WO2002051784A1 - Procede de preparation d'acide acrylique - Google Patents

Procede de preparation d'acide acrylique Download PDF

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Publication number
WO2002051784A1
WO2002051784A1 PCT/EP2001/015207 EP0115207W WO02051784A1 WO 2002051784 A1 WO2002051784 A1 WO 2002051784A1 EP 0115207 W EP0115207 W EP 0115207W WO 02051784 A1 WO02051784 A1 WO 02051784A1
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Prior art keywords
acrylic acid
tert
butyl
column
weight
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PCT/EP2001/015207
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German (de)
English (en)
Inventor
Ulrich Hammon
Gerhard Nestler
Jürgen Schröder
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Basf Aktiengesellschaft
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Publication of WO2002051784A1 publication Critical patent/WO2002051784A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
    • 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
    • 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 invention describes a process for the production of acrylic acid, by heterogeneously catalyzed gas phase partial oxidation of at least one C 3 precursor with molecular oxygen, the resulting product gas mixture containing acrylic acid being cooled and subsequently subjected to either a fractional condensation or a rectification process.
  • Acrylic acid is a valuable monomer because of its acid function and the very reactive double bond, e.g. is used in the production of acrylic acid esters, superabsorbents or polymer dispersions, which are used, for example, as adhesives or paint dispersions.
  • acrylic acid is obtainable by heterogeneously catalyzed gas phase partial oxidation of C 3 precursors of acrylic acid with molecular oxygen on catalysts in the solid state at elevated temperature.
  • C 3 precursor of acrylic acid summarizes those chemical compounds which are formally obtainable by reducing acrylic acid.
  • Known C 3 precursors of acrylic acid are, for example, propane, propene and acrolein. Compounds such as propionaldehyde or propionic acid are also among the C 3 precursors.
  • the heterogeneously catalyzed gas phase partial oxidation with molecular oxygen is at least partially an oxidative dehydrogenation.
  • inert gases such as nitrogen, carbon monoxide, carbon dioxide and / or water vapor
  • DE-OS 2 241 714 Absorption of acrylic acid in high-boiling solvents is described, for example, in DE-OS 2 241 714 and DE-Al 43 08 087.
  • DE-OS 2 241 714 describes the use of esters of aliphatic or aromatic mono- or dicarboxylic acids which have a melting point below 30 ° C and a boiling point at normal pressure above 160 ° C.
  • DE-Al 43 08 087 recommends the use of a high-boiling mixture of 0.1 to 25% by weight of ortho-dimethylphthalate based on a mixture consisting of 70 to 75% by weight of diphenyl ether for the separation of acrylic acid from reaction gases of catalytic oxidation by countercurrent absorption and 25 to 30% by weight diphenyl.
  • the processes consist essentially in that the acrylic acid contained in the reaction gas mixture and the condensable by-products are largely absorbed in the solvent or solvent mixture, for which purpose countercurrent absorption is preferably used, followed by the low-boiling components, e.g. low-boiling aldehydes, such as acetaldehyde, propionaldehyde or acrolein, acetone, acetic acid or propionic acid, are partially stripped, for which purpose countercurrent desorption is preferably used, and finally the acrylic acid is separated off from the solvent by distillation.
  • the low-boiling components e.g. low-boiling aldehydes, such as acetaldehyde, propionaldehyde or acrolein, acetone, acetic acid or propionic acid
  • Phenothiazine is recommended as a stabilizer in the above applications.
  • a disadvantage of the processes described is that when the acrylic acid is separated off, polymer formation occurs, which severely limits the running time of the separation devices, that is to say columns and evaporators, by the formation of deposits.
