WO2014021560A1 - Procédé de récupération en continu du (méth)acrylate, et appareil de récupération associé - Google Patents

Procédé de récupération en continu du (méth)acrylate, et appareil de récupération associé Download PDF

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Publication number
WO2014021560A1
WO2014021560A1 PCT/KR2013/006101 KR2013006101W WO2014021560A1 WO 2014021560 A1 WO2014021560 A1 WO 2014021560A1 KR 2013006101 W KR2013006101 W KR 2013006101W WO 2014021560 A1 WO2014021560 A1 WO 2014021560A1
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Prior art keywords
meth
acrylic acid
tower
water separation
supplied
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PCT/KR2013/006101
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English (en)
Korean (ko)
Inventor
백세원
송종훈
유설희
Original Assignee
주식회사 엘지화학
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Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to BR112015002422-0A priority Critical patent/BR112015002422B1/pt
Priority to IN430DEN2015 priority patent/IN2015DN00430A/en
Priority to US14/415,113 priority patent/US9517997B2/en
Priority to CN201380037821.6A priority patent/CN104470884B/zh
Priority claimed from KR1020130080189A external-priority patent/KR101546464B1/ko
Publication of WO2014021560A1 publication Critical patent/WO2014021560A1/fr

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
    • B01J8/0449—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds
    • B01J8/0457—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds the beds being placed in separate reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00004—Scale aspects
    • B01J2219/00006—Large-scale industrial plants
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals

Definitions

  • the present invention relates to a continuous recovery method of (meth) acrylic acid and an apparatus used in the method.
  • (Meth) acrylic acid is generally produced by a gas phase oxidation reaction of a compound such as propane, propylene or (meth) acrelane in the presence of a catalyst.
  • propane and propylene are converted to (meth) acrylic acid via (meth) arlane by gas phase oxidation reaction, and at the end of the reaction vessel, (meth) acrylic acid and unreacted propane.
  • a reaction mixture mixed gas comprising propylene, (meth) acrelane, inert gas, carbon dioxide, water vapor and various organic by-products (acetic acid, low boiling point by-product, high boiling point by-product, etc.) obtained by the above reaction.
  • the said (meth) acrylic acid containing mixed gas is contacted with absorption solvents, such as process water, in a (meth) acrylic acid absorption tower, and is collect
  • the (meth) acrylic acid aqueous solution is distilled and purified through a water separation column to obtain (meth) acrylic acid.
  • the method of distilling the (meth) acrylic acid aqueous solution using a hydrophobic co-solvent in a water separation column can reduce the amount of wastewater and effectively suppress the inflow of organic matter, thereby simplifying the subsequent purification step.
  • the method and the method of recovering the (meth) acrylic acid previously disclosed not only consume a very large amount of energy in the distillation of the (meth) acrylic acid aqueous solution, but also generate polymers by polymerization of (meth) acrylic acid in the distillation process. Due to this, there is a problem in that the stability of the process operation is lowered, such as normal operation is impossible.
  • the present invention is to provide a method for continuously recovering (meth) acrylic acid that can significantly reduce energy usage and exhibit improved operational stability.
  • the present invention is to provide an apparatus for the continuous recovery of the (meth) acrylic acid.
  • the step of dividing the (meth) acrylic acid aqueous solution into the (meth) acrylic acid extraction tower 200 and the water separation tower 300, the 5 to 70% by weight of the (meth) acrylic acid aqueous solution obtained It may be supplied to the meth) acrylic acid extraction tower 200, the remainder is supplied to the water separation tower (300).
  • the synthesis reaction of (meth) acrylic acid is a method of oxidizing one or more compounds selected from the group consisting of propane, propylene, butane, isobutylene, t-butylene and (meth) acrelane under a gas phase catalyst It can be performed as.
  • the internal temperature of the (meth) acrylic acid absorption tower 100 may be maintained at 50 to 100 ° C.
  • the step of obtaining the (meth) acrylic acid aqueous solution is discharged the (meth) acrylic acid containing aqueous solution to the lower portion of the (meth) acrylic acid absorption tower 100, the (meth) acrylic acid absorption tower 100 to the (meth ) Acrylic acid may be carried out so that the degassed non-combustible gas is discharged.
  • the method for continuously recovering (meth) acrylic acid according to the present invention may be performed by contacting the non-condensable gas with an absorption solvent to recover acetic acid contained in the non-condensable gas.
  • the water supplied to the (meth) acrylic acid absorption tower 100 may include an organic byproduct having a concentration of 3 to 20% by weight.
  • the (meth) acrylic acid aqueous solution obtained in the (meth) acrylic acid absorption tower 100 may include (meth) acrylic acid in a concentration of 40 to 90 weight 3 ⁇ 4.
  • the (meth) acrylic acid extract may be obtained by contacting a (meth) acrylic acid aqueous solution supplied to the (meth) acrylic acid extraction tower 200 with a hydrophobic extraction solvent to remove water contained in the aqueous solution.
  • the (meth) acrylic acid extract is obtained at the top of the (meth) acrylic acid extraction tower 200 and supplied to the water separation tower 300, at least a portion of the lower discharge of the (meth) acrylic acid extraction tower 200 It can be supplied to the upper end of the (meth) acrylic acid absorption tower 100 and used as an absorption solvent of (meth) acrylic acid.
  • the lower effluent of the (meth) acrylic acid extraction tower 200 may include (meth) acrylic acid at a concentration of 5% by weight or less.
  • the upper end of the (meth) acrylic acid absorption tower 100 to which at least a portion of the lower discharge liquid of the (meth) acrylic acid absorption tower 200 is supplied is at least one point corresponding to a height of 70% or more from the bottom of the absorption tower. Can be.
  • distillation in the water separation tower 300 may be carried out in the presence of a hydrophobic cosolvent.
