottom discharge stream 130, and the second aqueous (meth)acrylic acid solution may be supplied to the absorption tower side discharge stream 120. It can be introduced into the process of obtaining distillate containing (meth)acrylic acid and high boiling point by-products.
  • the amount of energy consumed in the subsequent process can be reduced.
  • the first aqueous (meth)acrylic acid solution has a high concentration of (meth)acrylic acid, it is directly used in the crystallizer 300 without undergoing a separate purification or separation process for the first aqueous (meth)acrylic acid solution.
  • overall process energy can be reduced, and at the same time, high purity (meth)acrylic acid can be obtained in the crystallizer 300. This is possible because, as described above, the content of (meth)acrylic acid in the first aqueous (meth)acrylic acid solution is high.
  • the first aqueous (meth)acrylic acid solution also contains a certain amount of water.
  • the mother liquid separated from the purified (meth)acrylic acid in the crystallizer 300 is circulated to the absorption tower, so the amount of water contained in the second aqueous (meth)acrylic acid solution is reduced by the amount of water contained in the mother liquid. , the energy consumption involved in the purification process for the second aqueous (meth)acrylic acid solution can be reduced.
  • the first aqueous (meth)acrylic acid solution is supplied to a crystallizer 300 and crystallized to produce purified (meth)acrylic acid and the purified (meth)acrylic acid. It may include obtaining a mother liquor separated from acrylic acid.
  • (meth)acrylic acid crystallized in the crystallizer may be referred to as purified (meth)acrylic acid.
  • (meth)acrylic acid contained in the first aqueous (meth)acrylic acid solution supplied to the crystallizer 300 can be recrystallized through a crystallization process to obtain high purity purified (meth)acrylic acid.
  • the discharge stream from the top of the high boiling point by-product separation tower 600, which will be described later, and containing a high content of (meth)acrylic acid is also discharged from the top of the high boiling point by-product separation tower 600. It can be introduced as (300).
  • This crystallization process can be performed under conventional conditions.
  • the crystallization method for obtaining the product through crystallization is not limited to suspension crystallization and layer crystallization, and 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, acetic acid, and high boiling point by-products in addition to water, and the (meth)acrylic acid here may be residual (meth)acrylic acid that has not been crystallized in the crystallizer 300.
  • Separation of the mother liquor and crystallized purified (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 310, and the mother liquor can be discharged from the crystallizer 300 through a mother liquor discharge stream.
  • a portion of the mother liquor discharged from the crystallizer 300 may be circulated to the absorption tower 100 through the first mother liquor recovery line 320, and the remainder of the mother liquor may be circulated to the second mother liquor 100. It can be circulated to the water separation tower 500 through the mother liquor recovery line 330.
  • the water separation tower 500 is a device for receiving all or part of the second aqueous (meth)acrylic acid solution and distilling it to obtain a distillate containing (meth)acrylic acid and high boiling point by-products. .
  • the mother liquor discharged from the crystallizer 300 may contain 50% to 80% by weight of (meth)acrylic acid, specifically 60% to 75% by weight. Additionally, the mother liquid may contain 20% to 50% by weight of water, specifically 25% to 40% by weight. Additionally, the mother liquor discharged from the crystallizer 300 may contain a remaining amount of organic by-products.
  • the second aqueous (meth)acrylic acid solution may be introduced into a process for obtaining distillate containing (meth)acrylic acid and high boiling point by-products.
  • a portion of the second aqueous (meth)acrylic acid solution is sent to the extraction tower as the extraction tower feed stream 170. (400) and supplying the remainder as a water separation tower feed stream (160) to the water separation tower (500), wherein the extraction solvent is brought into contact with the extraction tower feed stream in the extraction tower (400) to contain the extract liquid. supplying an extract stream to the water separation tower (500), and a water separation tower top discharge stream (510) containing water and (meth)acrylic acid and high boiling point by-products from the water separation tower (500). It may be performed including the step of separating the distillate into a water separation tower bottom discharge stream (520).
  • the flow rate ratio of the extraction tower feed stream 170 supplied to the extraction tower compared to the flow rate of the second aqueous (meth)acrylic acid solution may be 20% by weight to 60% by weight.
  • the flow rate ratio is 20% by weight or more, the flow rate introduced into the water separation tower 500 is reduced, and the amount of energy consumed in distilling water with high specific heat in the water separation tower 500 can be reduced.
