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WO2001085665A1 - Procede de production d'acide acrylique - Google Patents

Procede de production d'acide acrylique Download PDF

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Publication number
WO2001085665A1
WO2001085665A1 PCT/JP2001/003648 JP0103648W WO0185665A1 WO 2001085665 A1 WO2001085665 A1 WO 2001085665A1 JP 0103648 W JP0103648 W JP 0103648W WO 0185665 A1 WO0185665 A1 WO 0185665A1
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WO
WIPO (PCT)
Prior art keywords
acrylic acid
ppm
acid
crude
maleic
Prior art date
Application number
PCT/JP2001/003648
Other languages
English (en)
Japanese (ja)
Inventor
Takashi Nakagawa
Hironori Tashiro
Kouji Tomita
Ikuya Nagao
Original Assignee
Idemitsu Petrochemical Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Idemitsu Petrochemical Co., Ltd. filed Critical Idemitsu Petrochemical Co., Ltd.
Publication of WO2001085665A1 publication Critical patent/WO2001085665A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
    • C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
    • 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

Definitions

  • the present invention relates to a method for producing acrylic acid, and more particularly to a method for economically producing high-purity acrylic acid by purifying crude acrylic acid obtained by catalytic gas phase oxidation.
  • Acrylic acid is a highly reactive compound, and is an important compound used as a raw material for various polymer monomers and various polymerizable esters.
  • This acrylic acid is industrially produced by a method of oxidizing propylene and z or lactone by molecular oxygen in the gas phase in the presence of a solid oxidation catalyst, that is, by catalytic gas phase oxidation. I have.
  • the oxidation product is usually obtained in the form of an acrylic acid-containing oxidation product solution (aqueous solution).
  • This oxidized solution containing acrylic acid contains a large amount of aldehydes such as furfural and benzaldehyde, which are difficult to separate from acrylic acid, and carboxylic acids such as maleic acid, maleic anhydride and acetic acid, in addition to acrylic acid. ing.
  • aldehydes such as furfural and benzaldehyde
  • carboxylic acids such as maleic acid, maleic anhydride and acetic acid, in addition to acrylic acid.
  • a method of dehydrating the product solution and then obtaining acrylic acid using a purification means by distillation is generally used.
  • the method for dehydrating the oxidation product solution there are generally a solvent extraction method using a solvent such as ketone and acetate, and an azeotropic dehydration method using a solvent azeotropic with water such as toluene and methylisobutyl ketone. well known.
  • a solvent extraction method using a solvent such as ketone and acetate
  • azeotropic dehydration method using a solvent azeotropic with water such as toluene and methylisobutyl ketone.
  • water such as toluene and methylisobutyl ketone
  • Acrylic acid has recently been used in many fields such as superabsorbent resins and polymer flocculants, but its polymerizability has become important, and impurities such as aldehydes contained in crude acrylic acid have become important. Is a major problem. Therefore, it is necessary to remove and purify these impurities, and many methods have been proposed.
  • Japanese Patent Publication No. 58-372900 discloses that in the dehydration step of crude acrylic acid, hydrazine hydrate is reacted with aldehydes and ketones having the same level of volatility as acrylic acid.
  • a method of converting into a hydrazine diazine, which is a condensate, for separation and removal has a problem that the efficiency of removing aldehydes is not sufficient.
  • Japanese Patent Application Laid-Open No. 7-228584 discloses a method of adding a hydrazine compound and copper dithiolbamate to crude acrylic acid and distilling the crude acrylic acid at a temperature of 100 ° C. or less. Proposed. By adopting this method, it is intended to purify crude acrylic acid by separating and removing impurities such as aldehydes while suppressing the adhesion of acrylic acid produced by polymerization to the distillation column in the purification process.
  • impurities such as aldehydes
  • the final distillation column in the continuous method for producing acrylic acid is 25 to 100.
  • the crude acrylic acid and the specific amines are added in an amount of 0.1 to 2% based on the total moles of aldehyde and maleic acid and maleic anhydride in the crude acrylic acid.
  • a feed stream containing a minimum effective level of a molar ratio of 0 is provided, and at the top of the final distillation column, an act of supplying the other specific amines at a molar ratio of 0.01 to 1.0 as the standard.
