DE102007055086A1 - Manufacture of acrylic acid involves subjecting precursor to heterogeneously catalyzed gas phase partial oxidation with oxygen in catalyst, reducing gas mixture, and subjecting crude acrylic acid to thermal separation process - Google Patents

Abstract

A 3C or more of precursor is subjected to heterogeneously catalyzed gas phase partial oxidation with molecular oxygen in solid-state catalyst to obtain product gas mixture. The product gas mixture is reduced by direct cooling, passed into a condensation column, and crude acrylic acid is conducted, and acid water is disposed. A residual gas mixture is recycled, and crude acrylic acid is subjected to thermal separation process. The acrylic acid is taken in organic solvent to form organic extract, and thermal separation processed to form acrylic acid. A 3C or more of precursor is subjected to heterogeneously catalyzed gas phase partial oxidation with molecular oxygen in solid-state catalyst at elevated temperature to obtain product gas mixture comprising acrylic acid, steam and secondary components. The product gas mixture is reduced by direct/indirect cooling, passed into a condensation column equipped with separating internals, allowed to ascend into the condensation column, and fractionally condensed. The crude acrylic acid comprising water and secondary components, is conducted as the target product from the condensation column through a side draw (A1) disposed above the feed point of the product gas mixture into the condensation column, and acid water comprising acrylic acid and secondary components is disposed above the side draw (A1) through a liquid phase draw (A2). A residual gas mixture comprising secondary components having lower boiling points than water at the top of the condensation column and a bottoms liquid comprising acrylic acid and conversion products, and secondary components having higher boiling points than acrylic acid from the bottom space of the condensation column, is recycled after cooling with reflux liquid, into the condensation column, and the crude acrylic acid is subjected to thermal separation process and purified. The acrylic acid in a portion of acid water not recycled into the condensation column is taken up from the acid water into an organic solvent by extraction with the organic solvent to form an organic extract comprising acrylic acid. The acrylic acid is removed from the organic extract using thermal separation process, and the acrylic acid removed from the extract is recycled into the condensation column into the aqueous solution of a metal hydroxide. Thus, acrylic acid is manufactured.

Description

The present invention relates to a process for the preparation of acrylic acid in which by heterogeneously catalyzed gas phase partial oxidation of at least one C ₃ precursor of acrylic acid with molecular oxygen to solid state catalysts at elevated temperature produces an acrylic acid, water vapor and minor components containing product gas mixture, the Temperature of the acrylic acid, water vapor and secondary components containing product gas mixture optionally reduced by direct and / or indirect cooling, and the acrylic acid, water vapor and secondary components containing product gas mixture then passes into a equipped with separating internals condensation column, within the condensation column can rise in itself and thereby fractionally condensed and via a first, located above the feed of the product gas mixture in the condensation column, side draw a water and Nebenkompon containing a total of depleted (depleted) crude acrylic acid as the target product and a second, located above the first side draw liquid abstraction (preferably a side draw) still acrylic acid and minor components containing acidic water and at the top of the condensation column a deeper (at lower temperature (relative to atmospheric pressure )) as water boiling secondary components containing residual gas mixture and from the bottom space of the condensation column still acrylic acid and heavier than acrylic acid boiling (based on atmospheric pressure) by-products and secondary components containing sump liquid leads out of the condensation column, a subset of the withdrawn acidic water as such and / or after cooling the same returns as reflux liquid in the condensation column and the crude acrylic acid optionally subjected to at least one further thermal separation process for the purpose of further purification.

acrylic acid is a significant intermediate, for example, in the context the preparation of polymer dispersions (optionally also in the form of their esters with alkanols) as well as superabsorbent water Polymers are used.

Acrylic acid is inter alia by heterogeneously catalyzed gas phase partial oxidation of C ₃ precursors (of C ₃ precursor compounds) of acrylic acid (this term is intended in particular to encompass those chemical compounds which are obtainable formally by reduction of acrylic acid, known C ₃ precursors of acrylic acid are, for example, propane, propene, acrolein, propionaldehyde and propionic acid, but the term should also include precursor compounds of the abovementioned compounds, for example glycerol (starting from glycerol, acrylic acid can be produced, for example, by heterogeneously catalyzed oxidative dehydration in the gas phase for example, see EP-A 1 710 227 . WO 06/114506 and WO 06/092272 ) with molecular oxygen on solid state in the state of catalysts available at elevated temperature.

In this case, the said starting gases, usually with inert gases such. B. nitrogen, CO ₂ , saturated hydrocarbons and / or steam, in admixture with molecular oxygen at elevated temperatures and optionally elevated pressure over (eg. Transition metal) mixed oxide catalysts passed and oxidatively in an acrylic acid, water and undesired by-products such. As furfurals, benzaldehyde, acetone, formaldehyde and maleic anhydride etc. containing product gas mixture, from which the acrylic acid must be separated (the by-products and the different of water vapor inert diluent gases are to be summarized in this document under the term "minor components"; Term comprising the polymerization inhibitors commonly added in the acrylic acid removal processes).

From Propionaldehyde and / or propionic acid starting it is in the heterogeneously catalyzed gas phase partial oxidation with molecular oxygen at least partially an oxidative Dehydration.

From the scriptures DE-A 199 24 533 . DE-A 199 24 532 . WO 01/77056 . DE-A 101 56 016 . DE-A 102 43 625 . DE-A 102 23 058 . DE-A 102 35 847 . WO 2004/035514 . WO 00/53560 and DE-A 103 32 758 are known as the initially described method for the production of acrylic acid, in which a basic separation of a crude acrylic acid by fractional condensation of the product gas mixture of the heterogeneously catalyzed gas phase partial oxidation is carried out. The term crude acrylic acid or crude acrylic acid expresses the fact that the acrylic acid withdrawn via the first side draw is not a pure product but a mixture which, in addition to acrylic acid (usually ≥ 50 or ≥ 60% by weight). , usually ≥ 70 or ≥ 80 wt .-%, often ≥ 90 wt .-% and often ≥ 95 wt .-% or more of the total weight) nor water and secondary components such. Lower aldehydes (e.g., furfurals, acrolein, benzaldehyde), never carboxylic acids (eg acetic acid, propionic acid, formic acid) etc. contains. In any case, the total content of water and minor components, based on the content of acrylic acid, in the crude acrylic acid is lower than in the product gas mixture of the gas phase partial oxidation, which is why it is also said that the crude acrylic acid contains these components as a whole depleted (individual components, however contained in the crude acrylic acid comparatively enriched).

Partially is the purity of the thus separated crude acrylic acid already for the intended use of acrylic acid sufficient (eg for the purpose of esterification of the same, or for Purpose of the construction of available by radical polymerization Polymers). In many cases, however, the separated crude acrylic acid subject at least one further thermal separation process, to make a purer (one in the Compared to crude acrylic acid higher acrylic acid content in wt .-% having) to obtain the acrylic acid degree of purity required for the respective purpose having.

Under Thermal separation processes are understood to mean those in which under supply or with removal of (usually thermal) energy a physically at least two-phase system is generated, wherein it due to the existing between the phases temperature and molar gradients to a heat and mass transfer, ultimately the desired separation conditions, and the extraction.

Often Thermal separation processes are contained in separating internals Separation carried out columns in which the aforementioned at least two material phases usually led to each other in countercurrent become. In many cases one of the two material phases is gaseous (It is usually in a separation column as an ascending phase led) and the other liquid (it is in one Separation column usually performed as a descending phase). In principle, the at least two material Phases but also liquid (eg in the case of an extraction) or solid and liquid (eg in the case of crystallization), or solid and gaseous (eg in the case of adsorption) be.

Examples for case designs of thermal separation processes in which one of the at least two material phases liquid and a gaseous, and therefore natural element of the term "thermal Separation process ", are the rectification (an ascending vapor phase is in the separation column in countercurrent to a descending liquid phase guided), and the desorption (the reverse process for absorption; the gas dissolved in a liquid phase is passed through Lowering the pressure above the liquid phase, by raising the temperature of the liquid phase and / or by passing a gas phase through the Liquid phase led out of the liquid phase; is the passage of a gas phase involved the desorption also referred to as stripping). But also the absorption (As a rule, a rising in a separation column gas to at least one liquid descending in the separation column Absorbent in countercurrent) and the fractionating Condensation of a gas mixture (gas / liquid phase example) are part of the term thermal separation process. A special favorable thermal separation process for further purification of crude acrylic acid is the crystallisative further purification (the crystallization).

A disadvantage of the known processes for the basic separation of a crude acrylic acid by fractional condensation of the product gas mixture of a heterogeneously catalyzed gas phase partial oxidation of at least one C ₃ precursor of acrylic acid, however, is the additional accumulation of acrylic acid and secondary components containing acidic water (also called "sour water"). The term "sour water" initially expresses that the acid water is generally ≥ 50% by weight, frequently ≥ 60% by weight, often ≥ 70% by weight and often ≥ 80% by weight of water contains (it is usually both to water of reaction, as well as diluent water (water vapor) used as inert diluent gas in the context of the gas phase partial oxidation).

she but also expresses the fact that it is next to water or Nebenkomponentensäuren such as For example, propionic acid, acetic acid and formic acid as well as acrylic acid and thus a pH of <7 (The total content of the secondary component carboxylic acids other than acrylic acid is usually, based on the weight of the sour water, at Values ≦ 10% by weight, in some cases ≦ 5% by weight).

Normally, the acrylic acid content of the sour water will be 4 or 5 to 15, often about 10 wt .-%. A disadvantage of the method recommended in the cited prior art for the basic separation of acrylic acid from the product gas mixture of the heterogeneously catalyzed gas phase partial oxidation is that it does not recycle the acrylic acid-containing acid water which is not recycled into the rectification column in its entirety (see in particular US Pat DE-A 102 43 625 . WO 2004/035514 and DE-A 103 32 758 ).

This is so far disadvantageous as the acid water combustion z. B. the yield of the desired product acrylic acid decreases.

The Object of the present invention was in view of the described Prior art therein, an improved method of manufacture of acrylic acid, in particular by doing so It is excellent that there is an increased yield of acrylic acid guaranteed, without the purity of the same appreciable to impair.

Accordingly, a process for the preparation of acrylic acid in which by heterogeneously catalyzed gas phase partial oxidation of at least one C ₃ precursor (a C ₃ precursor compound) of the acrylic acid with molecular oxygen to solid state catalysts at elevated temperature, an acrylic acid, water vapor and Produces minor components containing product gas mixture, the temperature of the acrylic acid, water vapor and secondary components containing product gas mixture optionally reduced by direct (by direct contact with a cooling liquid) and / or indirect cooling, and the acrylic acid, water vapor and secondary components containing product gas mixture then in a equipped with separating elements condensation column leads, within the condensation column can rise in itself and thereby fractionally condensed condensed and via a first, above the feed point of the product gas mixture in the Condensation column located, side draw a water and secondary components depleted total containing crude acrylic acid as the target product and a second, located above the first side draw, liquid phase withdrawal (preferably a side draw; all statements in this document are particularly valid in the case of such a sourwasserseitenabzugs) still acrylic acid and secondary components containing acidic water (acid water) and at the top of the condensation column a lower (at lower temperature (based on atmospheric pressure)) as water boiling secondary components containing residual gas mixture and from the Bottom of the condensation column still leads acrylic acid and heavier than acrylic acid boiling by-products and secondary components containing bottom liquid from the condensation column, a portion of the withdrawn acidic water as such and / or after cooling thereof as reflux liquid in the condensation column and the crude acrylic acid optionally at least one further thermal Separation process for the purpose of their further purification subjects found, which is characterized in that at least at a subset of not zurückf in the condensation column In this acrylic acid contained in this contained acrylic acid by extraction with an organic solvent to form an acrylic acid-containing organic extract from the acidic water out into the organic solvent, subsequently separating the acrylic acid from the organic extract using at least one thermal separation process and separated from the extract acrylic acid returns to the condensation column, or the further purification of the crude acrylic acid feeds and / or receives in the aqueous solution of a metal hydroxide.

According to the invention advantageous is at least 25% by weight, more preferably at least 50% by weight, more preferably at least 75 wt .-% and preferably the total amount of not in the condensation column recycled acid water extracted according to the invention and further treated.

in principle come to carry out the invention required Extraction all for liquid-liquid extractions known extraction apparatus into consideration. This should be as possible the generation of a large phase interface and a fine distribution of these drops in the continuous phase as well as a quick and as complete as possible Ensure phase separation after mass transfer.

In the simplest case, a mixer (eg a stirred tank or a static mixer) with a separator (eg a settling tank) can be used as an extraction unit. Suitable stirrers are in principle all common stirrers. Examples include disc stirrer, impeller stirrer, crossbar stirrer, lattice stirrer, blade stirrer, anchor stirrer, paddle stirrer, propeller stirrer, helical stirrer and multi-stage pulse countercurrent stirrer. The stirrers can also be multi-stage, that is, several stirrer are mounted on a common axis one above the other. Preferably, a two-stage impeller agitator is used. In principle, all common containers come into consideration as settling tanks. Preferably, a recumbent container is used. Such an extraction unit can be operated continuously or discontinuously, wherein discontinuing the settling tank can be omitted and the phase separation is carried out in the stirred tank. The transition of the substance to be extracted (the valuable material) in the Aufnehmerphase done in the mixer, the separation of the two phases (by gravity) in the separator. In continuous operation, the separation of the feed can be in a settling tank in a heavy and light phase by a built transversely to the flow direction can be improved. As internals come in principle all common fixtures into consideration, such as perforated plates, plates, packings and / or beds. Of the beds, those with rings, coils, calipers, Raschig, Intos or Pall rings, Barrel or Intalox saddles, Top-Pak etc. or braids are preferred. Particularly preferred are perforated plates in combination with beds. The residence time in the settling tank is typically 0.05 to 2 hours.

switches one several mixer-separator units in a row, so speaks one from a cascade. The units can be used in both as well as be switched in DC or cross-current.

application point It will be useful to carry out the invention Extraction in a separation-effective internals containing extraction column make. The specific heavier phase occurs above and specifically lighter phase at the bottom of the column. Move in the column Both phases are in countercurrent. In principle, same extraction columns the columns for a countercurrent distillation (rectification). That is, for the extraction method of the invention suitable extraction columns can be known per se Be type and have the usual fittings.

Possible column types are both extraction columns with and without energy input into consideration. Extraction columns containing internals in the form of packages (in particular structured or ordered) and / or beds can be operated both with and without energy input. Among the beds, those having rings, coils, calipers, Raschig, Intos or Pall rings, Barrel or Intalox saddles, Top-Pak etc. are preferred. For example, for the extraction columns to be used according to the invention particularly suitable packages are z. B. packs of Julius Montz GmbH in D-40705 Hilden, such. For example, the pack Montz-Pak B1-350. Preferably used perforated structured packages of stainless steel sheets. Packing columns with ordered packs are known in the art and z. In Chem.-Ing.Tech. 58 (1986) No. 1, pp. 19-31 as well as in the Technical Review Sulzer 2/1979, p. 49 ff. Of the Sulzer Aktiengesellschaft in CH-Winterthur described. Furthermore, extraction columns with internals in the form of soils are also suitable, it being necessary to differentiate between pulsed sieve tray columns and crossflow sieve tray columns. In the pulsed sieve tray columns, both phases are passed through the passage openings (usually holes, ie, circular passage openings) in the sieve bottom. During the upstroke of the pulsation, the lighter phase is pushed upwards through the holes of the sieve bottom, while on the downstroke the heavy phase is pressed downwards. The Karr column works similarly, except that the liquid is not pulsed here, but the sieve trays are moved up and down. The pulsed sieve tray column is preferred. On the other hand, when using cross-flow tower columns, the continuous phase passes through downshafts from one floor to the next floor and only the disperse phase is forced through the holes in the trays due to the difference in density (the designations used herein for mass transfer trays are based on those of Figs DE-A 103 32 758 ).

In the rule are to be carried out according to the invention Sour water extraction 1 to 10 theoretical plates sufficient. As a theoretical soil (or theoretical separation stage) should be in this Writing generally the one room unit for one thermal separation process used, separation-containing internals containing Separation column to be understood, which corresponds to a material enrichment causes the thermodynamic equilibrium. That is, the term of the theoretical soil is both on extraction columns with Mass transfer trays, as well as on extraction columns with Packings and / or packing applicable.

used one for the inventive method an extraction column, you will be the specific heavier of the two Phases application technically appropriate means Distributor at the top of the column, over the cross section as possible evenly distributed, give up. The specific lighter phase is appropriate in terms of application technology also via a distributor into the bottom of the column. Accordingly, the lighter phase rises in the column and the heavy phase sinks down. Will be the lighter of the two phases dispersed, so this is in drop form, so finds the Phase separation in the head of the column instead, in the opposite case, at the heavier phase is dispersed, the phase separation takes place in the bottom of the column. Cheap drop sizes have in both cases a diameter (a longitudinal expansion) in Range of 1 to 10 mm, preferably in the range of 2 to 5 mm.

