WO2004022518A1 - (メタ)アクリル酸類の製造方法 - Google Patents
(メタ)アクリル酸類の製造方法 Download PDFInfo
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- WO2004022518A1 WO2004022518A1 PCT/JP2003/011205 JP0311205W WO2004022518A1 WO 2004022518 A1 WO2004022518 A1 WO 2004022518A1 JP 0311205 W JP0311205 W JP 0311205W WO 2004022518 A1 WO2004022518 A1 WO 2004022518A1
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- meth
- water
- distillation column
- distillation
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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
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/34—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances
- B01D3/36—Azeotropic distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/34—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances
- B01D3/40—Extractive distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B9/00—Cleaning hollow articles by methods or apparatus specially adapted thereto
- B08B9/08—Cleaning containers, e.g. tanks
-
- 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
- C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
-
- 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
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
- C07C51/46—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation by azeotropic distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in 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
- 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
Definitions
- the present invention relates to a method for purifying acrylic acid, methacrylic acid or an ester thereof by distillation. Specifically, the present invention relates to a method for stopping the operation of a distillation column required for separating and purifying crude acrylic acid, methacrylic acid or their esters obtained by catalytic gas phase oxidation of propylene, propane or isobutylene. Regarding the cleaning method at the start.
- acrylic acid and methacrylic acid may be collectively referred to as “(meth) acrylic acid”.
- (meth) acrylic acid and their esters may be collectively referred to as “(meth) acrylic acids”. Background art
- Distillation is a common method for separating and purifying acrylic monomers such as (meth) acrylic acids.
- acrylic monomers such as (meth) acrylic acids.
- high-performance packing has been developed for the purpose of improving the separation efficiency of distillation and increasing the throughput, and has begun to be used in distillation columns in various processes.
- (meth) acrylic acids are very easy to polymerize, and the formation of polymer in the distillation column was a major problem, both in the conventional tray-type distillation column and especially in the high-performance packed column.
- an object of the present invention is to provide a method for cleaning a distillation column for separating and purifying crude (meth) acrylic acids.
- a method is provided in which valuable substances are recovered by using substances used in processes before and after the distillation column, and the distillation column is efficiently cleaned in a short time. Is to do. Disclosure of the invention
- the obstruction in the distillation column is mainly composed of an acidic polymer obtained by polymerizing (meth) acrylic acid, and easily swells or dissolves in water.
- washing with water is effective for removing alkali components
- the gist of the present invention is to provide a method for producing purified (meth) acrylic acids by distilling (meth) acrylic acids in a distillation column, wherein the operation includes stopping and starting the distillation column.
- a method for producing a purified (meth) acrylic acid which comprises washing a column with water and then washing the column with an organic solvent and / or azeotropic distillation in the presence of the organic solvent.
- another gist of the present invention is to contain (meth) acrylic acid obtained by subjecting propylene, propane or isobutylene to gas phase contact oxidation and absorbing the oxidation reaction mixture with water.
- the aqueous solution is concentrated in the presence of an azeotropic agent, and the resulting (meth) acrylic acid is distilled in a distillation column to produce a purified (meth) acrylic acid.
- the distillation column is washed with water and then azeotropically distilled in the presence of the azeotropic agent.
- another gist of the present invention is to provide an aqueous solution containing (meth) acrylic acid obtained by subjecting propylene, propane or isobutylene to gas phase contact oxidation and absorbing the oxidation reaction mixture with water to obtain an azeotropic agent.
- the operation including stopping and starting the distillation column includes the steps of: Is washed with alkali water, washed with water, and further azeotropically distilled in the presence of the azeotropic agent in the method for producing (meth) acrylic acid.
- Figure 1 is an example of a process flow diagram for producing acrylic acid using propylene as a raw material.
- FIG. 2 is another example of a process flow chart for producing acrylic acid using propylene as a raw material.
- FIG. 3 is another example of a process flow chart for producing acrylic acid using propylene as a raw material.
- FIG. 4 is an example of a process flow chart for producing an acrylate ester.
- Figure 5 shows an example of a crude (meth) acrylic acid distillation column and its accompanying equipment. Explanation of reference numerals
- Dehydration tower B and light-boiling separation tower acetic acid separation tower
- the mixture to be distilled in the present invention is acrylic acid, methacrylic acid or their esters, that is, (meth) acrylic acids.