  • the hydrophobic co-solvent may include a compound such as a hydrophobic extraction solvent in the (meth) acrylic acid extraction tower (200).
  • the discharge liquid containing (meth) acrylic acid is recovered to the bottom of the water separation tower 300, hydrophobic non-solvent, water to the top of the water separation tower 300 And effluent containing acetic acid can be recovered.
  • the upper discharge liquid of the water separation tower 300 is separated into an organic layer containing a hydrophobic cosolvent and an aqueous layer containing acetic acid; At least a portion of the organic layer may be supplied to the upper end of the water separation tower 300 as a non-solvent, and at least a portion of the aqueous layer may be supplied to the upper end of the (meth) acrylic acid absorption tower 100 as an absorption solvent.
  • (Meth) acrylic acid extraction tower which obtains the (meth) acrylic acid extract having reduced water content from the (meth) acrylic acid * aqueous solution supplied through the (meth) acrylic acid aqueous solution transfer line 102 and supplies it to the water separation tower 300 ( 200);
  • a (meth) acrylic acid extract transfer line 203 connected to the water separation tower 300 from the (meth) acrylic acid extraction tower 200 and supplied with (meth) acrylic acid extract; And Separation of water to obtain (meth) acrylic acid by distilling the (meth) acrylic acid aqueous solution supplied through the (meth) acrylic acid aqueous solution transfer line (103) and the (meth) acrylic acid extract supplied through the (meth) acrylic acid extract liquid delivery line 203.
  • a continuous recovery apparatus of (meth) acrylic acid comprising a.
  • the continuous recovery method of (meth) acrylic acid according to the present invention can maintain the recovery rate of (meth) acrylic acid at the same level as compared with the previous recovery method, while significantly reducing the energy consumption, and polymerization of (meth) acrylic acid in the recovery process. Improved operational stability can be achieved by minimizing reactions.
  • the continuous rare water method of (meth) acrylic acid according to the present invention is introduced by introducing the (meth) acrylic acid extraction tower 200 before the water separation tower 300 for distilling the (meth) acrylic acid aqueous solution to recover the (meth) acrylic acid.
  • Energy consumption in the water separation tower 300 can be greatly reduced, thereby improving the energy efficiency of the entire process.
  • the aqueous (meth) acrylic acid solution obtained from the (meth) acrylic acid absorption tower (10Q) was separately supplied to the (meth) acrylic acid extraction tower (200) and the water separation tower (300).
  • the capacity can be reduced to reduce the burden on the facility and at the same time maintain the ability of the (meth) acrylic acid aqueous solution supplied from the (meth) acrylic acid absorption tower to the same level as the previous method, resulting in high energy efficiency and improved productivity. Can be.
  • the method of the present invention can effectively distribute the treatment of the (meth) acrylic acid aqueous solution in the (meth) acrylic acid extraction tower 200 and the water separation tower 300, reducing the load in the water separation tower (300)
  • FIG. 1 is a process diagram schematically showing a continuous recovery method of (meth) acrylic acid according to an embodiment of the present invention. [Specific contents to carry out invention]
  • '(meth) acrylic acid' refers to acrylic acid (acrylic acid) and / or methacrylic acid (methacrylic acid) collectively.
  • (meth) acrylic acid containing mixed gas refers to the mixed gas which can be produced when manufacturing (meth) acrylic acid by a gas phase oxidation reaction. That is, according to one embodiment of the present invention, at least one compound ('raw compound') selected from the group consisting of propane, propylene, butane, i-butylene, t-butylene and (meth) acrene
  • the (meth) acrylic acid-containing mixed gas can be obtained by a gas phase oxidation reaction in the presence of a catalyst.
  • the (meth) acrylic acid-containing mixed gas includes (meth) acrylic acid, unreacted raw material compound, (meth) aclein, inert gas, carbon monoxide, carbon dioxide, water vapor and various organic byproducts (acetic acid, low boiling point byproduct, high boiling point byproduct, etc.). ) May be included. Here, 'low boiling point.
  • By-products (light ends) or “heavy boiling by-products" (heavies) are by-products that can be produced in the production and recovery of the desired (meth) acrylic acid.
  • (meth) acrylic acid aqueous solution means an aqueous solution in which (meth) acrylic acid is dissolved.
  • the (meth) acrylic acid aqueous solution is obtained by contacting the (meth) acrylic acid-containing mixed gas with water. Can be. .
  • (meth) acrylic acid extract means an aqueous solution having a higher concentration of (meth) acrylic acid than the (meth) acrylic acid aqueous solution.
  • the (meth) acrylic acid extract is (meth) acrylic acid extraction. It may be obtained by lowering the content of water contained in the aqueous (meth) acrylic acid solution in the tower 200.
  • the present inventors in the course of research on the continuous recovery method of (meth) acrylic acid, the method of recovering (meth) acrylic acid through the azeotropic distillation method disclosed previously in a water separation column (or distillation column) to distill the (meth) acrylic acid aqueous solution Not only a very large amount of energy is consumed, it is confirmed that there is a problem in that the stability of the process operation is deteriorated due to the generation of a polymer by polymerization of (meth) acrylic acid in the distillation process.
  • the inventors of the present invention before the water separation tower 300 for distilling the (meth) acrylic acid aqueous solution obtained in the (meth) acrylic acid absorption tower 100 in the course of repeated studies to improve this problem, as shown in FIG. A (meth) acrylic acid extraction tower 200 was introduced, and in particular, the (meth) acrylic acid aqueous solution obtained from the (meth) acrylic acid absorption tower 100 was divided into a (meth) acrylic acid extraction tower 200 and a water separation tower 300. When supplied, it was confirmed that the energy efficiency of the whole process can be improved. Furthermore, the present inventors can effectively share the load of the water separation tower 300 in accordance with the process as shown in Figure 1 in the distillation process
  • a mixed gas containing (meth) acrylic acid, organic by-products and water vapor produced by the synthesis reaction of (meth) acrylic acid is carried out in the (meth) acrylic acid absorption tower (100). Contacting with water to obtain an aqueous (meth) acrylic acid solution;
  • the (meth) acrylic acid and the continuous recovery method according to the present invention include the step of obtaining an aqueous (meth) acrylic acid solution.