According to the invention advantageous the extractant is a higher boiling point than Acrylic acid (in each case based on atmospheric pressure) as this is usually the subsequent separation of the acrylic acid facilitated from the organic extract.

In the context of the extraction to be carried out according to the invention, it will therefore be more likely that the organic solvent to be used as the extraction agent will be one of the two worth higher viscosity than water. In this case, it is advantageous according to the invention if the organic extraction agent entering the extraction column is in the form of a disperse phase and the acid water is a continuous phase (this necessitates, for example, an accelerated mass transfer between the two phases and ultimately allows shorter columns with the same separation result; If a continuous aqueous phase wets out extraction columns made of stainless steel and their internals better, transport of the substance to be extracted from the continuous phase into the disperse phase leads to a stabilization of the latter (lower tendency to coalesce). When using an organic extractant having a higher mass density than the mass density of the acid water, this means that the extractant is added and dispersed at the top of the column and the resulting extractant drops in the column fall down. In the reverse case, ie, when using an extractant having a lower mass density than the mass density of sour water, the extractant is dispersed in the bottom of the column and the resulting extractant drops rise in the column. In the previously mentioned types of extraction columns with internals in the form of packings, packings and / or soils, the undivided continuous phase should wet the selected internals well, since otherwise the droplets of the dispersed phase usually creep along the internals.

In The simplest way is the organic extractant here by means of the column cross section and arranged over the respective cross-sectional length of the normally circular cylindrical Extending column extending, usually circular Through holes (holes) having pipes (the normally have an identical cross-section; one speaks also of manifolds) give up. Will the organic extractant abandoned at the top of the column indicate the circular Passages down, when the extraction agent at the bottom of the column to the top. The diameter (the longest dimension) the aforementioned passage openings is usually 1 mm to 10 mm, preferably 3 mm to 6 mm and often 2 to 5 mm. In doing so, the extractant is allowed to become easier Way in the distribution pipes on and out of the openings emanate again.

in principle can be carried out for the invention Acid water extraction also stirred columns or centrifugal extractors be used. Stirred columns improve the touch both phases. All stirrers of the column sit in terms of application technology expedient on a common shaft. The column tube is useful on the walls with stator rings equipped. The usually arranged in the middle Shaft typically carries stirring elements in the shaft Kind that in each case between two stator rings, a stirrer rotates. To name a few are for the stirred ones Columns the RDC (rotating disc contactor) column, the ARD (asymmetrical rotating disc) column, the Kühni column (stirred Column according to Kühni type) or the QVF stirred cell extractor. Use centrifugal extractors the centrifugal force for mixing and separating the two in countercurrent guided phases. The centrifugal force also provides good raffinate / extract separation when both phases are forming tend a stable emulsion. To name a few are here the apparatuses Podbielnak Extractor or Westfalia Separator.

made is the extraction unit for the inventive Process preferably of the material 1.4571. This is true also to the other devices, which for the separation of the acrylic acid from the product gas mixture of heterogeneously catalyzed gas phase partial oxidation can be used can.

The driving force for the separation of extract and raffinate is the difference in the mass density (g / cm ³ ) between the two phases. A high mass density difference between the two liquid phases facilitates phase separation and reduces emulsion formation.

For the extraction to be carried out according to the invention, it is therefore advantageous to use organic solvents whose mass density in kg / m ³ differs from the mass density of water (also in kg / m ³ ) by ≥ 25 kg / m ³ , preferably by ≥ 50 kg / m ³ differs (based on the pressure used in the extraction and the temperature used in the extraction). In general, however, the aforementioned mass density difference will be ≤ 250 kg / m ³ , generally ≤ 150 kg / m ³ .

Furthermore it is for the inventive method favorable when the dynamic viscosity of the organic Extraction agent under the extraction conditions ≤ 100 mPa · s, preferably ≤ 50 mPa · s. As a rule, the aforementioned dynamic viscosity however, ≥ 1 mPa · s. Particularly according to the invention favorable are dynamic viscosities in the range from 2 to 10 mPa · s.

Furthermore, it is advantageous in the method according to the invention if the interfacial tension between the two fluid phases is comparatively high. Against the background of what has been said so far, suitable extractants for the extraction of acid water according to the invention include, inter alia, organic Liquids whose boiling point at atmospheric pressure (1 atm) is above 150 or above 160 ° C. Examples include middle oil fractions from the Paraffindestillation, diphenyl ether, diphenyl, or mixtures of the aforementioned liquids, such as. B. a mixture of 70 to 75 wt .-% diphenyl ether and 25 to 30 wt .-% diphenyl. It is also beneficial to use a mixture consisting of a mixture of 70 to 75 wt .-% diphenyl ether and 25 to 30 wt .-% diphenyl, and based on the mixture, 0.1 to 25 wt .-% o-dimethyl phthalate.

Particularly preferred organic solvents for acid water extraction according to the invention are the esters of aliphatic or aromatic mono- or dicarboxylic acids (especially when both carboxyl groups are esterified), the alcoholic component of which contains 1 to 8 C atoms and their carboxylic acid component 5 to 20 C atoms. The alcoholic component preferably has only two or only one hydroxyl group before the esterification. The alcoholic component is particularly preferably monohydric (an OH group) or divalent (two OH groups) alkanols. Advantageously, the number of C atoms of the alcoholic component (in particular in the case of monohydric or dihydric alkanols) is 1 to 6, more preferably 1 to 4 and most preferably 1 or 2. The aliphatic or aromatic mono- or dicarboxylic acids advantageously contain 5 to 15 C-atoms, preferably 5 to 10 C-atoms and particularly preferably 6 to 8 C-atoms (in particular in the case of a respective esterification (also in the diester case) with 1 to 4 or with 1 or 2 C-atoms having alkanols ). Dicarboxylic acids are preferred over monocarboxylic acids as the acid component of the relevant esters (especially when both carboxyl groups are esterified). Phthalic acid, isophthalic acid and terephthalic acid and adipic acid are very particularly preferred according to the invention acid components of the relevant esters. The latter is particularly true in the case of dialkyl (C ₁ - to C ₈ alkyl, preferably C ₁ - to C ₆ alkyl, most preferably C ₁ - to C ₄ alkyl and even better C ₁ - or C ₂ alkyl ) too. D. h., Most favorable for the inventive method extractants are the dimethyl phthalate that diethyl phthalate (z. B. Palatinol ^® A from BASF Aktiengesellschaft), the dimethyl isophthalate, the diethyl isophthalate, dimethyl terephthalate, the diethyl, dimethyl adipate and diethyl adipate. Further suitable for the acid extraction according to the invention esters are the triesters of phosphoric acid, such as. For example, tributyl phosphate or tricresyl phosphate. Suitable cresyl radicals are both ortho-cresyl, meta-cresyl and para-cresyl. In addition, as extraction agents for the acid water extraction according to the invention are esters of acrylic acid and branched or linear monohydric C ₆ - to C ₁₂ alkanols (eg 2-propylheptyl acrylate or 2-ethylhexyl acrylate) and mono- and diesters of maleic acid and monohydric C ₄ - C ₁₀ alkanols into consideration. It also applies to all of the above-mentioned extractants, that those of them, the normal pressure at a boiling point above 150 ° C or above 160 ° C, or above 170 ° C, or above 180 ° C, or above 190 ° C are preferred according to the invention.

In usually the sour water to be extracted is next to acrylic acid and water as another ingredient (usually in wt .-% relative on the total amount of acid water the third largest Component) contain acetic acid. Depending on the way the partial oxidation carried out (selected Catalyst, water vapor content of the reaction gas mixture, temperature the partial oxidation), the acidic acid up to 10 wt .-%, or up to 5% by weight (often 2 to 8% by weight) or more of acetic acid contain. Often the sour water contains about the 2-fold weight fraction of acrylic acid based on the Weight fraction of acetic acid. The contents of the other possible Acid minor components are usually significantly lower. According to the invention, therefore, those extractants are preferred the acrylic acid compared to acetic acid preferably record. One of these extractants in particular, diethyl phthalate.

According to the invention advantageous it is also when the extractant is under the extraction conditions not reacted with water and only slightly soluble in water having. So z. As the diethyl phthalate particularly hydrolysis. Another advantage of diethyl phthalate is its at normal pressure (1 atm) comparatively high boiling point, the invention advantageous for using extraction agents (organic solvents) ≥ 200 ° C, better ≥ 225 ° C and even better ≥ 250 ° C is.

In addition, it has a comparatively low solubility in water (this also reduces the extraction agent losses). In general, the sour water falls in accordance with the invention to be carried out fractional condensation of the product gas mixture at a temperature of 50 to 80 ° C, preferably 60 to 70 ° C. That is, at this temperature, it is normally withdrawn via the second liquid phase draw (preferably a side draw) (the lower the temperature, the lower the need for the polymerization inhibitor, and in favorable cases, the separate addition of such to the sour water, extractant, is not required , Raffinate and / or extract). From an application point of view, therefore, the extraction in this temperature range will be carried out. D. h., According to the invention advantageously, the acid water is substantially at its aforementioned temperature in the extraction unit, preferably an Extrak tion column (particularly preferably a packed column, advantageously Montz-Pak B1-350) lead. Advantageously, the feed from below into the extraction column and from above the specific heavier extractant (with advantage diethyl phthalate) is abandoned. Usually, the temperature of the charged extractant will not be very different from that of the supplied sour water. Typically, the amount of this temperature difference is ≥ 0 ° C and ≤ 20 ° C, preferably ≥ 0 ° C and ≤ 15 ° C, and many times ≥ 0 ° C and ≤ 10 ° C. The pressure of the condensation water withdrawn from the condensation column is according to the invention typically> 1 to 1.5 bar, often 2 bar. The withdrawn sour water is fed by means of a pump into the extraction column. The delivery pressure can z. B. 2 to 6 bar. The working pressure in the extraction column is selected according to the invention so that it requires no additional pump to promote the organic extract in the first stripping. In principle, however, the extraction of acid water can also be carried out at higher or lower temperatures and at higher or lower pressures. When putting an extraction column into operation, it will be advantageous in terms of application that the extraction column is first filled with acid water and then, as already described, the dropwise addition of the organic extractant at the top of the extraction column. The supply of the sour water (the preferably continuous phase) can in principle take place directly via a corresponding feed nozzle. In principle, however, the sour water can also be supplied via a feed tube (diameter of the passage openings lying at typically 5 to 10 mm) which has one (or more) passage openings in its wall.

As already mentioned, the extraction column is application technology expediently made of stainless steel. Typical wall thicknesses be 5 to 20 mm. Outwardly is the extraction column normally thermally isolated in a conventional manner.

The Ratio V of the extraction column fed Flow rates of organic extractant (E, in kg / h) and acidic water (S, in kg / h), d. h., E: S, in the inventive Method 0.05 to 20, preferably 0.1 to 10, more preferably 0.8 to 1.2 and more preferably 1: 1.

The leached with acrylic acid (extracted, depleted) Sour water is usually sent for disposal (eg burned or driven into the sewage treatment plant). It leaves the extraction column according to the invention typically at the head (as raffinate), while the organic, the Acrylic acid containing, extract the extraction column typically leaving below.

The Separation of the acrylic acid from the organic extract, its removal temperature from the extraction column substantially the feed temperature of the sour water into the extraction column can, in principle, using different thermal separation process or even using combinations be made of such thermal separation process.

A suitable separation variant is the crystallisative separation. All crystallization processes which are used in the DE-A 19838845 and in the DE-A 10 2005 015 637 recommended. The advantage of the crystallative separation is that crystallization, unlike other thermal separation processes, is a sharp separation process. In other words, the composition of the acrylic acid crystals which form is largely independent (in the ideal case, there is complete independence) of the composition of the liquid phase, the liquid extract. In contrast, a fuzzy thermal separation process is one in which the composition of the phase comprising the target product enriched in the application of the separation process is markedly dependent on the composition of the mixture to be separated. D. h., In the sharp separation method is in the thermodynamic theory, a one-time equilibrium attitude sufficient to obtain the pure target product, while it requires in fuzzy separation a repeated successive adjustment of the thermodynamic equilibrium. Crystallization processes which are particularly suitable according to the invention for the purpose of separating acrylic acid from the extract are suspension crystallization and layer crystallization.

Very particularly advantageous according to the invention (in particular if the extraction agent used is one whose boiling point (at atmospheric pressure) is at least 60 ° C., preferably at least 80 ° C. and very particularly preferably at least 100 ° C. above the corresponding boiling point of the acrylic acid (= 141 ° C), the separation of the acrylic acid from the extract by desorption will be carried out. The desorption unit used is usually a column with separation-active internals. In principle, all known separating internals come into consideration as such column internals. These include, in particular, soils, packings and / or fillings. Among the mass transfer trays are bubble trays, sieve trays (eg forced sieve trays or rain sieve trays (dual-flow trays), valve trays and / or Thor manure (or Thormann ^® floors) preferred. Among the beds, those with rings, coils, calipers, Raschig, Intos or Pall rings, Barrel or Intalox saddles, Top-Pak etc. or braids are preferred. Very particular preference is given to dual-flow trays and / or Thormann trays. Among the Thormann floors, the single-flow Thormann floors are preferred. When using dual-flow trays and Thormann floors, the dual-flow trays are most preferably used in the lower section of the desorption unit and the Thormann trays in the upper section of the desorption unit. As a rule, 5 to 10 theoretical plates in the desorption unit are sufficient. Basically, the desorption can be effected solely by lowering the pressure. Especially advantageous in terms of application is the partial pressure of the acrylic acid to be desorbed by dilution with a condensate which is not condensable under the desorption conditions (preferably the boiling point of the stripping gas is at least 50 ° C. below the boiling point of water at 1 atm.) And substantially inert gas (relative to chemical change) lowered. D. h., Very particularly preferably, the separation of the acrylic acid from the extract phase of the acid water extraction by stripping by means of a gas (by stripping out with a gas) made. That is, by passing a gas through the extract, the acrylic acid is taken up in the gas and taken out of the extract. The driving force behind this process is that the vapor pressure of the acrylic acid to be removed from the extract is greater than its partial pressure in the gas itself, so that the acrylic acid is transferred from the extract to the gas. Advantageously, the extract for the purpose of stripping against the flow direction of the stripping gas (ie, in countercurrent) out. That is, the extract is advantageously applied to the top of the stripping column and the stripping gas is fed down into the stripping column. Very particularly advantageous as stripping the led out at the head of the condensation column residual gas (or residual gas mixture), or a portion of this residual gas with the same or different composition as the entire residual gas, or gas used whose composition corresponds to one or more inert constituents of the residual gas ( eg water vapor, N ₂ , CO ₂ , and / or air). The inventively preferred use of residual gas mixture as the stripping gas has the advantage that on the one hand no additional stripping gas must be provided (which would later be additionally disposed of) and on the other hand so that a stripping gas is used which does not for the entire separation process of acrylic acid from the product gas mixture of the partial oxidation contains foreign components. As a rule, residual gas consists predominantly of the inert diluent gases used for the partial oxidation of the C ₃ precursor of the acrylic acid (remain essentially unchanged chemically in the partial oxidation) and of water vapor which is usually formed by-product in the partial oxidation and optionally added as diluent gas and by undesired complete Oxidation as a side reaction formed carbon oxides (often also a residual gas mixture composition having partial amount of the residual gas is recycled as a diluent gas in the partial oxidation, this will be referred to in this document as partial oxidation gas or cycle gas). In some cases it still contains small amounts of molecular oxygen not consumed in the partial oxidation (residual oxygen, which is advantageous (for example to avoid undesirable polymer formation)) and / or unreacted C ₃ precursor and / or unreacted intermediate. The inert diluent gases used in the partial oxidation (eg N ₂ , CO ₂ , H ₂ O and / or saturated hydrocarbons, etc.) on the one hand help to absorb the heat of reaction liberated during the partial oxidation and on the other hand generally ensure one at the same time safe operation of the heterogeneously catalyzed gas-phase partial oxidation of the C ₃ precursor by keeping the reaction gas mixture either outside the explosion range or in a region of the explosive region which can still be reliably controlled (cf. DE-A 197 40 253 . DE-A 197 40 252 . DE-A 102 43 625 . DE-A 103 32 758 and WO 2004/035514 ).