  • EP-A 1 041 062 attempts to prevent the formation of polymer during purification by distillation in that the mixture to be cleaned, acrylic acid-containing mixture, contains not more than 2000 ppm, based on acrylic acid, of C - C 4 aldehydes and acetone ,
  • N-oxyl compounds e.g. 4-hydroxy-2, 2,6, 6-tetramethyl-piperidine-N-oxyl, 4-oxo-2, 2,6, 6-tetramethyl-piperidine-N- oxyl, 4-acetoxy-2, 2,6, 6-tetramethyl-piperidine-N-oxyl, 2,2,6, 6-tetramethyl-piperidine-N-oxyl, 4,4 ', 4' 'tris (2,2,6, 6-tetramethyl-piperidine-N-oxyl) phosphite, 3-oxo-2, 2, 5, 5-tetramethyl-pyrrolidine-N-oxyl), aromatic amines (e.g.
  • Phenols e.g. hydroquinone or hydroquinone monomethyl ether
  • the object was achieved by a process for the production of acrylic acid, by heterogeneously catalyzed gas phase partial oxidation of at least one C 3 precursor with molecular oxygen, the resulting product gas mixture containing acrylic acid being subsequently cooled, either subjected to a fractional condensation or a rectification process , if phenothiazine and at least one phenolic compound are introduced into the column head or in the area of the column head of the rectification or condensation column (s)
  • the product gas mixture is obtainable in a manner known per se by heterogeneously catalyzed gas phase partial oxidation of at least one C 3 precursor of acrylic acid with molecular oxygen at elevated temperature.
  • the starting gas is generally diluted with gases which are inert under the selected reaction conditions, such as nitrogen (N), C0, saturated C 1 -C 6 -hydrocarbons and / or water vapor, and mixed with molecular oxygen (0 2 ) or an oxygen-containing gas at elevated temperatures (usually 200 to 450 ° C.) and, if appropriate, increased pressure, passed over solid, transition-metallic (containing Mo and V or Mo, W, Bi and Fe) mixed oxide catalysts and converted oxidatively into the acrylic acid ,
  • gases which are inert under the selected reaction conditions, such as nitrogen (N), C0, saturated C 1 -C 6 -hydrocarbons and / or water vapor, and mixed with molecular oxygen (0 2 ) or an oxygen-containing gas at elevated temperatures (usually 200 to 450 ° C.) and, if appropriate, increased pressure, passed over solid, transition-metallic (containing Mo and V or Mo, W, Bi and Fe) mixed oxide catalysts and converted oxidatively into the acrylic acid ,
  • the product gas mixture used according to the invention is preferably obtained from the partial oxidation of propane or propene and / or acrolein.
  • the hot product gas mixture generally has a temperature between 200 and 400 ° C. and can be cooled to a temperature between 100 and 180 ° C. in a manner known per se.
  • the cooling can take place partially or completely indirectly, for example with tube bundle or plate heat exchangers with a suitable cooling medium, but mainly takes place as a rule by direct cooling with a high-boiling liquid in a quench, which may be preceded by a pre-quench.
  • the temperature of the quench liquid is usually 70 to 200 ° C, often 100 to 150 ° C.
  • Suitable cooling media in heat exchangers for indirect cooling or for recooling the quench liquid are air in the case of corresponding air coolers and cooling liquids, in particular water, in the other cooling devices.
  • a high-boiling liquid can at least partially be a rectification process sequence, optionally after distillation, containing high-boiling substances (see below) or an absorbent known per se for separating acrylic acid from the product gas mixture.
  • the latter can be, for example, tri (n-butyl) phosphate (US Pat. No.
  • High-boiling here means boiling higher than acrylic acid, ie boiling higher than 141 ° C under normal pressure, preferably boiling at least at 151 ° C under normal pressure.
  • the acrylic acid-containing liquid thus obtained is rectified, that is to say fed to a rectification process which consists of at least one rectification column.
  • the acrylic acid contained in the liquid is essentially separated as a medium boiler from higher and lower boiling components.
  • the higher-boiling components essentially comprise the high-boiling liquid mentioned above, as well as the components which have a boiling point above the medium boilers at normal pressure, for example above 151 ° C. and in particular above 141 ° C.
  • These can include polymeric acrylic acid, Michael addition products of acrylic acid, such as di-, tri- and tetraacrylic acid, etc., higher mono- and dicar- be bonic acids and their anhydrides and stabilizers, and of course also incompletely separated, lower-boiling components.