  • the (meth) acrylic acid aqueous solution can be obtained according to a conventional method in the art, the specific method is not particularly limited.
  • the step may include a mixed gas containing (meth) acrylic acid, organic by-products and water vapor generated by the synthesis reaction of (meth) acrylic acid in the (meth) acrylic acid absorption tower 100 as water. It can be carried out by the method of contacting with to obtain an aqueous (meth) acrylic acid solution.
  • the synthesis reaction of the (meth) acrylic acid is a method of oxidizing reaction of at least one compound selected from the group consisting of propane, propylene, butane, isobutylene, t- butylene and (meth) acrelane under a gas phase catalyst It can be performed as.
  • the gas phase oxidation reaction may be performed under a gas phase oxidation reactor and reaction conditions of a conventional structure.
  • the catalyst in the gas phase oxidation reaction may also be used, preferably the catalyst disclosed in the Republic of Korea Patent No. 0349602 and 037818 and the like can be used.
  • the gas phase oxidation reaction in the present invention is not limited to the above examples.
  • (Meth) acrylic acid-containing mixture produced by the gas phase oxidation reaction In addition to the desired product (meth) acrylic acid, the gas contains not only semi-ungung raw compounds, intermediate (meth) aclein, other inert gases, carbon dioxide, water vapor and various organic by-products (acetic acid, low-boiling by-products, high-boiling by-products, etc.). Can be.
  • the (meth) acrylic acid-containing mixed gas (1) is supplied to the (meth) acrylic acid absorption tower 100 and brought into contact with water as an absorption solvent.
  • the (meth) acrylic acid absorption tower 100 a (meth) for the contact efficiency of the acrylic acid-containing heunhap gas 1 and the absorption solvent, lashing ring (ras hing ring), polling (pall ring) therein; It may be in the form of a packed column containing a layering agent such as saddle, gauze, structured packing, or a general multistage column.
  • the (meth) acrylic acid-containing mixed gas 1 can be supplied to the lower portion of the (meth) acrylic acid absorption tower 100. Then, an absorption solvent for absorbing the (meth) acrylic acid contained in the mixed gas 1 is supplied from the upper portion of the (meth) acrylic acid absorption tower 100.
  • the absorption solvent of (meth) acrylic acid may be water such as scum water, deionized water, and the like, and the absorption solvent may include circulating process water introduced from another process.
  • the absorption solvent may include a small amount of organic by-products (for example, acetic acid) introduced from another process, and according to one embodiment of the present invention, the absorption solvent supplied to the (meth) acrylic acid absorption tower 100 May include organic byproducts at a concentration of 3 to 20% by weight. That is, in consideration of the absorption efficiency of (meth) acrylic acid in the (meth) acrylic acid absorption tower (100), the amount of organic by-products is increased by 20 in the absorption solvent (particularly the circulating process water) supplied to the (meth) acrylic acid absorption tower (100). It is preferred to be included in% or less.
  • organic by-products for example, acetic acid
  • the (meth) acrylic acid absorption tower 100 may be operated at an internal pressure of 1 to 1.5 bar, preferably 1 to 1.3 bar in consideration of condensation conditions of the (meth) acrylic acid and moisture content conditions according to saturated steam pressure. And; In addition, the internal temperature of the (meth) acrylic acid absorption tower 102 may be adjusted to be maintained at 50 to 100 ° C., preferably 50 to 80 ° C.
  • Non-condensable gases from which (meth) acrylic acid has been degassed may be emitted.
  • the (meth) acrylic acid aqueous solution discharged to the lower portion of the (meth) acrylic acid absorption tower 100 has a concentration of 40 to 90 weight 3 ⁇ 4, preferably 50 to 90 weight%, more preferably 50 to 80 weight% Including acrylic acid is advantageous in terms of improving process efficiency.
  • at least a portion of the non-condensable gas discharged to the upper portion of the (meth) acrylic acid absorption tower 100 may be supplied to recover the organic by-products (particularly acetic acid) contained in the non-condensable gas, the rest to the waste gas incinerator Can be supplied.
  • the step of contacting the non-uniform gas discharged to the upper portion of the (meth) acrylic acid absorption tower 100 with water as the absorption solvent to recover acetic acid contained in the non-uniform gas may be further included.
  • the step of contacting the non-uniform gas with the absorption solvent may be performed in the acetic acid absorption tower 150.
  • the acetic acid absorption tower 150 can be operated at a pressure of 1 to 1.5 bar, preferably 1 to 1.3 bar;
  • the internal degree of silver of the acetic acid absorption tower 103 may be adjusted to be 50 to 100 ° C., preferably 50 to 80 ° C.
  • specific operating conditions of the acetic acid absorption tower 150 may be in accordance with the Republic of Korea Patent Publication No. 2009-0041355 of the applicant.
  • the upper portion of the acetic acid absorption tower 150 is supplied with an organic solvent by-products included in the non-condensable gas, the absorption solvent for absorbing acetic acid, and the aqueous solution containing acetic acid is discharged to the lower portion of the acetic acid absorption tower 150 Can be.
  • the acetic acid absorbing solvent may be the same kind as the aforementioned (meth) acrylic acid absorbing solvent, preferably the acetic acid-containing aqueous solution discharged from the acetic acid absorbing tower 150 to the (meth) acrylic acid absorbing tower 100 It can be supplied and used as an absorption solvent.
  • the acetic acid degassed gas is discharged to the upper portion of the acetic acid absorption tower 150, which may be circulated to the synthesis reaction step of the (meth) acrylic acid and reused.