When using dual-flow trays as separating internals in the desorption column (stripping column), the hole diameter (the diameter of the passage openings in the trays) is usually 8 to 50 mm, preferably 10 to 35 mm. Preferably, the hole diameter increases from top to bottom. The ground clearance (usually the soils are arranged equidistantly) is often 300 to 800 mm, often 400 to 600 mm and often 500 mm. As already mentioned, the desorption unit is usually made of austenitic steel, preferably of the material 1.4571 (cf. DIN EN 10020 ).

The column feed to extract to be stripped takes place in the upper region of the desorption unit, preferably on its uppermost (theoretical) bottom. In terms of application, the extract is previously heated (typically at temperatures of 80 to 120 ° C, often about 100 ° C). Via internal and / or external indirect heat exchangers of conventional design (eg Robert evaporator, forced circulation tube bundle heat exchangers, forced circulation tube bundle expansion heat exchangers, plate heat exchangers, etc .; EP-A 854 129 ) and / or double wall heating (as heat carrier is advantageously used with the waste heat of the partial oxidation of recovered steam) is advantageously fed to the bottom of the stripping column (the desorption) heat in addition. Preferably, it takes place via external circulation evaporator with natural or forced circulation. Particularly preferred are external Umlaufver steamer with forced circulation (in particular expansion circulation) used. The use of several evaporators, connected in series or in parallel, is possible (typical bottom temperatures are at 145 to 165 ° C, often at about 155 ° C).

The Uncondensable under the applied desorption conditions and inert stripping gas is advantageously directly in the bottom of the Desorption initiated. The inlet from the external heat exchanger (in which previously removed bottoms liquid required Heat is supplied) is with advantage on one the lower (theoretical) column bottoms (preferably in the theoretical soil 2 to 4 from below) or made under it. The in the bottom of the desorption column resulting, to acrylic acid substantially free extractant is advantageously recycled to the head of sour water extracts.

There it compared to the extract obtained in the extraction unit it is usually an elevated temperature, it is appropriate, that of the extraction to the stripping column to extract and that from the bottom of the stripping column Extractants to be recycled for extraction (an optionally required active polymerization inhibition of the extraction and stripping column would be due to the Return advantageously in the bottom of the stripping column into it; z. Example by MEHQ and / or PTZ when the stripping gas containing molecular oxygen) in indirect heat exchange through an indirect heat exchanger conventional design (tube bundle heat exchanger or plate heat exchanger), to heat the extract and to cool the extractant. Subsequently, the extractant is usually added in an indirect heat exchanger by means of z. B. Water cooling to its operating temperature in the extraction of acid water brought. Based on the from the bottom of the stripping in the Extraction of recycled extractant stream are normally additionally 0.01 to 1 wt .-% of the bottom liquid the stripping column discharged (purge stream) (behind the above Water cooling will normally be a corresponding flow rate fresh extractant in the extractant recycle stream added). This purge stream can be disposed of (eg together burned with residual gas) or rectificatively worked up and into fresh Extractants are transferred.

The stripping gas is preferably passed into the stripping column at a temperature which at least largely corresponds to that of the bottom liquid in the stripping column (as a rule, the two temperatures will not be more than 30 ° C., better still not more than 20 ° C.). If residual gas is used as the stripping gas, it may, for. B. be brought to the aforementioned temperature that it is compressed to an elevated pressure. Advantageously, this compression can be carried out together with recycle gas to a pressure which is suitable also for the recirculation of residual gas into the C ₃ precursor partial oxidation (usually with the aid of a radial compressor). Typically, the aforementioned pressure is 2 to 4 bar, often 2.5 to 3.5 bar (at a residual gas pressure of typically> 1 and ≤ 1.5 bar).

Based on 1 kg of extract, the amount of stripping gas required for free-stripping the acrylic acid is typically 1.5 to 2.5 Nm ³ stripping gas. Typical loadings of the stripping gas with acrylic acid are (at the top of the stripping column) 2 to 6 wt .-%.

in principle is true that with increasing used Strippgasmenge the heat input in the bottom of the stripping column can be reduced. The privilege a separation of the acrylic acid from the extract by stripping with one under the desorption conditions usually non-condensable and inert stripping gas is among other things in that it is a particularly efficient one and at the same time energetically as well as with regard to apparatus little complicated separation is. In addition, unlike the z. B. crystallisative or rectificative separation from the extract the advantage of having no extra, acrylic acid in an elevated concentration, liquid Phase generated, the cost of an additional distinct Polymerization inhibition required.

prominent is not least due to the fact that the stripping gas charged with acrylic acid, especially then if residual gas was used for stripping, as such into the condensation column (For the fractional condensation of the product gas mixture the partial oxidation is used) are recycled can. Appropriately, such a return occurs below the first side draw into the condensation column. Advantageous the return will be made directly to the swamp area make the condensation column. Basically they are made directly into the bottoms liquid.

The present application therefore comprises in particular such a process according to the invention which is characterized in that at least one partial amount (advantageously a partial amount of at least 25% by weight, more preferably at least 50% by weight, preferably at least 75% by weight) is used. , or the total menu ge) of not recycled to the condensation column acidic water contained in this acrylic acid by extraction with an organic solvent to form an acrylic acid-containing organic extract from the acidic water in the organi cal solvent, then the acrylic acid from the organic extract by stripping with a stripping gas separates and the recycled with acrylic acid stripping gas in the condensation column. In principle, the recycling of the acrylic acid contained in the loaded stripping gas into the condensation column could also be carried out in a condensed out form. However, this condensed acrylic acid could also be combined with the crude acrylic acid taken from the condensation column for further purification thereof.

In the process according to the invention, however, the stripping gas (or at least a portion thereof thereof) charged with acrylic acid is very particularly advantageous in order to freeze acrylic acid still present in a second stripping column in the bottoms liquid withdrawn from the condensation column (and only then to return it to the condensation column ) before the bottoms liquid is sent for disposal. According to the invention, the loaded stripping gas of this second stripping is still subjected to a (countercurrent) rectification, as already described in the WO 2004/035514 and in the DE-A 103 32 758 (but with the direct use of residual gas as the stripping gas) is described (and then returned to the condensation column).

Of the Swamp space in the method according to the invention used condensation column (or quite generally in a separating effective Built-in column) is the space below the lowest separating effective Built-in components (eg trays, packings and packing, which is the interface between those in the separation column in Increase countercurrent phases) within the condensation column.

In he collects the so-called bottoms liquid, in particular includes such constituents whose boiling point at normal pressure (1 atm) is above the boiling point of acrylic acid. This are heavier than acrylic acid boiling by-products such as B. maleic anhydride, minor components such as phenothiazine, which are added as polymerization inhibitors, but also by-products, in the course of the fractional condensation of the product gas stream form the partial oxidation of the constituents of the same first. These secondary products include in particular radical Polymers of acrylic acid, which despite the polymerization inhibition form in an undesirable way. Also count higher molecular weight compounds, resulting from condensation reactions different constituents of the product gas mixture of the partial oxidation form. These include not least the Michael adducts, which is due to reversible Michael addition of acrylic acid to itself as well as to the resulting acrylic acid dimer ("diacrylic acid") or form oligomers (the term acrylic acid oligomers Therefore, in this document always means the corresponding Michael adducts and non-free radical acrylic acid oligomers). By the action of elevated temperature with simultaneous Separation of the acrylic acid formed (eg by "stripping") with one under the appropriate conditions preferably (chemically) inert and non-condensable gas) can be the Michael addition be reversed. But also monomeric acrylic acid itself is to a considerable extent still part of the bottoms liquid in the condensation column, making a free-ripping same worthwhile power. As the bottom liquid of the condensation column but also contains by-products, which at normal pressure only slightly higher in boiling point than acrylic acid (eg benzaldehyde, furfurals and maleic anhydride) it is advantageous, the loaded stripping of this second stripping (before, for example, its return to the condensation column) additionally a (countercurrent) rectification (i.e. a countercurrent of reflux liquid) (Expediently in the same column), what an improved purity of acrylic acid loaded second stripping gas conditional.

The Recycling the first loaded stripping gas and / or of the second loaded stripping gas into the condensation column not necessarily done directly.

Much more may be the first loaded stripping gas and / or the second loaded stripping gas also at least partially or completely with product gas mixture mixed and the resulting gas mixture in the condensation column be guided.

The Merge can be done before, during, and / or after any direct and / or indirect cooling of the product gas mixture of the gas phase partial oxidation respectively.

In the following, for reasons of differentiability, the stripping gas from the extract stripping loaded with acrylic acid is to be referred to as "first laden gas" and the stripping gas from the (condensation column) bottoms stripping loaded with acrylic acid (preferably rectified) as "second laden gas" (Similarly, the extract stripping should be referred to as "first stripping" and the sump stripping as "second stripping", etc.). As a rule, the first laden gas leaves the extract stripping at a pressure of 1.5 to 3.5 bar, often 2 to 3 bar, z. B. 2.5 bar. Its temperature is usually about 10 ° C below that temperature at which the extract is applied to the first stripping column. Typical temperatures of the first laden gas are 65 to 95 ° C, often 75 to 95 ° C, or 85 ° C.

to Carrying out the second stripping (including the rectification of the stripping gas) come in principle all columns with separating internals into consideration, with possible Built-in z. As packs, packing and / or Floors are. In principle, columns can also be used rotating inserts, so-called rotating columns used be that the return liquid is in drops spray. According to the invention preferred is used as a second stripping column such that only soils and / or Contains packs. As soils are involved Advantage dual-flow trays used and with particular advantage the stripping column contains only dual-flow trays as separating internals.

Under Dual-flow trays are said to be simple in this writing plates Passages (holes, slots, etc.) are understood. The ascending gas in the second stripping column and that in the second stripping column descending reflux liquid occur countercurrently flowing through the same passages. Of the Cross section of the passage points is in a conventional manner adapted to the load of the second stripping. Is he too small the rising gas flows at such a high speed through the passages that descend in the stripping column Return liquid essentially without separation effect being carried away. If the cross-section of the passages is too large, are moving ascending gas and descending return essentially without exchange past each other and the ground is running Danger of running dry. Usually have dual-flow trays no drainpipe connecting them to the next floor. Needless to say, can any dual-flow soil with the walls of the second stripping column finish flush. He can also over Bars connected with these. With decreasing load of the second Stripping column run in contrast to dual-flow trays hydraulically sealed crossflow trays dry.

According to the invention expedient can be used for the second stripping (including the mentioned rectification) usable dual-flow bottom stripping column contain up to 60 dual-flow trays. With advantage this an aperture ratio (the ratio D: U, formed by the area fraction of the soil used for the Fissile gas is permeable (D) and the total area the soil (U)) of 10 to 20%, preferably from 10 to 15%.

The passage points of the dual-flow trays are preferably circular holes with a uniform inside diameter of the circle diameter. The latter is suitably 10 to 30 mm. In the upper part of the column it is advantageously 10 to 20 mm, or 10 to 15 mm, and in the lower part of the column it is advantageously 20 to 30 mm. Furthermore, the circular holes above the individual dual-flow trays are preferably evenly arranged in a strict triangular division (cf. DE-A 102 30 219 ). Furthermore, the punching burr of the through-openings punched out in the dual-flow trays in the second stripping column preferably points downwards. Usually, the dual-flow trays are arranged equidistantly in the second stripping column. Typically, the ground clearance is 300 mm to 500 mm. Also favorable according to the invention is a ground clearance of 400 mm. Conveniently, the feed of the bottoms liquid to be stripped (previously used for direct cooling of the product gas mixture of the partial oxidation and / or supplemented by high boiler bottoms taken from the bottom of the condensation column) may be added to the fourth to tenth dual-flow bottoms of the second stripping column (calculated from below). The bottom temperature in the second stripping column is advantageously maintained at 150 to 190 ° C, preferably at 160 to 180 ° C. The working pressure in the second stripping column will normally be> 1 to 3 bar, frequently 1.5 to 2.5 bar. The energy input required in the second stripping column is advantageously fed by means of an external forced circulation tube bundle expansion evaporator, fed to the bottom liquid withdrawn from the second stripping column for the purpose of overheating and subsequently returned to the second stripping column in an overheated condition (cf. DE-A 103 32 758 ). Basically, at this point but also a pure forced circulation evaporator or a natural circulation evaporator, z. As a Robert evaporator, are used, which can also be integrated into the second stripping.

The second stripping column itself (as well as the condensation column and the first stripping column) are suitable for use thermally insulated against the environment.

The generation of the return liquid can be done by direct and / or indirect cooling. According to the invention, the method of direct cooling is advantageously used. For this purpose, the last (theoretical) bottom flowing gas is fed to a quench device in the simplest way, the z. B. over a chimney tray from the separating internals of the second stripping column separated into the second stripping integrated (can be placed on the separating effective part) may be. In principle, however, the quench device can also be spatially outsourced from the second stripping column. Any such device known in the art (e.g., spray scrubbers, venturi scrubbers, bubble columns or other sprinkler-type apparatus) may be used as such a quench apparatus, preferably using Venturi scrubbers or spray coolers. Advantageously, a DC device (eg one with baffle plate nozzle) is used. For indirect cooling of the quench liquid, it is usually passed through an (indirect) heat exchanger or heat exchanger. In this regard, all common heat exchangers or heat exchangers are suitable. Preference is given to tube-bundle heat exchangers, plate heat exchangers and air coolers. Suitable cooling media are air in the corresponding air cooler and cooling liquids, in particular water (eg surface water), in the other cooling devices. A small amount of the condensate formed during quenching is used as the quench liquid (hereinafter also referred to as "quench liquid O") .The other portion of the condensate formed during quenching is essentially recycled as reflux liquid to the uppermost (theoretical) tray of the second stripping column (US Pat. a small portion of the condensate can also be branched off at this point and fed to and combined with the bottoms liquid taken from the condensation column, a portion of the resulting mixture being used as quench liquid 1 to be introduced later in this document, another part of this Mixture forms the feed to the second stripping column and the remaining (relatively small) residual amount of this mixture is combined with the remaining portion of the condensate and forms in this union then partly the return liquid au f the top (theoretical) bottom of the second stripping column and the other part the quench liquid 0). Typically, the temperature of the quench liquid 0 immediately prior to its quenching use is about 40 ° C, whereas the reflux liquid is typically recycled at about 80 ° C. The mass ratio of recycled reflux liquid to the second stripping column fed bottom (and optionally high boilers) liquid is typically ≥ 2. Often it is 2 to 10 and preferably 4 to 8.

Of course must the second stripping column (like all other apparatuses in those having liquid, appreciable acrylic acid contents Phases) are operated polymerization inhibited become. As such, polymerization inhibitors can be used for this purpose in principle all known in the art polymerization inhibitors be used.

exemplary may be mentioned as such phenothiazine (PTZ) and p-methoxyphenol (MEHQ). Often these two are used in combination. Appropriately, they are in a pure Acrylic acid dissolved added. MEHQ is preferred added as a melt.

In the polymerization inhibition is particularly elegant However, the Quenchkreises 0 and the second stripping column thereby accomplish that the quench circle 0 is a subset of the Condensation led out, polymerization-inhibited, d. h., containing polymerization inhibitors, bottoms liquid (and optionally high boiler fraction) added. In typical Way contains the quench liquid 0 so z. B. 0.01 to 0.1 wt% MEHQ and 0.01 to 0.5 wt% PTZ. The first loaded gas (as the stripping gas for the second stripping column functions) usually still contained molecular oxygen additionally promotes the polymerization inhibition.

A subset of the sump liquid arising in the bottom of the second stripping column is continuously discharged and disposed of. By addition of an organic solvent, for. As of methanol, the highly volatile residue is kept fluid when needed. Instead of methanol, other hydrophilic organic liquids such. As ethanol or in the WO 2004/035514 Recommended (or mixtures of such liquids) can be used. Based on the feed stream of bottoms liquid fed from the condensation column, the aforementioned discharge stream is about 10 or 20 to 30% by weight. From an application point of view, the effluent stream is branched off from the forced circulation evaporator, which supplies the second stripping column with energy, and leaves superheated material flow. He is degassed and z. B. diluted with methanol z. B. the residue combustion supplied.

The second laden gas leaving the quench circle 0 (typical temperatures 70 ° C. to 90 ° C.) can now be recirculated as such to the condensation column (it should be noted that in the second stripping column 1 kg was fed from the condensation column Bottoms liquid typically 1 to 10 Nm ³ of first loaded gas may be used as the stripping gas, usually the liquid in the bottom of the second stripping column is in the boiling state). Its acrylic acid content is typically 15 to 20% by weight. Basically, the return of ent holding acrylic acid in the condensation column in condensed form. However, such an acrylic acid condensate can also be combined with the crude acrylic acid taken from the condensation column for further purification thereof. According to the invention, preference is given to recycling the acrylic acid into the condensation column as part of the second laden gas as such, ie, in gaseous form (in principle, the recirculation may also take place partially condensed).