  • the lower-boiling components essentially comprise those components which have a boiling point below the medium boiler fraction at normal pressure, for example in the temperature interval from about 30 to 120 ° C., in particular 30 to 131 ° C.
  • This low boiler fraction can partly be returned to the top of the column and partly but also completely removed. It usually consists of
  • the non-condensable constituents of the product gas mixture i.e. those with a boiling point at normal pressure below approx. 30 ° C. and, for example, those which are stripped out by the gaseous constituents, for example nitrogen, oxygen, propane, propene or carbon monoxide, carbon dioxide etc. discharged at the top of the column or via a quench system or, if appropriate after purification, at least partly recycled as cycle gas into the gas phase oxidation if they have not already been substantially removed in the absorption step (see above).
  • the temperature in the bottom of the column is typically 90 to 130 ° C., the top temperature depends on the type of discharge of the low boilers. If this separation takes place via a side draw, it is normally 15 to 70 ° C, often 20 to 50 ° C. If the separation takes place via a quench, e.g. can be operated with acid water, it is usually 50 - 90 ° C, preferably 60 - 80 ° C.
  • the withdrawal temperature of the crude acrylic acid in the side hood is usually 80 to 110 ° C.
  • the return temperature of the acid water to the column is usually 25 to 35 ° C.
  • the rectification column which in this case is operated as fractional condensation, as described for example in the German application with the file number 100 53 086.9 or DE-A 197 40 253, is operated, for example, at a pressure between 500 and 1200 hPa, preferably between 800 and 1100 hPa and particularly preferably at atmospheric pressure.
  • the isolation of the acrylic acid by distillation is preferably carried out as follows:
  • Acrylic acid is generally contained in the feed to 5 to 30% by weight, preferably to 10 to 20% by weight.
  • columns with separating internals are suitable as rectification columns.
  • Column internals are all common internals, in particular trays, packings and / or packing. Of the trays, bubble trays, sieve trays, valve trays, Thormann trays and / or dual-flow trays or any combination thereof are preferred.
  • the rectification is preferably carried out in a tray column with, for example, 25 to 50 trays, preferably with 30 to 40 trays, with external circulation evaporators, the feed generally being in the lower quarter of the column.
  • the acrylic acid is discharged in liquid form via a side draw in the upper half of the column.
  • the low boilers still present e.g. water, acetic acid
  • the low boilers are separated in gaseous form via the top of the column and condensed, whereby part of the condensate can be returned to the column as reflux.
  • the acrylic acid is preferably removed by distillation under reduced pressure. It is expedient to work at a head pressure of at most 500 hPa, usually at 10-200 hPa, preferably at 10-100 hPa.
  • the associated temperatures in the bottom of the column are generally 100-230 ° C and 30-80 ° C at the top of the column.
  • an oxygen-containing gas preferably air
  • a rectification column can be flowed through the rectification column.
  • the crude acrylic acid taken off as a medium boiler fraction which essentially comprises the components which, at normal pressure, have a boiling point in the temperature interval, for example from 120 to 160 ° C., in particular in the range of +/- 10 ° C. around that of the product of value
  • Acrylic acid ie about 131 to 151 ° C.
  • Such crude acrylic acid taken off as a middle boiler, usually also contains acrylic acid
  • low molecular weight carbonyl compounds such as e.g. Furfural, formaldehyde, acrolein, acetaldehyde, propionaldehyde, acetone
  • the crystallization is generally carried out without the addition of a solvent, in particular without the addition of an organic solvent.
  • the crystallization method to be used is not limited.
  • the crystallization can be carried out continuously or discontinuously, in one or more stages up to almost any degree of purity.
  • water can be added to the crude acrylic acid to be crystallized before crystallization (based on the amount of acrylic acid contained up to 10% by weight or more, preferably up to 5% by weight).
  • Such an addition facilitates the separation of lower carboxylic acid contained as a by-product in the crude acrylic acid, e.g. Acetic acid, because it is incorporated to a lesser extent in the acrylic acid crystals in the presence of water.