  • the continuous recovery method of (meth) acrylic acid according to the present invention is the continuous recovery method of (meth) acrylic acid according to the present invention.
  • the (meth) acrylic acid absorption tower 100 is a (meth) acrylic acid extraction tower 200 and a water separation tower through respective (meth) acrylic acid aqueous solution transfer lines 102 and 103 ( 300 is simultaneously connected, and the (meth) acrylic acid extraction tower 200 is connected to the water separation tower 300 through the (meth) acrylic acid extract transfer line 203.
  • the (meth) acrylic acid extraction tower 200 performs a process of removing the water used as the absorption solvent in the step of obtaining the aqueous (meth) acrylic acid solution described above and recovering the extract having a higher concentration of (meth) acrylic acid therefrom.
  • the water separation tower 300 azeotropically distills the (meth) acrylic acid aqueous solution supplied from the (meth) acrylic acid absorption tower 100 and the (meth) acrylic acid extract supplied from the (meth) acrylic acid extraction tower 200 to thereby It is a device for performing a process for recovering (meth) acrylic acid from.
  • the (meth) acrylic acid extraction tower 200 and the water separation tower 300 will be described later.
  • the method of recovering (meth) acrylic acid through the azeotropic distillation method disclosed above is distilling the entire (meth) acrylic acid aqueous solution obtained from the (meth) acrylic acid absorption tower (100) by supplying it to the water separation tower (300). It was the way.
  • the method for continuous recovery of (meth) acrylic acid according to the present invention is characterized in that the (meth) acrylic acid aqueous solution in the water separation tower 300 is introduced by introducing the (meth) acrylic acid extraction tower 200 before the water separation tower 300.
  • the processing burden and energy consumption can be greatly reduced.
  • the process according to the present invention supplies the (meth) acrylic acid aqueous solution obtained from the (meth) acrylic acid absorption tower 100 to the (meth) acrylic acid extraction tower 200 and the water separation tower 3Q0 in order to supply the whole eye. While reducing the burden, it is possible to minimize the polymerization reaction of the (meth) acrylic acid in the water separation column 300 can provide more improved operational stability.
  • the ratio of dividing and supplying the (meth) acrylic acid aqueous solution obtained in the (meth) acrylic acid absorption tower 100 to the (meth) acrylic acid extraction tower 200 and the water separation tower 300 is (meth) acrylic acid extraction. It may be determined in consideration of the capacity ratio of the tower 200 and the water separation tower 300, the treatment capacity, the effect of increasing the energy efficiency of the overall process. Given the above conditions, 5 to 70% by weight, more preferably 20 to 50% by weight of the (meth) acrylic acid aqueous solution obtained in the (meth) acrylic acid absorption tower 100, more preferably 20 to 50% by weight is the (meth) acrylic acid extraction tower (200). Can be supplied; Its balance is to be supplied to the water separation tower 300, it is advantageous in terms of the manifestation of the above-described effect.
  • the content ratio (weight 3 ⁇ 4) of the (meth) acrylic acid aqueous solution supplied from the (meth) acrylic acid absorption tower (loo) to the (meth) acrylic acid extraction tower 200 and the water separation tower 300 is 5:95, 10:90, 15:85, 20:80, 25:75, 30:70, 35:65, 40:60, 45:55, 50:50, 55:45, 60:40, 65:35, 70: 30, etc., preferably 20:80 to 70:30, more preferably 30:70 to 60:40, even more preferably 40:60 to 50:50.
  • the present invention is not limited to the above example ratio, and in addition, the present invention may be adjusted to various ratios within the above-described range in consideration of the spirit and effect of the present invention.
  • the efficiency of processing sharing with the water separation tower 300 may be improved, thereby improving energy efficiency of the entire process. Can be improved.
  • a larger capacity extraction tower 200 is required, and the operating conditions of the water separation tower 300 at the rear end are poor, resulting in (meth) acrylic acid. Since the process efficiency may be rather lowered, such as a large loss, the supply ratio of the (meth) acrylic acid aqueous solution is advantageously controlled within the above-mentioned range.
  • the amount of the (meth) acrylic acid aqueous solution supplied to the water separation tower 300 increases, the amount of water to be removed by azeotropic distillation in the water separation tower 300 increases, thereby reducing energy use according to the present invention. Since it may fall, the supply ratio of the (meth) acrylic acid aqueous solution is advantageously adjusted within the above-mentioned range.
  • the (meth) acrylic acid aqueous solution is obtained from the (meth) acrylic acid absorption tower (100).
  • the (meth) acrylic acid extraction tower 200 and the water separation tower 300 may be supplied by dividing through the (meth) acrylic acid aqueous solution transfer line (102, 103), respectively.
  • the (meth) acrylic acid aqueous solution may be supplied by dividing the aforementioned ratio by conventional means installed in the transfer lines 102 and 103.
  • the (meth) acrylic acid extract obtained by reducing the water content from the (meth) acrylic acid aqueous solution supplied to the (meth) acrylic acid extraction tower 200 to obtain a water separation column Supplying to 300 (hereinafter referred to as the 'extraction process').
  • the (meth) acrylic acid extraction tower 200 is configured to extract (meth) acrylic acid extraction tower 200
  • a portion of the (meth) acrylic acid aqueous solution obtained from the (meth) acrylic acid absorption tower 100 is supplied to remove most of the water contained in the (meth) acrylic acid aqueous solution without using a large amount of energy, and the water is supplied to the water separation tower 300. By doing so, it is possible to reduce the energy used for azeotropic distillation in the water separation tower 300 to be described later.
  • the (meth) acrylic acid extract is a (meth) acrylic acid extraction tower (200).
  • the aqueous (meth) acrylic acid solution supplied may be contacted with a hydrophobic extraction solvent to remove water contained in the aqueous solution. That is, the extraction in the (meth) acrylic acid extraction tower 200 is preferably in the liquid-liquid contact method in terms of improving the energy efficiency of the entire process.