The Return of the second loaded gas in the Condensation column (all statements apply equally to a return of the first loaded gas as such in the condensation column) is preferably below of the first page deduction (basically They also in the direct cooling circuit of the product gas mixture the gas phase partial oxidation take place). application point It is expedient in the bottom space of the condensation column. One can see this recycle in both the bottoms liquid immersed, as well as above the liquid level of the Bottom liquid and below the first (theoretical) Make the bottom of the condensation column. Advantageously contains the bottom space of the condensation column a mist eliminator (z. B. a Zentrifugaltropfenabscheider) to entrainment from bottoms drops due to rising gas suppress. In addition, the swamp area can through a first chimney tray from the lowest separating fixture be separated.

The residence time of the bottoms liquid fed to the second stripping column from the condensation column (optionally including removed high-boiling fraction) in the second stripping apparatus should usually be 0.5 to 4 hours (for a high-boiling-ether component finally discharged). Of course, can be added to the bottom of the second stripping back-cooling catalysts for the cleavage of the acrylic oligomers, as it is z. B. the WO 2004/035514 recommends.

Naturally, the bottom of the second stripping column also aids such Komad 313 ^® of the company Mol (Hungary) and / or dispersants may (for. Example, those of the EP-A 1 062 197 and / or the US-A 3,271,296 ) such. For example, tertiary amines (eg, trimethylamine, triethylamine, N, N, N ', N'-tetramethyl-1,6-hexanediamine, and pentamethyldiethylenetriamine) may be added to reduce fouling in the indirect heat exchanger providing the required energy input, and to reduce the acrylic acid yield promote. The additional amounts may be from 0.1 to 10% by weight, based on the bottom of the second stripping column. Since these are already advantageously high-boiling substances or these additives form with acrylic acid, they are not stripped off.

The Advantageousness of the described invention Procedures is u. a. in that they are one Allow increasing the yield of acrylic acid without the purity of the taken over the first side print to significantly reduce crude acrylic acid. This does not apply last to the stripping variant described and even then, if for the purpose of stripping as described residual gas from the condensation column is used.

In this case, the purity of both the first and the second laden gas with respect to incidental components which interfere with subsequent use of the acrylic acid (such as, for example, for the preparation of water-based superabsorbent polymers) is so good that (of the respective total or even only from a subset of the first and / or second loaded gas) the acrylic acid contained therein also directly from the gas phase of the first or second loaded gas out into the aqueous solution of a metal hydroxide (eg an alkali metal hydroxide and / or alkaline earth metal hydroxide, eg. NaOH, KOH, Ca (OH) ₂ and / or Mg (OH) ₂ ) (eg in complete correspondence to those described in US Pat WO 2003/095410 described procedure) and in the case of a recording in z. For example, aqueous sodium hydroxide z. B. resulting aqueous solution of sodium acrylate z. B. directly for the production of water superabsorbent polymers by appropriate free-radical polymerization (see also WO 2003/014172 ) can be used.

This is not least because of by - products such as formaldehyde and Formic acid is usually preferred in the aqueous Phase of the sour water remain. The z. B. a countercurrent wash with aqueous sodium hydroxide solution (or another of the aforementioned aqueous metal hydroxide solutions) in a separating effective Internals containing column (trays, packing and / or packs) of acrylic acid-free first or second loaded gas can subsequently be recycled to the extract stripping and / or combustion are supplied.

Typically, the acrylic acid-containing product gas mixture of a heterogeneously catalyzed gas phase partial oxidation of C ₃ precursors of acrylic acid with molecular oxygen to be in the solid state catalysts z. B. the following contents (especially if as C ₃ precursor Pro is used) 1 to 30% by weight Acrylic acid, 0.05 to 10% by weight molecular oxygen, 1 to 30% by weight Water, > 0 to 5% by weight Acetic acid, > 0 to 3% by weight propionic acid, > 0 to 1% by weight Maleic acid and / or maleic anhydride, 0 to 2% by weight acrolein, 0 to 1% by weight Formaldehyde, > 0 to 1% by weight furfural, > 0 to 0.5% by weight benzaldehyde, 0 to 1% by weight Propylene, and as a residual amount substantially i nerten gases such. Nitrogen, carbon monoxide, Carbon dioxide, methane and / or propane.

Usually contains the product gas mixture, based on contained acrylic acid, ≥ 0.005 mol%, often ≥ 0.03 mol%, of furfurals. In As a rule, however, the so-called furfural content is ≤ 3 mol .-%.

The gas phase partial oxidation itself can be carried out as described in the prior art. Starting from propylene, the gas phase partial oxidation z. B. be carried out in two successive oxidation stages, as described in the EP-A 700 714 and in the EP-A 700 893 are described. Of course, but also in the DE-A 197 40 253 as well as in the DE-A 197 40 252 cited gas phase partial oxidations are used.

In terms of a small amount of secondary components formed, the propylene-gas phase partial oxidation is preferred as in DE-A 101 48 566 described carried out. As a propylene source to polymer grade propylene or chemical grade propylene according to the DE-A 102 32 748 be used. If the C ₃ precursor used is propane, the partial oxidation can be carried out as described in US Pat DE-A 102 45 585 be described described.

In principle, the gas phase partial oxidation but also as in the writings US 2006/0161019 . WO 2006/092410 . WO 2006/002703 . WO 2006/002713 . WO 2005/113127 . DE-A 10 2004 021 763 . EP-A 1 611 076 . WO 2005/108342 . EP-A 1 656 335 . EP-A 1 656 335 . EP-A 1 682 478 . EP-A 1 682 477 , the German applications no. 10 2006 054 214.2 and no. 10 2006 024 901.1 . EP-A 1 611 080 . EP-A 1 734 030 , the German applications no. 10 2006 000 996.7 , No. 10 2005 062 026.4 , No. 10 2005 062 010.8 , the international application no. PCT / EP 2006/065416 . PCT / EP 2006/067784 such as PCT / EP 2006/067080 be described described.

Often is the temperature of the gas phase partial oxidation leaving product gas mixture 150 to 350 ° C, many times 200 to 300 ° C, sometimes up to 500 ° C.

application point expedient is the hot product gas mixture then in a quenching device 1 by direct Cooling usually to a temperature of 100 to 180 ° C cooled before it, in terms of application, advantageous in common with the quench liquid 1 used, for the purpose of fractionating Condensation preferably in the lower section (preferably the lowest, z. B. the bottom space) containing a separating internals Condensation column is passed.

When Condensation column internals come in principle all common Built-in, especially soils, packs and / or Packing. The floors are bubble-capped, Sieve trays, valve trays and / or dual-flow trays prefers. Typically, in the case of a tray column the total number of shelves 20 to 100, often 20 to 80 and preferably 50 to 80.

According to the invention the condensation column is one which contains from bottom to top, first dual-flow trays and subsequently hydraulically sealed crossflow trays (z. B. Thormann ^® -floors) as separating internals, as the DE-A 102 43 625 , the DE-A 199 24 532 and the DE-A 102 43 625 recommend. The number of dual-flow trays can be 5 to 60, often 25 to 45, and the number of hydraulically sealed crossflow trays also 5 to 60, often 30 to 50. For the inventively preferred range of sour water formation (acrylic acid content of the reflux liquid from bottom to top, usually ≤ 15 wt .-%, or partially ≤ 10 wt .-%) come as a separation effective internals preferred valve bottoms into consideration, as is the DE-A 199 24 532 and the DE-A 102 43 625 describe. In principle, however, it would also be possible to use other conventional separation-active internals (the individual regions within the condensation column can, of course, be designed in a completely equivalent manner (instead of one above the other in a column) as a series connection of correspondingly smaller columns, for which reason the term used in this document (US Pat. Condensation column "in particular, as well as the term used in this document the column generally also includes such series connections of corresponding smaller columns).

When Quenching device 1 can all be used in the prior art for devices known for this purpose (eg spray scrubbers, Venturi scrubbers, bubble columns or other apparatus sprinkled surfaces), preferably Venturi scrubber or spray cooler used become.

to indirect cooling or heating of the quench liquid 1, this is preferred, but not especially when starting in a necessary way, via a heat exchanger or heat exchanger out. In this regard, All common heat exchangers are suitable or heat exchanger. Preferred are tube bundle heat exchangers, Plate heat exchanger and air cooler called. Suitable cooling media are air in the corresponding air cooler and cooling fluids, especially water, at the other cooling devices.

When Quench liquid 1 may, for. B. from the bottom of the condensation column withdrawn bottoms liquid (optionally combined with condensate discharged from the quench circuit 0), or via a side outlet high boiler fraction located near the swamp or a mixture of such bottoms liquid and high boiler fraction (especially when the swamp space and the lowest (theoretical Floor (the lowest separating fixtures) through a chimney tray are separated) are used. If necessary, only the off fraction of the quench liquid 1 withdrawn from the bottom of the condensation column passed the above heat exchanger. The Temperature of the quench liquid 1 is at entry in the quenching device 1 in the rule appropriate 90 ° C to 120 ° C.

The Launch point for the quenched (or otherwise cooled or not cooled) Product gas mixture of the catalytic Gas phase partial oxidation (according to the invention as described preferably in admixture with for direct cooling used Quenchflüssigkeit 1) in the condensation column is advantageous in the bottom space of this column, with advantage contains a Zentrifugaltropfenabscheider integrated and usually by a first chimney tray from the lowest separating effective Built-in is separated (application technology appropriate one leads in this case over a connecting line or via an overflow constantly high boiler fraction in the bottom of the condensation column). In an exemplary and preferred embodiment (which in the following without Restriction of general executability exclusively described) this is the first dual-flow soil a first series of appropriately equidistant arranged, dual-flow trays. The fireplace floor acts at the same time as collecting ground, from which continuously condensate (high boiler fraction) taken and as part of the quench liquid 1 in the quenching device 1 or in the sump space. The first series of Dual-flow trays is powered by a second chimney tray (trapped bottom) completed. From this second catch bottom is in the first side draw as a medium boiler fraction crude acrylic acid continuously which preferably has a purity of ≥ 90 or ≥ 95 % By weight.

Conveniently, Is this crude acrylic acid further distillative (rectificative) and / or crystallizing further purification steps and at least part of this distillation (rectification) and / or crystallization incurred bottoms and / or mother liquors below the first side draw, but above of the first catch tray return to the condensation column. Preferably, this recycling is carried out integrated with heat. D. h., Cold recycled mother liquor is through one or more indirect heat exchangers connected in series (eg spiral heat exchanger) led to in this taken from the condensation column and in the heat exchanger guided on the opposite side, crystallisative To cool further to be purified, crude acrylic acid. At the same time this causes a warming of the mother liquor causes. Preferably, two series-connected for this purpose Plate heat exchanger used.

In expediently, one becomes the (as medium boiler fraction) taken crude acrylic acid for the purpose of further purification to crystallize. The crystallization process to be used is subject in principle no restriction. The crystallization can be continuous or discontinuous, single-stage or multi-stage be carried out to any degree of purity.

at Demand may be the crystalline acrylic acid to be purified Pre-crystallization advantageously be added to water (in The rule then contains these, based on the contained Amount of acrylic acid, up to 20% by weight or up to 10% by weight, usually up to 5% by weight of water). At elevated aldehyde or other minor constituents may not be added to water, since the aldehydes in this case take over the function of the water capital. Very particular according to the invention Advantageously, the water is added in the form of acid water. This leads to an increase in the yield of pure acrylic acid.

It is surprising that even with prior addition of acidic acid to the crude acrylic acid (this measure also requires an increase in the acrylic acid yield) most suitable esterification (eg for the production of n-butyl acrylate, 2-ethylhexyl acrylate, methyl acrylate and ethyl acrylate) acrylic acid (purity ≥ 98% by weight) can already be achieved by a single crystallization stage. Conveniently, this crystallization stage is carried out as suspension crystallization, as shown in column 10 of DE-A 199 24 532 or in Example 1 of DE-A 102 23 058 is described (for example, in a cooling disk crystallizer as in WO 2006/111565 described). The resulting in the suspension crystallization acrylic acid crystals have a cubic to cuboid appearance. The length (L) to thickness (D) ratio is usually in the range from L: D = 1: 1 to L: D = 6: 1, preferably in the range 1: 1 to 4: 1, and particularly preferably in the range 1 , 5: 1 to 3.5: 1. The thickness D of the crystals is usually in the range of 20 to 600 μm, often 50 to 300 μm. The length L of the crystals is usually in the range of 50 to 1500 μm, often 200 to 800 μm. The separation of the suspension crystals from the remaining mother liquor can be carried out in the case of acrylic acid suitable for esterification on a centrifuge (eg a 2-stage or 3-stage pusher centrifuge), the separated crystals being advantageously washed on the centrifuge by means of melted pure crystals. Separating the suspension crystals of the remaining mother liquor by means of a wash column, for. For example, a melt scrubbing column (eg, one according to the WO 01/77056 , or the DE-A 101 56 016 , or the DE-A 102 23 058 , or as in the WO 2006/111565 , of the WO 04/35514 , of the WO 03/41833 , of the WO 02/09839 , of the WO 03/41832 , of the DE-A 100 36 881 , of the WO 02/55469 as well as the WO 03/78378 even a superabsorbent acrylic acid (purity ≥ 99.7 or ≥ 99.9 wt .-%), ie, acrylic acid, which is suitable for the production of water superabsorbent or other polyacrylates, can be achieved by means of a single crystallization stage. In this case, the total amount of the separated mother liquor is expediently returned to the condensation column.

The crystallization can also be carried out as a fractional falling film crystallization, as they EP-A 616 998 recommends. This can, for. For example, two, three or more (e.g., 2 to 4) purification steps (suitable falling-film crystallizers in this respect may contain, for example, 1000 to 1400 crystallization tubes of 10 to 15 meters in length and 50 to 100 mm in outer diameter). The separated in a higher purification stage mother liquor can be recycled to one of the previous purification stages. The mother liquor separated in the first purification stage is advantageously completely recycled to the condensation column. As an alternative to returning to one of the preceding purification stages, the mother liquors of the individual purification stages can also be recycled in their total amount into the condensation column. The pure product of the penultimate purification stage can be supplied completely or only partially to the last purification stage. If only a part of the feed is to mix the remaining amount usually with the pure product of the last cleaning stage to then consumption-friendly end product.

According to the invention expedient you get a subset of over the first page subtraction withdrawn crude acrylic acid below the to this feeding the appropriate catch floor to the dual-flow floor. This soil is usually also optionally in the condensation column feed the mother liquor to be recycled. In advance of the feed you will usually the mother liquor, as already described heat-in-warm to a temperature, the approximately at the withdrawal temperature of the crude acrylic acid equivalent.

A other subset of taken over the first page deduction Raw acrylic acid is advantageously obtained by indirect Heat heat exchange by 10 to 15 ° C and above the sampling point, preferably immediately below of the first subsequent dual-flow tray, return to the condensation column. This measure has a favorable effect on the acetic acid content the withdrawn crude acrylic acid.

Above the second catch tray, a second series of expediently equidistant dual-flow trays follows, which is then separated from hydraulically sealed cross-flow mass transfer trays (eg Thormann trays or modified Thormann trays according to US Pat DE-A 102 43 625 ), which are expediently also arranged equidistantly, are replaced. The top dual-flow soil may be considered as Equipped distributor base. That is, he has z. B. overflow troughs with serrated overflow.

Of the The first of the Thormann floors from below is application-oriented appropriate one in which the ground draining liquid over six formed as tubes Downpipes expires. These pipes are against the gas space of the underlying dual-flow soil hydraulically sealed. The weir height of the six drainpipes increases Direction of flow of the cross flow system in terms of application technology expediently. Advantageously, the hydraulic Seal idle openings with baffle plate on. The drainpipes are preferred in the second half, more preferred in the last third of the floor cross-section (the inlet to the floor opposite) evenly distributed.

The hydraulic sealing takes place in a cup with sloping overflow weir (45 ° C).

The Cross-flow mass transfer trays are mixed with a third Kaminboden (catch bottom) completed.

