WO2003095411A1 - Procede pour produire de l'acide acrylique et/ou des esters de celui-ci et de l'acide propionique et/ou des esters de celui-ci sous forme de compose - Google Patents

Procede pour produire de l'acide acrylique et/ou des esters de celui-ci et de l'acide propionique et/ou des esters de celui-ci sous forme de compose Download PDF

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Publication number
WO2003095411A1
WO2003095411A1 PCT/EP2003/004710 EP0304710W WO03095411A1 WO 2003095411 A1 WO2003095411 A1 WO 2003095411A1 EP 0304710 W EP0304710 W EP 0304710W WO 03095411 A1 WO03095411 A1 WO 03095411A1
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WIPO (PCT)
Prior art keywords
acrylic acid
weight
acid
column
ppm
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PCT/EP2003/004710
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German (de)
English (en)
Inventor
Christoph Adami
Ralf Böhling
Otto Machhammer
Peter Zehner
Claus Hechler
Volker Schliephake
Joachim Thiel
Original Assignee
Basf Aktiengesellschaft
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Publication date
Priority claimed from DE2002120752 external-priority patent/DE10220752A1/de
Priority claimed from DE2002124341 external-priority patent/DE10224341A1/de
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to AU2003224144A priority Critical patent/AU2003224144A1/en
Publication of WO2003095411A1 publication Critical patent/WO2003095411A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
    • C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds

Definitions

  • the present invention relates to a process for the preparation of acrylic acid and / or its esters and of propionic acid and / or their esters in combination.
  • Acrylic acid either by itself or in the form of its salts or its esters, is particularly important for the preparation of polymers for a wide variety of applications (e.g. adhesives, superabsorbents, binders).
  • Acrylic acid esters can be obtained by direct esterification of acrylic acid with the corresponding alcohol, e.g. Alkanol available.
  • Propionic acid is e.g. used in the form of their Ca or Na salts for the preservation of feed and food or used as a starting material for the production of herbicides.
  • esters of propionic acid are used as a solvent, plasticizer or comonomer (vinyl propionate).
  • acrylic acid is by selective heterogeneously catalyzed gas phase partial oxidation of propane, propene and / or
  • Acrolein available are generally diluted with inert gases such as nitrogen, CO, water vapor, molecular hydrogen, noble gases, other saturated and / or unsaturated hydrocarbons, in a mixture with molecular oxygen at elevated temperatures and, if appropriate, increased pressure via transition metals
  • Mixed oxide catalysts passed and oxidatively converted into a product gas mixture containing acrylic acid (e.g. EP-A 1090684, DE-A 10122027, DE-A 10101695, DE-A 10059713, DE-A 10028582, DE-A 19955168, DE-A 19955176, EP-A 1159247, DE-A 19948248 and DE-A 19948241).
  • a disadvantage of the aforementioned partially oxidative method of producing acrylic acid is that not only the main product, acrylic acid, but also secondary components typical of the gas-phase catalytically oxidative method of production are formed in its framework. These are, in particular, Al carboxylic acids (such as formic acid, acetic acid and / or propionic acid) and / or aldehydes (such as acrolein, methacrolein, propionaldehyde, n-butyraldehyde, benzaldehyde, furfural and crotonaldehyde) and allyl acrylate.
  • Al carboxylic acids such as formic acid, acetic acid and / or propionic acid
  • aldehydes such as acrolein, methacrolein, propionaldehyde, n-butyraldehyde, benzaldehyde, furfural and crotonaldehyde
  • allyl acrylate such as acro
  • the secondary components mentioned can be formed in total amounts of up to 5% by weight (in the case of aldehydes (including allyl acrylate)) and 5% by weight (in the case of alkane carboxylic acids).
  • esters from C 1 -C 6 -alkanols and acrylic acid the corresponding formic, acetic and / or propionic esters would also be formed in side reactions, which relates to the yield of the desired acrylic ester to the amount of alkanol used.
  • the aldehyde content usually has an effect, e.g. disadvantageous in that it e.g. the induction time of polymerization reactions, i.e. affects the period between reaching the polymerization temperature and the actual start of the polymerization. Furthermore, it usually influences the degree of polymerization and can also cause discoloration in the polymers. Allyl acrylate has the same disadvantageous effect. Allyl acrylate is therefore to be understood in this document as aldehyde.
  • the procedure is to this end so that one component acrylic acid, accompanied by a portion of the relevant side, optionally after direct 'and / or indirect cooling of the product gas mixture of the gas phase oxidation of this product gas mixture by absorption initially in a suitable absorbent (in the Usually water or a high-boiling organic solvent) and subsequently largely separates the acrylic acid from the absorption medium and the secondary components by distillative, rectificative, extractive and / or crystallizing processes (cf. e.g. DE-A 10115277, EP-A 982289, EP-A 982288, EP-A 982287, DE-A 19606877, DE-A 19631645 and DE-A 10218419 and the prior art cited in these documents).
  • a suitable absorbent in the Usually water or a high-boiling organic solvent
  • the product gas mixture of the selective heterogeneously catalyzed gas phase partial oxidation can also be subjected to fractional condensation, as is the case e.g. describe DE-A 19740253, DE-A 19627847 and DE-A 19924532.
  • the condensation is the case e.g. describe DE-A 19740253, DE-A 19627847 and DE-A 19924532.
  • processing zone The sum of all processing steps is referred to as processing zone in this document. You (this also applies to that
  • an acrylic acid quality is generally removed, the acrylic acid content of which is 90% by weight.
  • the boiling point of several aldehydic secondary components at normal pressure is in the range T S ⁇ 60 ° C or in the range T S ⁇ 50 ° C or ⁇ 40 ° C, where T s is the boiling point of acrylic acid at normal pressure 45 (1 at) , Similarly, the boiling point of acrylic acid and propionic acid almost coincide at normal pressure, whereas acetic acid, for example, clings to acrylic acid in a crystallisative separation.
  • the aforementioned fractions are therefore generally not led directly out of the processing zone, but are at least partially returned to the processing zone at another location in the processing zone which differs from the place where they were formed.
  • fractions containing secondary components enriched in the processing zone are also not always desirable from a different point of view. Namely, if you take into account that the corrosion effect of e.g. lower alkane carboxylic acids is considerable, which is why their local accumulation, especially in the case of formic acid, should be avoided.
