WO2010002191A2 - Procédé de production d'acide téréphtalique - Google Patents

Procédé de production d'acide téréphtalique Download PDF

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Publication number
WO2010002191A2
WO2010002191A2 PCT/KR2009/003591 KR2009003591W WO2010002191A2 WO 2010002191 A2 WO2010002191 A2 WO 2010002191A2 KR 2009003591 W KR2009003591 W KR 2009003591W WO 2010002191 A2 WO2010002191 A2 WO 2010002191A2
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terephthalic acid
reaction
acetic acid
catalyst system
acid
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PCT/KR2009/003591
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English (en)
Korean (ko)
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WO2010002191A3 (fr
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박찬식
주영환
김대학
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삼성석유화학(주)
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Publication of WO2010002191A2 publication Critical patent/WO2010002191A2/fr
Publication of WO2010002191A3 publication Critical patent/WO2010002191A3/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
    • C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B33/00—Oxidation in general
    • 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
    • C07C51/50—Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
    • C07C63/14—Monocyclic dicarboxylic acids
    • C07C63/15—Monocyclic dicarboxylic acids all carboxyl groups bound to carbon atoms of the six-membered aromatic ring
    • C07C63/26—1,4 - Benzenedicarboxylic acid
    • 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
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a method for preparing terephthalic acid, and more particularly, to a method for converting a reaction intermediate into terephthalic acid when the crude terephthalic acid obtained after the solid-liquid separation process contains a large amount of reaction intermediate.
  • Terephthalic acid is a useful compound used as a raw material for a wide range of products and is used as a main raw material for polyethylene terephthalate (PET), polyester fibers, and polyester films for packaging and containers.
  • PET polyethylene terephthalate
  • Terephthalic acid is manufactured in more than 50 million tons annually worldwide and can be produced from 100,000 to 800,000 tons annually in a single plant.
  • terephthalic acid is used as a source of air or other oxygen molecules as an oxidizing agent, and at least one heavy metal compound and at least one reaction promoter compound in the liquid phase are used as catalysts for the exothermic oxidation of p-xylene in acetic acid solvent.
  • Can be generated by The method of oxidizing paraxylene using this liquid phase oxidation reaction is widely used in the art as a so-called Amoco MC process.
  • This new oxidation reaction has a relatively low yield and a slow reaction rate compared with the conventional oxidation reaction using acetic acid solvent and bromine catalyst.
  • the new oxidation reaction is less intense than the conventional one, by-products caused by excessive oxidation reactions such as terephthalic acid decomposing substances such as benzoic acid, isophthalic acid recombination of some functional groups such as acid), trimellitic acid, etc., and no paratolualdehyde, p-tolualdehyde, p-toluic acid, or 4-carboxybenzaldehyde Large amounts of reaction intermediates are produced.
  • terephthalic acid produced by such a new oxidation reaction contains relatively more reactive intermediates than the terephthalic acid produced by the conventional oxidation reaction even after the solid-liquid separation process, it is possible to use a purification method known in the art. It causes a problem that it is difficult to remove the large amount of the reaction intermediate. Therefore, the development of a technique for removing such a reaction intermediate from terephthalic acid is a very important factor in increasing the yield of terephthalic acid as well as ensuring the quality of the final product.
  • the reaction intermediate when the solid terephthalic acid separated by the solid-liquid separation process in the preparation of terephthalic acid includes a large amount of reaction intermediates such as paratoluic acid and 4-carboxybenzaldehyde, the reaction intermediate is converted to terephthalic acid through oxidation. It aims to increase the yield of final terephthalic acid and to ensure quality.
  • the present invention comprises the steps of: 1) mixing a solid crude terephthalic acid containing a reaction intermediate of at least one of paratoluic acid and 4-carboxybenzaldehyde with an acetic acid solvent or an aqueous acetic acid solution to form a slurry; And 2) a first catalyst system comprising at least one selected from the group consisting of a) cobalt precursors and manganese precursors and bromine precursors in the reactor, or b) a second catalyst system comprising a cobalt precursor and a manganese precursor. It provides a method for producing terephthalic acid comprising the step of oxidizing with terephthalic acid.
  • 1 is a process chart for preparing a crude crude terephthalic acid by the crystallization process and the solid-liquid separation process after the oxidation reaction of the aromatic feedstock.
  • FIG. 2 is a process diagram for preparing terephthalic acid from a solid crude terephthalic acid according to an embodiment of the present invention.