Above the third catch tray are, preferably double-flow, valve trays. The principle of valve floors as well as inventively usable valve floors can be found for. In Technical Progress Reports, Volume 61, Fundamentals of Column Sizing, pp. 96-138 , They are essentially characterized by the fact that they provide the flow-through steam over a wide load range corresponding to the respective load flow opening. Ballast floors are preferably used according to the invention. That is, in the openings of the floor there are cages with openings closed by weights. Particularly preferred according to the invention are VV12 valves from the company Stahl, DE, Viernheim. In the valve floor space condenses essentially water and more volatile than water volatile components. The condensate obtained is sour water.

from third catch bottom is continuous in a second side draw taken the sour water. Part of the extracted sour water is on the top of the cross-flow mass transfer trays returned to the condensation column. Another Part of the extracted sour water is by indirect heat exchange cooled and, as appropriate split, also returned to the condensation column. A cooled subset is thereby on the uppermost valve bottom (at a temperature of 15 to 25, preferably 20 to 25 ° C) and the other cooled subset to one between the third catch bottom and the uppermost valve bottom approximately in the middle Returned valve bottom in the condensation column (with a temperature of 20 to 35, preferably 25 to 30 ° C). From the remaining extracted amount of acid water, the contained Acrylic acid amount separated according to the invention become.

Part of the cooling (which can be done via one or more indirect heat exchangers connected in series) is effected by passing the corresponding amount of acid water through the evaporator of the C ₃ precursor (eg the propylene evaporator) to give liquid C ₃ . Precursor, e.g. As propylene, for the heterogeneously catalyzed gas phase oxidation in the gas phase.

The volatiles will be on your head more easily than water the condensation column as residual gas (or residual gas mixture) in gaseous form withdrawn and normally at least partially as a diluent gas (cycle gas) recycled to the gas phase partial oxidation. To avoid condensation in the cycle gas compressor, the residual gas mixture previously overheated by indirect heat exchange. The not circulated part of the residual gas mixture is normally fed to combustion. Part of the (preferably compressed) residual gas mixture is, as already described, in advantageous as stripping gas for the separation of acrylic acid from the extract and from the bottom liquid of the condensation column used. Advantageously, the gas phase partial oxidation with an excess carried out on molecular oxygen, so that the residual gas mixture and thus the first and second stripping gas molecular oxygen contained when residual gas mixture is used as such stripping gas.

To the The purpose of the polymerization inhibition is the top of the hydraulic sealed cross-flow mass transfer trays a solution of p-methoxyphenol (= MEHQ) in acrylic acid or (preferred according to the invention) an MEHQ melt and (in both cases) optionally in addition a solution of phenothiazine in acrylic acid fed. As acrylic acid is preferably a pure acrylic acid used as in the further purification the removed crude acrylic acid is produced. For example can be generated as part of the crystallisative purification Pure acrylic acid (pure product) can be used. This solution is also useful for pure product stabilization used.

additionally is about in the middle of the column section with the hydraulic sealed cross-flow mass transfer trays a solution of phenothiazine (= PTZ) fed into rice product.

In principle, the sour water formation z. B. also be practiced behind a first condensation column (see. DE-A 102 35 847 ). In this case, from the then at the top of the first condensation column Leichtsiedergasstrom expediently by direct cooling in a free internals (this can be integrated for the purpose of sour water formation in the condensation column, then such an internals free quenching z B. separated via a chimney tray from the top separating components within the condensation column) or internals containing downstream space (second column) by means of a quench liquid 2 essentially water condense. The condensate obtained is again the sour water. A portion of the acid water will then be recirculated in a meaningful way to increase the separation efficiency at the top of the first condensation column in selbige. Another portion of the sour water is indirectly cooled in an external heat exchanger and used as the quench liquid 2 and from the remaining amount of acid water, the acrylic acid can be extracted according to the invention again. Volatile constituents of the low-boiler stream, in turn, form residual gas which is normally at least partially recycled as recycle gas into the gas-phase partial oxidation or used as stripping gas.

expedient The dual-flow trays extend at the preferred level Variant of the method according to the invention in the Condensation column in about up to the cross section in the condensation column, from from the acrylic acid contents of the return liquid considered to the column head ≤ 90 wt .-%, based on the weight of the return fluid, amount.

The number of dual-flow trays is, as already stated, for the described preferred variant of the fractional condensation usually 25 to 45. Their opening ratio is suitably 12 to 25%. As passage points, the dual-flow trays preferably have circular holes with a uniform circular diameter. The latter is suitably 10 to 20 mm. If necessary, the hole diameter in the condensation column can be tapered or enlarged from top to bottom and / or the number of holes can be reduced or increased (eg the hole diameter can be uniformly 14 mm and the opening ratio from top to bottom 17.4%). increase to 18.3%). However, the number of holes can also be constant across all dual-flow trays. Furthermore, the circular holes on the individual dual-flow trays are preferably uniformly arranged in strict triangular division (see. DE-A 102 30 219 ).

Furthermore shows the punching burr of the punched out in the dual-flow trays Passage openings in the condensation column are preferred down (unwanted polymerisation is thereby reduced).

According to the invention makes sense it is when the number of used in the condensation column Dual-flow trays contain about 10 to 15 theoretical plates equivalent.

The Number of the to the dual-flow trays in the inventively preferred Condensation column subsequent hydraulically sealed Cross-flow mass transfer trays, as already mentioned, in usually 30 to 50 amount. Your opening ratio is suitably 5 to 25%, preferably 10 to 20% (The opening ratio is generally the Percentage of the passage cross sections on the total cross section again; it is with the preferably used cross-flow mass transfer trays quite generally useful in the aforementioned area).

single-flow Cross-flow mass transfer trays are preferred according to the invention used.

In The rule is the number of hydraulically sealed crossflow trays for the preferred variant of the fractionating product gas mixture condensation so that they are about 10 to 30, often 25 theoretical Separators corresponds.

Either the hydraulically sealed crossflow trays as well as optionally used valve floors have at least one downcomer on. You can do both single-flow and multi-flow, z. B. be designed double-ended. They can do that as well have a single-flow design more than one downcomer. As a rule, the inlet shafts of the valve trays are also hydraulically sealed.

The polymerization inhibition of the quench system 1 for the product gas mixture of the partial gas phase oxidation can be achieved both via polymerization inhibitors present in the bottoms used for quenching (from the condensation column) and via high boilers used for quenching fraction (from the condensation column) contained polymerization inhibitors are accomplished.

Of the Advantage of the method lies again justified in that it is at substantially the same Purity an increased yield of crude acrylic acid allows. All statements made in this document apply in particular for a product gas mixture which is replaced by (preferably two-stage) heterogeneous partial oxidation of propylene to acrylic acid was obtained. The preferred embodiment described above limited the method of the invention in no way the general feasibility.

Finally It should be noted that both the first stripping gas and the second stripping gas advantageously contains molecular oxygen.

It should also be added that in the process according to the invention, the condensation column is optionally supplied with a liquid (different from the return liquid) via a feed point located between its first side draw and its second side draw, whose boiling temperature T _{S is} greater than or equal to 1 atm at a pressure the boiling point T _W of water at a pressure of 1 atm. Basically, z. B. as in the EP-A 1 818 324 be described described. As such absorbents come z. B. higher boiling organic liquids into consideration. For example, those organic liquids which are used in the DE-A 103 36 386 and the prior art cited in this document are recommended as absorbents. Needless to say, but also in the EP-A 1 818 324 recommended absorbent can be used at this point.

For example, as such absorbent high-boiling (inert) liquid hydrophobic organic liquids are suitable, as described in the EP-A 722 926 , of the DE-A 44 36 243 and the DE-A 103 36 386 are listed (for example Dimethyphthalat, diethyl phthalate and / or diphyl). These are z. As liquids whose boiling point at atmospheric pressure (1 atm) is above the boiling point of acrylic acid and which consist of at least 70 wt .-% of such molecules that do not contain outward polar group and thus, for example, are not able to hydrogen bonds to build. As such absorbents are exemplified as Diphyl ^® called mixtures of diphenyl ether (70 to 75 wt .-%) and diphenyl (25 to 30 wt .-%) and the mixture of a mixture of 70 to 75 wt .-% diphenyl ether and 25 to 30 wt .-% diphenyl and, based on this mixture, 0.1 to 25 wt .-% dimethyl phthalate.

Of course, as such absorbents and aqueous liquids can be used. For example, such aqueous liquids are those which are used in the EP-A 1 818 324 recommended. Among other things, water belongs to these absorbents. Of course, the aqueous phase remaining in the extraction of acid water to be carried out according to the invention can also be used as such an aqueous absorption medium.

Usually the abovementioned absorption additive will serve the purpose of the proportion of certain, in the over the first side draw from the condensation column led out crude acrylic acid specifically to reduce contained secondary components. It is therefore of Advantage, if the absorbent used itself these minor components at most in a very small proportion by weight (preferably at all not).

in the Case of using an aqueous absorbent is it z. B. low, if its individual minor component weight shares smaller than the respective ones of the sour water.

The Supply of aqueous absorbents (eg of water) is suitable u. a. in a particularly favorable way to the salary to a comparable with acrylic acid boiling point Aldehydes (especially the content of furfurals) in the over led out the first side draw from the condensation column to reduce crude acrylic acid. in principle may also be a mixture of a aqueous and from an organic liquid be used. In principle, such a mixture can also be multiphase be.

The Absorbent can be beneficial at the same height in the condensation column be performed as the reflux liquid. Both can also be mixed in the condensation column be guided.

The temperature of the absorbent may vary over a wide range as it is fed to the condensation column. It can be both above and below the temperature of the return liquid. Frequently, the temperature of the absorbent within the interval ± 20 ° C to the temperature of the Return fluid lie around. Preferably, the temperature of the reflux liquid and the absorbent are the same.

contains the crude acrylic acid removed via the first side draw Parts of the absorbent used, they are usually via the crystallisative described in this document Further purification of the crude acrylic acid separated from the same. Otherwise, a co-used absorbent normally falls in the led out of the condensation column bottoms liquid and, after separation from the same in the above be reused as absorbent as described.

According to the invention expedient is the mass flow of a guided into the condensation column absorbent, based on the supplied as part of the condensation column Product gas mixture guided in the condensation column Mass flow of acrylic acid, 0 to 30%.

Based on the between the first side print and the second side print from the condensation column located longitudinal section of the Condensation, it is the supply of an absorbent in the condensation column application technology appropriate into the upper third of this longitudinal section.

Instead of a crude acrylic acid obtainable according to the invention, the crystallisative further purification of crude acrylic acid described in this document can also be carried out in accordance with the method described in US Pat DE-A 103 36 386 crude acrylic acid obtainable by the procedure described (in particular, such a crystallisative further purification according to claims 16 to 20 of the present specification). Of course, such a further purification by crystallization can also be applied to any mixture of the two abovementioned types of crude acrylic acid. From such a procedure you will z. B. make use of when the separation process according to the invention and a separation process according to the DE-A 103 36 386 operated in parallel to separate acrylic acid from product gas mixtures of (possibly in parallel) heterogeneously catalyzed partial gas phase oxidations of C ₃ precursors of acrylic acid. In the event that the operation of the fractionating condensation according to the invention for such an acrylic acid separation should be temporarily out of service, according to the DE-A 103 36 386 but further crude acrylic acid produced this crystalline further purification would be fed, one would a partial flow (based on the crystallization of the further supplied purge mass flow of crude acrylic acid, a mass flow of 5 to 30%, typically 10 to 20% (the separated crystals must remain in accordance with specifications); remaining residual flow of mother liquor will normally (together (in a mixture) with the mass flow of crude acrylic acid) in the crystallization recycle) in the separation of the suspension crystallizate from the Acrylsäurekristallisatsuspension accumulating mother liquor in a storage tank (the supply to the storage tank can be continuous or clocked take place) and after the re-commissioning of the fractionating condensation successively in the mixture with then inventively accumulating mother liquor in the fractionating condensation recycle (based on the then on according to the invention falling mother liquor in the fractionating condensation recycled mass flow in a mass flow of> 0 to 20%, preferably> 0 to 10%). The removal from the storage tank can be done continuously or clocked for this purpose. Normally, it is made to conform to the specification (the design capacity of the crystallization is usually above the design capacity of the crude acrylic acid, but in the short term crystallization can be further refined above the design capacity of the crystallization).