  • Acrylic acid target product quality separates a substance mixture containing secondary components and acrylic acid without significantly impairing the economics of the process due to acrylic acid losses.
  • Such a process would also be a process for the production of acrylic acid esters, since acrylic acid can be converted into the associated acrylic acid ester in the same way by direct reaction with the corresponding alcohol.
  • a method is provided as a solution to the problem, in which one produces acrylic acid and / or its ester and propionic acid and / or its ester in combination and is characterized in that
  • a by-substance mixture containing acrylic acid which is characterized in that either its total content (in mol%) of aldehydes based on the amount of acrylic acid contained and / or its total content based on the amount of acrylic acid contained (in mol %) of alkane carboxylic acids is greater than the respective al ehydric and / or alkane carboxylic acid content, obtained in the same way, of the acrylic acid quality separated off under i),
  • the method according to the invention is based, inter alia, on the fact that propionic acid and / or its ester can be obtained from acrylic acid and / or its ester by hydrogenation with molecular hydrogen.
  • DE-A 2310754 recommends a heterogeneously catalyzed (a supported catalyst is recommended as the catalyst to which palladium is applied as the catalytically active material), which is carried out under pressure in the liquid phase.
  • the process of DE-A 2310754 is preferably carried out in a fluidized bed.
  • the basis of the liquid phase is a Solvent. As such, water comes into consideration.
  • preferred solvent is propionic acid.
  • the aforementioned hydrogenation is expediently carried out at moderate temperatures (e.g. 20 to 80 ° C) and moderate hydrogen pressures (e.g. 1 to 10 atm).
  • Polish patent PL-94748 recommends producing propionic acid by heterogeneously catalyzed hydrogenation in the gas phase.
  • a copper-zinc catalyst which is applied to aluminum oxide is considered appropriate as the catalyst.
  • the hydrogenation process takes place e.g. Temperatures of 250 to 350 ° C in the fixed catalyst bed at pressures from normal pressure to 6 atm with propionic acid selectivities of at least 95 mol%.
  • the acrylic acid is advantageously diluted in the gas phase by means of water vapor.
  • the finished product can be obtained directly by liquefying the propionic acid vapors in coolers.
  • DE-A 2834691 discloses e.g. a process for the preparation of ethyl propionate by catalytic hydrogenation of ethyl acrylate. Rhodium complex compounds are used as catalysts.
  • EP-A 408338 recommends similar catalysts for the catalytic hydrogenation of acrylic acid derivatives.
  • Electroanalytical Chemistry and Interfacial Electrochemistry, 60 (1975) 75-80 teaches a cathodic reduction of acrylic acid to propionic acid on a platinized platinum electrode.
  • the method according to the invention is also based on the fact that the presence of small amounts of formic acid or acetic acid is only slightly disruptive in most uses of propionic acid.
  • the problem of separating propionic acid from acrylic acid, which can hardly be achieved by distillation, is virtually eliminated when the hydrogenation variant according to the invention is used. Since propionic acid and its esters are not used for the purposes of radical polymerizations, any aldehydes contained in them cannot adversely affect them.
  • a first design variant is based on the procedure of EP-A 982288.
  • a selective heterogeneously catalyzed gas-phase partial oxidation of propane, propene and / or acrolein is first carried out in a reaction zone, as described, for example, in column 3 of EP-A 982288.
  • the resulting product gas mixture A usually contains, based in each case on the total reaction gas mixture, 1 to 30% by weight of acrylic acid, 0.05 to 1% by weight of propene, 0.05 to 1% by weight of acrolein, 0.05 to 10 wt .-% molecular 'oxygen, 0.05 to 2 wt .-% formic acid, 0.05 to 2 wt .-% acetic acid is 0.01 to 2 wt .-% propionic acid, 0.05 to 1 weight % Formaldehyde, 0.05 to 2% by weight of other aldehydes such as furfural and benzaldehyde, 0.01 to 0.5% by weight (as a total) of maleic acid and maleic anhydride and 20 to 97% by weight, preferably 50 to 97% by weight of inert diluent gases.
  • the latter can, in particular, saturated C 1 -C 6 -hydrocarbons, for example 0 to 95% by weight ⁇ % methane ' and / or propane, in addition 1 to 30% by weight water vapor, 0.05 to 15% by weight carbon dioxide and 0 to 95 % By weight of nitrogen, in each case based on 100% by weight of product gas mixture A.
  • saturated C 1 -C 6 -hydrocarbons for example 0 to 95% by weight ⁇ % methane ' and / or propane, in addition 1 to 30% by weight water vapor, 0.05 to 15% by weight carbon dioxide and 0 to 95 % By weight of nitrogen, in each case based on 100% by weight of product gas mixture A.
  • the acrylic acid and some of the secondary components are initially absorbed from product mixture A in a high-boiling organic solvent in a first process step.
  • the boiling point of the high-boiling organic solvent at normal pressure is preferably at least 20 ° C., in particular 50 ° C., more preferably 70 ° C. above the boiling point of the acrylic acid.
  • Preferred solvents, the term solvent also comprising solvent mixtures in the present application have boiling points (at atmospheric pressure) from 180 to 400 ° C., in particular from 220 to 360 ° C.