  • the presence of water reduces the tendency to crust in the crystallizer.
  • the pure acrylic acid obtained in this way generally contains significantly less of the impurities specified above for the crude acrylic acid, for example up to a total of 2000 ppm by weight.
  • the column is stabilized by adding a stabilizer solution in a suitable solvent in the area of the column top This includes the addition of the stabilizer solution into the reflux mentioned or directly into the column.
  • the stream provided with stabilizer solution or the direct feed of the stabilizer solution into the column in the area of the column head is fed, which for example comprises the area of the upper quarter of the separation stages, preferably the upper 20% and particularly preferably the upper 15%.
  • the area of the column head can also mean a cooling device, for example quench or condenser, for cooling the low boilers, into which stabilizer solution can likewise be metered in, and of course also the column head itself.
  • the stabilizer solution can be added at one point or at several points in the area of the column top, it being possible for the composition of the stabilizer solution supplied at the various points in the column to be the same or different.
  • Stabilizers are understood to be those compounds which delay and / or inhibit the polymerization of acrylic acid or methacrylic acid. These can be inhibitors, for example.
  • the stabilization takes place according to the invention with phenothiazine and at least one phenolic component.
  • the phenolic component can e.g. an alkyl phenol, for example 2-tert-butyl-4-methylphenol, 6-tert-butyl-2, 4-dimethyl-phenol, 2, 6-di-tert. -Butyl-4-methylphenol, 2-methylhydroquinone or 2, 2 '-methylene-bis- (6-tert-butyl-4-methylphenol) to a hydroxyphenol, for example hydroquinone, pyrocatechol or benzoquinone an aminophenol, such as para-aminophenol, a nitrosophenol, such as para-nitrosophenol, or a methoxyphenol, for example 4-methoxyphenol, mono- or di-tert-butyl-4-methoxyphenol. Methoxyphenol (hydroquinone monomethyl ether) used.
  • an alkyl phenol for example 2-tert-butyl-4-methylphenol, 6-tert-butyl-2, 4-dimethyl-phenol, 2, 6-di-tert. -Butyl
  • butylphenol nonylphenol [11066-49-2], Octylphenol [140-66-9], 2, 6-dimethylphenol, bisphenol A, bisphenol F, bisphenol B, bisphenol S, bisphenol C, 3,3 ', 5, 5'-tetrabromo-bisphenol A, 3, 5 -Di-tert-butyl-4-hydroxyanisole, Koresin® from BASF AG, 3, 5-di-tert-butyl-4-hydroxybenzoic acid methyl ester, 4-tert-butylpyrocatechol, 2-hydroxybenzyl alcohol,
  • 1,1,4-Tris (5'-butyl-4'-hydroxy-2'-methylphen-1'-yl) utane, 2-methoxyphenol (guaiacol, pyrocatechol onomethyl ether), 2-ethoxyphenol , 2-isopropoxyphenol, 4-ethoxyphenol, 4-butoxyphenol, hydroquinone monobenzyl ether, p-phenoxyphenol, 4,4'-oxydiphenyl, 3, 4-methylenedioxydiphenol (sesamol), 3, 4-dimethylp ⁇ enol,
  • Phenothiazine and the phenolic component can be metered in together in a mixture or separately, preferably as solutions.
  • the amount of stabilizer is chosen so that the phenothiazine concentration in the isolated acrylic acid 50-1000 ppm by weight, preferably 100-600 ppm by weight, and the concentration of the phenolic component 10-1000 ppm by weight, preferably 50-500 Ppm by weight.
  • Suitable solvents are both components that are contained in the system and components that are external to the system, preferably components that are contained in the system.
  • the stabilizers can be dissolved in acrylic acid, water, aqueous acrylic acid solution or the acid water obtained, preferably in acrylic acid or acid water.
  • the concentration of the solution for phenothiazine is 0.1-1% by weight and for the phenolic components 0.01-1% by weight in a suitable solvent.
  • At least one metal salt can also be added as a stabilizer.