• 1. Ein Verfahren zur Herstellung von Acrylsäure, bei dem man durch heterogen katalysierte Gasphasen-Partialoxidation wenigstens eines C₃-Vorläufers der Acrylsäure mit molekularem Sauerstoff an im festen Aggregatzustand befindlichen Katalysatoren bei erhöhter Temperatur ein Acrylsäure, Wasserdampf und Nebenkomponenten enthaltendes Produktgasgemisch erzeugt, die Temperatur des Acrylsäure, Wasserdampf und Nebenkomponenten enthaltenden Produktgasgemischs gegebenenfalls durch direkte und/oder indirekte Kühlung verringert, und das Acrylsäure, Wasserdampf und Nebenkomponenten enthaltende Produktgasgemisch anschließend in eine mit trennwirksamen Einbauten ausgerüstete Kondensationskolonne leitet, innerhalb der Kondensationskolonne in sich selbst aufsteigen lässt und dabei fraktionierend kondensiert sowie über einen ersten, oberhalb der Zuführstelle des Produktgasgemischs in die Kondensationskolonne befindlichen, Seitenabzug eine Wasser und Nebenkomponenten entreichert enthaltende rohe Acrylsäure als Zielprodukt und über einen zweiten, oberhalb des ersten Seitenabzugs befindlichen, Flüssigphasenabzug (vorzugsweise einen Seitenabzug) noch Acrylsäure und Nebenkomponenten enthaltendes saures Wasser und am Kopf der Rektifikationskolonne ein tiefer als Wasser siedende Nebenkomponenten enthaltendes Restgasgemisch sowie aus dem Sumpfraum der Kondensationskolonne eine noch Acrylsäure und schwerer als Acrylsäure siedende Folgeprodukte und Nebenkomponenten enthaltende Sumpfflüssigkeit aus der Kondensationskolonne herausführt, eine Teilmenge des entnommenen sauren Wassers als solches und/oder nach Abkühlung desselben als Rücklaufflüssigkeit in die Kondensationskolonne rückführt und die rohe Acrylsäure gegebenenfalls wenigstens einem weiteren thermischen Trennverfahren zum Zweck ihrer Weiterreinigung unterwirft, dadurch gekennzeichnet, dass man wenigstens bei einer Teilmenge von nicht in die Kondensationskolonne rückgeführtem saurem Wasser in diesem enthaltene Acrylsäure durch Extraktion mit einem organischen Lösungsmittel unter Ausbildung eines Acrylsäure enthaltenden organischen Extraktes aus dem sauren Wasser heraus in das organische Lösungsmittel aufnimmt, nachfolgend die Acrylsäure aus dem organischen Extrakt unter Anwendung wenigstens eines thermischen Trennverfahrens abtrennt und vom Extrakt abgetrennte Acrylsäure in die Kondensationskolonne zurückführt, oder der Weiterreinigung der rohen Acrylsäure zuführt und/oder in die wässrige Lösung eines Metallhydroxids aufnimmt.
• 2. Ein Verfahren gemäß Ausführungsform 1, dadurch gekennzeichnet, dass der C₃-Vorläufer Propylen, oder Acrolein, oder ein Gemisch aus Propylen und Acrolein ist.
• 3. Ein Verfahren gemäß Ausführungsform 1 oder 2, dadurch gekennzeichnet, dass man bei wenigstens 25 Gew.-% von nicht in die Kondensationskolonne rückgeführtem saurem Wasser in diesem enthaltene Acrylsäure durch Extraktion mit einem organischen Lösungsmittel unter Ausbildung eines Acrylsäure enthaltenden organischen Extraktes in das organische Lösungsmittel aufnimmt, nachfolgend die Acrylsäure aus dem organischen Extrakt unter Anwendung wenigstens eines thermischen Trennverfahrens abtrennt und die vom Extrakt abgetrennte Acrylsäure entweder in die Kondensationskolonne zurückführt, oder der Weiterreinigung der rohen Acrylsäure zuführt und/oder in die wässrige Lösung eines Metallhydroxids aufnimmt.
• 4. Ein Verfahren gemäß einer der Ausführungsformen 1 bis 3, dadurch gekennzeichnet, dass die Extraktion der Acrylsäure aus dem Sauerwasser in einer Extraktionskolonne durchgeführt wird, die als trennwirksame Einbauten Packungen und/oder Siebböden enthält.
• 5. Ein Verfahren gemäß Ausführungsform 4, dadurch gekennzeichnet, dass das organische Lösungsmittel am Kopf der Extraktionskolonne und das Sauerwasser im Sumpfbereich der Extraktionskolonne aufgeben wird und das organische Lösungsmittel als dispers verteilte Phase in der kontinuierlichen Sauerwasserphase absteigt oder dadurch gekennzeichnet, dass das Sauerwasser am Kopf der Extraktionskolonne und das organische Lösungsmittel im Sumpfbereich der Extraktionskolonne aufgegeben wird, und das organische Lösungsmittel als dispers verteilte Phase in der kontinuierlichen Sauerwasserphase aufsteigt.
• 6. Ein Verfahren gemäß einer der Ausführungsformen 1 bis 5, dadurch gekennzeichnet, dass das organische Lösungsmittel wenigstens einen Ester aus einer 5 bis 20 C-Atome enthaltenden aliphatischen oder aromatischen Monocarbonsäure und einem 1 bis 8 C-Atome aufweisenden Alkohol enthält.
• 7. Ein Verfahren nach einer der Ausführungsformen 1 bis 5, dadurch gekennzeichnet, das das organische Lösungsmittel wenigstens einen Diester aus einer 5 bis 20 C-Atome enthaltenden aliphatischen oder aromatischen Dicarbonsäure und einem 1 bis 8 C-Atome aufweisenden Alkohol enthält.
• 8. Ein Verfahren gemäß einer der Ausführungsformen 1 bis 5 oder gemäß Ausführungsform 7, dadurch gekennzeichnet, dass das organische Lösungsmittel Dimethylphthalat, Diethylphthalat, Dimethylisophthalat, Diethylisophthalat, Dimethyltherephthalat und/oder Diethyltherephthalat ist.
• 9. Ein Verfahren gemäß einer der Ausführungsformen 1 bis 8, dadurch gekennzeichnet, dass der Siedepunkt des organischen Lösungsmittels bei Atmosphärendruck ≥ 200°C beträgt.
• 10. Ein Verfahren gemäß einer der Ausführungsformen 1 bis 9, dadurch gekennzeichnet, dass man die Acrylsäure aus dem organischen Extrakt durch Strippen mit einem ersten Strippgas abtrennt und das mit Acrylsäure beladene erste Strippgas in die Kondensationskolonne rückführt und/oder die im ersten belade nen Strippgas enthaltene Acrylsäure in die wässrige Lösung eines Metallhydroxids aufnimmt.
• 11. Ein Verfahren gemäß einer der Ausführungsformen 1 bis 9, dadurch gekennzeichnet, dass man die Acrylsäure aus dem organischen Extrakt durch Strippen mit einem ersten Strippgas abtrennt und das dabei anfallende mit Acrylsäure beladene erste Strippgas als ein zweites Strippgas dazu verwendet, um in aus der Kondensationskolonne herausgeführter Sumpfflüssigkeit noch enthaltene Acrylsäure freizustrippen und das dabei anfallende mit Acrylsäure beladene zweite Strippgas in die Kondensationskolonne rückführt und/oder die im zweiten Strippgas enthaltene Acrylsäure in die wässrige Lösung eines Metallhydroxids aufnimmt.
• 12. Ein Verfahren gemäß Ausführungsform 11, dadurch gekennzeichnet, dass die Strippung der aus der Kondensationskolonne herausgeführten Sumpfflüssigkeit in einer mit trennwirksamen Einbauten versehenen Strippkolonne durchgeführt wird, und die Temperatur im Sumpf der Strippkolonne 150 bis 190°C beträgt.
• 13. Ein Verfahren gemäß Ausführungsform 11 oder 12, dadurch gekennzeichnet, dass man das mit Acrylsäure beladene zweite Strippgas einer Gegenstrom-Rektifikation unterwirft, bevor es mit Acrylsäure beladen in die Kondensationskolonne rückgeführt und/oder die in ihm enthaltene Acrylsäure in die wässrige Lösung eines Metallhydroxids aufgenommen wird.
• 14. Ein Verfahren gemäß einer der Ausführungsformen 10 bis 13, dadurch gekennzeichnet, dass als erstes Strippgas Luft, N₂, CO₂ und/oder Wasserdampf verwendet wird.
• 15. Ein Verfahren gemäß einer der Ausführungsformen 10 bis 13, dadurch gekennzeichnet, dass als erstes Strippgas Restgasgemisch verwendet wird.
• 16. Ein Verfahren gemäß einer der Ausführungsformen 1 bis 16, dadurch gekennzeichnet, dass die rohe Acrylsäure kristallisativ weitergereinigt wird.
• 17. Ein Verfahren gemäß Ausführungsform 17, dadurch gekennzeichnet, dass der rohen Acrylsäure vorab der kristallisativen Weiterreinigung eine Teilmenge des nicht in die Kondensationskolonne rückgeführten sauren Wassers zugeführt wird.
• 18. Ein Verfahren gemäß Ausführungsform 16 oder 17, dadurch gekennzeichnet, dass die kristallisative Weiterreinigung der rohen Acrylsäure oder deren Gemisch mit saurem Wasser durch Suspensionskristallisation erfolgt.
• 19. Ein Verfahren gemäß Ausführungsform 18, dadurch gekennzeichnet, dass zur Trennung von bei der Suspensionskristallisation verbliebener Mutterlauge und gebildetem Suspensionskristallisat eine Waschkolonne mitverwendet wird.
• 20. Ein Verfahren gemäß einer der Ausführungsformen 17 bis 19, dadurch gekennzeichnet, dass sich ein Verfahren der radikalischen Polymerisation anschließt, in welchem aufgeschmolzenes Acrylsäurekristallisat und/oder dessen Metallsalz miteinpolymerisiert wird.
• 21. Ein Verfahren gemäß einer der Ausführungsformen 10, 11, 13, dadurch gekennzeichnet, dass sich ein Verfahren der radikalischen Polymerisation anschließt, in welchem aus beladenem erstem und/oder zweitem Strippgas in die wässrige Lösung eines Metallhydroxids aufgenommene Acrylsäure miteinpolymerisiert wird.
• 22. Ein Verfahren gemäß einer der Ausführungsformen 1 bis 21, dadurch gekennzeichnet, dass eine Teilmenge des Restgasgemischs als Kreisgas in die Gasphasen-Partialoxidation rückgeführt wird.
• 23. Ein Verfahren gemäß einer der Ausführungsformen 1 bis 22, dadurch gekennzeichnet, dass das organische Lösungsmittel eine Massendichte aufweist, die sich unter den Bedingungen der Extraktion von derjenigen von Wasser um ≥ 25 kg/m³ unterscheidet.
• 24. Ein Verfahren gemäß einer der Ausführungsformen 1 bis 23, dadurch gekennzeichnet, dass die wässrige Lösung eines Metallhydroxids NaOH, KOH, Ca(OH)₂ und/oder Mg(OH)₂ gelöst enthält.
• 25. Ein Verfahren gemäß einer der Ausführungsformen 1 bis 24, dadurch gekennzeichnet, dass der Kondensationskolonne über eine zwischen ihrem ersten Seitenabzug und ihrem zweiten Seitenabzug gelegene Zufuhrstelle ein flüssiges Absorptionsmittel zugeführt wird, dessen Siedetemperatur T_S bei einem Druck von 1 atm größer oder gleich der Siedetemperatur T_W von Wasser bei einem Druck von 1 atm ist.

Thus, the present invention particularly includes the following embodiments:

• 1. A process for the preparation of acrylic acid, in which by heterogeneously catalyzed gas phase partial oxidation of at least one C ₃ precursor of acrylic acid with molecular oxygen to solid state catalysts at elevated temperature produces an acrylic acid, water vapor and minor components containing product gas mixture, the temperature the acrylic acid, water vapor and secondary components containing product gas mixture optionally reduced by direct and / or indirect cooling, and the acrylic acid, water vapor and secondary components containing product gas mixture then passes into a equipped with separation internals condensation column, within the condensation column can rise in itself and thereby fractionally condenses and via a first, located above the feed point of the product gas mixture in the condensation column, side draw containing a water and minor components entreichert containing e raw acrylic acid as the target product and via a second, located above the first side draw, liquid phase withdrawal (preferably a side draw) still acrylic acid and secondary components containing acidic water and at the top of the rectification column deeper than water boiling secondary components containing residual gas mixture and from a bottoms of the removed acidic water as such and / or after cooling thereof as reflux liquid in the condensation column and the crude acrylic acid optionally at least one further recycles the bottom space of the condensation column still containing acrylic acid and heavier than acrylic acid boiling by-products and secondary components bottoms liquid out of the condensation column thermal separation process for the purpose of their further purification, characterized in that at least in a subset of not recycled to the condensation column acidic water contained in this acrylic acid by extraction with an organic solvent to form an acrylic acid-containing organic extract from the acidic water out in the organic Solvent, subsequently separating the acrylic acid from the organic extract using at least one thermal separation process and ex trakt separated acrylic acid in the condensation column, or the further purification of the crude acrylic acid feeds and / or receives in the aqueous solution of a metal hydroxide.
• 2. A process according to embodiment 1, characterized in that the C ₃ precursor is propylene, or acrolein, or a mixture of propylene and acrolein.
• 3. A process according to embodiment 1 or 2, characterized in that in at least 25 wt .-% of not recycled to the condensation column acidic water contained in this acrylic acid by extraction with an organic solvent to form an acrylic acid-containing organic extract in the organic Solvent, subsequently separating the acrylic acid from the organic extract using at least one thermal separation process and either recirculating the acrylic acid separated from the extract to the condensation column, or further purifying the crude acrylic acid and / or incorporating it into the aqueous solution of a metal hydroxide.
• 4. A method according to any one of embodiments 1 to 3, characterized in that the extraction of the acrylic acid from the sour water is carried out in an extraction column, which contains as separable internals packings and / or sieve plates.
• 5. A method according to embodiment 4, characterized in that the organic solvent at the top of the extraction column and the acidic water in the bottom region of the extraction column is abandoned and the organic solvent descends as disperse distributed phase in the continuous acid phase or characterized in that the sour water at the top the extraction column and the organic solvent is fed in the bottom region of the extraction column, and the organic solvent ascends as a disperse phase in the continuous acid phase.
• 6. A method according to any one of embodiments 1 to 5, characterized in that the organic solvent contains at least one ester of an aliphatic or aromatic monocarboxylic acid containing 5 to 20 C atoms and an alcohol having 1 to 8 C atoms.
• 7. A method according to any one of embodiments 1 to 5, characterized in that the organic solvent contains at least one diester of an aliphatic or aromatic dicarboxylic acid containing 5 to 20 C atoms and an alcohol having 1 to 8 C atoms.
• 8. A method according to any of embodiments 1 to 5 or according to embodiment 7, characterized in that the organic solvent is dimethyl phthalate, diethyl phthalate, dimethyl isophthalate, diethyl isophthalate, dimethyl terephthalate and / or diethyl terephthalate.
• 9. A method according to any one of embodiments 1 to 8, characterized in that the boiling point of the organic solvent at atmospheric pressure ≥ 200 ° C.
• 10. A process according to any one of embodiments 1 to 9, characterized in that the acrylic acid is separated from the organic extract by stripping with a first stripping gas and the acrylic acid laden first stripping gas is recycled to the condensation column and / or the first loading stripping gas contained acrylic acid in the aqueous solution of a metal hydroxide.
• 11. A method according to any one of embodiments 1 to 9, characterized in that one separates the acrylic acid from the organic extract by stripping with a first stripping gas and the resulting charged with acrylic acid first stripping gas used as a second stripping gas to in from Extracting condensation column still carried out bottoms liquid still contained acrylic acid and recycles charged thereby charged with acrylic acid second stripping gas in the condensation column and / or receives the acrylic acid contained in the second stripping gas in the aqueous solution of a metal hydroxide.
• 12. A method according to embodiment 11, characterized in that the stripping of the led out of the condensation column bottoms liquid is carried out in a stripping column provided with separating internals, and the temperature in the bottom of the stripping column is 150 to 190 ° C.
• 13. A process according to embodiment 11 or 12, characterized in that the second stripping gas charged with acrylic acid is subjected to a countercurrent rectification before being charged with acrylic acid in the condensation column and / or the acrylic acid contained in it in the aqueous solution of a metal hydroxide is recorded.
• 14. A method according to any one of embodiments 10 to 13, characterized in that is used as the first stripping gas air, N ₂ , CO ₂ and / or water vapor.
• 15. A method according to any one of embodiments 10 to 13, characterized in that residual gas mixture is used as the first stripping gas.
• 16. A process according to any of embodiments 1 to 16, characterized in that the crude acrylic acid is further purified by crystallization.
• 17. A method according to embodiment 17, characterized in that the raw acrylic acid before the crystallization further purification, a subset of not recycled to the condensation column acidic water is supplied.
• 18. A process according to embodiment 16 or 17, characterized in that the crystallisative further purification of the crude acrylic acid or its mixture with acidic water takes place by suspension crystallization.
• 19. A process according to embodiment 18, characterized in that a washing column is used for the separation of remaining in the suspension crystallization mother liquor and formed suspension crystals.
• 20. A method according to any one of embodiments 17 to 19, characterized in that a subsequent process of free radical polymerization, in which molten acrylic acid crystallizate and / or its metal salt is co-polymerized.
• 21. A method according to any one of embodiments 10, 11, 13, characterized in that followed by a method of free radical polymerization in which is loaded from loaded first and / or second stripping gas into the aqueous solution of a metal hydroxide incorporated acrylic acid.
• 22. A method according to any one of embodiments 1 to 21, characterized in that a partial amount of the residual gas mixture is recycled as recycle gas in the gas phase partial oxidation.
• 23. A method according to any one of embodiments 1 to 22, characterized in that the organic solvent has a mass density which differs under the conditions of extraction of that of water by ≥ 25 kg / m ³ .
• 24. A method according to any one of embodiments 1 to 23, characterized in that the aqueous solution of a metal hydroxide NaOH, KOH, Ca (OH) ₂ and / or Mg (OH) ₂ dissolved.
• 25. A method according to any one of embodiments 1 to 24, characterized in that the condensation column is fed via a location between its first side draw and its second side draw feed a liquid absorbent whose boiling temperature T _S at a pressure of 1 atm greater than or equal to Boiling temperature T _W of water at a pressure of 1 atm.

Examples and Comparative Example

Example 1 (described is a stationary Status)

From a two-stage executed heterogeneously catalyzed gas phase partial oxidation of propylene of purity "Chemical grade" in three parallel operated tandem reactor reactor lines is a temperature of 270 ° C and a pressure of 1.5 bar exhibiting common product gas mixture of the following composition obtained: 10.3141% by weight Acrylic acid, 0.2609% by weight Acetic acid, 4.6513% by weight Water, 0.0251% by weight formic acid, 0.0851% by weight Formaldehyde, 0.1052% by weight acrolein, 0.0024% by weight propionic acid, 0.0028% by weight furfural, 0.0012% by weight allyl, 0.0013% by weight allyl formate, 0.0032% by weight benzaldehyde, 0.115% by weight maleic anhydride, 0.0096% by weight benzoic acid, 0.0126% by weight phthalic anhydride, 2.0334% by weight CO ₂ , 0.6604% by weight CO, 0.6259% by weight Propane, 0.1459% by weight propylene, 2.3772% by weight O ₂ , and 78.5670% by weight N ₂ .

The the three tandem reactor reactor lines respectively to be supplied Reaction gas mixture is in each case a mixture of cycle gas and chemical grade propylene, to which primary air is subsequently added becomes. The mixture accomplishes in each case a static mixer.

Between the first and the second stage reactor is still secondary air fed.

The quantitative ratios are adapted to the operating state of the respective reactor line and before the first-stage reactor are: A) Cycle gas = 25339 kg / h, Chemical grade propylene = 3481 kg / h, Air = 17791 kg / h. B) Cycle gas = 38341 kg / h, Chemical grade propylene = 4035 kg / h, Air = 19561 kg / h. C) Cycle gas = 30874 kg / h, Chemical grade propylene = 4689 kg / h, Air = 23936 kg / h.

The essential contents of the three resulting reaction gas mixture streams are: A) 10.2909% by weight O ₂ , 1.2926% by weight CO ₂ , 0.4136% by weight CO, 0.6533% by weight Propane, 7.2976% by weight propylene, 1.5383% by weight H ₂ O, and 78.2693% by weight N ₂ ; B) 8.9782% by weight O ₂ , 1.4660% by weight CO ₂ , 0.4710% by weight CO, 0.6744% by weight Propane, 6.3907% by weight propylene, 1.6626% by weight H ₂ O, and 80.0789% by weight N ₂ ; and C) 10.6981% by weight O ₂ , 1.2357% by weight CO ₂ , 0.3948% by weight CO, 0.6500% by weight Propane, 7.6922% by weight propylene, 1.4968% by weight H ₂ O, and 77.5992% by weight N ₂ .

The Product gas mixture (177184 kg / h) is operated in a co-current Spray cooler (quench 1) by direct cooling cooled to a temperature of 107.3 ° C.