  • FIG. 3 is a process diagram for preparing terephthalic acid from a solid crude terephthalic acid according to another embodiment of the present invention.
  • 25 solid crude terephthalic acid
  • 26 crude terephthalic acid-acetic acid slurry
  • terephthalic acid is prepared through an oxidation process, a crystallization process, a solid-liquid separation process, and a purification process.
  • an aromatic feedstock compound (ex. Paraxylene) 21 is introduced into an oxidation reaction zone 11 having 1 to 3 high pressure vessels and an upper heat exchanger.
  • an oxygen supply source such as oxygen gas or air is supplied to the oxidation reaction region 11 through a line (not shown).
  • an oxidation reaction of the introduced aromatic feedstock compound 21 and oxygen gas occurs, and not only terephthalic acid is generated by this oxidation reaction, but also p-toluic acid, 4- Reaction intermediates such as 4-carboxybenzaldehyde are also produced.
  • This reaction product that is, the slurry 22 containing terephthalic acid and the reaction intermediate is then crystallized in the crystallization zone 12 having one to three high pressure vessels and an upper heat exchanger, and then separation equipment such as a filter and a centrifuge.
  • the crude terephthalic acid 25 containing the reaction intermediate is separated into a solid phase in the solid-liquid separation region 13 having a vessel or the like for storing the mother liquid, and the mother liquid 24 is separated into a liquid phase.
  • the mother liquor 24 is refluxed back into the oxidation reaction region 11 and used as a reaction solvent.
  • the reaction intermediate contained in the mother liquor 24 is converted into terephthalic acid by an oxidation reaction.
  • reaction intermediates such as p-toluic acid and 4-carboxybenzaldehyde remain.
  • it is prepared from p-xylene through an oxidation reaction using a water solvent instead of an acetic acid solvent and a catalyst containing no bromine precursor, such as a catalyst containing at least one of a manganese precursor and a cobalt precursor.
  • a catalyst containing no bromine precursor such as a catalyst containing at least one of a manganese precursor and a cobalt precursor.
  • the reaction intermediate of about 5,000 ppm or more remains after the crystallization process and the solid-liquid separation process.
  • reaction intermediate When such a reaction intermediate remains in the final terephthalic acid, not only does not only cause a decrease in the polymerization performance of the polyester polymer but also negatively affects the color and transparency, the content of the reaction intermediate should be minimized. Therefore, a purification process for removing the reaction intermediate is necessary. However, the purification process known in the art can remove a small amount of reaction intermediate from crude terephthalic acid, but it is difficult to remove a large amount of reaction intermediate.
  • the present invention by slurrying the solid crude terephthalic acid separated after the solid-liquid separation with an acetic acid solvent and then oxidized to convert the remaining reaction intermediate in the solid crude terephthalic acid to terephthalic acid, thereby improving the quality of terephthalic acid It is characterized by increasing the yield of terephthalic acid.
  • the solid crude terephthalic acid 25 separated in the solid-liquid separation region 13 contains a reaction intermediate such as paratoluic acid and 4-carboxybenzaldehyde in addition to terephthalic acid.
  • This solid crude terephthalic acid 25 is mixed with the acetic acid solvent or acetic acid solutions 29 and 35 in the slurrying region 14 to be converted into a slurry 26.
  • the slurry 26 is oxidized with an oxygen source such as air or oxygen gas in the refining zone 15 in which a catalyst system such as cobalt / bromine, manganese / bromine, cobalt / manganese / bromine, cobalt / manganese is present, and this oxidation
  • an oxygen source such as air or oxygen gas
  • a catalyst system such as cobalt / bromine, manganese / bromine, cobalt / manganese / bromine, cobalt / manganese is present, and this oxidation
  • the reaction intermediate contained in the slurry that is, paratoluic acid or 4-carboxybenzaldehyde, is converted into terephthalic acid.
  • high purity terephthalic acid can be prepared through an additional purification process such as terephthalic acid or hydrogen reduction of medium purity capable of polymerizing with polyester.
  • the present invention comprises the steps of: 1) dissolving a crude crude terephthalic acid comprising a reaction intermediate of at least one of paratoluic acid and 4-carboxybenzaldehyde in acetic acid solvent or acetic acid solution to form a slurry; And 2) oxidation of the slurry with terephthalic acid in the presence of a) a first catalyst system comprising a) cobalt precursor and a manganese precursor and a bromine precursor; or b) a second catalyst system comprising a cobalt precursor and a manganese precursor.
  • a method comprising the step of making a high purity terephthalic acid is prepared.
  • the solid crude terephthalic acid 25 separated from the mother liquor 24 in the solid-liquid separation region 13 contains a large amount of reaction intermediates, in particular, the content is about 0.01 to about the total weight of the solid crude terephthalic acid.
  • Paratoluic acid in the range of 5 wt% and / or 4-carboxybenzaldehyde in the range of about 0.3 to 3 wt% may be included.