- propylene is subjected to gas-phase catalytic oxidation in the presence of a Mo-Bi-based composite oxide catalyst to produce acrolein, and is further subjected to gas-phase catalytic oxidation in the presence of a Mo-V-based composite oxide catalyst.
- the resulting acrylic acid can be mentioned.
- the two-stage reaction in which the first-stage reaction in which propylene is oxidized to mainly generate acrolein and the second-stage reaction in which acrolein is oxidized to mainly generate acrylic acid are performed in separate reactors, one reactor is used.
- a single-stage reaction in which a catalyst for performing the first-stage reaction and a catalyst for performing the second-stage reaction are simultaneously filled to perform the reaction may be used.
- the process for producing acrylic acid obtained by subjecting a bread pan to a Mo-V—Te-based composite oxide catalyst or a Mo—V—Sb-based composite oxide catalyst is used. Applicable. Further, an acrylic ester or a methacrylic ester obtained in a process of producing an ester thereof using (meth) acrylic acid as a raw material is exemplified.
- acrylates include methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, tertiary butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, and 2-acrylate.
- -Hydroxypropyl, methoxyethyl acrylate, and the like, and the same compounds can be exemplified for methyl acrylate.
- An aqueous solution containing (meth) acrylic acid is obtained by absorbing the reaction mixture of the gas phase catalytic oxidation with water. By concentrating the aqueous solution in the presence of an azeotropic agent such as alcohols, ketones and aromatic hydrocarbons, crude (meth) acrylic acid is obtained. It is.
- an azeotropic agent such as alcohols, ketones and aromatic hydrocarbons
- These unpurified (meth) acrylic acids include (meth) acrylic acid dimers and trimers, their esters, maleic anhydride, benzaldehyde, i3-hydroxypropionic acid,) 3-hydroxypropion Contains high boiling impurities such as acid esters, jS-alkoxypropionic acid, and 8-alkoxypropionic acid esters.
- the content of the (meth) acrylic acid fed to the distillation column is usually at least 2% by weight, preferably at least 5% by weight, more preferably at least 10% by weight, in the present invention.
- the mixed composition formed with these impurities and / or water is extremely polymerized under the temperature and pressure conditions in the column where distillation is performed.
- the distillation of (meth) acrylic acids in the present invention is usually a step (purification step) of obtaining high-purity (meth) acrylic acids, but is not limited thereto. It is also applied to the step of recovering a component rich in (meth) acrylic acids from a mixture containing acrylic acids (separation step).
- Figure 1 is an example of a process flow diagram for producing acrylic acid using propylene as a raw material.
- the symbols and numbers in the figure are as follows.
- An acrylic acid-containing gas obtained by contacting propylene and Z or acrolein with a molecular oxygen-containing gas in a gas phase is introduced into an acrylic acid collecting tower A via a line 4 and brought into contact with water to form an aqueous acrylic acid solution. obtain.
- an aqueous acrylic acid solution is supplied to the dehydration tower B.
- an azeotropic agent is supplied, an azeotropic mixture composed of water and an azeotropic agent is distilled from the top of the column, and acrylic acid containing acetic acid is obtained from the bottom of the column.
- An azeotropic mixture consisting of water and an azeotropic agent distilled off from the top of the dehydration tower is introduced into a storage tank 10, where it is separated into an organic phase mainly consisting of azeotrope 1 and an aqueous phase mainly consisting of water.
- the organic phase is circulated to dehydration tower B.
- the aqueous phase is circulated to the acrylic acid collecting tower A via the line 7 and can be effectively used by using it as collected water to be brought into contact with the acrylic acid-containing gas. Top up with water from line 8 as needed.
- the crude acrylic acid extracted from the bottom of the dehydration tower B via the line 11 is introduced into a light boiling separation column (acetic acid separation column) C in order to remove residual acetic acid.
- acetic acid is separated and removed from the top of the tower via lines 12 and 13. Since the acetic acid in line 13 contains acrylic acid, some or all may be returned to the process.
- acrylic acid substantially free of acetic acid is obtained from the bottom of the column via line 14. Since this acrylic acid has a considerably high purity, it can be used as it is as a raw material for producing an acrylate ester, and in some cases, is made into a product via a line 15.