The for direct cooling of the product gas mixture to be used Liquid (quench liquid 1) is a subset a mixture 1 of bottoms liquid, which is the bottom of the is taken in the condensation column described below, and a small amount (251 kg / h) of taken from the Quenchkreis 0 Condensate.

Levels of this mixture 1 (temperature = 104.9 ° C) are: 64.6170% by weight Acrylic acid, 0.3883% by weight Acetic acid, 1.0300% by weight Water, 0.0132% by weight formic acid, 0.0011% by weight Formaldehyde, 0.0083% by weight acrolein, 0.0384% by weight propionic acid, 0.3331% by weight furfural, 0.0016% by weight allyl, 0.0008% by weight allyl formate 0.1609% by weight benzaldehyde, 4,4001% by weight maleic anhydride, 0.3976% by weight benzoic acid, 0.5228% by weight phthalic anhydride, 12.8970% by weight Diacrylic acid - Michael adducts 13.9178% by weight Polyacrylic acid - Michael adducts 0.1258% by weight phenothiazine, 0.4408% by weight MEHQ 0.7052% by weight other high-boiling components, and 0.0002% by weight Oxygen.

The spray cooler of Quenchkreises 1 for direct cooling of the product gas mixture is fed with the aforementioned temperature only an amount of 458 m ³ / h.

3137 kg / h are fed as feed to the second stripping column and 1195 kg / h are supplied to the quench circuit 0 so as the quench liquid 0 and the top soil the second stripping column to leading reflux liquid to inhibit unwanted polymerization.

The in the direct cooling resulting mixture from to 107.3 ° C. cooled product gas mixture and non-evaporated quench liquid 1 is fed as such into the bottom of the condensation column. Of the Pressure in the sump chamber and quench 1 is 1.50 bar.

Of the Inner diameter of the condensation column is in the range the Thormann floors 6.5 m and otherwise 6.0 m.

3137 kg / h of the mixture 1 are the second stripping column as feed fed as separating internals 50 dual-flow trays contains. As well as the condensation column is the second Stripping column thermally insulated from the environment. The inner diameter the second stripping column is above all dual-flow trays uniformly 2.4 m. The dual-flow trays are in the second Stripping column arranged equidistantly (400 mm). Your opening ratio is uniformly 12%. Viewed from the bottom up the hole diameter is the first eight dual-flow trays uniformly 14 mm (hole arrangement according to strict triangular division; Distance from center of hole to center of hole = 26 mm) and the hole diameter All subsequent dual-flow trays are uniformly included 14 mm (hole arrangement also according to strict triangle division; Distance from center of hole to center of hole = 25 mm).

The Supply of 3137 kg / h of the mixture 1 takes place at a temperature from 105.2 ° C to the eighth dual-flow bottom (from below).

The energy is supplied to the second stripping column by means of an external forced three-flow tube bundle expansion evaporator (cf. Basic Operations of Chemical Process Engineering, 4th Edition, Steinkopff Verlag Dresden, 1974, p. 434 ).

This 271650 kg / h are fed to from the bottom of the second stripping column with a temperature of 151.7 ° C and a pressure of 1.655 bar withdrawn bottoms liquid, which has the following contents: 2.0713% by weight Acrylic acid, 0.2201% by weight Acetic acid, 0.2608% by weight Water, 0.0094% by weight formic acid, 0.0001% by weight Formaldehyde, 0.0036% by weight acrolein, 0.0017% by weight propionic acid, 0.0001% by weight furfural, 0.0008% by weight allyl formate, 0.5731% by weight diethyl phthalate, 0.7638% by weight benzaldehyde, 23.2670% by weight maleic anhydride, 2.2693% by weight benzoic acid, 2.9848% by weight phthalic anhydride, 38.3947% by weight Diacrylic acid - Michael adducts, 21.2842% by weight Polyacrylic acid - Michael adducts, 0.7185% by weight phenothiazine, 2.5151% by weight MEHQ 4.6615% by weight other high-boiling components, and 0.0001% by weight Oxygen.

When Heat transfer medium becomes water vapor (pressure = 16 bar) passed through the space surrounding the heat exchanger tubes (meandering, guided by corresponding baffles). When flowing through the heat exchanger tubes is the bottoms liquid is heated and 270900 kg / h of passed through the heat exchanger Ge total amount are at a temperature of 158.6 ° C in the swamp of the recycled second stripping. 750 kg / h of total guided by the heat exchanger Amount of bottoms liquid are diverted, degassed and diluted with methanol of the residue combustion fed.

In addition, in the bottom of the second stripping column with a temperature of 82.2 ° C. and a pressure of about 2.50 bar, 17424 kg / h of first stripping column are fed out to the top of the first laden gas, which has the following contents: 3.3977% by weight Acrylic acid, 1.1198% by weight Acetic acid, 4.1030% by weight Water, 0.0622% by weight formic acid, 0.0321% by weight Formaldehyde, 0.1181% by weight acrolein, 0.0030% by weight propionic acid, 0.0006% by weight furfural, 0.0139% by weight allyl formate, 0.0247% by weight diethyl phthalate, 2.5667% by weight O ₂ , 2.1951% by weight CO ₂ , 0.7129% by weight CO, 0.6756% by weight Propane, 0.1575% by weight Propylene, and 84.8133% by weight N ₂ .

Out the head of the second stripping column is in an amount of 25,831 kg / h of second charged gas (temperature = 96.7 ° C, pressure = 1.58 bar) and in a countercurrent Spray cooler (quench 0) by direct cooling cooled to a temperature of 80.9 ° C and partially condensed.

The remaining gas mixture in the direct cooling is recycled at a pressure of 1.58 bar in an amount of 20755 kg / h and with the following contents in the bottom space of the condensation column (not immersed): 18.5793% by weight Acrylic acid, 0.9849% by weight Acetic acid, 3.6185% by weight Water, 0.0571% by weight formic acid, 0.0271% by weight Formaldehyde, 0.1006% by weight acrolein, 0.0099% by weight propionic acid, 0.0436% by weight furfural, 0.0003% by weight allyl, 0.0117% by weight allyl formate, 0.0053% by weight Benzaldeyd, 0.0642% by weight maleic anhydride, 0.0001% by weight benzoic acid, 0.0001% by weight diacrylic 0.0001% by weight MEHQ 2.1548% by weight O ₂ , 1.8428% by weight CO ₂ , 0.5985% by weight CO, 0.5672% by weight Propane, 0.132% by weight Propylene, and 71.2018% by weight N ₂ .

When Quench liquid 0 32956 kg / h of a mixture of 1195 kg / h of mixture 1 and 37761 kg / h in quench 0 in the direct cooling formed condensate (this is this subset of the mixture in an indirect heat exchanger (type: spiral heat exchanger; against water) from 80.9 ° C to 40.1 ° C cooled). 6020 kg / h of this mixture, which has a temperature of 80.9 ° C. is, as reflux liquid on the led topmost bottom of the second stripping.

The mixture has the following contents: 87.9166% by weight Acrylic acid, 2.3313% by weight Acetic acid, 2.6130% by weight H ₂ O, 0.0688% by weight formic acid, 0.0010% by weight Formaldehyde, 0.0151% by weight acrolein, 0.0480% by weight propionic acid, 0.2980% by weight furfural, 0.0008% by weight allyl, 0.0096% by weight allyl formate, 0.0568% by weight benzaldehyde, 1.1099% by weight maleic anhydride, 0.0761% by weight benzoic acid, 0.1000% by weight phthalic anhydride, 2.4592% by weight diacrylate 2.6522% by weight Polyacrylic acid Michael adducts, 0.0240% by weight phenothiazine, 0.0847% by weight MEHQ 0.1345% by weight other high-boiling components, and 0.0004% by weight Oxygen.

In the bottom space of the condensation column is a Zentrifugaltropfenabscheider integrated, which prevents dripping of the sump liquid be carried upwards from the sump space.

The bottom space of the condensation column is, as already mentioned, at a column height (as all heights from the bottom of the bottom calculated) of 7.80 m by a first collecting bottom (collection floor; floors with 16 equally distributed roofed fireplaces; Chimney diameter: 600 mm; Chimney height: 1 m) completed.

Of the Collecting bottom is double-walled with 2 ° downward slope Inside and with central drain and drain (DN ~ 200) designed. The free gas cross section is about 30%.

From 88579 kg / h of high - boiling fraction in led the bottom space located under the first catch bottom.

The high boiler fraction has at a temperature of 99.8 ° C and a pressure of about 1.50 bar the following contents: 94.6665% by weight Acrylic acid, 0.5402% by weight Acetic acid, 1.3577% by weight Water, 0.0160% by weight formic acid, 0.0014% by weight Formaldehyde, 0.0071% by weight acrolein, 0.0577% by weight propionic acid, 0.3814% by weight furfural, 0.0023% by weight allyl, 0.0010% by weight allyl formate, 0.1227% by weight benzaldehyde, 2.1925% by weight maleic anhydride, 0.0051% by weight benzoic acid, 0.0046% by weight phthalic anhydride, 0.6008% by weight diacrylic 0.0061% by weight phenothiazine, 0.0314% by weight MEHQ, and 0.0002% by weight O ₂ .

The Sump temperature is 104.9 ° C and the sump pressure (at the liquid level) is 1.51 bar.

2.0 m above the first catching ground is the first of first 15 dual-flow trays. These dual-flow trays (number of holes uniform 33678) are equidistantly attached with a Ground clearance of 380 mm. The passages exist from circular openings of uniform diameter of 14 mm, with the burr in the separation column pointing downwards. The arrangement of the centers of the passage circles follows one strict triangular division. The nearest distance of two Circle center is 24.5 mm.

Of the fifteenth dual-flow floor acts as a distributor floor. For this purpose, the column wall contains between the second Catch bottom and the fifteenth dual-flow bottom two insertion tubes (DN ~ 150) with 45 drain holes (diameter: 15 mm) per plug-in tube.

about the plug-in tubes becomes crude acrylic acid and mother liquor returned to the condensation column.

The first series of dual-flow trays will come with a second Fangboden (collecting floor, chimney floor with 16 approximately evenly distributed roofed fireplaces; Chimney height about 1.70 m, central Discharge cup with drain (DN ~ 250), free gas cross section of ~ 30%), which is 1.50 m above the last dual-flow soil is housed.

From this second collecting tray, crude acrylic acid with a temperature of 97.1 ° C., which has the following contents, is withdrawn continuously at 1.48 bar as the first side draw: 96.7716% by weight Acrylic acid, 0.8253% by weight Acetic acid, 1.6640% by weight Water, 0.0213% by weight formic acid, 0.0018% by weight Formaldehyde, 0.0070% by weight acrolein, 0.0681% by weight propionic acid, 0.1642% by weight furfural, 0.0027% by weight allyl, 0.0012% by weight allyl formate, 0.0164% by weight benzaldehyde, 0.1052% by weight maleic anhydride, 0.3278% by weight diacrylic 0.0050% by weight phenothiazine, 0.0180% by weight MEHQ, and 0.0002% by weight Oxygen.

18474 kg / h of the second catch bottom removed crude acrylic acid be together with in the context of crystallisative purification from withdrawn crude acrylic acid accumulating and in the indirect heat exchange with removed crude acrylic acid and water vapor as the heat transfer medium At 90 ° C heated mother liquor (72716 kg / h) on the aforementioned insertion tubes immediately below the second catch tray on the down this following dual-flow soil in the condensation column recycled.

89303 kg / h of the second catch bottom removed crude acrylic acid are multi-stage by indirect heat exchange (u. thermally integrated against to be recycled to the condensation column aforementioned mother liquor) to a temperature of Cooled to 29 ° C and optionally buffered in a tank farm.

Then The cooled crude acrylic acid 1204 kg / h taken from the second side draw of the condensation column Added acid water.

The sour water has the following contents: 10.7677% by weight Acrylic acid, 6.4390% by weight Acetic acid, 79.5610% by weight Water, 0.7038% by weight formic acid, 2.4712% by weight Formaldehyde, 0.0132% by weight acrolein, 0.0082% by weight propionic acid, 0.0013% by weight furfural, 0.0331% by weight allyl formate, 0.0001% by weight MEHQ, and 0.0013% by weight Oxygen.

The resulting mixture is cooled by repeated indirect heat exchange (against cooling brine (water / glycol mixture, 25-35 wt .-% glycol and 65-75 wt .-% water) to 16 ° C and then into two to three parallel operated Kühlscheibenkristallisatoren (see. WO 2006/111565 ) distributed. These are in each case a trough in which 24 wiped circular cooling plates (which in each case are internally flowed through by a cooling medium (mixture of water and glycol, glycol fraction = 25 to 35% by weight)) are at an equidistant distance of 30 + 1 cm are arranged hanging one behind the other (plate diameter = 3.3 m). The respective cooling medium is passed in countercurrent to the crystallizing mixture through the respective crystallizer from the cooling disk to the next to the cooling disk. D. h., The respective cooling medium is guided divided in the form of two parallel streams on the cooling plates of the respective crystallizer. A current passes through the numerically straight cooling plates, the other current passes through the numerically odd cooling plates (numbering of the cooling disks in the direction of flow starting with 1). The respective amount of cooling medium per crystallizer totals 180-220 t / h (metric tons), ie 90-110 t / h per stream. The pressure loss per cooling disk is 60 to 100 mbar. The inlet temperature of the cooling medium (the brine) be carries +2.5 to + 3 ° C. The outlet temperature is 2.5 ° C higher. The wall thickness of the cooling surfaces made of stainless steel is 4 mm. The heat transfer coefficient is on the side at about 1500 to 2500 W / (m ² · K). The heat transfer coefficients are usually 380 to 420 W / (m ² · K). The specific cooling capacity is 1.5 + 0.2 kW / m ² cooling surface. By wiping the cooling plates, the formation of a crystal layer is suppressed. The dehydrated crude acrylic acid is passed continuously from back to front through the respective crystallizer (pumped or overflow controlled). The single-phase, drained crude acrylic acid thickened (residence time 2.5 h) to a two-phase, acrylic acid crystals as solid phase-containing suspension of a temperature of 7 to 8.5 ° C and a solids content at the outlet of about 25 wt .-%. The bulk density of the suspension is usually 1110 to 1115 kg / m ³ . The speed of the wiper is 5 to 6 revolutions per minute. The shaft driving the wipers, centered through the cooling disks, is sealed with water-flushed stuffing box packings (packing cords made of teflon or graphite, flushing volume = few liters per hour up to some 10 l / h per seal).

On the circumference of the cooling disks, where it is not possible to wipe is a hollow profile (eg in the simplest embodiment a tube) is applied (eg welded on) by means of a second heat carrier (eg also water / glycol Mixture) is heated (to a temperature above the crystallization temperature; usually from the temperature range 8 to 20 ° C, preferably 10 up to 14 ° C). These peripheral heaters are with the second Heat transfer medium flows in parallel.

In addition, the wipers are preferably segmented in the radial direction (4 segments). The specific contact pressure of the wiper is in the installed state perpendicular to the cooling surface at 3 to 5 N per cm active wiper edge length. As a wiper material is High Molecular Weight Polyethylene or Ultra High Molecular Weight Polyethylene, z. B. Multilene ^® PE 1000 used. In addition to the wipers, the shaft drives paddles (expediently two each in symmetrical arrangement between two cooling disks and before the first and last cooling disks), which effect an improved mixing.

In the conveying direction of the suspension rear part of the respective crystallizer (preferably behind the last cooling disk), the suspension is attached via a connected tube (expediently immersed; alternatively, the suspension can flow via an overflow weir into a stirred collecting tank, from which the washing columns are fed) led to hydraulic melt-washing columns, as in the EP-A 1 272 453 . EP-A 1 448 283 . WO 03/041833 . EP-A 1 305 097 . DE-A 101 56 016 . DE-A 10 2005 018 702 and in the DE-A 102 23 058 are described to separate the mother liquor from the suspension crystallizate. The washing column diameter is 1.4 m. The loading of the washing columns with crystal suspension by means of a centrifugal pump (type channel wheel), the quantity control is preferably carried out via a speed control of the pump. The control flow pump is also designed as a centrifugal pump with control valve. Usually, the control flow amount used to control a wash column is 5 to 60 t / h, usually 8 to 30 t / h. In some cases, it is possible to operate the respective scrubbing column without control flow if the amount of liquid supplied with the suspension is already sufficient for the transport of the crystal bed. Typical ratios of effective transport pressure difference to effective wash pressure difference are 1.1 to 3, usually 1.2 to 1.8. The blade speed is usually at values of 5 to 10 per minute. The temperature in the melt circuit is normally 13 to 16 ° C. The detection of the filtration front is according to the DE-A 10 2005 018 702 made over two mutually relative pressure drop measurements over different bed lengths. The wash front is controlled by means of temperature measurement in the crystal bed.