  • There is a method for producing lylic acid Japanese Patent Application Laid-Open No. 7-33059, Japanese Patent Application Laid-Open No. 9-124659).
  • a crude acrylic acid that has been subjected to azeotropic dehydration treatment is added with a dehydrating agent such as hydracine and at least one kind of an amine such as an aliphatic amine, a heterocyclic amine or an aromatic monoamine, and then purified by distillation.
  • a dehydrating agent such as hydracine
  • an amine such as an aliphatic amine, a heterocyclic amine or an aromatic monoamine
  • the method for producing acrylic acid uses aldehydes, maleic acid, maleic anhydride as hydrazines, amines, ammonia, etc. as impurities contained in crude acrylic acid. By the addition, it is intended to be removed as a reaction product.
  • these methods for producing acrylic acid there is known a problem that the dealdehyde reaction with hydrazines or the like is inhibited by maleic acids.
  • the present invention relates to a method for producing high-purity acrylic acid from crude acrylic acid obtained by a catalytic gas phase oxidation method, comprising an aldehyde, a ketone and a maleic acid. It is an object of the present invention to provide a highly economical method that can remove impurities such as acids in a minute, suppress generation of sludge, and enable long-term continuous operation.
  • the present inventors have studied the above-mentioned problems in the production of acrylic acid, such as the relationship between additives such as dehydrating agents and amines, the amount of sludge formed, and the amount of impurities remaining in purified acrylic acid.
  • additives such as dehydrating agents and amines
  • the amount of sludge formed and the amount of impurities remaining in purified acrylic acid.
  • the present invention has been made based on these findings.
  • Crude acrylic acid obtained by azeotropic dehydration of an acrylic acid-containing oxidation product solution obtained by catalytic gas phase oxidation is converted into maleic acid and maleic anhydride in the crude acrylic acid.
  • a process for producing acrylic acid, wherein the total concentration is 2, OOO ppm or less and distillation is performed in the presence of hydrazines.
  • I 1 and R 2 each represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a phenyl group, a substituted phenyl group or an alicyclic hydrocarbon group.
  • the crude acrylic acid obtained by the catalytic gas-phase oxidation in the present invention is obtained by azeotropic dehydration of the acrylic acid-containing oxidation product obtained by the catalytic gas-phase oxidation of propylene and Z or lactone. Crude acrylic acid is used.
  • the acrylic acid-containing production solution may be a reaction product solution obtained by a one-stage oxidation method of propylene, or may be a product solution obtained by a two-stage oxidation method. These acrylic acid-containing product liquids are obtained in the form of an aqueous acrylic acid solution because steam is used for the reaction.
  • the composition of the acrylic acid-containing oxidation product solution varies depending on the type of oxidation method, oxidation reaction conditions, and the like. However, in general, the content of each component, Atta acrylic acid 5 0-8 0 weight 0/0, water 2 0-5 0 weight 0/0, maleic acid 0.3 to 2 wt%, Funorefuranore 1 It is about 0 to 500 ppm, and about 100 to 500 ppm of benzanoledaldehyde.
  • crude acrylic acid is obtained by removing water from the acrylic acid-containing oxidation product solution by an azeotropic dehydration method, which is an economical dewatering means.
  • This azeotropic dehydration treatment method is not particularly limited, and a known method in the method for producing atalylic acid can be employed.
  • azeotropic agent for example, toluene, xylene, ethynolebenzene, heptane, methyl isobutyl ketone, diisobutyl ketone, disobutylene or a mixture thereof is used under a reduced pressure of about 10 to 25 kPa. Perform azeotropic dehydration treatment.
  • the water concentration in the bottom liquid of the azeotropic dehydration column becomes less than 1,000 ppm.
  • Water, acetic acid, azeotropic agents and low-boiling aldehydes are removed from the top of the azeotropic dehydration tower. It is desirable that the water and the azeotropic agent do not dissolve in each other, the distillate is led out of the system, and the oil phase is returned to the azeotropic column as a reflux liquid and recycled.
  • crude acrylic acid is obtained from the bottom of the column. Further, light components such as acetic acid may be removed as necessary.