  • This can include, for example, a manganese, cerium or copper salt, preferably manganese acetate, cerium acetate, copper acetate, copper dimethyldithiocarbamate, copper diethyldithiocarbamate, copper di-butyldithiocarbamate and / or copper salicylate.
  • Manganese acetate is particularly preferred.
  • Nickel and chromium salts are also suitable as metal salts.
  • Suitable anions of the metal salts are acetates, dithiocarbamates and salicylates and also the sulfates of the metals mentioned.
  • the metal salt can be dissolved in a suitable one of the abovementioned solvents and metered in together with or separately from in the region of the column top.
  • the metal salt can be added at any point in the entire column, for example below the withdrawal of the acrylic acid and / or at the top of the column.
  • the metal salt is generally added in an amount of 0.5 to 30% by weight, based on the amount of phenothiazine added, preferably 1 to 20% by weight, particularly preferably 1 to 10% by weight.
  • the metal salt is added in a suitable solvent, preferably in water, acid water, aqueous acrylic acid or acrylic acid.
  • a suitable solvent preferably in water, acid water, aqueous acrylic acid or acrylic acid.
  • concentration in the solution is usually 0.01 to 0.5% by weight, preferably 0.05 to 0.1% by weight.
  • N-oxyl compounds i.e. those compounds which have at least one> N-0 group, e.g. the N-oxyl compounds mentioned at the beginning. This means that no N-oxyl compounds are detectable in the rectification column.
  • the reaction gas mixture which is cooled and contains acrylic acid is subjected to an absorption process with the high-boiling liquid.
  • This absorption process can take place both in cocurrent and in countercurrent, preferably in countercurrent.
  • Thormann, valve or sieve trays, with ordered or unordered packings and / or fillings, venturi washers or film washers, bottom columns are preferably used.
  • the absorption process is generally carried out at a top temperature of 15 to 50 ° C and a bottom temperature of 120 to 180 ° C. Since non-condensable constituents are removed overhead in the absorption process, they no longer enter the subsequent rectification process, so that they do not occur there or only to a small extent.
  • the liquid discharge of the absorption process containing acrylic acid is additionally subjected to a desorption process in which low boilers, such as low-boiling aldehydes, such as acetaldehyde, propionaldehyde or acrolein, acetone, acetic acid or propionic acid, are at least partially separated off.
  • low boilers such as low-boiling aldehydes, such as acetaldehyde, propionaldehyde or acrolein, acetone, acetic acid or propionic acid
  • the acrylic acid-containing solution is treated with a gas in cocurrent or countercurrent, preferably in countercurrent to desorb the low boilers.
  • a gas which is inert under the reaction conditions can be used as the gas.
  • Desorption can be carried out both in the presence and in the absence of oxygen (0). If they are carried out in the presence of oxygen, an oxygen-containing gas can be used, in which the oxygen may be mixed with an inert gas such as carbon dioxide (CO 2 ), nitrogen (N) or noble gases, such as helium or argon, or mixtures thereof is diluted. Nitrogen is preferably used for dilution.
  • the oxygen content of the oxygen-containing gas can be between 1 and 100 vol%, preferably between 2 and 80 vol%, particularly preferably between 5 and 50 vol% and in particular between 10 and 30 vol%.
  • air is used as the oxygen-containing gas.
  • any of the inert gases listed above can be used individually or in a mixture, but the process is preferably carried out in the presence of an oxygen-containing gas.
  • the apparatuses known per se are suitable for such a desorption process, as described, for example, in Ulimann's Encyclopedia of Industrial Chemistry (6 th ed, 1999 Electronic Release. Chapter: Absorption), for example columns with bell, Thorman, valve or sieve trays, with ordered or unordered packings and / or fillings, venturi washers, film washers, Stripping or flash devices, preferably column columns, stripping or flash devices are used.
  • a high-boiling substance sequence of the rectification process e.g. the high boilers, subjected to a reclassification.
  • the high boilers separated off in the rectification process are subjected to thermal and / or catalytic cleavage, as described, for example, in US Pat. No. 4,317,926, DE-C2 240 72 36 and US Pat. No. 3,086,046 and WO 00/53560, the oligomeric acrylic acids being known Be split into acrylic acid.