  • the hydrophobic extracting solvent may be azeotropic with water and organic by-products (such as acetic acid) and may be a hydrocarbon solvent which does not form an azeotropy with (meth) acrylic acid but can be extracted in a sufficient manner, and also 10 to 120 ° C. Having a boiling point of is advantageous in terms of improving the extraction process efficiency.
  • the hydrophobic extraction solvent that satisfies the physical properties is benzene, toluene, xylene, n-heptane, heptane, cycloheptane, cycloheptene cycloheptene) ,
  • 6-methyl-1-heptene (6— methyl-1-heptene), 4-methyl-1-heptene (4-methyl-l-heptene), 2-ethyl-1-nuxene (2-ethyl-l— hexene) , Ethylcyclopentane, 2-methyl- 1-hexene, 2, 3-dimethylpentane (2, 3-dimet hy 1 pent ane), 5- It may be at least one solvent selected from the group consisting of 5-methyl-1-hexene and isopropyl-butyl-ether.
  • the temperature of the aqueous (meth) acrylic acid solution in the extraction step is 10 to 70 ° C is advantageous in terms of improving the process efficiency.
  • the extraction device may be a Karr type reciprocating plate column, a rotary-disk contactor, a Scheibel column, a Kuhni column, a spray extraction tower. , Packed extraction towers, pulsed packed columns, banks of mixer-settlers, mixers, and centrifugal counter current extractors.
  • the (meth) acrylic acid extract obtained by removing most of the water contained in the (meth) acrylic acid aqueous solution may be obtained.
  • the (meth) acrylic acid extract is The extracted extract may be supplied to the water separation tower 300 through the (meth) acrylic acid extract transfer line 203.
  • At least a portion of the lower discharge of the (meth) acrylic acid extraction tower 200 may be supplied to the upper end of the (meth) acrylic acid absorption tower 100 to be used as part of the (meth) acrylic acid absorption solvent, the lower discharge liquid Some of the can be treated as wastewater.
  • the upper end of the (meth) acrylic acid absorption tower 100 is preferably at least one point corresponding to a height of 70% or more from the bottom of the absorption tower 100 in view of improving the efficiency of the absorption process.
  • the (meth) acrylic acid may be included in the lower discharge liquid of the (meth) acrylic acid extraction tower 200, a part thereof may be included, and the amount thereof may be 5% by weight or less of the process efficiency. It is preferable in terms of improvement.
  • the continuous recovery method of (meth) acrylic acid according to the present invention comprises the step of distilling the (meth) acrylic acid aqueous solution and (meth) acrylic acid extract supplied to the water separation tower 300 to obtain (meth) acrylic acid. (Hereinafter referred to as 'distillation process').
  • the distillation process is a (meth) acrylic acid aqueous solution supplied to the water separation tower 300 from the (meth) acrylic acid absorption tower 100, and is supplied to the water separation tower 300 from the (meth) acrylic acid extraction tower 200 ( It is a process for removing water and organic by-products and separating (meth) acrylic acid by azeotropic distillation of meth) acrylic acid extract.
  • the (meth) acrylic acid aqueous solution and the (meth) acrylic acid extract are respectively supplied to the water separation tower 300 through separate transfer lines 103 and 203, wherein the position of the water separation tower 300 to which each solution is supplied is Although it may be the same or different, it is advantageous to be supplied at the same location in terms of improving process efficiency.
  • the distillation in the water separation tower 300 is performed in the presence of a hydrophobic cosolvent, thereby simultaneously recovering the cosolvent, water, and organic byproducts (such as acetic acid).
  • the hydrophobic non-solvent may be azeotropic with water and acetic acid, and may not be azeotropic with (meth) acrylic acid, and a hydrocarbon solvent that satisfies the above properties may be applied without limitation.
  • the hydrophobic co-solvent may have a lower breaking point than (meth) acrylic acid, and preferably may have a boiling point of 10 to 120 ° C.
  • the hydrophobic co-solvent that satisfies the above properties is benzene, toluene, xylene, n-heptane, Cycloheptane (eye 1 ohept ane), cycloheptene (eye 1 oheptene),
  • 6-methyl-1-heptene (6-methy l-heptene), 4-methyl-1-heptene (4-! 1 1: 1 1-1-1 1 61),
  • It may be at least one solvent selected from the group consisting of 5-methyl-1-nuxene (5-methy ⁇ 1-hexene) and isopropyl-butyl-ether.
  • the hydrophobic co-solvent may be the same as or different from the hydrophobic extraction solvent applied to the (meth) acrylic acid extraction tower 200.
  • the hydrophobic co-solvent preferably includes a compound such as a hydrophobic extraction solvent.
  • a compound such as a hydrophobic extraction solvent.
  • the inside of the water separation tower 300 may be provided with a pack column or a multi-stage column, preferably a tray column (sieve tray column), a dual flow tray column (dual flow tray column) containing the above-mentioned layer agent. have. .
  • the hydrophobic non-solvent When the hydrophobic non-solvent is added to the upper portion of the water separation tower 300 as described above, the azeotropy of (meth) acrylic acid and its absorption solvent (for example, water) is broken. Accordingly, water and acetic acid in the (meth) acrylic acid aqueous solution supplied directly from the (meth) acrylic acid absorption tower 100; Some and water, acetic acid and hydrophobic extraction solvents not removed from the (meth) acrylic acid extraction tower 200; And the hydrophobic azeotrope used in azeotropic distillation may be azeotrope together and recovered to the top of the water separation tower 300. Then, the discharge liquid containing (meth) acrylic acid may be recovered to the lower portion of the water separation tower 300. have.