  • the crude acrylic acid is guided to a heavy component separation treatment, for example, a heavy component separation column, and a distillate is obtained by ordinary distillation means.
  • a heavy component separation treatment for example, a heavy component separation column
  • a distillate is obtained by ordinary distillation means.
  • crude acrylic acid containing impurities such as water, acetic acid, an azeotropic agent, and aldehydes, which are low-boiling substances, can be obtained.
  • the bottom liquid becomes acrylic acid having a high concentration of maleic acids such as maleic acid and maleic anhydride.
  • the distillation conditions in the heavy component separation column are such that the total concentration of maleic acid and maleic anhydride in the crude acrylic acid is 2,000 ppm or less, preferably 1,500 ppm.
  • it is more preferably set to be 1, OOO ppm.
  • it is preferable to reduce the concentration of maleic acid in the heavy component separation column.
  • 500 to 1, OOO ppm it is possible to produce high-purity acrylic acid in the next distillation step. It became clear.
  • the present inventors have clarified that the problem can be solved by a simple means of physical removal at a certain level. Therefore, it is a major feature of the present invention that the distillation column which requires enormous cost and does not require distillation conditions, such as the use of maleic acids as much as possible, can be carried out economically.
  • the distillation separation for separating and removing the heavy components is not particularly limited, but is usually performed at a pressure of 5 to 15 kPa and a bottom temperature of about 60 to 90 ° C. Done in
  • the crude acrylic acid having a reduced maleic acid concentration is processed in a distillation column, which is a final purification treatment.
  • This distillation treatment is performed in the presence of hydrazines. What is important in the present invention is that (a) the concentration of maleic acid in the crude acrylic acid supplied to the distillation column is 2, OO Oppm or less. (Mouth) Hydrazines are added to crude acrylic acid under these conditions.
  • the conditions for adding the hydrazine to the crude acrylic acid having a reduced maleic acid concentration are not particularly limited, and the hydrazine can be added to a stage before the distillation column and / or into the distillation column.
  • a method in which crude acrylic acid is previously mixed and then supplied to a distillation column, supplied simultaneously at a supply port, or supplied separately can be adopted.
  • a method using a crude acrylic acid tank having a stirrer or a pump circulation line or a method of providing a static mixer or a line mixer in the supply line can be adopted.
  • hydrazines there are no particular restrictions on the hydrazines to be added, but Preferred examples include the compound represented by the formula (1) or a hydrate thereof.
  • R 1 and R 2 each represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fuunyl group, a fuunyl group having a substituent, or an alicyclic hydrocarbon group.
  • hydrazines include hydrazine, phenylhydrazine, tolylhydrazine, a, monomethylphenylhydrazine, a, ⁇ -diphenylhydrazine,] 3-naphthylhydrazine, or a hydrate of these. Can be illustrated. In addition, a plurality of these hydrazines or hydrates thereof may be used.
  • the amount of hydrazine added can be appropriately selected depending on the concentration of impurities contained in crude acrylic acid supplied to the distillation column. Specifically, it is 1 to 8 times, preferably 3 to 5 times [each molar equivalent], relative to the impurity aldehydes.
  • distillation conditions include a pressure of about 5 to 10 kPa and a liquid temperature at the bottom of the column of 60 kPa. A condition of about 90 ° C is adopted. High-purity acrylic acid as a distillate overhead is obtained in the range of about 60 to 90% by volume of the crude acrylic acid supplied. In this purified acrylic acid, impurities such as furfural, penzaldehyde, and maleic acid can be reduced to 1 ppm or less by selecting purification conditions.
  • the method for producing acrylic acid according to the present invention comprises an azeotropic dehydration treatment and a heavy component separation treatment.
  • Process such as processing and distillation. These steps, equipment, processing conditions, and the like differ depending on the processing means, equipment size, crude acrylic acid composition, recovery rate, and the desired purity of the purified atalilic acid, and are appropriately determined except for those specified in the present invention.
  • acrylic acid is a compound which is easily polymerized, it is preferable to employ conditions such as distillation under conditions of low pressure and low temperature as much as possible.