  • solvents are high-boiling, hydrophobic organic solvents which do not contain any polar group acting outwards, such as, for example, aliphatic or aromatic hydrocarbons, for example middle oil fractions from paraffin ' distillation, or ethers with bulky groups on the O atom, or mixtures thereof, a polar solvent such as the 1, 2-dimethylphthalate disclosed in DE-A-43 08 087 is advantageously added to these.
  • Esters of benzoic acid and phthalic acid with straight-chain, 1 to 8 are also suitable
  • Alkanols containing carbon atoms such as benzoic acid n-butyl ester, methyl benzoate, ethyl benzene, ethyl phthalate, diethyl phthalate, and so-called heat transfer oils, such as diphenyl, diphenyl ether or their chlorine derivatives and triarylalkanes, e.g. 4-methyl-4 '-benzyl-diphenylmethane and its isomers 2-methyl-2'-benzyl-diphenylmethane, 2-methyl-4' -benzyl-diphenyleneethane and 4-methyl-2'-benzyl-diphenylmethane.
  • a particularly preferred solvent is a solvent mixture of diphenyl and diphenyl ether, preferably in the azeotropic composition, in particular from about 25% by weight of diphenyl (biphenyl) and about 75% by weight of diphenyl ether, for example the commercially available Diphyl®.
  • This solvent mixture preferably also contains a polar solvent such as dimethyl phthalate in an amount of 0.1 to 25% by weight, based on the total solvent mixture.
  • high and low boilers, medium and low boilers as well as corresponding adjective terms refer to compounds that have a higher boiling point than normal acrylic acid (high boilers) or those that have approximately the same boiling point as acrylic acid (middle low boilers) or those that have a low boiling point as acrylic acid (low boilers).
  • the hot product gas mixture A is advantageously cooled by partial evaporation of the solvent in a direct condenser or quench apparatus before absorption.
  • a direct condenser or quench apparatus are suitable for this especially venturi washers, bubble columns or spray condensers.
  • the high-boiling secondary components of the reaction gas condense into the non-evaporated solvent.
  • a partial stream of the unevaporated solvent preferably 1 to 10% by weight of the mass stream fed to the absorption column, is drawn off and subjected to solvent cleaning.
  • the solvent is distilled over and the high-boiling secondary components remain, which - if necessary further thickened - can be disposed of, eg burned. This solvent distillation is used to avoid an excessive concentration of high boilers in the solvent stream.
  • the distilled solvent is preferably fed to the loaded solvent stream from the absorption column.
  • the absorption takes place in a countercurrent absorption column, which is basically equipped with any type of column internals, preferably with packing or structured packing, and which is charged with solvent from above.
  • the gaseous reaction product and any evaporated solvent from the quench apparatus are introduced into the column from below and then cooled to the absorption temperature.
  • the cooling is advantageously carried out by cooling circuits, i.e. heated, loaded solvent is drawn off from the column, cooled in heat exchangers and fed back to the column at a point above the point of withdrawal. After absorption, all of the high boilers, most of the acrylic acid and some of the low boilers are in the solvent.
  • the remaining, not absorbed remainder of the product gas mixture A is further cooled in order to separate the condensable part of low-boiling secondary components such as water, formaldehyde and acetic acid contained therein by condensation.
  • This condensate is called acid water in the following.
  • the gas stream then remaining consists predominantly of nitrogen, carbon oxides and unreacted starting materials. Preferably, this is partly fed back into the reaction zone as a diluent gas, hereinafter referred to as circulating gas.
  • the other part is discharged as waste gas and preferably burned.
  • the acrylic acid is separated from the solvent together with the low-boiling components and the low-boiling secondary components contained. This separation takes place by means of rectification, whereby basically every rectification column can be used. A column with dual-flow trays is advantageously used for this purpose.
  • the acrylic acid is largely freely distilled from the solvent and the medium-boiling secondary components, such as maleic anhydride.
  • the buoyancy part of the column is advantageously lengthened and the acrylic acid is withdrawn as a side draw from the column in a quality of 95% by weight acrylic acid.
  • the secondary substance mixture carried away in this way contains:
  • the .. acrylic acid separated as the target product usually contains:
  • a stream is drawn off from the bottom of the rectification column which predominantly contains solvents. Before being returned to the absorption stage, the solvent stream is largely cleaned of acrylic acid in order to be able to absorb acrylic acid from product gas mixture A again.
  • the solvent of acrylic acid is preferably depleted by stripping with inert gas, particularly preferably with a partial stream of the circulating gas, or in the case that propane is diluent gas, with propane.
  • the stripping is generally carried out at pressures of about 1.1 to 2.0 bar, preferably at pressures of 1.3 to 1.6 bar and at temperatures of about 80 to 120 ° C., preferably from 110 to 120 ° C.
  • the solvent stream to be cleaned is added to the top of a stripping column; it flows over the internals towards the swamp.