  • the solid crude terephthalic acid 25 is mixed with the acetic acid solvent 35 and converted into a slurry 26.
  • an acetic acid solution containing an acetic acid solvent and water can be used in addition to the acetic acid solvent.
  • the acetic acid solvent and the water solvent may be mixed in a mass ratio of 5 ⁇ 15: 1.
  • an oxygen source such as air, oxygen gas, etc.
  • the acetic acid solvent or acetic acid solution is included in the range of about 50 wt% to 90 wt% in the whole material (crude terephthalic acid including the reaction intermediate; acetic acid solvent or acetic acid solution; and the first catalyst system or the second catalyst system) in the reactor.
  • crude terephthalic acid, including the reaction intermediate in the range of about 20 wt% to 40 wt%.
  • the type of catalyst usable in the present invention includes a) a first catalyst system including a cobalt precursor and a manganese precursor and a bromine precursor, or b) a second catalyst system including a cobalt precursor and a manganese precursor. It doesn't work.
  • the cobalt precursor and the manganese precursor are 50 to 400 ppmw, respectively, in the whole material in the reactor (crude terephthalic acid including a reaction intermediate; acetic acid solution or acetic acid solution; and first catalyst system or second catalyst system), respectively. It is appropriate to include in a concentration range, and in the first catalyst system, the bromine precursor is about 10 to 500 in the whole material in the reactor (crude terephthalic acid including the reaction intermediate; acetic acid or acetic acid solution; and the first catalyst system). It is appropriate that the concentration is included in the ppmw range.
  • the cobalt precursor is not particularly limited as long as cobalt ions can be generated in a solvent, and examples thereof include cobalt acetate hydrate.
  • the manganese precursor is not particularly limited as long as manganese ions can be produced in the solvent, and examples thereof include manganese acetate hydrate.
  • the bromine precursor is not particularly limited as long as bromine ions can be produced in a solvent, for example, hydrogen bromide (HBr), tetrabromoethane (C 2 H 2 (Br) 4 ), and cobalt bromide (CoBr 2). ) And manganese bromide (MnBr 2 ).
  • the reaction temperature of the oxidation reaction is not particularly limited, but it is preferable to perform the oxidation reaction at an appropriate temperature because the content of the reaction intermediate in the final terephthalic acid is affected by the reaction temperature. However, if the reaction temperature of the oxidation reaction is too low, the conversion of the reaction intermediate is lowered, so that the content of the reaction intermediate in the final terephthalic acid may not decrease, so the reaction temperature is appropriately about 180 to 280 °C.
  • the reaction temperature of the oxidation reaction can be adjusted in accordance with the purpose used.
  • the slurry 26 may be removed in the presence of a first catalyst system in which a bromine precursor and a precursor of at least one of a cobalt precursor and a manganese precursor are combined. It can be oxidized.
  • the temperature of the oxidation reaction is suitably in the range of about 190 to 230 ° C.
  • terephthalic acid can be obtained in which the concentration of the reaction intermediate is reduced to about 300 ppmw or less.
  • the obtained terephthalic acid may contain paratoluic acid at a concentration of 150 ppmw or less, and 4-carboxybenzaldehyde may be included at a concentration of about 300 ppmw or less.
  • the slurry 26 may be oxidized in the presence of a second catalyst system in which cobalt precursor and manganese precursor are combined.
  • the oxidation temperature is suitably in the range of about 180 to 210 ° C.
  • terephthalic acid can be obtained in which the concentration of the reaction intermediate is reduced to about 3000 ppmw or less.
  • a hydrogen reduction reaction may be further performed in order to further reduce the concentration of 4-carboxybenzaldehyde contained in the terephthalic acid obtained after the oxidation reaction.
  • the reaction time of the oxidation reaction is suitably in the range of 30 to 120 minutes. If the reaction time is too short, the conversion of the reaction intermediate is lowered.
  • the oxidation reaction occurring in the purification region 15 is an exothermic reaction.
  • some of the materials in the reactor such as acetic acid or some of the water, may be converted into a gaseous material 32 by the heat of reaction and flow out.
  • the outflowing gaseous substance 32 is condensed in the cooling zone 19, part 33 is returned to the refining zone 15 and the remainder 34 is sent to the acetic acid dehydration zone 20.
  • the material (34) sent to the acetic acid dehydration zone (20) is separated into water (36) and acetic acid (35), the separated water (36) flows out, and only acetic acid (35) is re-slurryed (14) Can be recovered and reused.
  • the oxidation reaction in the purification region 15 is an oxidation reaction of the reaction intermediate (ex. 4-carboxybenzaldehyde, paratoluic acid), the calorific value is smaller than that of the paraxylene. Accordingly, the amount of acetic acid solvent burned by the reaction heat is also small, and the amount of gaseous substances flowing out to the upper part of the reactor is small, so that the acetic acid dehydrator for recovering acetic acid from them can be made small, thereby reducing the investment cost.