  • water and acetic acid in the (meth) acrylic acid aqueous solution supplied directly from the (meth) acrylic acid absorption tower 100 Some and water, acetic acid and hydrophobic extraction solvents not removed from the (meth)
  • the upper discharge liquid of the water separation tower 300 may be supplied to the phase separation tank 350 to be reused after a predetermined treatment.
  • the phase separation tank 350 is a device for separating the liquid phase that does not mix with each other using gravity or centrifugal force, etc., the relatively light liquid to the top of the phase separation tank 350, the relatively heavy liquid phase separation tank May be recovered to the bottom of 350.
  • the upper discharge liquid supplied to the phase separation tank 350 is separated into an organic layer containing a hydrophobic cosolvent and an aqueous layer containing water. Can be.
  • the organic layer separated in the phase separation tank 350 may be supplied to the upper end of the water separation tower 300 to be used as a non-solvent; The remainder of the organic layer may be supplied to the (meth) acrylic acid extraction tower 200 as needed to be used as an extraction solvent. At least a part of the aqueous layer separated from the phase separation tank 350 may be supplied to an upper end of the (meth) acrylic acid absorption tower 100 to be used as an absorption solvent, and some may be treated with wastewater. '
  • acetic acid may be partially included in the aqueous layer, and the concentration of acetic acid included in the aqueous layer may vary depending on the type of non-solvent and the reflux ratio of the column installed in the water separation tower.
  • the concentration of acetic acid included in the aqueous layer of the upper discharge liquid may be 1 to 50% by weight, preferably 2 to 40% by weight, more preferably 3 to 30% by weight.
  • the discharge liquid containing (meth) acrylic acid is recovered to the lower portion of the water separation tower 300, which is crude (meth) acetic acid, which may be supplied as an additional purification process if necessary.
  • the bottom discharge liquid of the water separation tower 300 may include some water, acetic acid and non-solvent, preferably to include less than 0.1 weight 3 ⁇ 4 each of water, acetic acid and non-solvent, bottom discharge Suitable for use as a crude (meth) acetic acid.
  • the (meth) acrylic acid aqueous solution passes through the (meth) acrylic acid absorption tower 100, the (meth) acrylic acid extraction tower 200, the water separation tower 300, and the like, and at least one of (meth) acrylic acid contained in the aqueous solution.
  • Some are polymerized to produce dimers or oligomers Polymers may be produced.
  • a polymerization inhibitor may be added to the water separation tower 300, and the polymerization inhibitor may be used in a conventional manner, and thus the configuration thereof is not particularly limited.
  • the bottom discharge liquid of the water separation tower 300 may include a high boiling point by-product such as a polymer of (meth) acrylic acid, a polymerization inhibitor, and the like. Therefore, if necessary, the step of separating the high-boiling by-product contained in the bottom discharge liquid by supplying the bottom discharge liquid of the water separation tower 300 to the high boiling point by-product separation tower 400 may be further performed.
  • a high boiling point by-product such as a polymer of (meth) acrylic acid, a polymerization inhibitor, and the like. Therefore, if necessary, the step of separating the high-boiling by-product contained in the bottom discharge liquid by supplying the bottom discharge liquid of the water separation tower 300 to the high boiling point by-product separation tower 400 may be further performed.
  • High-boiling by-product separation tower 400 may have a conventional configuration, and can be operated under conventional reaction conditions, the configuration and reaction conditions of the separation tower is not particularly limited. Through this, the high boiling point by-product contained in the bottom discharge of the water separation tower 300 can be recovered to the lower portion of the high boiling point by-product separation tower 400, the crude (meth) acrylic acid ( CAA) may be recovered to the top of the high boiling point byproduct separation tower 400.
  • CAA crude (meth) acrylic acid
  • the crude (meth) acrylic acid (CM) can be obtained with higher purity (meth) acrylic acid (HPAA) through an additional crystallization process.
  • each step that may be included in the method for recovering (meth) acrylic acid according to the present invention may be continuously performed, and in addition to the above-described steps, the steps of the present invention may be performed before or after each step. Steps may be further included and performed.
  • the (meth) acrylic acid aqueous solution obtained in the (meth) acrylic acid absorption tower 100 is divided into (meth) acrylic acid extraction tower 200 and water separation tower 300, and then supplied to a separate degassing tower.
  • a process for removing low boiling point by-products (arclein, propionaldehyde, acetaldehyde, formaldehyde, isopropyl acetate, etc.) dissolved in aqueous (meth) acrylic acid solution may be further performed.
  • low boiling point by-products arlein, propionaldehyde, acetaldehyde, formaldehyde, isopropyl acetate, etc.
  • (Meth) acrylic acid extraction tower (200) which obtains (meth) acrylic acid extract having reduced water content from the (meth) acrylic acid aqueous solution supplied through the (meth) acrylic acid aqueous solution transfer line (102) and supplies it to the water separation tower (300) );
  • a (meth) acrylic acid extract transfer line 203 connected to the water separation tower 300 from the (meth) acrylic acid extraction tower 200 and supplied with (meth) acrylic acid extract; Supplied through the (meth) acrylic acid aqueous solution transfer line (103)
  • a continuous recovery apparatus of (meth) acrylic acid comprising a.
  • the (meth) acrylic acid absorption tower 100 is a (meth) acrylic acid extraction tower 200 and a water separation tower through respective (meth) acrylic acid aqueous solution transfer lines 102 and 103. Simultaneously connected to 300, the (meth) acrylic acid extraction tower 200 is connected to the water separation tower 300 through the (meth) acrylic acid extract liquid transfer line 203.
  • the (meth) acrylic acid absorption tower 100 includes a (3 ⁇ 4) crashing ring and a pall ring in order to improve the contact efficiency between the (meth) acrylic acid-containing mixed gas (1) and water as an absorption solvent. It may have the form of a packed column or a general multi-stage column including a layering agent such as saddle, gauze, structured packing, or the like.