  • the stripping gas is introduced into the bottom of the stripping column in countercurrent. While the stripping gas flows in the direction of the column top, it absorbs acrylic acid from the liquid solvent stream, so that a purified solvent stream can be drawn off from the bottom of the stripping column, which has an acrylic acid concentration of at most 1% by weight, preferably of at most 0.5%. -% contains. This largely acrylic acid-free solvent can then be recirculated to the absorption stage.
  • the stripping gas loaded with acrylic acid is expediently recirculated to the stage in which the partial evaporation of the solvent takes place or to the absorption column.
  • the acidic water which can also still contain acrylic acid in solution, is treated extractively with a partial stream of the solvent fraction which has been almost completely freed from acrylic acid as described above.
  • the aqueous stream from the acid water extraction can still be concentrated and subsequently disposed of.
  • the organic stream is also returned to the absorption stage.
  • the bottom stream from the countercurrent absorption column which, in addition to the solvent, contains about 10 to 40% by weight of acrylic acid, essentially all the high boilers and part of the low boilers, in the upper region of a first rectification column I is added, and in the rectification column I at a bottom temperature of 165 to 210 ° C., preferably from 180 to 200 ° C., particularly preferably from 190 to 195 ° C.
  • the top stream is passed on for the rectificative recovery of the target product acrylic acid quality, and the bottom stream is returned to the absorption stage, that is to say fed into the upper region of the countercurrent absorption column (in a special embodiment, the acid water, which may still contain acrylic acid in solution, is mixed with a treated small extract stream of the bottom stream extractive.
  • the aqueous stream of acid water extraction can then be disposed of while the organic stream is also returned to the absorption stage).
  • the target product acrylic acid quality is preferably obtained from the top stream in the following process steps:
  • a separating plate rectification column with two condensers and one evaporator is preferably used for this separation problem. Dual-flow floors are particularly suitable as internals.
  • the top stream coming from the rectification column I is first condensed and then runs downward in the left-hand sub-column (stripping column) of the separating plate column used.
  • steam predominantly vaporous acrylic acid
  • a stream rich in low boilers is then drawn off at the top of this partial column after condensation.
  • this stream still contains significant amounts of acrylic acid, it is normally returned to the absorption stage and / or the quenching apparatus.
  • this stream rich in low boilers, containing acrylic acid, on the other hand, is passed out of the work-up zone as a by-product mixture and fed to the hydrogenation according to the invention, if appropriate after esterification of the acrylic acid beforehand.
  • the secondary substance mixture carried away in this way has the following contents:
  • the target product acrylic acid quality is obtained from the liquid stream arriving in the sump in the right-hand partial column (buoyancy column) of the separating plate column (this could also be replaced by a crystallizing separation step).
  • the stripping column and the lifting column have a common sump. This contains predominantly the solvent which, if necessary after cleaning, for example by evaporation in a quench, recirculates into the absorption stage.
  • the substantially free low-boiling acrylic acid vapor rises, the medium boilers and high boilers being washed out of the steam by the liquid reflux.
  • the vapor is condensed at the top of the column Part is subtracted from the head as the target product acrylic acid quality and the rest forms liquid reflux.
  • the target product acrylic acid quality usually has the following contents:
  • the removal of the secondary substance mixture from the workup zone results in reduced polymer formation in the workup zone, in which the individual working steps are of course in a known manner in the presence of polymerization inhibitors such as e.g. Phenothiazine or monomethyl ether of hydroquinone (MEHQ) can be performed.
  • polymerization inhibitors such as e.g. Phenothiazine or monomethyl ether of hydroquinone (MEHQ) can be performed.
  • FIGS. 4, 5 and 6 of DE-A 19 606 877 can also refrain from recirculating the top stream from column K30 into the absorption column and instead supply this top stream as a by-product mixture to the hydrogenation according to the invention.
  • the measure according to the invention results in an extended running time in the processing zone.
  • a third design variant lies in the documents DE-A 19 833 049, DE-A 19 814 375, DE-A 19 814 421,
  • DE-A 19 814 449, DE-A 10053086, DE-A 19 740 252, DE-A 19 814 387, DE-A 19 740 253 and DE-A 19 924 532 disclose the procedure for the fractional condensation of the, in advance optionally the rectified and / or indirectly cooled product gas mixture A.
  • this target product acrylic acid quality will be fed to further distillation and / or crystallization purification stages and at least some of the bottom liquids and / or mother liquor obtained in the course of these distillations and / or crystallizations will be returned to the fractionating condensation column.
  • a disadvantage of the procedure of fractional condensation is that the medium-boiling secondary components (e.g. acetic acid) form concentration bellies over their length in the condensation column. In other words, they accumulate over certain column lengths (heights) until they leave the column either overhead or at the bottom, depending on the boiling point.