  • acetic acid which is a by-product
  • the flow rate is 60% by weight or less
  • acetic acid which is a by-product
  • the amount of acetic acid introduced into the high-boiling point by-product separation tower (600) can be minimized.
  • the acetic acid content in the upper discharge stream of the high boiling point by-product separation tower (600) can be lowered, and as a result, high purity purified (meth)acrylic acid can be obtained in the crystallizer (300).
  • the extraction tower 400 removes most of the water contained in the extraction tower supply stream 170 without using a large amount of energy and supplies it to the water separation tower 500, which will be described later. It allows saving the energy used in azeotropic distillation. In this respect, it is preferable for extraction in the extraction tower 400 to bring the extraction solvent into contact with the extraction tower feed stream through a liquid-liquid contact method in terms of improving the 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 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 extraction tower feed stream 170 can be recovered as a raffinate.
  • 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 reduced by reducing the operating burden of the distillation process described later.
  • the water separation tower feed stream 160 and the extract stream 410 in the second aqueous (meth)acrylic acid solution are supplied to the water separation tower 500, and the A distillation process may be performed.
  • the flow rate of water in the stream supplied to the water separation tower 500 may be 30% by weight to 70% by weight, specifically 40% by weight to 60% by weight, based on the flow rate of water introduced into the absorption tower. If the water flow rate is less than 30% by weight, it may be difficult to separate acetic acid in the water separation tower 500, and if the flow rate is more than 70% by weight, the water separation tower 500 and the high boiling point by-product separation tower In (600), the amount of energy consumed for distillation of water may be increased.
  • 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, a hydrophobic azeotropic solvent, and acetic acid, and (meth)acrylic acid and high boiling point by azeotropic distillation. It may be a process of separating a lower fraction containing by-products.
  • the process it is advantageous for the process to perform distillation in the water separation tower 500 in the presence of a hydrophobic azeotropic solvent because the azeotropic solvent, water, and organic by-products (acetic acid, etc.) can be recovered simultaneously.
  • 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 azeotropic solvent and the extraction solvent, at least a portion of the azeotropic solvent distilled and recovered in the water separation tower 500 may be supplied to the lower part of the extraction tower 400 and 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 discharged as a layer separator discharge stream 560, and a portion of the layer separator discharge stream 560 is supplied to the top of the water separation tower 500 and reused as an azeotropic solvent. The remainder can be supplied to the extraction tower 400 and reused as an extraction solvent.
  • part of the aqueous layer containing water and acetic acid 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 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.
  • process flexibility can be secured compared to the previous attempt, which has the advantage of minimizing the amount of (meth)acrylic acid loss from the top of the absorption tower.
  • 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 520 from the bottom of the water separation tower 500 is supplied to the high boiling point by-product separation tower 600, and the (meth)acrylic acid is produced. It may include supplying the upper discharge stream of the high boiling 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.
  • the first aqueous (meth)acrylic acid solution discharged from the bottom of the absorption tower and the upper discharge stream of the high boiling point by-product separation tower may be supplied to the crystallizer 300 as separate streams, and these streams may be supplied to the crystallizer 300 as separate streams. It can be supplied to the crystallizer 300 as a mixed stream.
  • the content of (meth)acrylic acid contained in the upper discharge stream of the high boiling point by-product separation tower may be higher than the content of (meth)acrylic acid contained in the first aqueous (meth)acrylic acid solution, and discharged from the bottom of the absorption tower.
  • the first aqueous (meth)acrylic acid solution and the upper discharge stream of the high boiling point by-product separation tower form a mixed stream and are supplied to the crystallizer
  • the content of (meth)acrylic acid in the mixed stream may be 85 to 99% by weight. there is. Therefore, it is possible to directly introduce the mixed stream into the crystallizer without a separate distillation process.
  • 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 (6.6 mol%), water (16.4 mol%), high boiling point material (0.09 mol%), and inert gas (76.3 mol%).
  • a mixed gas (2) was obtained.
  • the mixed gas (2) was introduced into the 11th 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 a first (meth)acrylic acid aqueous solution and a second (meth)acrylic acid aqueous 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 10.6 weight compared to the mass flow rate of the mixed gas 2. It was supplied to the top of the absorption tower (100) at a flow rate of %. At this time, 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 82°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 sent to the cooling tower (20). was supplied, and the remainder was discharged outside the system.
