WO2005044772A1 - 精製(メタ)アクリル酸の製造方法 - Google Patents
精製(メタ)アクリル酸の製造方法 Download PDFInfo
- Publication number
- WO2005044772A1 WO2005044772A1 PCT/JP2004/015367 JP2004015367W WO2005044772A1 WO 2005044772 A1 WO2005044772 A1 WO 2005044772A1 JP 2004015367 W JP2004015367 W JP 2004015367W WO 2005044772 A1 WO2005044772 A1 WO 2005044772A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acrylic acid
- meth
- crude
- hydrazines
- maleic
- Prior art date
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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
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
Definitions
- the present invention relates to a method for producing purified (meth) acrylic acid, and more particularly, to a method for distilling crude (meth) acrylic acid obtained by gas phase catalytic oxidation and containing maleic acids and aldehydes as impurities.
- the present invention relates to a method for producing pure (meth) acrylic acid.
- (meth) acrylic acid is a general term for acrylic acid and methacrylic acid.
- Step (A) is a step for converting maleic acids and aldehydes to high boiling substances
- step (B) is a step for converting maleic acids and hydrazines. This is the step of converting the reaction product into a soluble substance.
- the reaction product of the aldehyde and the hydrazine generated in the step (A) is soluble.
- Patent Document 1 JP 2003-206257 A
- the present invention has been made in view of the above circumstances, and has as its object to produce purified (meth) acrylic acid from crude (meth) acrylic acid containing maleic acids and aldehydes as impurities. In doing so, it is an object of the present invention to provide the above-mentioned production method capable of sufficiently removing aldehydes in addition to maleic acids, suppressing generation of sludge, and enabling long-term continuous operation.
- the present invention has been completed based on the above findings, and the gist of the present invention is to purify (meth) acrylic acid by distilling crude (meth) acrylic acid containing maleic acids and aldehydes as impurities.
- the manufacturing method prior to distillation,
- (A) a step of adding hydrazines to crude (meth) acrylic acid and reacting maleic acids and hydrazines under a condition not lower than the melting point of acrylic acid and not higher than 50 ° C;
- crude (meth) acrylic acid which is obtained by gas phase catalytic oxidation and contains maleic acids and aldehydes as impurities is efficiently removed, and the impurity content is significantly reduced.
- Low-purity (meth) acrylic acid can be obtained economically, and its industrial value is extremely large.
- a general method for producing (meth) acrylic acid will be described.
- crude acrylic acid is manufactured through the following (1)-(5) steps sequentially.
- (1) A one-step oxidation method for producing acrylic acid directly by reacting propane, propylene and Z or acrolein with a molecular oxygen-containing gas in the presence of an oxidizing molybdenum-based solid oxidation catalyst, or
- propylene and a molecular oxygen-containing gas are reacted in the presence of a molybdenum oxide-based solid oxidation catalyst to produce acrolein, and then in the second reaction zone, the molybdenum oxide-based solid oxidation catalyst is produced.
- a process in which acrylic acid-containing gas is formed by a two-step oxidation method of producing acrylic acid by reacting acrolein with molecular oxygen in the presence of a catalyst or the like.
- Methacrylic acid is obtained by, for example, using isobutylene or the like as a raw material and bringing a reaction gas and water into contact with each other by gas phase contact oxidation in the same manner as in the production of acrylic acid.
- a methacrylic acid-containing liquid is obtained and then obtained as a bottom fraction in a methacrylic acid recovery step.
- maleic acids and aldehydes contained as impurities have a similar boiling point to (meth) acrylic acid and similar physical properties. They are not sufficiently separated by the treatment and are entrained by (meth) acrylic acid.
- the production method of the present invention is obtained as described above, and maleic acids and a In the method of producing purified (meth) acrylic acid by distilling crude (meth) acrylic acid containing aldehydes, the following (A)-(C) step (distillation pretreatment step) prior to distillation Are sequentially performed.
- (A) a step of adding hydrazines to crude (meth) acrylic acid and reacting maleic acids and hydrazines at a temperature not lower than the melting point of acrylic acid and not higher than 50 ° C.
- the concentration of maleic acid in the crude (meth) acrylic acid used as a raw material in the distillation pretreatment step is usually 2,000 to 10, OOOppm, preferably 2,000 to 5, ppm.