  • the medium-boiling secondary components e.g. acetic acid
  • concentration bellies over their length in the condensation column.
  • water forms a high-boiling azeotrope with formic acid, which boils between water and acrylic acid at normal pressure, so that a concentration belly of formic acid is formed above the side deduction of the target product quality, which contains up to 30% by weight can be.
  • This leads to corrosion problems which the application of complex measures such as require the use of corrosion inhibitors, catalytic decomposition of formic acid or esterification of formic acid.
  • the accumulation of other secondary components puts a strain on subsequent cleaning stages.
  • the procedure according to the invention can also remedy this. This is done in a simple manner in that it allows the secondary component antinodes to be pierced in the condensation column without significant economic disadvantage. That is, at the level of the respective concentration belly, the respective secondary components and the liquid phase containing acrylic acid are partially carried up from the condensation column and the acrylic acid contained therein, if appropriate after its esterification, is converted into propionic acid and / or ester by hydrogenation using molecular hydrogen. This measure reduces the amplitude of the concentration bellies and makes it easier to separate the secondary components from the acrylic acid (Subsequent cleaning stages can be dimensioned smaller). The latter is a very general advantage of the procedure according to the invention.
  • fractional condensation can be carried out in detail as in the cited prior art documents (in particular DE-A 19 924 532). The same applies to the polymerization inhibition in fractional condensation.
  • hydrogenations of acrylic acid to propionic acid in the gas phase are generally preferred over liquid phase processes, since the problem of acrylic acid polymerization arises less with gas phase processes.
  • liquid substance mixtures that have been removed must be converted into the gas phase by evaporation.
  • the target esters are, in particular, methyl acrylate, ethyl acrylate, n-butyl acrylate and tert. -Butyl acrylate into consideration.
  • An optionally desired separation of propionic acid and / or its ester from the hydrogenation product mixture can be carried out in a manner known per se, e.g. by rectification.
  • the process according to the invention is particularly suitable when the propene used as the starting material for the selective heterogeneously catalyzed gas phase oxidation, as in WO 01/96270, EP-A 11 71 146, DE-A 33 13 573 and US Pat 31 61 670 described, was generated by catalytic pre-dehydrogenation of propane.
  • the molecular hydrogen formed in the process can subsequently be used for the hydrogenation in step c) of the process according to the invention.
  • the product gas mixture (3600 g / h) was cooled to a temperature of 136 ° C. in a spray cooler (2).
  • 750 g / h (7) of a total of 7000 g / h via the collecting tray (5) (with a temperature of 100 ° C.) of the high boiler fraction (6) removed from the separating column (3) were used as spray liquid (bottom liquid 4 did not occur)
  • the spray liquid was circulated over the tube bundle heat exchanger (8) described with heat transfer oil. 40 g / h high boilers were continuously removed from the circuit (9).
  • the product gas mixture cooled to a temperature of 136 ° C. was fed to the separation column (10) below the tray (5).
  • the column was a tray column with, viewed from bottom to top, first 25 dual-flow trays and then 50 bubble trays (1 bell per tray). The bottom diameter was 49 mm.
  • the dual flow floors had 6 holes per floor.
  • the hole diameter of the first five dual-flow trays was 9.5 mm.
  • the subsequent 10 trays had a hole diameter of 9 mm and the hole diameter of the last 5 dual-flow trays was 8.7 mm.
  • the floor above floor 15 was another collecting floor (11). staltet. Above it were 1800 g / h containing a temperature of 97 ° C acrylic acid quality (12)
  • the crystallizer was a stirred tank (3 1 internal volume) with a spiral stirrer. The heat of crystallization was removed via the double jacket of the container. The equilibrium temperature of the solution was 9.7 ° C.
  • the suspension produced during crystallization (solids content approx. 25% by weight) was discontinuously separated into crystals and mother liquor on a centrifuge at 2000 rpm (centrifuge diameter 300 mm) and a centrifuging time of 3 min. The crystals were then washed with melted (previously washed) crystals (80 g) for 20 seconds at 2000 rpm.
  • a gaseous mixture (17) was removed from the top of the column and subjected to a partial condensation in the spray cooler (18).
  • 480 g / h of the resulting acid water were at the top of Ko ⁇ lonne with a temperature of 30 ° C thereinto recycled (26).
  • 220 g / h of the sour water were continuously removed (the Sour water contained 3% by weight of acrylic acid and 2.6% by weight of acetic acid).
  • 90 g / h of the acid water removed were mixed with MEHQ (22) and as a 0.5% by weight aqueous stabilizer solution (21) together with the remaining amount of acid water (23) via the water-cooled tube bundle heat exchanger (24) to 18 ° C cooled used as spray liquid (25).
  • a 0.5% by weight aqueous solution of 4-hydroxy-TEMPO (4-hydroxy-2, 2,6, 6-tetramethyl-piperidine-1-oxyl) was prepared, which in an amount of 18 g / h at a temperature of 20 ° C was fed to the 75th tray of the separation column (27).