  • the reaction intermediate ex. 4-carboxybenzaldehyde, paratoluic acid
  • the crystallization process and the solid-liquid separation process may be performed again.
  • the purified terephthalic acid 27 obtained through the slurry zone and the purification zone may optionally pass through the crystallization zone 16 and the solid-liquid separation zone 17.
  • the terephthalic acid (27) purified in the purification zone (15) is further reduced in temperature by depressurizing and depressurizing in the crystallization zone (16), and the crystallization product (28) is then terephthalic acid (30) in the solid-liquid separation zone (17). Is separated into a solid phase, and the mother liquid 29 containing acetic acid is separated into a liquid phase.
  • the separated solid terephthalic acid 30 is dried in the drying zone 18 to completely remove the remaining small amount of acetic acid, the final terephthalic acid 31 can be recovered. Meanwhile, the mother liquor 29 including acetic acid separated in the solid-liquid separation region 17 may be recovered and reused in the slurrying region 14.
  • a slurry was prepared by mixing 60 g of solid terephthalic acid comprising 6.1 wt% of paratoluic acid and 2.6 wt% of 4-carboxybenzaldehyde together with 90 g of acetic acid and 13 g of water. Then, cobalt acetate hydrate 0.42 g, manganese acetate hydrate 0.42 g and tetra-dibromoethane (tetrabromoethane) 0.18 g are then added to the slurry in which the mixed catalyst reactor, the air of about 20 kgf / cm 2 g reaction of Inject until pressure was reached. Thereafter, the oxidation reaction was carried out batchwise at a reaction temperature of about 195 ° C. and at a reaction pressure of about 20 kgf / cm 2 g for about 90 minutes. In this case, the results obtained are analyzed using high performance liquid chromatography are shown in Table 1 below.
  • a slurry was prepared by mixing 60 g of solid terephthalic acid comprising 1.75 wt% of paratoluic acid and 1 wt% of 4-carboxybenzaldehyde together with 90 g of acetic acid and 13 g of water. Thereafter, the slurry was introduced into a reactor in which a catalyst containing 0.42 g of cobalt acetate hydrate and 0.42 g of manganese acetate hydrate was present, and then air was introduced until a reaction pressure of about 20 kgf / cm 2 g was reached. Thereafter, the oxidation reaction was carried out batchwise at a reaction temperature of about 204 ° C. and a reaction pressure of about 20 kgf / cm 2 g for about 90 minutes. In this case, the results obtained are analyzed using high performance liquid chromatography are shown in Table 2 below.
  • a slurry was prepared by mixing 32 g of solid terephthalic acid comprising 2 wt% of paratoluic acid and 1 wt% of 4-carboxybenzaldehyde together with 90 g of acetic acid and 7.6 g of water. Then, after the slurry was added to a reactor in which a catalyst containing 0.05 g of cobalt acetate hydrate, 0.023 g of manganese acetate hydrate, and 0.045 g of tetrabromoethane was present, air of about 21 kgf / cm 2 g was added. It was added until the reaction pressure was reached. Thereafter, the oxidation reaction was carried out batchwise at a reaction temperature of about 221 ° C. and a reaction pressure of about 21 kgf / cm 2 g for about 90 minutes. At this time, the result obtained by analyzing the result using high performance liquid chromatography is shown in Table 3 below.
  • the concentration of the reaction intermediate in the terephthalic acid was found to decrease from about 3 wt% to about 0.055 wt%.
  • a catalyst containing cobalt / manganese / bromine as in Example 3, it can be seen that even if a small amount of the catalyst is used, a significant amount of the reaction intermediate can be converted to terephthalic acid.
  • a slurry was prepared by mixing 32 g of solid terephthalic acid containing 2 wt% of paratoluic acid and 1 wt% of 4-carboxybenzaldehyde together with 90 g of acetic acid and 9 g of water. Then, after the slurry was introduced into the reactor in which a catalyst containing 0.06 g of cobalt acetate hydrate and 0.05 g of tetrabromoethane is present, when the air reaches a reaction pressure of about 24 kgf / cm 2 g Was added until. Thereafter, the oxidation reaction was carried out batchwise at a reaction temperature of about 230 ° C. and a reaction pressure of about 24 kgf / cm 2 g for about 90 minutes. In this case, the results obtained are analyzed using high performance liquid chromatography are shown in Table 4 below.
  • the reaction intermediate can be effectively removed to improve the yield and quality of the final terephthalic acid.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de production d'acide téréphtalique consistant : 1) à mélanger un acide téréphtalique brut en phase solide, contenant au moins un composé intermédiaire d'acide para-toluique et de 4-carboxybenzaldéhyde, avec un solvant d'acide acétique ou une solution aqueuse d'acide acétique pour former une bouillie; et 2) à permettre une réaction d'oxydation de la bouillie dans un acide téréphtalique dans un réacteur, en présence a) d'un premier système de catalyseur contenant un ou plusieurs éléments sélectionnés dans le groupe composé d'un précurseur du cobalt et d'un précurseur du manganèse et un précurseur du brome, ou b) d'un second système de catalyseur contenant un précurseur du cobalt et un précurseur du manganèse.
PCT/KR2009/003591 2008-07-01 2009-07-01 Procédé de production d'acide téréphtalique WO2010002191A2 (fr)