- OOOppm the concentration of maleic acid in crude (meth) acrylic acid
- the load of the refining process required is large, while the concentration of maleic acid in crude (meth) acrylic acid is 10, OOOppm. If it exceeds 3, the consumption of hydrazines becomes too large and it is not economical.
- the (meth) acrylic acid-containing liquid obtained in the above-mentioned step (3) may be used as a raw material, but from the above-mentioned viewpoint, usually the above-mentioned (4) And the crude (meth) acrylic acid obtained in step (5) is used.
- step (A) hydrazines are added to crude (meth) acrylic acid to produce a reaction product of maleic acids and hydrazines.
- the hydrazines include hydrazine, hydrazine hydrate, and a mixture thereof.
- the maleic acids include maleic acid, maleic anhydride, citraconic acid, and the like.
- the reaction apparatus to be used is not particularly limited as long as the required temperature and reaction time can be secured, and for example, a reaction tank with a stirrer, a tubular reaction tank, and the like are suitable.
- the reaction temperature between the maleic acid and the hydrazine is not lower than the melting point of acrylic acid and not higher than 50 ° C, preferably 15 to 40 ° C, and the reaction time is generally not shorter than 10 minutes, preferably 30 minutes to 3 hours. It is.
- the reaction temperature is lower than the melting point of acrylic acid, the reaction between maleic acid and hydrazine is slowed, and when the reaction temperature is higher than 50 ° C, hydrazine tends to decompose.
- the amount of hydrazines added is usually 0.1 to 5 moles, preferably 0.5 to 3 moles, based on the total amount of maleic acids and aldehydes in the crude (meth) acrylic acid. is there.
- the amount of hydrazine added is less than 0.1 mole, the reaction of the hydrazine with maleic acid becomes insufficient, and when the added amount exceeds 5 mole, it is not economical.
- step (A) hydrazines mainly react with maleic acids, but unreacted maleic acids may slightly remain.
- the reaction product of hydrazines and maleic acid is presumed to be maleic monohydrazide.
- the reaction solution of the step (A) is subjected to a heat treatment.
- the above reaction product is converted into a substance soluble in the reaction solution.
- the heating device is not particularly limited as long as the temperature inside the device can be set in the above range, and for example, heat exchange is preferable.
- the heat treatment temperature is 60 to 90 ° C, preferably 62 to 80 ° C, and the heat treatment time is usually 10 minutes or more, preferably 30 minutes to 3 hours.
- the temperature is lower than 60 ° C, the reaction product of maleic acid and hydrazine is not sufficiently converted into a soluble substance, and the reaction product precipitates and causes sludge.
- the temperature exceeds 90 ° C, there is a disadvantage that polymerization of acrylic acid occurs.
- step (C) hydrazines are added to the heat-treated solution in the step (B) to produce a reaction product of the aldehydes and the hydrazines.
- the reaction product of the hydrazine and the aldehyde is presumed to be a hydrazonei conjugate.
- the same hydrazines as those used in the step (A) can be used.
- Aldehydes include furfural and benzaldehyde
- hydrazone compounds include furfural hydrazone and benzaldehyde hydrazone.
- the same device as in the step (A) can be used as the reaction device.
- the reaction temperature of the aldehydes with the hydrazines is not lower than the melting point of acrylic acid and not higher than 50 ° C, preferably 15-35 ° C, and the reaction time is generally not shorter than 10 minutes, preferably not longer than 30 minutes. 3 hours.
- the reaction temperature is lower than the melting point of acrylic acid, the reaction between aldehydes and hydrazines becomes slow, and when the reaction temperature exceeds 50 ° C, hydrazines tend to decompose.
- the temperature of the heat-treated solution obtained in the step (B) is set to a value equal to or higher than the melting point of acrylic acid and equal to or lower than 50 ° C.
- a device that can set the temperature in the device within the above range is not particularly limited, and for example, a refrigerator is suitable.
- the amount of hydrazines added is usually 0.1 to 5 times, preferably 0.5 to 5 times the total amount of maleic acids and aldehydes in the crude acrylic acid of the step exit liquid (B). 3 times the mole. If the added amount of hydrazine is less than 0.1 mol, the reaction of maleic acid and aldehyde with hydrazine becomes insufficient, and if the added amount exceeds 5 mol, it is not economical.