  • the non-condensable gas contained in a portion (3) of the absorption tower top discharge stream was dissolved in water.
  • the water was supplied through the water supply line (5).
  • 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).
  • the cooling tower bottom discharge stream (6) containing (meth)acrylic acid) was fed to the top of the absorption tower (100).
  • the above-described first aqueous (meth)acrylic acid solution contains (meth)acrylic acid (79.2% by weight), acetic acid (2.2% by weight), water (17% by weight), furfural (0.7% by weight), and maleic acid (0.8% by weight). %) and was fed to the crystallizer (300) as the absorption tower bottom discharge stream (130).
  • the absorption tower bottom discharge stream 130 formed a mixed stream with the high boiling point by-product separation tower top discharge stream 610, which will be described later, and was supplied to the crystallizer 300.
  • the content of (meth)acrylic acid in the mixed stream was 88.6% by weight.
  • the mother liquid separated from the (meth)acrylic acid was obtained in the crystallizer 300.
  • the mother liquid contained (meth)acrylic acid (63.2% by weight), water (25.3% by weight), acetic acid (3.9% by weight), furfural (3.1% by weight), and maleic acid (4.5% by weight).
  • the mother liquor was branched and supplied to the absorption tower 100 and the water separation tower 500 through the first mother liquor recovery line 320 and the second mother liquor recovery line 330, respectively.
  • the above-described second aqueous (meth)acrylic acid solution contains (meth)acrylic acid (43.8% by weight), acetic acid (4.3% by weight), water (50.9% by weight), furfural (0.4% by weight), and maleic acid (0.03% by weight). %) and was supplied to the extraction tower 400 and the water separation tower 500 as the absorption tower side discharge stream 120 at a height of 64% from the top of the absorption tower 100 downward. At this time, the absorption tower side discharge stream 120 containing the second aqueous (meth)acrylic acid solution is branched, and 45% by weight of the total weight of the second aqueous (meth)acrylic acid solution is extracted as the extraction tower feed stream 170.
  • a raffinate stream 420 containing water and an extract liquid stream 410 containing toluene and (meth)acrylic acid were obtained.
  • the extraction solvent (toluene) supplied to the lower part of the extraction tower (400) was supplied at a flow rate of 4.32 times the mass flow rate of water in the second aqueous (meth)acrylic acid solution supplied to the extraction tower (400).
  • the raffinate stream 420 was supplied to a layer separator 550 described later, and the extract stream 410 was mixed with the water separation tower feed stream 160 described above and 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 hydrophobic azeotropic solvent supplied to the water separation tower (500) was supplied at a flow rate of 1.5 times the mass flow rate of the extraction solvent 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 570 containing water and acetic acid and an organic layer 560 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-mentioned 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.
  • 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 absorption tower bottom discharge stream 130 as described above and supplied to the crystallizer 300. At this time, the content of (meth)acrylic acid in the high boiling point by-product separation tower top discharge stream 610 was 99.2% by weight.
  • the energy used in the water separation tower (500) was 369.1 kcal/kg AA
  • the energy used in the high boiling point by-product separation tower (600) was 82.3 kcal/kg AA
  • the energy used in the crystallizer (300) was 369.1 kcal/kg AA.
  • the energy was 130.5 kcal/kg AA, and a total of 581.8 kcal/kg AA of energy was used.
  • Comparative Example 1 the reaction product (2) obtained through the same process as Example 1 was introduced into the absorption tower under the same conditions (operating conditions and flow rate of water introduced into the absorption tower), but at the sides of the absorption tower (100) and An aqueous (meth)acrylic acid solution was not obtained from the bottom of the tower, but an aqueous (meth)acrylic acid solution was obtained only from the bottom of the absorption tower.
  • the (meth)acrylic acid aqueous solution was supplied to the degassing tower (150) to obtain a stripping tower top discharge stream containing low-boiling by-products and a stripping tower bottom discharge stream 160 containing the (meth)acrylic acid aqueous solution from which the low-boiling by-products were removed.
  • the upper discharge stream of the stripping tower had a flow rate of 13.6% by weight compared to the mass flow rate of water introduced into the absorption tower, and the lower discharge stream 160 of the stripping tower had a flow rate of 2.3 times the mass flow rate of water entering the absorption tower. It was.