Applications Claiming Priority (2)

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KR10-2008-0063671 2008-07-01
KR1020080063671A KR20100003674A (ko) 2008-07-01 2008-07-01 테레프탈산의 제조방법

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WO2010002191A3 WO2010002191A3 (fr) 2010-04-22

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR820000653B1 (ko) * 1979-01-17 1982-04-20 단노와 나리다다 테레프탈산의 제조 방법
US4330676A (en) * 1977-07-04 1982-05-18 Imperial Chemical Industries Limited Oxidation process
US6194607B1 (en) * 1998-12-22 2001-02-27 Samsung General Chemicals Co., Ltd. Method of producing aromatic carboxylic acids by oxidizing alkyl aromatic hydrocarbons or partially oxidized intermediates thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53105442A (en) * 1977-02-25 1978-09-13 Teijin Ltd Praparation of terephthalic acid

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4330676A (en) * 1977-07-04 1982-05-18 Imperial Chemical Industries Limited Oxidation process
KR820000653B1 (ko) * 1979-01-17 1982-04-20 단노와 나리다다 테레프탈산의 제조 방법
US6194607B1 (en) * 1998-12-22 2001-02-27 Samsung General Chemicals Co., Ltd. Method of producing aromatic carboxylic acids by oxidizing alkyl aromatic hydrocarbons or partially oxidized intermediates thereof

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KR20100003674A (ko) 2010-01-11

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