- the crude (meth) acrylic acid obtained by sequentially performing the above-mentioned steps (A) to (C) is distilled by a known method to produce highly purified (meth) acrylic acid.
- "high purity” means that the contents of maleic acid, furfural and benzaldehyde in purified (meth) acrylic acid are less than 30 ppm, 3 ppm and 10 ppm, respectively.
- the operating conditions of the distillation column vary depending on the composition of the distillation raw material, the recovery rate, the purity of the distilled (meth) acrylic acid, and the like.
- (meth) acrylic acid is an easily polymerizable compound
- the distillation temperature and the pressure are set as low as possible and as low as possible.
- the bottom temperature is usually 60-100 ° C
- the top pressure is usually 1.33-26.7 kPa.
- a known polymerization inhibitor may be added.
- the polymerization inhibitor include tertiary butyl nitroxide, 2,2,6,6-tetramethyl-4-hydroxypiberidyl-l-oxyl, 2,2,6,6-tetramethylpiberidyl-l-oxyl, 2,2,6 , 6-tetramethylpiperidinoxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidinoxyl, 4,4,4,4, tris 1- (2,2,6,6 N-methyl compounds such as tetramethylpiperidinoxyl phosphite; phenol compounds such as hydroquinone, methoquinone, pyrogallol, catechol, and resorcin; phenothiazine, bis- ( ⁇ -methylbenzyl) phenothiazine, 3, 7— Phenothiazine compounds such as dioctyl phenothiazine, bis- ( ⁇ -dimethylbenzy
- cupric chloride copper acetate, copper carbonate, copper acrylate, dimethyldithiamine
- copper compounds such as copper bamate, copper getyldithiocarbamate, and copper dibutyldithiocarbamate.
- These polymerization inhibitors may be used in combination of two or more.
- the addition amount of the polymerization inhibitor to the crude acrylic acid is preferably 11,000,000 ppm.
- distillation method for example, known methods such as simple distillation and precision distillation can be adopted.
- the Distillation may be either a batch type or a continuous type, but industrially, a continuous type is preferred. Also, a known apparatus can be used for the distillation apparatus.
- a tray or packing is used for the distillation column.
- Sulza-I 'Brothers As a filler, Sulza-I 'Brothers
- Irregular packing materials such as Terralet manufactured by Nippon Steel Kakoki Co., Ltd., pole ring manufactured by BASF, cascade 'mini' ring manufactured by Mass Transfer Co., Ltd., and flex ring manufactured by JGC Co., Ltd. No. These fillers may be used in combination of two or more. Further, it may be used in combination with a conventionally used tray. Suitable combinations include a combination of an ordered packing and a tray, a combination of an irregular packing and a tray, and the like.
- a tray a bubble bell tray having a downcomer, a perforated plate tray, a valve tray, a super-flux tray, a max flat tray, a dual flow tray without a downcomer, or the like can be used.
- crude acrylic acid obtained in the above-mentioned step (4) of the gas phase catalytic oxidation method and containing 3470 ppm of maleic acids, 267 ppm of furfural and 322 ppm of benzaldehyde as main impurities was used.
- the molar phase is equal to the total number of moles of the maleic acid and the aldehyde.
- the hydrazine hydrate (2100 ppm) was added, and the mixture was passed through the tubular reactor at a total flow rate of 5000 kgZhr, a temperature of 20 ° C, and a residence time of 2 hours.
- step (B) the liquid obtained by using heat exchange was heated to 65 ° C. After completion of the heating, the obtained liquid was visually observed, and it was found that the presence of a solid reactant of the maleic acids and hydrazines formed in the step (A) could not be confirmed. As a result of analyzing the composition of the solution, it was found that maleic acids were 994 ppm, furfural 5.6 ppm, and benzaldehyde 45.4 ppm.
- the hydrazine hydrate (equivalent to the same mole number as the total number of moles of maleic acid and aldehyde) ( 540 ppm), and flowed through the tubular reactor at a temperature of 20 ° C. and a residence time of 2 hours.
- maleic anhydride was 298 ppm
- furfural was less than 1.
- Oppm and benzaldehyde was less than 1.