- high-purity acrylic acid is introduced into a high-boiling separation tower (acrylic acid refining tower) D via line 16 to separate and remove high-boiling substances from line 17, and high-purity acrylic acid is supplied to lines 18 and 1. You can get it through 9.
- the high-boiling substances in line 17 are led to high-boiling decomposition reactor E, and a part of them is recovered as acrylic acid from line 20 to the process.
- High boilers are separated and removed from line 21.
- FIG. 2 is another example of a process flow chart for producing acrylic acid.
- FIG. 3 is another example of a process flow chart for producing acrylic acid.
- Acrylic acid-containing gas obtained by gas-phase oxidation of propylene and Z or acrolein using molecular oxygen-containing gas is introduced into acrylic acid collecting column A via line 4 and is brought into contact with a solvent to obtain an acrylic acid-containing solution. Get.
- the acrylic acid-containing solution is supplied to the stripping tower G.
- gas from the line 10 gas from the line 6 discharged from the top of the acrylic acid collecting tower A, or gas after oxidizing and removing organic substances in the gas in the line 6)
- Distill water and acetic acid from the top of the column and obtain acrylic acid containing solvent from the bottom of the column.
- the water and acetic acid distilled from the top of the stripping tower G are introduced into the acrylic acid collecting tower A, and the water and acetic acid are finally discharged from the acrylic acid collecting tower A.
- the line 11 from the bottom of the stripping tower G is introduced into a high-boiling separation tower (acrylic acid refining tower) D to obtain high-purity acrylic acid, and high-boiling substances are separated and removed from the line 14;
- High-purity acrylic acid can be obtained via line 19.
- the high-boiling substances in the line 14 are specifically maleic anhydride, benzaldehyde, etc., and are led to the high-boiling removal tower H. These high-boiling substances are discharged from the line 21.
- the solvent is led from the bottom of the column to a solvent recovery column K via a line 17.
- the recovered solvent is returned to the acrylic acid collecting tower A via the line 7 from the top of the tower. Further high-boiling substances are separated and removed from the bottom of the column via line 22.
- FIG. 4 is an example of a process flow chart for producing an acrylate ester.
- the symbols and numbers in the figure are as follows.
- Acrylic acid is supplied from line 31, alcohol is supplied from line 32, circulating acrylic acid is supplied from line 35, and circulating alcohol is supplied from line 48 to the esterification reactor L.
- the esterification reactor L is filled with a catalyst such as a strongly acidic ion exchange resin.
- a catalyst such as a strongly acidic ion exchange resin.
- an esterification reaction mixture consisting of the produced ester, unreacted acrylic acid, unreacted alcohol, and produced water is withdrawn and supplied to acrylic acid separation column M.
- a bottom liquid containing substantially all of the unreacted acrylic acid is withdrawn from the acrylic acid separation column M via a line 34, and supplied to the esterification reactor L as a circulating liquid via a line 35.
- a part of the bottom liquid is supplied to a high-boiling decomposition reactor N via a line 36, and valuables obtained by decomposition are circulated to a process via a line 40.
- the location in the cycled process depends on the process conditions.
- High boiling impurities such as oligomers are removed out of the system via line 37.
- From the top of the acrylic acid separation column M, the produced ester, unreacted alcohol, and produced water are distilled via line 38.
- a part of the effluent is circulated as a reflux liquid to the acrylic acid separation column M, and the remainder is supplied to the extraction column Q via the line 39.
- Water for alcohol extraction is supplied from a line 41, and water containing alcohol recovered via a line 42 is supplied to an alcohol recovery tower P. Recovered Arco Is recycled to the esterification reactor via line 48.
- the crude acrylate is supplied to the light boiling separation column R.
- Light boilers containing acrylates are extracted from line 44 and circulated into the process.
- the location in the process that is cycled depends on the process conditions.
- the crude acrylate from which light boilers have been removed is supplied to the acrylate ester product purification tower S via line 45.
- a high-purity acrylate ester is obtained via line 46 from the top of the tower.
- a liquid containing some high-boiling substances is withdrawn from the bottom of the column via a line 47 and circulated into the process.