  • the (meth) acrylic acid extraction tower 200 according to the liquid-liquid contact method Extraction devices on ⁇ may be used, including but not limited to Karr reci rocating plate columns, rotary- disk contactors, Scheibel columns, Kuhni columns, spraying Spray extract ion tower, packed extract ion tower, pulsed packed column, bank of mixer-settler, mixer and centrifugal counter current extractor And the like.
  • the water separation tower 300 may be a pack column or a multi-stage column, preferably a tray tray and a dual flow tray column including the above-described layering agent therein. have.
  • acetic acid absorption tower 150 (meth) acrylic acid aqueous solution transfer line (102, 103), (meth) acrylic acid extract transfer line (203), phase separation tank 350, high boiling point by-product shown in FIG. Separation tower 400 and the like may have a conventional configuration in the art to which the present invention belongs, and the melting and effects in each process are replaced by the above description.
  • preferred examples are provided to aid in understanding the present invention. However, the following examples are only for illustrating the present invention, and the present invention is not limited thereto.
  • the (meth) acrylic acid receiving section obtained in the (meth) acrylic acid absorption tower 100 was
  • Reaction gas obtained through the oxidation reaction of propylene is introduced into the (meth) acrylic acid absorption tower 100, and water is used as a (meth) acrylic acid absorption solvent, and the acrylic acid aqueous solution ( Composition: about 68% by weight acrylic acid, about 2% by weight acetic acid, and about 30% by weight water).
  • the acrylic acid aqueous solution was supplied to the (meth) acrylic acid extraction tower 200 and the water separation tower 300 in a weight ratio of 35:65.
  • composition about 64.8 wt% toluene, about 32.9 wt% acrylic acid, about 1.6 wt% water, and About 0.7 wt% acetic acid was obtained, and water (composition: about 95.1 wt% of water, about 1.8 wt% of acrylic acid, and about 3.1 wt% of acetic acid) flowed out to the bottom of the extraction tower 200.
  • the water separation tower 300 was supplied with 65% by weight of the aqueous acrylic acid solution discharged to the bottom of the (meth) acrylic acid absorption tower 100, and the acrylic acid extract liquid discharged to the top of the (meth) acrylic acid extraction tower 200. At this time, the acrylic acid aqueous solution at a flow rate of about 6.08 g / min from the top of the water separation tower 300 to the position of the fourteenth stage The acrylic acid extract was introduced at a flow rate of about 6.55 g / min from the top of the water separation tower 300 to the position of the fourteenth stage.
  • the temperature of the 16th stage of the water separation tower 300 is about 86 ° C or more, and the temperature of the 12th stage is about Adjusted not to exceed 58 ° C.
  • the removal rate of water and acetic acid contained in the aqueous acrylic acid solution and the acrylic acid extraction solution supplied to the water separation tower was about 99% or more, and the water and the lower portion of the water separation tower (300) An acetic acid stream with most of acetic acid removed was obtained, and acrylic acid lost to the top of the water separation tower 300 was found to be about 0.22 weight 3 ⁇ 4.
  • the water separation tower 300 was able to operate stably without generating polymer in the tower even after being operated for a long time for 10 days.
  • Table 1 shows the flow rate and concentration of each flow in the steady state operation of the water separation tower (300).
  • the obtained acrylic acid aqueous solution was supplied to the (meth) acrylic acid extraction tower 200 and the water separation tower 300 by 50 weight%, respectively.
  • the acrylic acid aqueous solution discharged from the (meth) acrylic acid absorption tower 100 and the acrylic acid extract liquid discharged from the (meth) acrylic acid extraction tower 200 are about 5.75 at positions of the fourteenth stage from the top of the water separation tower 300, respectively. It was allowed to be introduced together at a flow rate of g / min and about 11.5 g / min.
  • the toluene reflux stream at the top of the water separation tower 300 was introduced at about 4.4 g / min in the first stage.
  • heat is supplied through a reboiler at the bottom of the water separation tower 300 so that the temperature of the 16th stage is about 81 ° C or more, and the temperature of the 12th stage is adjusted so as not to exceed 49 ° C. .
  • distillate flowed out at a flow rate of about 14.0 g / min to the top of the water separation tower 300 in a normal state, and about 7.65 g / to the bottom of the water separation tower 300. min acrylic acid flow was obtained.
  • the temperature of the water separation tower 300 in the steady state was maintained at about 40.4 ° C, and the temperature at the bottom of about 96.2 ° C, respectively.
  • the removal rate of water and acetic acid contained in the acrylic acid aqueous solution and the acrylic acid extract solution supplied to the water separation tower was about 98% or more, and water and acetic acid were mostly used as the lower part of the water separation tower.
  • the removed acrylic acid stream was obtained and the acrylic acid lost to the top of the water separation column was about 0.50 wt%.
  • the water separation tower 300 as described above was able to operate stably without generating polymer in the tower even after long-term operation for 10 days.
  • Table 2 shows the flow of each flow in the steady state operation of the water separation tower (300) Flow rate and concentration are shown.
  • the whole of the obtained acrylic acid aqueous solution was supplied to the water separation tower 300.
  • the aqueous acrylic acid solution discharged from the (meth) acrylic acid absorption tower 100 was introduced at a flow rate of about 6.5 g / min from the top of the water separation tower 300 to the position of the fourteenth stage.
  • the flow of toluene reflux at the top of the water separation tower 300 was introduced at about 11.95 g / min in the first stage. Further, by supplying heat through a reboiler at the bottom of the water separation tower 300, the temperature of the sixteenth stage is about 88 ° C or more, and the temperature of the twelfth stage does not exceed about 65 ° C. It was. After stable operation was performed for about 10 hours, the distillate flowed out at a flow rate of about 14.14 g / min to the top of the water separation tower 300 in a steady state, and about 4.31 g / to the bottom of the water separation tower 300. min acrylic acid flow was obtained. At this time, the temperature of the water separation tower 300 in the normal state is about 40.4 ° C, and the lower The temperature was maintained at 97.1 ° C respectively.