  • the distillation operation in the method for producing acrylic acid of the present invention may be batch distillation, but continuous distillation is preferred from the viewpoint of industrial and productivity.
  • compounds known as polymerization inhibitors phenols such as hydroquinone, methoxyphenol, hydroquinone monomethinoleate ether, phenothiazine, etc.
  • Amines such as diphenylamine, copper salts such as dibutyl dithiopotassium copper rubinate, manganese salts such as manganese acetate, double-mouthed compounds, nitroso compounds and the like can be added.
  • Example 1 The gas chromatographic method was used for the determination of impurities in acrylic acid.
  • a small distillation unit (azeotropic dehydration unit) filled with a filler is used to convert the acrylic acid-containing oxidation product solution obtained by propylene one-step catalytic gas phase oxidation to a diameter of 2.
  • toluene was continuously supplied at a rate of 35 ml / hr and at a rate of 135 ml / hour as an azeotropic solvent, and the pressure at the top: 1
  • An azeotropic dehydration treatment was performed under the conditions of 7.5 kPa and a temperature of 85 ° C to obtain crude acrylic acid 1.
  • furfuranore 470 ppm
  • benzanoledide 450 ppm
  • maleate Acids 11,1000 ppm was contained.
  • the crude acrylic acid ⁇ obtained in (1) above was transferred to a small distillation apparatus (heavy component separation tower) filled with a filler [diameter: 2.6 mm, length: 600 mm]. Feed continuously at the rate of 0 ml Z-hour, pressure at the top: 5.3 kPa, temperature: 65 ° C, bottom pressure: 10.0 kPa, bottom temperature: 8
  • Hydrazine monohydrate 590 ppm (4 molar equivalents to aldehydes (sum of furfural and benzaldehyde)) was added together with the crude acrylic acid obtained in (2) above.
  • a small distillation device atrial acid distillation column
  • packing material (diameter: 2.6 mm, length: 600 mm)
  • Furfural, benzaldehyde, and maleic acid in the obtained high-purity acrylic acid were all 1 ppm or less, and the water content was 570 ppm.
  • Furfural in the bottom of the distillation column was 1 Oppm
  • benzaldehyde was 15 Oppm
  • maleic acid was 5 Oppm. At this time, no precipitate was observed at the bottom of the distillation column.
  • Example 2 In the same manner as in Example 1, except that hydrazine hydrate was preliminarily mixed with the crude acrylic acid for 5 minutes and then continuously supplied to the acrylic acid distillation column, the overhead was distilled off. As a liquid, purified high-purity acrylic acid was obtained. Furbural, benzaldehyde, and maleic acids in the high-purity acrylic acid obtained were all less than 1 ppm, and the water content was 590 ppm. Furfural in the bottom liquid of the distillation column was 7 ppm, benzaldehyde was 11 ppm, and maleic acids were 43 ppm. At this time, no precipitate was observed at the bottom of the distillation column.
  • the maleic acid obtained in (1) of Example 1 containing 11,000 ppm of crude atalylic acid and hydrazine monohydrate: 2,740 ppm [6 to hydrazine [Mole equivalent], and purified acrylic acid was obtained as the top distillate in the same manner as in Example 1 except that the mixture was continuously supplied to the acrylic acid distillation column.
  • 5 ppm of furfural, 1 ppm of benzaldehyde, 10 ppm of maleic acid, and 10 ppm of water in the obtained purified acrylic acid Minutes were 2,63 O ppm.
  • Furfurul in the bottom liquid of the distillation column was 110 ppm
  • benzaldehyde was 180 ppm
  • maleic acid was 23, OOO ppm. At this time, a larger amount of precipitate was observed at the bottom of the distillation column than in Comparative Example 1.
  • Example 2 The distillation conditions in (2) of Example 1 were changed to obtain crude acrylic acid 3 containing furfural: 290 ppm, benzanoledaldehyde: 130 ppm, and maleic acids: 2,500 ppm. .
  • hydrazine monohydrate 850 ppm [4 molar equivalents relative to hydrazines]
  • the mixture was fed continuously to the acrylic acid distillation column in the same manner as in Example 1.
  • purified acrylic acid was obtained as a top distillate.
  • the obtained purified acrylic acid contained 2 ppm of fullernole, 1 ppm of benzanoledaldehyde, 4 ppm of maleic acid, and 81 Ppm of water.
  • the bottoms in the distillation column had 40 ppm of phenol, 40 ppm of benzanoledaldehyde, and 4.5 ppm of maleic acid. At this time, a precipitate was observed at the bottom of the distillation column.
  • high-purity acrylic acid is converted from crude acrylic acid obtained by catalytic gas-phase oxidation of propylene and / or acrolein.
  • the generation of sludge during distillation purification is suppressed.
  • it can be manufactured economically advantageously.