  • the stripper bottom discharge stream 160 contains (meth)acrylic acid (64.3% by weight), acetic acid (2.7% by weight), water (31.9% by weight), furfural (0.5% by weight), and maleic acid (0.6% by weight). included.
  • the degassing tower bottom discharge stream 160 is fed to the water separation tower 500 and azeotropically distilled in the presence of a hydrophobic azeotropic solvent (toluene) to produce a water separation tower top discharge stream 510 containing toluene, water and acetic acid.
  • a water separation tower bottom discharge stream 520 containing (meth)acrylic acid and high boiling point by-products was obtained.
  • the hydrophobic azeotropic solvent (toluene) was supplied to the top of the water separation tower (500) at a flow rate of 2.1 times that of the discharge stream (160) from the bottom of the degassing tower.
  • the water separation tower top discharge stream 510 was supplied to the layer separator 550 to obtain an aqueous layer 570 containing water and acetic acid and an organic layer 560 containing toluene. Part of the water layer 570 was supplied to the absorption tower 100, and the remainder was discharged to the outside of the system as wastewater. Meanwhile, the organic layer 560 was circulated to the water separation tower 500.
  • the 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 bottom discharge stream 620 containing high boiling point by-products and (meth)acrylic acid.
  • a high boiling point by-product separation tower top discharge stream (610) was obtained.
  • the content of (meth)acrylic acid in the upper discharge stream 610 of the high boiling point by-product separation tower was 99.5% by weight or more, and ultimately, more than 99.5% by weight of (meth)acrylic acid was obtained from the high boiling point by-product separation tower 600.
  • the energy used in the water separation tower (500) was 683.6 kcal/kg AA
  • the energy used in the high boiling point by-product separation tower (600) was 179.5 kcal/kg AA, for a total of 863.1 kcal/kg AA. Energy was used.
  • Comparative Example 2 the stripping tower bottom discharge stream 160 of the same composition as Comparative Example 1 was branched into 35% by weight and 65% by weight, respectively, relative to the total weight of the stripping tower bottom discharge stream 160, and the extraction tower 400 ) and water separation tower (500), respectively.
  • a raffinate stream 420 containing water and an extract liquid stream 410 containing toluene and (meth)acrylic acid were obtained.
  • the extraction solvent was supplied to the lower part of the extraction tower 400 at a flow rate of 4.1 times the mass flow rate of water in the discharge stream 160 from the bottom of the degassing tower supplied by branching to the upper part of the extraction tower 400.
  • the raffinate stream 420 was supplied to the layer separator 550, and the extract stream 410 was mixed with the discharge stream from the bottom of the stripper branched to the water separation tower 500 and supplied to the water separation tower 500. supplied.
  • 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 hydrophobic azeotropic solvent was supplied to the top of the water separation tower (500) at a mass flow rate of 2.1 times the mass flow rate of the extraction solvent supplied to the extraction tower (400).
  • the water separation tower top discharge stream 510 was supplied to the layer separator 550 to obtain an aqueous layer 570 containing water and acetic acid and an organic layer 560 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 560 was supplied to the water separation tower 500 and the extraction tower 400.
  • the 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 bottom discharge stream 620 containing high boiling point by-products and (meth)acrylic acid.
  • a high boiling point by-product separation tower top discharge stream (610) was obtained.
  • the content of (meth)acrylic acid in the upper discharge stream 610 of the high boiling point by-product separation tower was 99.5% by weight or more, and ultimately, more than 99.5% by weight of (meth)acrylic acid was obtained from the high boiling point by-product separation tower 600.
  • the energy used in the water separation tower (500) was 474.5 kcal/kg AA
  • the energy used in the high boiling point by-product separation tower (600) was 179.5 kcal/kg AA, for a total of 654 kcal/kg AA. Energy was used.
  • the mass flow rate of the second (meth)acrylic acid aqueous solution discharged to the side of the absorption tower was 0.23 times the mass flow rate of the first (meth)acrylic acid aqueous solution discharged to the bottom of the absorption tower.
  • the first aqueous (meth)acrylic acid solution was supplied to the degassing tower (150) as a discharge stream (130) from the bottom of the absorption tower.
  • the absorption tower bottom discharge stream 130 is degassed in the degassing tower 150, and the low boiling point by-product is supplied to the absorption tower 100 as the degassing tower upper discharge stream 170, and the low boiling point by-product is degassed (meth)acrylic acid.