- the location in the process that is cycled depends on the process conditions.
- Figure 5 shows an example of a crude acrylic monomer distillation column and its accompanying equipment. The numbers in the figure are as follows.
- lines 53 and 61 are installed at one or more places in various parts of the distillation depending on the conditions of the distillation column.
- the distillation column to which the present invention is applied is a distillation device in which (meth) acrylic acid is involved in the gas-liquid equilibrium, and means a device for performing operations such as separation, concentration, recovery, and purification.
- a dehydration tower B a dehydration tower B, a light-boiling separation tower (acetic acid separation tower) C, and a high-boiling separation tower (acrylic acid purification tower) D shown in FIG.
- the tower S and the distillation tower 51 shown in FIG. 5 correspond to these.
- Distillation towers include a perforated plate tower, a bubble bell tower, a packed tower, or a combination of these (for example, a combination of a perforated plate tower and a packed tower; see Fig. 5). Any of them can be used in the present invention regardless of the presence or absence.
- Specific trays include foam bell trays, perforated plate trays, bubble trays, super flash trays, max flux trays, dual trays, and the like.
- Fillers include those conventionally used, such as cylinders, cylinders, saddles, spheres, cubes, and pyramids, as well as regular or irregular shapes with special shapes as high-performance fillers in recent years. Are commercially available, and are preferably used in the present invention.
- Examples of such commercially available products include regular packings such as Sluzer Packing (manufactured by Sulza Brothers), Sumitomo Sulza Packing (manufactured by Sumitomo Heavy Industries, Ltd.), Technovac (Mitsui Bussan), and EMSI Gauze-type structured packing such as Pack (Mitsubishi Chemical Engineering), sheet type such as Merapak (Sumitomo Heavy Industries, Ltd.), Technopack (Mitsui & Co., Ltd.), and Gemipak (Mitsubishi Chemical Engineering) Grid-type structured packing such as structured packing and flexigrid (manufactured by Cork Co., Ltd.).
- Regular packings such as Sluzer Packing (manufactured by Sulza Brothers), Sumitomo Sulza Packing (manufactured by Sumitomo Heavy Industries, Ltd.), Technovac (Mitsui Bussan), and EMSI Gauze-type structured packing such as Pack (Mitsubishi Chemical Engineering), sheet
- Gem Pack made by Glitch
- Mongpak made by Monk
- Good Roll Packing manufactured by Tokyo Specialty Wire Mesh
- Honeycomb Pack made by NGK
- Impulse Packing made by Naga Taikisha
- irregular packing materials such as Raschig rings, poling (manufactured by BASF), cascade mini rings (manufactured by Mass Transfer), IMTP (manufactured by Norton), interlox saddles (manufactured by Norton), Terralet (manufactured by Nippon Steel Kakoki Co., Ltd.), flexi ring (manufactured by JGC Corporation), and others.
- a major feature of the present invention is that when the distillation column for (meth) acrylic acid is operated for a predetermined period to wash the polymer adhered and accumulated in the column, (1) after washing with water, (2) organic solvent And / or (3) azeotropic distillation in the presence of an organic solvent. (2) and Z or (3) prior to (4) Alkaline water cleaning Alkaline water washing is effective for dissolving the polymer. If water cleaning is used, it is important to add (5) a water cleaning step afterwards. Hereinafter, description will be made sequentially.
- the main purpose of the water is to wash out the (meth) acrylic acid remaining in the tower.
- Water can be supplied to the reflux tank of the distillation column, supplied to the top of the distillation column from the reflux line, or supplied directly to the distillation column from the reflux line. Water flows down to the bottom while washing the inside of the tower.
- water supplied from the top and flowing down to the column bottom can be repeatedly supplied again from the column top. In the case of repetition, it is preferable to use after separating and removing solids contained in the water flowing down by a pump strainer or the like. Along with the top feed, additional feed can be provided from the feed stage.
- a distributor liquid disperser, liquid dispersing nozzle
- the water washing may be usually performed at a temperature of 10 to 100 for 30 to 360 minutes.
- the supply amount of water depending on the degree obstruction or fouling of the tower, usually those or cross-sectional area lm 2 of the distillation column, 0. 5 ⁇ 5 m 3 / hr of about (they when used repeatedly water The integrated value of) is appropriate.