  • the cleavage products are advantageously returned to the rectification process.
  • Oligomeric acrylic acids are Michael adducts of acrylic acid, optionally several times, on themselves and not by free-radical polymerization resulting acrylic acid polymers.
  • Polymers are formed by an essentially radical polymerization with the formation of carbon-carbon linkages. As a rule, these products cannot be split back.
  • the products cleaved in such a cleavage can be introduced at any point in the process according to the invention, preferably into the rectification process, particularly preferably there together with the feed into the rectification column.
  • acidic catalysts include, for example, sulfuric acid, organic sulfonic acids, such as para-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, xylenesulfonic acid or dodecylbenzenesulfonic acid, acidic ion exchangers or acidic metal oxides are suitable.
  • the temperature in the cleavage is generally 100 to 220 ° C, preferably 120 to 200 ° C, particularly preferably 140 to 180 ° C and in particular 150 to 180 ° C.
  • the removal of the low boilers can be supported by passing a gas stream (stripping) which is essentially inert under the reaction conditions, such as nitrogen, water vapor, but also an oxygen-containing gas, such as air.
  • a gas stream which is essentially inert under the reaction conditions, such as nitrogen, water vapor, but also an oxygen-containing gas, such as air.
  • the remaining residue can, for example, be partially discharged, distilled or subjected to a further cleavage.
  • a high-boiling substance in particular a run of the rectification process containing one of the abovementioned absorbents, is subjected to a distillation.
  • This process is particularly preferably subjected to a distillation as described in the simultaneous application with the German file number 100 64 642.5 and the title "Process for the Production of (Meth) Acrylic Acid” from BASF AG with the same filing date as the present application ,
  • the outflow is passed into a distillation apparatus and a low-boiler stream is removed from it in gaseous form, which stream may contain, in addition to acrylic acid and / or the absorbent present, further components such as, for example, diacrylic acid or stabilizer.
  • This low-boiling stream can, if appropriate after condensation and possibly further cooling, be fed to the work-up process at any point, for example the quench, absorption or rectification process, preferably the quench or absorption process, particularly preferably the absorption process.
  • Suitable distillation apparatus are all distillation apparatus known to the person skilled in the art, e.g. Circulation evaporator, thin film evaporator, falling film evaporator, wiper blade evaporator, if necessary, each with attached rectification columns and stripping columns.
  • a stripping current can also be applied, e.g. with nitrogen or an oxygen-containing gas, preferably with air.
  • the distillation apparatus can be operated at temperatures between 80 and 350 ° C, preferably between 100 and 280 ° C, particularly preferably between 120 and 200 ° C and in particular between 130 and 200 ° C and independently at pressures between 5 and 2000 hPa, preferably between 5 and 1200 hPa, particularly preferably between 20 and 500 hPa, very particularly preferably between 50 and 400 hPa and in particular between 50 and 300 hPa.
  • the stabilizers listed in Table 1 were dissolved in stabilizer-free acrylic acid (2 x distilled) and 20 ml of the solution were stored at 120 ° C. in air in a sealed 50 ml test vessel which was completely immersed in a heating bath. The time until the onset of polymerization (induction period) was determined.
  • MEHQ hydroquinone monomethyl ether
  • Example 2 A catalytic gas phase oxidation of propene or acrolein according to DE-A 43 02 991 produced a reaction mixture containing acrylic acid. 2.2 Nm3 / h of this reaction mixture were obtained in a gas cooler (quench) by injecting a coolant mixture which had been taken from the bottom of the rectification column (see below) from 58.8% by weight diphenyl ether, 21.2% by weight Diphenyl and 20 wt .-% o-dimethylphthalate cooled to 170 ° C.
  • a gas cooler quench
  • reaction gases cooled to 170 ° C.
  • 3 l / h was also composed of 58.8% by weight of diphenyl ether, 21.2% by weight of diphenyl and 20% by weight .-% o-Dimethylphthalat composite, applied to the column head at a temperature of 45 ° C, exposed to absorbent.