  • the aqueous solution was supplied to the water separation tower (500) as a degassing tower bottom discharge stream (160).
  • the stripping tower bottom discharge stream 160 contains (meth)acrylic acid (73% by weight), acetic acid (2.4% by weight), water (23.3% by weight), furfural (0.6% by weight), and maleic acid (0.7% by weight). ) was included.
  • the second aqueous (meth)acrylic acid solution was supplied to the extraction tower (400) as the absorption tower side discharge stream (120).
  • the second aqueous (meth)acrylic acid solution contains (meth)acrylic acid (26.4% by weight), acetic acid (4.1% by weight), water (68.8% by weight), furfural (0.14% by weight), and maleic acid (0.03% by weight). did.
  • a raffinate stream 420 containing water and an extract liquid stream 410 containing toluene and (meth)acrylic acid were obtained.
  • the extraction solvent was supplied to the bottom of the extraction tower at a flow rate of 3.35 times the mass flow rate of water in the second aqueous (meth)acrylic acid solution supplied to the top of the extraction tower.
  • the raffinate stream 420 was supplied to the layer separator 550, and the extract liquid stream 410 was supplied to the water separation tower 500.
  • the extract stream 410 was mixed with the above-mentioned degassing tower bottom discharge stream 160 and supplied as a mixed stream to the water separation tower 500.
  • the water separation tower top discharge stream 510 was supplied to the layer separator 550 to obtain an aqueous layer 570 containing water and acetic acid and an organic layer 560 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 circulated to the water separation tower (500) and the extraction tower (400).
  • the 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 bottom discharge stream 620 containing high boiling point by-products and (meth)acrylic acid.
  • a high boiling point by-product separation tower top discharge stream (610) was obtained.
  • the content of (meth)acrylic acid in the upper discharge stream 610 of the high boiling point by-product separation tower was 99.5% by weight or more, and ultimately, more than 99.5% by weight of (meth)acrylic acid was obtained from the high boiling point by-product separation tower 600.
  • the energy used in the water separation tower (500) was 455.9 kcal/kg AA
  • the energy used in the high boiling point by-product separation tower (600) was 179.5 kcal/kg AA, for a total of 635.5 kcal/kg AA. Energy was used.
  • Comparative Example 3 As in Comparative Examples 1 and 2, more than 99.5% by weight of (meth)acrylic acid could be obtained through the high boiling point by-product separation tower even without introducing the discharge stream from the bottom of the water separation tower to the crystallizer. It was confirmed that the total energy consumption increased compared to Example 1, which was equipped with an additional firearm.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
PCT/KR2023/012563 2022-08-30 2023-08-24 고순도 (메트)아크릴산의 제조방법 Ceased WO2024049106A1 (ko)

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CN202380014325.2A CN118201903A (zh) 2022-08-30 2023-08-24 制备高纯度(甲基)丙烯酸的方法
US18/710,686 US20250019337A1 (en) 2022-08-30 2023-08-24 Method for preparation of high purity (meth)acrylic acid
EP23860783.2A EP4491609A4 (en) 2022-08-30 2023-08-24 PROCESS FOR PREPARING HIGH-PURITY (METH)ACRYLIC ACID
JP2024525180A JP2025527382A (ja) 2022-08-30 2023-08-24 高純度（メタ）アクリル酸の製造方法

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KR10-2022-0109514 2022-08-30
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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
KR100755475B1 (ko) * 2003-06-05 2007-09-04 니폰 쇼쿠바이 컴파니 리미티드 아크릴산의 제조 방법
KR20160030715A (ko) * 2014-09-11 2016-03-21 주식회사 엘지화학 고순도 아크릴산의 제조방법

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KR20160032994A (ko) * 2014-09-17 2016-03-25 주식회사 엘지화학 (메트)아크릴산의 회수 방법 및 회수 장치

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KR20040108610A (ko) * 2003-06-05 2004-12-24 니폰 쇼쿠바이 컴파니 리미티드 아크릴산의 제조 방법
KR100755475B1 (ko) * 2003-06-05 2007-09-04 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
KR20160030715A (ko) * 2014-09-11 2016-03-21 주식회사 엘지화학 고순도 아크릴산의 제조방법

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