  • the separation device described could be operated for 40 days without any appreciable polymer formation.
  • the formic acid belly By removing a liquid side stream of 10 g / h at this column height, the formic acid belly could be reduced to 13% by weight.
  • the stationary composition of the liquid side stream removed was essentially:
  • the side stream removed is fed to a hydrogenation according to DE-A 23 10 754.
  • the purity of the crystals was slightly improved.
  • the gas phase which was at a temperature of approx. 150 ° C, was led into the lower part of a packed column 2 (3 m high; double jacket made of glass; inner diameter 50 mm, three packed zones of lengths (from bottom to top) 90 cm, 90 cm and 50 cm; the packing zones were thermostated from bottom to top as follows:
  • the penultimate and the last packing zone were separated by a chimney floor;
  • the packing elements were metal helices made of stainless steel with a helix diameter of 5 mm and a helix length v ⁇ n 5 mm; immediately above the middle packing zone, the absorbent was fed and the counterflow of 2900 g / h of 57.4% by weight of diphenyl ether, 20.7% by weight of diphenyl, 20% by weight of o-dimethylphthalate and the rest from others Components composite absorbent applied at a temperature of 50 ° C, exposed.
  • the non-absorbed gas mixture leaving the second packed zone in the absorption column 2 was cooled further in the third packed zone in order to separate off the condensable part of the secondary components contained therein, for example water and acetic acid, by condensation.
  • This condensate is called sour water.
  • part of the acid water above the third packing zone of the absorption column 2 was returned to the absorption column 2 at a temperature of 20 ° C.
  • the sour water was removed below the uppermost packing zone from the chimney floor attached there.
  • the ratio of recycled to withdrawn acid water was 200 g / g.
  • the acid water removed also contained 0.8% by weight of acrylic acid. If necessary, this can be recovered as described in DE-A 19 600 955. 1600 Nl / h of the gas stream ultimately leaving the absorption column 2 were recycled as recycle gas into the propene oxidation. The rest were burned.
  • a solvent stream loaded with acrylic acid of 5230 g / h (main components, each in% by weight or ppm by weight: solvent 61, acrylic acid 30, acetic acid 8118 ppm, maleic anhydride 200 ppm) was introduced into a first partial stream IIIA of 2160 g / h, which predominantly contained acrylic acid (main components, each in% by weight: solvent 20, acrylic acid 77 and acetic acid 0.22) and a second partial stream IIIB of 3070 g / h, which predominantly contained the solvent (main components each in wt. -% or ppm by weight: solvent 83, acrylic acid 5, and acetic acid 636 ppm) separated '.
  • Partial stream IIIB was fed to the top of stripping column 3. An air flow of 600 Nl / h was used as the stripping gas. Partial stream IIB from the evaporator was added to the top of stripping column 3; the stripping column 3 was used here to purify the solvent from acrylic acid. The solvent removed from acrylic acid was withdrawn from the bottom of the stripping column 3 and recirculated to the top of the absorption column 2. The diacrylic acid content in the solvent was 2.0% by weight.
  • the partial stream IIIA occurring in the evaporator 5 was condensed in a heat exchanger 6 at 100 mbar and the condensate was fed to the 28th tray of the two-part rectification column 4, namely its stripping section.
  • the low boilers were stripped from the partial stream IIIA with acrylic acid vapor in countercurrent, whereas the medium boilers and high boilers were predominantly dissolved in the liquid. remained.
  • an almost low-boiler-free stream b main components in% by weight or ppm by weight: solvent 28, acrylic acid 71, acetic acid 721 ppm, maleic anhydride 4026 ppm was removed.
  • the partial stream b was taken from the common evaporator 7 of the stripping section and the lifting section of the rectification column 4, a residual stream c was drawn off from the evaporator 7 (480 g / h, main components, in% by weight or ppm by weight: solvent 87, acrylic acid 10, maleic anhydride 700 ppm) and the Venturi quench 1.
  • the vapor stream from the evaporator 7 was fed to the lifting section of the rectification column 4 in order to obtain the desired acrylic acid quality and was cleaned of medium boilers and high boilers by the acrylic acid return flow.
  • a stream of 420 g / was at the top of the lifting section of the rectification column 4 h deducted from the target product, which still contained 1500 ppm acetic acid and 50 ppm maleic anhydride lt (otherwise the total aldehyde content (including allyl acrylate) was ⁇ 300 ppm by weight and the total alkane carboxylic acid content was also ⁇ 300 ppm by weight).
  • the vapor from the stripping section of the rectification column 4 was treated as a residual stream a with 87% by weight acrylic acid, 200% by weight solvent, 1510% by weight aldehydes, 1000% by weight allyl acrylate, 6% by weight acetic acid and 7% by weight of formic acid condensed, mixed with phenothiazine and likewise fed to the Venturi quench 1.
  • the diacrylic acid content of the acid water which was fed to the combustion was 2.6% by weight.
  • the residual stream a from comparative example 2 from c) was removed from the work-up zone and fed to a hydrogenation according to the invention of the acrylic acid contained.
  • the run-up time of the processing zone was increased to 28 days.