- the obtained liquid was supplied to a distillation column, and continuous distillation was performed under the following conditions. That is, 99% by weight of the feed liquid was continuously distilled at a bottom temperature of 74 ° C, and a part of the distillate was introduced into the column at a reflux ratio of 1.0 from the top as a reflux liquid. .
- metoquinone (polymerization inhibitor) corresponding to lOppm with respect to the amount of the feed liquid introduced into the distillation column was dissolved in the reflux liquid and introduced into the column.
- the operation was performed under the same conditions as in Example 1 except that the step (C) was not performed.
- the composition of the liquid before supply to the distillation column was analyzed by gas chromatography. The results were maleic anhydride power of 006 ppm, furfural 6.Oppm and benzaldehyde 50.Oppm.
- maleic anhydride was 188 ppm
- furfural was 5.6 ppm
- benzaldehyde was 15 ppm. .
- the obtained acrylic acid does not belong to the high-purity acrylic acid of the present invention.
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Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/019,649 US7041850B2 (en) | 2003-11-11 | 2004-12-23 | Process for producing purified (meth)acrylic acid |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2003-380582 | 2003-11-11 | ||
JP2003380582 | 2003-11-11 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/019,649 Continuation US7041850B2 (en) | 2003-11-11 | 2004-12-23 | Process for producing purified (meth)acrylic acid |
Publications (1)
Publication Number | Publication Date |
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WO2005044772A1 true WO2005044772A1 (ja) | 2005-05-19 |
Family
ID=34567243
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/JP2004/015367 WO2005044772A1 (ja) | 2003-11-11 | 2004-10-18 | 精製(メタ)アクリル酸の製造方法 |
Country Status (3)
Country | Link |
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US (1) | US7041850B2 (ja) |
CN (1) | CN100450992C (ja) |
WO (1) | WO2005044772A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110461811A (zh) * | 2017-04-04 | 2019-11-15 | 阿科玛法国公司 | 包括具有分隔壁的蒸馏塔的纯化(甲基)丙烯酸的方法 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102006036177B4 (de) | 2006-07-21 | 2013-05-08 | Evonik Degussa Gmbh | Vorrichtung und Verfahren zur Herstellung von Acrylsäure mit verminderter Autoxidationsneigung |
EP2970084B1 (en) * | 2013-03-15 | 2017-10-18 | Rohm and Haas Company | Process for purifying (meth)acrylic acid |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3725208A (en) * | 1971-08-20 | 1973-04-03 | Nippon Kayaku Kk | Process for purification of acrylic acid from aldehydes by distillation with a reagent |
JP2001253848A (ja) * | 2000-03-10 | 2001-09-18 | Nippon Shokubai Co Ltd | (メタ)アクリル酸の精製方法 |
WO2003045890A1 (en) * | 2001-10-30 | 2003-06-05 | Mitsubishi Chemical Corporation | Method for purifying (meth)acrylic acid |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5759358A (en) * | 1994-05-31 | 1998-06-02 | Rohm And Haas Company | Process for pure grade acrylic acid |
-
2004
- 2004-10-18 WO PCT/JP2004/015367 patent/WO2005044772A1/ja active Application Filing
- 2004-10-18 CN CNB2004800004168A patent/CN100450992C/zh not_active Expired - Fee Related
- 2004-12-23 US US11/019,649 patent/US7041850B2/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3725208A (en) * | 1971-08-20 | 1973-04-03 | Nippon Kayaku Kk | Process for purification of acrylic acid from aldehydes by distillation with a reagent |
JP2001253848A (ja) * | 2000-03-10 | 2001-09-18 | Nippon Shokubai Co Ltd | (メタ)アクリル酸の精製方法 |
WO2003045890A1 (en) * | 2001-10-30 | 2003-06-05 | Mitsubishi Chemical Corporation | Method for purifying (meth)acrylic acid |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110461811A (zh) * | 2017-04-04 | 2019-11-15 | 阿科玛法国公司 | 包括具有分隔壁的蒸馏塔的纯化(甲基)丙烯酸的方法 |
Also Published As
Publication number | Publication date |
---|---|
US20050187405A1 (en) | 2005-08-25 |
CN1697817A (zh) | 2005-11-16 |
US7041850B2 (en) | 2006-05-09 |
CN100450992C (zh) | 2009-01-14 |
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