  • the removal rate of water and acetic acid contained in the aqueous acrylic acid solution and the acrylic acid extract solution supplied to the water separation tower was about 99% or more, and water and acetic acid were mostly used as the lower part of the water separation tower.
  • the removed acrylic acid flow was obtained and the acrylic acid lost to the top of the water separation column was about 0.13% by weight.
  • Table 3 shows the flow rate and concentration of each flow in the steady state operation of the water separation tower (300).
  • the whole of the obtained acrylic acid aqueous solution was supplied to the (meth) acrylic acid extraction tower 200, and the acrylic acid extract liquid discharged from the (meth) acrylic acid extraction tower 200 was supplied to the water separation tower (300).
  • Water The feed to the separation tower 300 was only allowed to be the acrylic acid extract, and the acrylic acid extract was introduced at a flow rate of about 8.3 g / min from the top of the water separation tower 300 to the position of the 14th stage.
  • the temperature of the 16th stage is about 88 ° C or more, and the temperature of the 12th stage is adjusted not to exceed about 6 5 ° C. It was.
  • the distillate flowed out at a flow rate of about 14.10 g / min to the top of the water separation tower 300 in a steady state, and about 2.65 g / to the bottom of the water separation tower 300. min acrylic acid flow was obtained.
  • the silver of the upper portion of the water separation tower 300 in the steady state was maintained at about 41.2 ° C, and the temperature of the lower portion at about 96.5 ° C.
  • the removal rate of water and acetic acid contained in the acrylic acid extract supplied to the water separation tower was about 99% or more.
  • the acrylic acid flow from which water and acetic acid was mostly removed was obtained at the bottom of the water separation tower, and the acrylic acid lost to the top of the water separation tower was about 1.07 weight 3 ⁇ 4>.
  • the water separation tower 300 was able to operate stably without generating polymer in the tower even after a long operation for about 10 days.
  • Table 4 shows the flow rate and concentration of each flow in the steady state operation of the water separation tower (300).
  • Example 1 Compared with the method of Comparative Example 2, the calorie of about 31.52 cal per lg acrylic acid recovered was reduced, which shows an energy saving of about 58.1%. In addition, according to the method of Example 2, compared with the method of Comparative Example 2, it was found that the calorie of about 35.54 cal per lg acrylic acid recovered, which shows an energy saving of about 65.5%.
  • the method for continuously recovering (meth) acrylic acid according to the present invention can significantly reduce energy consumption while maintaining the (meth) acrylic acid recovery at an equivalent level compared with the previous recovery method using a single water separation column (comparative example). It can be confirmed that.
  • the method according to the present invention can further increase the treatment capacity of the (meth) acrylic acid aqueous solution, and with high energy efficiency (meth) acrylic acid Can be recovered. Furthermore, the method according to the present invention can keep the temperature near the feed end of the water separation column where the polymer generation probability of (meth) acrylic acid is relatively high, and is effective in preventing the formation of polymers, thereby providing improved operational stability. can confirm.

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

Cette invention concerne un procédé de récupération en continu du (méth)acrylate, et un appareil utilisé dans ce procédé. Le procédé de récupération en continu du (méth)acrylate selon de l'invention permet de réduire significativement la quantité d'énergie utilisée pour récupérer le (méth)acrylate à la même vitesse que les procédés de récupération habituels. L'invention permet également une meilleure stabilité des opérations. Par exemple, l'invention peut réduire à un minimum les réactions de polymérisation du (méth)acrylate pendant le processus de récupération.
PCT/KR2013/006101 2012-08-03 2013-07-09 Procédé de récupération en continu du (méth)acrylate, et appareil de récupération associé WO2014021560A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BR112015002422-0A BR112015002422B1 (pt) 2012-08-03 2013-07-09 método de recuperação contínua de ácido (met)acrílico
IN430DEN2015 IN2015DN00430A (fr) 2012-08-03 2013-07-09
US14/415,113 US9517997B2 (en) 2012-08-03 2013-07-09 Process for continuous recovering (meth)acrylic acid and apparatus for the process
CN201380037821.6A CN104470884B (zh) 2012-08-03 2013-07-09 (甲基)丙烯酸的连续回收方法及用于该方法的设备

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2012-0085339 2012-08-03
KR20120085339 2012-08-03
KR10-2013-0080189 2013-07-09
KR1020130080189A KR101546464B1 (ko) 2012-08-03 2013-07-09 (메트)아크릴산의 연속 회수 방법 및 회수 장치

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR810001298B1 (ko) * 1978-12-04 1981-10-13 래리 윌리암 에반스 아크릴산의 회수방법
KR100375780B1 (ko) * 1997-02-28 2003-08-19 니폰 쇼쿠바이 컴파니 리미티드 아크릴산의회수방법
KR100584677B1 (ko) * 2003-08-04 2006-05-29 주식회사 엘지화학 고효율의 아크릴산 제조 방법
KR20090041355A (ko) * 2007-10-23 2009-04-28 주식회사 엘지화학 (메타)아크릴산 회수방법 및 (메타)아크릴산 회수장치

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR810001298B1 (ko) * 1978-12-04 1981-10-13 래리 윌리암 에반스 아크릴산의 회수방법
KR100375780B1 (ko) * 1997-02-28 2003-08-19 니폰 쇼쿠바이 컴파니 리미티드 아크릴산의회수방법
KR100584677B1 (ko) * 2003-08-04 2006-05-29 주식회사 엘지화학 고효율의 아크릴산 제조 방법
KR20090041355A (ko) * 2007-10-23 2009-04-28 주식회사 엘지화학 (메타)아크릴산 회수방법 및 (메타)아크릴산 회수장치

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