- the washing liquid thus collected at the bottom of the column contains valuables (eg, acrylic acid, acrylic acid ester) remaining in the distillation column immediately after the operation was stopped. It is stored and recirculated to an appropriate location in the process (for example, dehydration column B in Fig. 1), taking into account the composition of the washing solution after the distillation column is restarted.
- valuables eg, acrylic acid, acrylic acid ester
- Organic solvents used for washing in the tower include (meth) acrylic acids, methanol, ethanol, butanol, benzene, toluene, methyl ethyl ketone, methyl isobutyl ketone, methyl n-butyl ketone, isopropyl acetate, diphenyl ether, Examples include biphenyl or mixtures thereof.
- organic solvent of the present invention not only the high-purity solvent as described above, but also the distillation column
- Organic solvent-based materials containing various azeotropic agents obtained from the preceding and following processes can also be used efficiently.
- Acrylics (products), off-spec products collected when the plant is shut down, etc. can be used.
- the water content of the organic solvent used is preferably 2% by weight or less, more preferably 1% by weight or less.
- (meth) acrylic acid products usually have a water content of 0.2% by weight or less, so that they can be used as they are.
- the method of replacing water by washing in the tower is not particularly limited.
- the organic solvent is supplied to a reflux tank of the distillation tower, and is supplied from the reflux line to the top of the distillation tower.
- the organic solvent that has come into contact with the tower wall, packing, tray, etc. and has flowed down to the bottom while taking in water may be extracted to the recovery system. It is preferable to circulate the water. If the water content in the circulating organic solvent exceeds 2% by weight, the dehydration effect is greatly reduced, and the organic solvent is extracted out of the system.
- the washing in the tower with an organic solvent is usually selected from the range of 50 ° C or less, preferably from 0 to 40 ° C.
- the amount of the organic solvent is usually, cross-sectional area lm 2 per distillation column, 0. 5 ⁇ 5 m 3 Z hr about well, if the removal of residual water from the structure of the distillation column is difficult, as appropriate flow rate You can increase it.
- azeotropic distillation washing is performed in the presence of an organic solvent azeotropic with water in order to remove water present in the column.
- the purpose of this step is to remove water, but when a small amount of polymer remains in the column, dissolution and removal are performed simultaneously. Water is distilled off from the top of the tower, and dissolved polymer etc. is extracted from the bottom of the tower.
- Examples of usable organic solvents include alcohols such as methanol, ethanol, and butyl alcohol; ketones such as methyl ethyl ketone, methyl n-butyl ketone, and methyl isobutyl ketone; aromatic hydrocarbons such as benzene, toluene, and xylene; and The above-mentioned (meth) acrylic acids are mentioned, Can be used.
- alcohols such as methanol, ethanol, and butyl alcohol
- ketones such as methyl ethyl ketone, methyl n-butyl ketone, and methyl isobutyl ketone
- aromatic hydrocarbons such as benzene, toluene, and xylene
- the above-mentioned (meth) acrylic acids are mentioned, Can be used.
- organic solvents are fed to the feed stage or the bottom of the distillation stock solution, and are treated under distillation conditions by a heat source from a reboiler.
- a tower top temperature of 20 to 80 ° C. and a tower top pressure of 0.5 to 120 kPa are preferable.
- the water content of the organic solvent is preferably kept at 2% by weight or less, more preferably 1% by weight or less, so that the dehydration efficiency is excellent.
- washing with water is not an essential step, but it can be appropriately incorporated as a pre-step and / or a post-step of water washing since the acidic polymer can be dissolved to enhance the washing effect.
- the distillation operation will be started after the water washing step and the dehydration step.
- aqueous solutions such as potassium hydroxide, sodium hydroxide, and sodium carbonate can be used.
- concentration is usually used in the range of 1 to 25% by weight.
- Ammonia water can also be used, and the concentration is usually in the range of 1 to 25% by weight, preferably 1 to 10% by weight. If the concentration is lower than the above range, the washing efficiency is inferior. If the concentration is too high, the heat of reaction with the acid component remaining in the tower increases, and a new polymer may be formed.
- the alkaline water can be supplied to the reflux tank of the distillation column, supplied from the reflux line to the top of the distillation column, or supplied directly to the distillation column from the reflux line.