  • the outlet of the absorption column was indirectly heated to 105 ° C. in a heat exchanger and placed on the top of a desorption column which was designed as a bubble tray column with 20 trays.
  • the rectification column was operated at a bottom temperature of 160 ° C. and a bottom pressure of 130 mbar and a top pressure of 80 mbar. Between the fifteenth and sixteenth trays (counted from the evaporator), 1500 ml of liquid acrylic acid were removed continuously in a purity of 99.7% by weight per side draw, with 970 ml / h of the acrylic acid discharged again immediately below the side draw were fed.
  • the vaporous top product was condensed (600 ml / h), mixed with 100 ml / h of a solution of phenothiazine (5 g / 1) and hydroquinone monomethyl ether (2 g / 1) in acrylic acid and again up to 60 ml / h above the top of the column returned to the rectification column.
  • the operating time of the rectification column was at least 700 hours.
  • the evaporator was only slightly occupied.
  • Example 3 (comparison) The procedure was as in Example 2. The stabilization was carried out with 100 ml / h of a solution of 7 g / l phenothiazine in acrylic acid. The distillation had to be stopped after 400 hours of operation due to the formation of polymer in the rope and strong fouling in the stripping section of the column. The evaporator was very busy.
  • Example 2 The procedure was as in Example 2. The stabilization was carried out with 100 ml / h of a solution of 5 g / 1 phenothiazine, 1 g / 1 hydroquinone monomethyl ether and 1 g / 1 4-hydroxy-2, 2, 6, 6-tetramethylpiperidine-N-oxyl in acrylic acid.
  • Example 2 The procedure was as in Example 2. The stabilization was carried out with 100 ml / h of a solution of 6 g / 1 phenothiazine and 1 g / 1 4-hydroxy-2, 2, 6, 6-tetramethylpiperidine-N-oxyl in acrylic acid. The distillation had to be stopped after about 450 hours of operation due to polymer formation in the rectifying section and the formation of a black coating in the stripping section of the column. The evaporator was very busy.
  • Example 2 The procedure was as in Example 2. The stabilization was carried out with 100 ml / h of a solution of 5 g / 1 phenothiazine, 2 g / 1 hydroquinone monomethyl ether and 0.1 g / 1 manganese diacetate (2% based on phenothiazine) in acrylic acid.
  • Example 7 The procedure was as in Example 2, but 2000 ppm of acetone were added to the feed to the rectification column.

Abstract

La présente invention concerne un procédé permettant la préparation d'acide acrylique, par oxydation partielle catalytique hétérogène en phase gazeuse d'au moins un précurseur en C3 Avec de l'oxygène moléculaire. Selon l'invention, le mélange gazeux contenant de l'acide acrylique formé est refroidit et est ensuite soumis soit à une condensation de fractionnement, soit à un processus de rectification, de la phénothiazine et au moins un composé phénolique étant introduits dans la tête de colonne ou aux environs de la tête de colonne de la/des colonne(s) de rectification ou de condensation.