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

Abstract

Selon la présente invention, une qualité d'acide acrylique de produit cible et un mélange de composants secondaires et d'acide acrylique sont séparés dans une zone de traitement du mélange gazeux de produits contenant de l'acide acrylique et des composants secondaires d'une oxydation partielle en phase gazeuse à catalyse hétérogène. La qualité de produit cible présente une teneur réduite en composants secondaires par rapport à celle du mélange de composants secondaires. L'acide acrylique contenu dans le mélange de composants secondaires est transformé par hydrogénation, éventuellement après une estérification ayant lieu au préalable, en acide propionique et/ou en esters de celui-ci.
PCT/EP2003/004710 2002-05-08 2003-05-06 Procede pour produire de l'acide acrylique et/ou des esters de celui-ci et de l'acide propionique et/ou des esters de celui-ci sous forme de compose WO2003095411A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003224144A AU2003224144A1 (en) 2002-05-08 2003-05-06 Method for the production of acrylic acid and/or the esters thereof and propionic acid and/or the esters thereof in a compound

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE2002120752 DE10220752A1 (de) 2002-05-08 2002-05-08 Verfahren zur Herstellung von Propionsäure und/oder Propionsäureestern durch Hydrierung von Acrylsäure und/oder Acrylsäureestern
DE10220752.6 2002-05-08
DE2002124341 DE10224341A1 (de) 2002-05-29 2002-05-29 Verfahren zur Herstellung von Acrylsäure und/oder deren Ester sowie von Propionsäure und/oder deren Ester im Verbund
DE10224341.7 2002-05-29

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Cited By (5)

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Publication number Priority date Publication date Assignee Title
WO2008090190A1 (fr) * 2007-01-26 2008-07-31 Basf Se Procédé de préparation d'acide acrylique
WO2008135676A1 (fr) * 2007-03-19 2008-11-13 Arkema France Procede ameliore de production d'acroleine et/ou d'acide acrylique a partir de propylene
WO2010010298A2 (fr) * 2008-07-22 2010-01-28 Arkema France Procede de fabrication d'acide propionique bio-ressource a partir de glycerol
WO2012163931A1 (fr) 2011-06-03 2012-12-06 Basf Se Solution aqueuse contenant de l'acide acrylique et sa base conjuguée
RU2472768C2 (ru) * 2007-01-26 2013-01-20 Басф Се Способ получения акриловой кислоты

Families Citing this family (1)

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Publication number Priority date Publication date Assignee Title
CN101589015B (zh) * 2007-01-26 2013-11-13 巴斯夫欧洲公司 生产丙烯酸的方法

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DE2310754A1 (de) * 1973-03-03 1974-09-12 Knapsack Ag Verfahren zur herstellung von propionsaeure
WO1999050219A1 (fr) * 1998-03-31 1999-10-07 Basf Aktiengesellschaft Procede de preparation d'acide acrylique et d'esters d'acide acrylique
WO1999050220A1 (fr) * 1998-03-31 1999-10-07 Basf Aktiengesellschaft Procede de preparation d'acide acrylique et d'esters d'acide acrylique

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
DE2310754A1 (de) * 1973-03-03 1974-09-12 Knapsack Ag Verfahren zur herstellung von propionsaeure
WO1999050219A1 (fr) * 1998-03-31 1999-10-07 Basf Aktiengesellschaft Procede de preparation d'acide acrylique et d'esters d'acide acrylique
WO1999050220A1 (fr) * 1998-03-31 1999-10-07 Basf Aktiengesellschaft Procede de preparation d'acide acrylique et d'esters d'acide acrylique

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008090190A1 (fr) * 2007-01-26 2008-07-31 Basf Se Procédé de préparation d'acide acrylique
US7566804B2 (en) 2007-01-26 2009-07-28 Basf Aktiengesellschaft Process for preparing acrylic acid
RU2472768C2 (ru) * 2007-01-26 2013-01-20 Басф Се Способ получения акриловой кислоты
WO2008135676A1 (fr) * 2007-03-19 2008-11-13 Arkema France Procede ameliore de production d'acroleine et/ou d'acide acrylique a partir de propylene
WO2010010298A2 (fr) * 2008-07-22 2010-01-28 Arkema France Procede de fabrication d'acide propionique bio-ressource a partir de glycerol
WO2010010298A3 (fr) * 2008-07-22 2011-08-18 Arkema France Procede de fabrication d'acide propionique bio-ressource a partir de glycerol
CN102216252A (zh) * 2008-07-22 2011-10-12 阿肯马法国公司 从丙三醇制备生物来源化的丙酸的方法
WO2012163931A1 (fr) 2011-06-03 2012-12-06 Basf Se Solution aqueuse contenant de l'acide acrylique et sa base conjuguée
DE102011076931A1 (de) 2011-06-03 2012-12-06 Basf Se Wässrige Lösung, enthaltend Acrylsäure und deren konjugierte Base
US9150483B2 (en) 2011-06-03 2015-10-06 Basf Se Aqueous solution comprising acrylic acid and the conjugate base thereof

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TW200407294A (en) 2004-05-16

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