- the alkaline water swells and dissolves the polymer in the column and flows down to the bottom of the column.
- the water supplied from the top and flowing down to the bottom can be repeatedly supplied from the top again. In the case of repetition, it is preferable to use after separating and removing solids contained in the flowed down alkaline water with a strainer of a pump or the like. Along with the feed from the top, additional feed can be provided from the feed stage.
- a distributor liquid disperser, liquid dispersion nozzle
- alkaline water it is preferable to supply alkaline water via the distributor.
- Alkaline water washing is usually performed at a temperature of 10 to 100 ° C. for 30 to 360 minutes.
- the supply amount of the alkaline water depends on the degree of blockage and dirt in the tower, Usually a distillation column Sectional area lm 2 per, 0. 5 ⁇ 5 m 3 Z hr approximately (integrated value thereof when used repeatedly alkaline water) is suitable.
- the water remaining in the column by washing with an organic solvent in the column while flowing down or by azeotropic distillation in the presence of the organic solvent is usually 1% by weight or less, preferably 0.5% by weight or less, and more preferably substantially It becomes zero. After the distillation operation is resumed, on-spec distillation can be performed immediately. If water remains, it is not unusual for it to take as long as 30 hours for it to go on-suck.
- a small amount of a polymerization inhibitor can be supplied during the azeotropic distillation washing.
- polymerization inhibitors sometimes called polymerization inhibitors, polymerization inhibitors, polymerization terminators, polymerization rate lowering agents, etc.
- hydroquinone methoquinone (methoxyhydroquinone), pyrogallol, catechol.
- phenolic compounds such as resorcinol; tert-butyl dithroxide, 2,2,6,6-tetramethyl-14-hydroxypiperidyl-1-oxyl, 2,2,6,6-tetramethylpiberidyl-l-oxyl, 2,2,6,6-tetramethylpiperidinoxyl, 4-hydroxy-1,2,2,6,6-tetramethylpiveridinoxyl, 4,4 ', 4 "tris- (2,2,6,6-te N-yl xyl compounds such as phosphite; phenothiazine, bis- (h-methylpentyl) phenothiazine, 3, 7-dioctyl phenothiazine, bis Phenothiazine compounds such as (a, hi, -dimethylbenzyl) phenothiazine; cupric chloride, copper acetate, copper carbonate, copper acrylate, dimethyldithiophene, copper rubmate, diethyldi
- Distillation stock is supplied and distillation operation is resumed This distillation can be applied to both continuous and batch distillation Noh.
- the operation conditions for the distillation are appropriately determined in consideration of the type and content of impurities contained in the crude (meth) acrylic acids, and are not particularly limited.
- the reaction is performed at a tower top temperature of 20 to 80 and a tower bottom temperature of 60 to 120 ° (:, a tower top pressure of about 0.5 to 120 kPa).
- the high-boiling separation column is a stainless steel (SUS316) distillation column with an inner diameter of 110 Omm, a height of 2000 Omm, and 21 multi-hole plates as shown in Fig. 5. It is used to distill crude acrylic acid. Was done. Prior to the distillation, 1000 kg of a product acrylic acid containing 0.03% by weight of water supplied to the reflux tank 56 was supplied from the top of the column to the high boiling separation column. The supplied liquid dropped to the bottom of the tower, and the liquid collected at the bottom of the tower was discharged from the bottom of the tower. The water content of the discharged acrylic acid was 3% by weight.
- the light-boiling separation column R is a distillation column made of stainless steel (SUS 304) with an inner diameter of 1100 mm, a height of 26000 mm and 36 perforated plates (dual trays) installed inside, as shown in Fig. 5. Distillation of ethyl acrylate was performed.
- a liquid in which 5% by weight of hydroquinone was dissolved in ethanol was supplied at a rate of 60 k / hr from an ink 59 containing a polymerization inhibitor.
- Example 2 was the same as Example 2 except that the substitution in the column with ethyl acrylate was omitted. Distillation was started as in 2. Initially, ethyl acrylate obtained from the bottom of the column contained 3.1% by weight of water. The water gradually decreased, and it took about 53 hours until the water content reached 0.01% by weight. Since the distillation state of excess water was continued, the bottom pressure of the distillation column gradually increased from the start of the operation, and one month later, the operation was stopped because the bottom pressure became 82 kPa. As a result of an inspection inside the tower, a large amount of polymer was confirmed.