PCT/EP2001/015207 2000-12-22 2001-12-21 Procede de preparation d'acide acrylique WO2002051784A1 (fr)

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Application Number Priority Date Filing Date Title
DE2000164641 DE10064641A1 (de) 2000-12-22 2000-12-22 Verfahren zur Herstellung von Acrylsäure
DE10064641.7 2000-12-22

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PCT/EP2001/015207 WO2002051784A1 (fr) 2000-12-22 2001-12-21 Procede de preparation d'acide acrylique

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114409500A (zh) * 2022-01-25 2022-04-29 福建钰融科技有限公司 一种从电子废液中回收丙二醇甲醚和丙二醇单甲醚醋酸酯的方法
WO2024011191A1 (fr) * 2022-07-08 2024-01-11 Ecolab Usa Inc. Compositions d'agent antisalissure synergiques et leurs procédés d'utilisation

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MY135762A (en) 2002-01-09 2008-06-30 Basf Ag Method for producing acrylic acid
JP4440518B2 (ja) 2002-07-16 2010-03-24 株式会社日本触媒 アクリル酸の製造方法

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4021310A (en) * 1972-12-22 1977-05-03 Nippon Shokubai Kagaku Kogyo Co., Ltd. Method for inhibiting the polymerization of acrylic acid or its esters
US4061545A (en) * 1976-02-19 1977-12-06 Cosden Technology, Inc. Polymerization inhibitor for vinyl aromatic compounds
US4177110A (en) * 1978-07-18 1979-12-04 Cosden Technology, Inc. Method for the distillation of vinyl aromatic compounds using polymerization inhibitors with low-volatility
EP0188775A1 (fr) * 1985-01-11 1986-07-30 Röhm Gmbh Procédé de récupération de l'acide méthacrylique anhydre
JPH06211735A (ja) * 1993-01-21 1994-08-02 Nippon Shokubai Co Ltd （メタ）アクリル酸の重合防止方法
US5426221A (en) * 1993-03-13 1995-06-20 Basf Aktiengesellschaft Separation of acrylic acid from the reaction gases from the catalytic oxidation of propylene and/or acrolein
GB2285046A (en) * 1993-12-24 1995-06-28 Sumitomo Chemical Co Purifying acrylic acid
GB2285983A (en) * 1994-01-25 1995-08-02 Sumitomo Chemical Co Inhibiting polymerization of vinyl compounds
EP0855376A1 (fr) * 1995-10-02 1998-07-29 Idemitsu Petrochemical Co., Ltd. Procede pour inhiber la polymerisation de composes vinyliques
EP1162192A2 (fr) * 2000-06-06 2001-12-12 Nippon Shokubai Co., Ltd. Procédé d'inhibition de la polymérisation de monomères oléfiniques et leur préparation

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4021310A (en) * 1972-12-22 1977-05-03 Nippon Shokubai Kagaku Kogyo Co., Ltd. Method for inhibiting the polymerization of acrylic acid or its esters
US4061545A (en) * 1976-02-19 1977-12-06 Cosden Technology, Inc. Polymerization inhibitor for vinyl aromatic compounds
US4177110A (en) * 1978-07-18 1979-12-04 Cosden Technology, Inc. Method for the distillation of vinyl aromatic compounds using polymerization inhibitors with low-volatility
EP0188775A1 (fr) * 1985-01-11 1986-07-30 Röhm Gmbh Procédé de récupération de l'acide méthacrylique anhydre
JPH06211735A (ja) * 1993-01-21 1994-08-02 Nippon Shokubai Co Ltd （メタ）アクリル酸の重合防止方法
US5426221A (en) * 1993-03-13 1995-06-20 Basf Aktiengesellschaft Separation of acrylic acid from the reaction gases from the catalytic oxidation of propylene and/or acrolein
GB2285046A (en) * 1993-12-24 1995-06-28 Sumitomo Chemical Co Purifying acrylic acid
GB2285983A (en) * 1994-01-25 1995-08-02 Sumitomo Chemical Co Inhibiting polymerization of vinyl compounds
EP0855376A1 (fr) * 1995-10-02 1998-07-29 Idemitsu Petrochemical Co., Ltd. Procede pour inhiber la polymerisation de composes vinyliques
EP1162192A2 (fr) * 2000-06-06 2001-12-12 Nippon Shokubai Co., Ltd. Procédé d'inhibition de la polymérisation de monomères oléfiniques et leur préparation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 199435, Derwent World Patents Index; Class A41, AN 1994-283299, XP002195553 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114409500A (zh) * 2022-01-25 2022-04-29 福建钰融科技有限公司 一种从电子废液中回收丙二醇甲醚和丙二醇单甲醚醋酸酯的方法
CN114409500B (zh) * 2022-01-25 2024-03-15 福建钰融科技有限公司 一种从电子废液中回收丙二醇甲醚和丙二醇单甲醚醋酸酯的方法
WO2024011191A1 (fr) * 2022-07-08 2024-01-11 Ecolab Usa Inc. Compositions d'agent antisalissure synergiques et leurs procédés d'utilisation

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