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

Abstract

L'invention concerne un procédé de production d'acide acrylique, qui consiste à soumettre à une déshydratation azéotropique un produit d'oxydation liquide contenant de l'acide acrylique obtenu par une méthode catalytique de dépôt chimique en phase vapeur mise en oeuvre pour produire un acide acrylique brut. Le procédé consiste ensuite à réguler la concentration totale d'acide maléique et d'anhydride maléique dans l'acide acrylique brut à 2000 mg/l au plus, puis à distiller l'acide brut en présence d'un composé d'hydrazine. Ce procédé permet de produire de façon économique un acide acrylique très pur à partir de l'acide acrylique brut obtenu par la méthode catalytique de dépôt chimique en phase vapeur, en même temps qu'on élimine suffisamment des impuretés, telles que des aldéhydes, des cétones, de l'acide maléique, et analogues, et qu'on inhibe la production de boues.
PCT/JP2001/003648 2000-05-08 2001-04-26 Procede de production d'acide acrylique WO2001085665A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2000134344A JP4601120B2 (ja) 2000-05-08 2000-05-08 アクリル酸の製造方法
JP2000-134344 2000-05-08

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WO2001085665A1 true WO2001085665A1 (fr) 2001-11-15

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Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4068886B2 (ja) * 2001-05-01 2008-03-26 株式会社日本触媒 アクリル酸（塩）重合体、その製造方法およびその用途
US7393976B2 (en) * 2003-11-26 2008-07-01 Rohm And Haas Company Process for manufacturing reduced water content (meth)acrylic acid
FR2934264B1 (fr) * 2008-07-22 2012-07-20 Arkema France Fabrication d'esters de vinyle a partir de matieres renouvelables, esters de vinyle obtenus et utilisations
FR2935971B1 (fr) * 2008-09-16 2010-11-19 Arkema France Acide bio-acrylique de grade polymere et son procede de fabrication a partir de glycerol.

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0685448A1 (fr) * 1994-05-31 1995-12-06 Rohm And Haas Company Procédé de purification d'acide acrylique
JPH09208515A (ja) * 1996-02-07 1997-08-12 Idemitsu Petrochem Co Ltd アクリル酸の製造方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6054939B2 (ja) * 1977-08-04 1985-12-03 住友化学工業株式会社 粗製アクリル酸の精製方法
JPH089567B2 (ja) * 1992-01-09 1996-01-31 株式会社日本触媒 アクリル酸製造においてアクリル酸を高純度に精製する方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0685448A1 (fr) * 1994-05-31 1995-12-06 Rohm And Haas Company Procédé de purification d'acide acrylique
JPH09208515A (ja) * 1996-02-07 1997-08-12 Idemitsu Petrochem Co Ltd アクリル酸の製造方法

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JP4601120B2 (ja) 2010-12-22
TWI242550B (en) 2005-11-01

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