- the dehydration tower B is a stainless steel (SUS316L) distillation tower having an inner diameter of 400 mm, a height of 2500 mm, and 30 perforated plates, and is used for distillation of crude acrylic acid. I got it.
- SUS316L stainless steel
- toluene Prior to the distillation, toluene was supplied to the reflux tank at 500 kg / hr, and supplied to the high-boiling separation column from the top. The supplied liquid dropped to the bottom of the tower, and after a liquid level was confirmed at the bottom of the tower, a heat source was supplied. Distilled toluene and water were discharged from the top of the tower, and after about 5 hours, no water flowed out. During this time, there was no extraction from the bottom of the tower.
- the distillation column for separating and purifying (meth) acrylic acids can be easily washed.
- valuable substances can be recovered by using substances used in processes before and after the distillation column, and the distillation column can be efficiently cleaned.
- stable on-spec operation can be performed promptly.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mechanical Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
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Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR0306213-9A BR0306213A (pt) | 2002-09-03 | 2003-09-02 | Processo para produção de composto de ácido (met)acrìlico |
AU2003264366A AU2003264366A1 (en) | 2002-09-03 | 2003-09-02 | Process for producing (meth)acrylic acid compound |
ES03794184.6T ES2639166T3 (es) | 2002-09-03 | 2003-09-02 | Procedimiento para producir un compuesto de ácido (met)acrílico |
EP03794184.6A EP1535893B1 (en) | 2002-09-03 | 2003-09-02 | Process for producing (meth)acrylic acid compound |
US10/837,177 US7166741B2 (en) | 2002-09-03 | 2004-05-03 | Process for producing (meth) acrylic acid compound |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2002257275A JP3971974B2 (ja) | 2002-09-03 | 2002-09-03 | (メタ)アクリル酸類の製造方法 |
JP2002-257275 | 2002-09-03 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/837,177 Continuation US7166741B2 (en) | 2002-09-03 | 2004-05-03 | Process for producing (meth) acrylic acid compound |
Publications (1)
Publication Number | Publication Date |
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WO2004022518A1 true WO2004022518A1 (ja) | 2004-03-18 |
Family
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Family Applications (1)
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---|---|---|---|
PCT/JP2003/011205 WO2004022518A1 (ja) | 2002-09-03 | 2003-09-02 | (メタ)アクリル酸類の製造方法 |
Country Status (9)
Country | Link |
---|---|
US (1) | US7166741B2 (ja) |
EP (1) | EP1535893B1 (ja) |
JP (1) | JP3971974B2 (ja) |
CN (1) | CN1277799C (ja) |
AU (1) | AU2003264366A1 (ja) |
BR (1) | BR0306213A (ja) |
ES (1) | ES2639166T3 (ja) |
RU (1) | RU2333194C2 (ja) |
WO (1) | WO2004022518A1 (ja) |
Cited By (1)
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---|---|---|---|---|
CN111111248A (zh) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | 从制备聚烯烃催化剂的有机溶剂中回收甲苯的装置及回收方法 |
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AU2002344613A1 (en) | 2001-10-30 | 2003-06-10 | Mitsubishi Chemical Corporation | Method for purifying (meth)acrylic acid |
JP3971974B2 (ja) | 2002-09-03 | 2007-09-05 | 三菱化学株式会社 | (メタ)アクリル酸類の製造方法 |
AU2004293259A1 (en) * | 2003-11-28 | 2005-06-09 | Mitsubishi Chemical Corporation | Method of purifying (meth)acrylic acid |
JP2005247714A (ja) * | 2004-03-02 | 2005-09-15 | Mitsubishi Chemicals Corp | (メタ)アクリル酸の製造方法 |
JP2005336066A (ja) * | 2004-05-25 | 2005-12-08 | Mitsubishi Chemicals Corp | (メタ)アクロレイン又は(メタ)アクリル酸の製造方法 |
JP2005336065A (ja) * | 2004-05-25 | 2005-12-08 | Mitsubishi Chemicals Corp | (メタ)アクロレイン又は(メタ)アクリル酸の製造方法 |
JP2005336110A (ja) * | 2004-05-27 | 2005-12-08 | Mitsubishi Chemicals Corp | (メタ)アクリル酸および(メタ)アクリル酸エステルの製造方法 |
EP2017255A1 (de) * | 2007-07-19 | 2009-01-21 | Basf Se | Verfahren zur Herstellung von teritären Alkylestern der (Meth)Acrylsäure mit mindestens 4 Kohlenstoffatomen im Alkylrest |
JP5729085B2 (ja) * | 2010-03-31 | 2015-06-03 | 三菱化学株式会社 | ペンタメチレンジアミンの製造方法及びポリアミド樹脂の製造方法 |
CN102211102B (zh) * | 2010-04-02 | 2013-05-29 | 中国石油化工集团公司 | Pbt装置酯化釜的清洗方法 |
KR101496488B1 (ko) * | 2010-12-29 | 2015-02-26 | 주식회사 엘지화학 | 고순도 2-에틸헥실-아크릴레이트 생산을 위한 분리벽형 증류탑 및 이를 이용한 제조방법 |
US9815097B2 (en) | 2011-09-27 | 2017-11-14 | Rohm And Haas Company | Method for cleaning a (meth)acrylate ester process tank |
FR3012140B1 (fr) | 2013-10-18 | 2016-08-26 | Arkema France | Unite et procede pour la purification de methacrylate de methyle brut |
EP3166705B1 (de) | 2014-07-08 | 2018-08-15 | Basf Se | Kolonne mit trennwirksamen einbauten zur auftrennung eines gemisches von kohlenwasserstoffen und/oder kohlenwasserstoffderivaten durch extraktivdestillation mit einem selektiven lösungsmittel |
CN104384132A (zh) * | 2014-11-05 | 2015-03-04 | 华玉叶 | 反应器除垢的方法 |
CN111574375B (zh) * | 2020-06-22 | 2023-11-24 | 北京旭阳科技有限公司 | 丙烯酸甲酯粗产品气的分离方法及分离设备 |
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-
2002
- 2002-09-03 JP JP2002257275A patent/JP3971974B2/ja not_active Expired - Fee Related
-
2003
- 2003-09-02 BR BR0306213-9A patent/BR0306213A/pt not_active Application Discontinuation
- 2003-09-02 EP EP03794184.6A patent/EP1535893B1/en not_active Expired - Lifetime
- 2003-09-02 RU RU2004119837/04A patent/RU2333194C2/ru active
- 2003-09-02 CN CNB038014653A patent/CN1277799C/zh not_active Expired - Lifetime
- 2003-09-02 AU AU2003264366A patent/AU2003264366A1/en not_active Abandoned
- 2003-09-02 ES ES03794184.6T patent/ES2639166T3/es not_active Expired - Lifetime
- 2003-09-02 WO PCT/JP2003/011205 patent/WO2004022518A1/ja active Application Filing
-
2004
- 2004-05-03 US US10/837,177 patent/US7166741B2/en not_active Expired - Lifetime
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US5728272A (en) * | 1995-09-28 | 1998-03-17 | Basf Aktiengesellschaft | Separation by rectification of unsaturated carboxylic acids from solvents |
EP1033359A2 (en) * | 1999-03-02 | 2000-09-06 | Nippon Shokubai Co., Ltd. | Method for production of (methyl)acrylic acid and/or (methyl)acrylic esters |
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Also Published As
Publication number | Publication date |
---|---|
JP3971974B2 (ja) | 2007-09-05 |
EP1535893B1 (en) | 2017-06-14 |
ES2639166T3 (es) | 2017-10-25 |
EP1535893A4 (en) | 2006-06-21 |
BR0306213A (pt) | 2004-08-24 |
US20050059838A1 (en) | 2005-03-17 |
US7166741B2 (en) | 2007-01-23 |
RU2004119837A (ru) | 2006-02-27 |
EP1535893A1 (en) | 2005-06-01 |
CN1277799C (zh) | 2006-10-04 |
JP2004091424A (ja) | 2004-03-25 |
RU2333194C2 (ru) | 2008-09-10 |
CN1622930A (zh) | 2005-06-01 |
AU2003264366A1 (en) | 2004-03-29 |
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