• [a) Zur Herstellung einer veresterungsgerechten Acrylsäure ist es ausreichend die Abtrennung des Suspensionskristallisats anstelle in einer Schmelze-Waschkolonne mittels einer Zentrifuge (z. B. einer 2- oder 3-stufigen Schubzentrifuge) durchzuführen. Geeignete Siebspaltweiten liegen bei 150 bis 300 μm; anwendbare Zentrifugalbeschleunigungen liegen bei 500 bis 900 g, meist 600 bis 800 g; geeignet sind Hubzahlen von 40 bis 80 Schüben/min.. Vorzugsweise werden die auf der 2. oder 3. Stufe der Zentrifuge abgetrennten Kristalle mit 0,15 bis 0,3 kg Waschflüssigkeit pro kg Kristallisat gewaschen. Die Temperatur der Waschflüssigkeit liegt bei 15 bis 30°C, bevorzugt bei 20 bis 30°C. Zur Vermeidung von Ablagerungen wird der Feststoffabwurfschacht der Zentrifuge mit auf 15 bis 30°C temperierter Spülflüssigkeit gespült. Spül- und Waschflüssigkeit sind bevorzugt aufgeschmolzenes, über die Zentrifuge abgetrenntes und gewaschenes Kristallisat. Zur Vermeidung von Ablagerungen und Verkrustungen ist es zweckmäßig, das Zentrifugengehäuse, das Suspensionszuführrohr und das Waschflüssigkeitszuführrohr auf eine Temperatur ≥ 15°C und ≤ 40°C zu temperieren. Der Produktraum der Zentrifuge wird zweckmäßig mit Stickstoff oder mit einem Gemisch aus Luft und Stickstoff inertisiert. Die Wellenabdichtung wird mit Gas (z. B. Stickstoff oder ein Gemisch aus Luft und Stickstoff) oder mit Wasser gespült.
• b) Alternativ zur Suspensionskristallisation kann auch eine Schichtkristallisation (z. B. Fallfilmkristallisation gemäß EP-A 616 998 oder voll durchströmtes Rohr) mit 2 bzw. 3 oder mehr (z. B. 2 bis 4) Reinigungsstufen angewendet werden. Anstelle die Mutterlauge einer nachgehenden Reinigungsstufe in eine vorgehende Reinigungsstufe rückzuführen, kann man sie auch gemeinsam in die Kondensationsskolonne rückführen.]

The total height of the crystal bed is due to regulation at 250 to 1500 mm, usually 600 to 1100 mm. The wash front is typically 100 to 200 mm above the knife. As a melt circuit pump is a centrifugal pump with product-side flushing of the shaft seal (mechanical seal, double executed, with 15-30 ° C cooled barrier medium (water / glycol mixture)) or a magnetically coupled pump with increased plain bearing flushing. The circulating amount in the respective melt circle is 10 to 15 m ³ / h per ton of cleaned crystals removed with the knife. Depending on the subsequent use, the melt cycle is stabilized column-specifically with 200 to 300 ppm by weight of MEHQ, or with 40 to 70 ppm by weight of MEHQ, or with 100 to 300 ppm by weight of PTZ. In addition, air is introduced into the melt circuit or lean air (nitrogen-air mixture with ≦ 6% by volume of oxygen) whose excess (= fraction not dissolved in the wash melt) is separated before entry of the wash melt into the wash column via a gas separator. This results in a content of dissolved oxygen of 5 to 40 ppm by weight in the molten pure product.

• [a) For the preparation of an acrylic acid suitable for esterification it is sufficient to carry out the separation of the suspension crystallizate instead of in a melt washing column by means of a centrifuge (eg a 2-stage or 3-stage pusher centrifuge). Suitable sieve gap widths are 150 to 300 μm; applic The centrifugal accelerations are 500 to 900 g, usually 600 to 800 g; Strokes of 40 to 80 cycles / min are suitable. Preferably, the crystals separated off on the 2nd or 3rd stage of the centrifuge are washed with 0.15 to 0.3 kg of washing liquid per kg of crystallizate. The temperature of the washing liquid is 15 to 30 ° C, preferably 20 to 30 ° C. To avoid deposits, the solids discharge shaft of the centrifuge is rinsed with dishwashing liquid heated to 15 to 30 ° C. Rinsing and washing liquids are preferably melted, separated and washed via the centrifuge crystallizate. To avoid deposits and encrustations, it is expedient to temper the centrifuge housing, the suspension feed tube and the washing liquid feed tube to a temperature ≥ 15 ° C and ≦ 40 ° C. The product space of the centrifuge is expediently rendered inert with nitrogen or with a mixture of air and nitrogen. The shaft seal is flushed with gas (eg nitrogen or a mixture of air and nitrogen) or with water.
• b) As an alternative to suspension crystallization, it is also possible to use a layer crystallization (for example falling film crystallization according to EP-A 616 998 or full flow-through pipe) with 2 or 3 or more (eg 2 to 4) purification stages are used. Instead of recycling the mother liquor to a subsequent purification stage in a preceding purification stage, they can also be recycled together into the condensation column.]

Melting circles obtained by the addition of a total of 104 kg / h of a solution (temperature = 25 ° C, pressure = 1,1 bar) of 3 kg / h of MEHQ in 101 kg / h of pure acrylic acid (25 ° C) withdrawn from the melting circuits 17894 kg / h of pure acrylic acid (temperature = 14 ° C, pressure = 1.5 bar) are taken from the following contents: 99.7334% by weight Acrylic acid, 0.2091% by weight Acetic acid, 0.0180% by weight Water, 0.0230% by weight propionic acid, 0.0001% by weight furfural, <0.0001% by weight benzaldehyde, 0.0001% by weight maleic anhydride, 0.0002% by weight diacrylic 0.0150% by weight MEHQ, and 0.001% by weight O ₂ .

she is outstandingly suitable for the production of superabsorbents based on poly-Na-acrylate.

In 352 kg / h of the aforementioned heated pure acrylic acid be 5 kg / h PTZ to produce a 25 ° C having Inhibitor solution 1 solved. In 30 kg / h inhibitor solution 1 are 19 kg / h MEHQ to form the also 25 ° C. dissolved inhibitor solution 2 dissolved.

17439 kg / h of pure acrylic acid stabilized with MEHQ (25 ° C, 1.5 bar) are continuously fed to the storage tank.

The separated in the wash columns mother liquor is first moved into a heatable collection container and from there into a tank. From this it is (as already mentioned) heat-integrated heated to 90 ° C and in an amount of 72716 kg / h, together with 18474 kg / h at the second catch bottom removed crude acrylic acid on the fifteenth dual-flow tray of the condensation column (from below calculated). The composition of this recycled mother liquor is as follows: 94.6188% by weight Acrylic acid, 1.0690% by weight Acetic acid, 3.3562% by weight Water, 0.0378% by weight formic acid, 0.0431% by weight Formaldehyde, 0.0088% by weight acrolein, 0.0782% by weight propionic acid, 0.2016% by weight furfural, 0.0034% by weight allyl, 0.0021% by weight allyl formate, 0.0202% by weight benzaldehyde, 0.1292% by weight maleic anhydride, 0.4025% by weight diacrylic 0.0061% by weight phenothiazine, 0.0227% by weight MEHQ, and 0.0003% by weight Oxygen.

2.9 m above the second catcher floor is in the condensation column the first of 21 other dual-flow trays already described Type (hole diameter uniform again 14 mm, number of holes, however uniform 32020, nearest distance of two passage circle centers = 24.5 mm), which again equidistant with a ground clearance of 380 mm are arranged.

800 mm above the last dual-flow tray, the condensation column begins conically expand. 500 mm above the last dual-flow tray this extension ends with a column inside diameter of 6.50 m.

On this height, d. h., 1.50 m above the last dual-flow soil, begins an equidistant (ground clearance = 500 mm) arrangement of 28 conventional, single-flow Thormann trays. Of the first of the Thormann bottoms from below is one such, at the overflowing liquid from above six drain tubes designed as tubes expire. These pipes are against the gas space of the underlying dual-flow soil hydraulically sealed. The weir height of the six drainpipes decreases in the flow direction of the crossflow mode. The hydraulic seal has no-load openings with baffle plate on. The drainpipes are in the last third of the floor cross section (the inlet opposite to the ground) evenly distributed. The hydraulic sealing takes place in a cup with sloping overflow weir (45 ° C).

Furthermore the Thormann floors are designed in such a way that over the arrangement of the drive slots in the hoods of Thormannn floors in each case in successive troughs in the transverse flow direction opposite flow direction of the liquid is produced.

The aperture ratio the Thormann soil is 14%. The relationship from chimney surface to slot exit surface amounts 0.8. The chimney height and the height of the drain weir is 40 mm. The ground clearance of the bell (distance between Bottom edge of slot and bottom) is 10 mm. The slot height is 15 mm. The angle between flared slot and longitudinal edge of the hood is 30 degrees. The Length of the longitudinal edge of the hood amounts maximum 800 mm. In the edge region of the column, the hood length is reduced up to 200 mm for reasons of adjustment to roundness the column. The distance between two in the cross-flow direction A line hood is 66 mm. The drainage area of the discharge shaft is 1.5% relative to the cross-sectional area of the soil. The width between the two lower longitudinal edges a hood is 64 mm.

On the height of the upper Thormann floor begins the Constrict the column again conically. 700 mm above the top Thormann-Bodens is completed this constriction and the column inner diameter shrunk back to 6.00 m.

1.70 m above the top Thormann floor is the third Mooring floor (collecting floor, chimney floor with 16 approximately evenly distributed roofed fireplaces, chimney height = 1.50 m).

from third catch bottom will be 535506 kg / h sour water as second side take-off with a temperature of 65.1 ° C and at a pressure of ~ 1.24 bar.

The sour water has, as already mentioned, the following contents: 10.7677% by weight Acrylic acid, 6.4390% by weight Acetic acid, 79.5610% by weight Water, 0.7038% by weight formic acid, 2.4712% by weight Formaldehyde, 0.0132% by weight acrolein, 0.0082% by weight propionic acid, 0.0013% by weight furfural, 0.0331% by weight Allyl formate, and 0.0001% by weight MEHQ, and 0.0013% by weight Oxygen.

25537 kg / h of the extracted sour water (65.1 ° C) are combined with the inhibitor solution 2 on the top Thormann soil recycled.

329 kg / h of inhibitor solution 1 (viewed from below) returned to the 19th Thormann soil (with a temperature of 25 ° C).

316 kg / h of the extracted sour water are fed to the combustion.

310 m ³ / h of the extracted sour water are recycled at a temperature of 29.1 ° C to the sixth of the valve plates to be described below (calculated from below) (the cooling takes place by multi-stage indirect heat exchange).

194011 kg / h of the extracted sour water are at a temperature of 23 ° C on the top of the following to be described Returned valve bottoms (the cooling takes place together with the above amount of acid water by multi-stage indirect heat exchange; the last cooling stage from 29.1 ° C to 23 ° C is separated and heat integrated (Liquid chemical grade propylene is used as the refrigerant and it evaporates; the resulting gaseous propylene then becomes the design of the reaction gas mixture used for the gas phase partial oxidation).

1204 kg / h of the withdrawn sour water are, as already described, the crystalline to be further purified crude acrylic acid added.

6010 kg / h of the withdrawn sour water are used for the purpose of the following still to be carried out according to the invention Extraction of the extraction column supplied.

2300 mm above the third trap bottom are in the condensation column in equidistant arrangement (ground clearance = 500 mm) 11 double-flow Valve bottoms attached.

The Height of the drain weir is 18 to 35 mm (the the upper bottoms are higher than those of the lower ones Soils). The aperture ratio (specific Bore area) is 14.8% and the sum of drainage areas the downcomers of two successive valve trays is ~ 10% of the column cross-sectional area. When Valves were used VV12 valves from the company Stahl, DE, Viernheim.

Of the Pressure at the top of the column is 1.17 bar.

At the top of the column leave 170121 kg / h residual gas at a temperature of 31 ° C and the following contents, the separation column: 0.1946% by weight Acrylic acid, 0.1246% by weight Acetic acid, 2.3031% by weight Water, 0.0062% by weight formic acid, 0.1212% by weight acrolein, 0.0002% by weight propionic acid, 0.0001% by weight furfural, 0.0027% by weight allyl formate, 2.3427% by weight CO ₂ , 0.7609% by weight CO, 0.7211% by weight Propane, 0.1681% by weight propylene 2.7387% by weight O ₂ , and 90.5158% by weight N ₂ .

In an indirect heat exchanger, the residual gas Heated to 38 ° C and then 110880 kg / h of this residual gas via a cycle gas compressor compressed a pressure of 2.9 bar, the temperature at about 160 ° C rises. 94553 kg / h of compressed residual gas recycled as recycle gas into the gas phase partial oxidation. 16327 kg / h of the compressed residual gas are the first stripping to the Purpose of stripping the extract from the sour water extraction fed and 59241 kg / h of the residual gas are the combustion fed.

The Extraction column for the extraction of acid water contains punched as flush-mounted internals fitted flush with the edge structured packings (height of one packing element: 200 mm) made of stainless steel sheets (material 1.4571) of the type Montz-Pak B1-350 with an active total height of 10 m, one above the other are arranged.

The inner diameter of the extraction column is uniform across all packages 800 mm. Its height is 14 m. As extracting agents Palatinol® ^® A is used.

Swamp- and head of the column are in diameter extended to 1100 mm to improve the phase separation in the sump and to reduce the entrainment of extractant in the top of the column. In addition, in the top of the column is a bed of plastic filling bodies (eg polyethylene or Teflon) introduced as a coalescing aid.

The Supply of 6010 kg / h of sour water to be extracted (temperature = 65.1 ° C) takes place below the lowest packing in the Extraction column via corresponding passages (8 mm diameter holes) have manifolds.

Above the uppermost packing of the extraction column a mixture of about 25 kg / h of fresh Palatinol ^® A) and 5987 kg / h recirculated from the first stripping column and above (in this freigestripptem extractant abandoned temperature = 50 ° C).

The recycled extractant has the following contents: ≤ 0.5% by weight Acrylic acid, ≤ 0.03 wt% Acetic acid, ≤ 0.02 wt% Water, ≤ 0.001% by weight formic acid, ≤ 0.0035% by weight acrolein, ≤ 0.0005% by weight propionic acid, ≤ 00.001% by weight furfural, ≤ 0.001% by weight allyl formate, 0.03% by weight MEHQ 0.0001% by weight Oxygen, and ≥ 99.5% by weight Palatinol® ^® A.

The specific mass of the sour water is 967.5 kg / m ³ . The extractant is also given through appropriate openings (holes of diameter 4 mm) having manifolds.

The Acid water forms the continuous phase and the extractant forms the drop-shaped dispersed phase (drop diameter ranging from 2 to 5 mm), which are in the aqueous Phase descends.

At the top of the extraction column 4930 kg / h of raffinate (temperature ~ 57.6 ° C) are taken, which has the following contents: 1.7618% by weight Acrylic acid, 4.3046% by weight Acetic acid, 90.1197% by weight Water, 0.6446% by weight formic acid, 2.8993% by weight Formaldehyde, and 0.27% by weight Palatinol® ^® A.

It is fed together with burning residual gas of combustion.

The bottom of the extraction column is taken from 7090 kg / h of extract, which has the following contents (temperature ~ 64.5 ° C) 8.156% by weight Acrylic acid, 2.4838% by weight Acetic acid, 4.7901% by weight Water, 0.1490% by weight formic acid, 0.0788% by weight Formaldehyde, 0.0140% by weight acrolein, 0.0073 wt% propionic acid, 0.0014% by weight furfural, 0.0282% by weight Allyl formate, and 0.0192% by weight MEHQ 84.2726% by weight Palatinol® ^® A.

The Total amount of the extract is at the top of the first stripping column guided.

before The extract is converted by indirect heat exchange in one Plate heat exchanger heated to 95 ° C. As heat transfer 5987 kg / h at the first Strippkolonne withdrawn bottom liquid used. The first stripping column contains as separating internals 5 dual-flow trays and 15 Thormann trays. As well like the extraction column, the first stripping column is against the Environment thermally insulated. The inner diameter of the first stripping column is uniform across all soils 1.5 m.

Your Height is 14.5 m. The bottom 5 floors are designed as dual-flow trays and are in the first Stripping column equidistant (500 mm) arranged. Your opening ratio is uniformly 18%. The hole diameter of the dual-flow trays is uniformly 14 mm (hole arrangement corresponding to strict threefold division). Above the top dual-flow floor are 15 single-flow Thormann floors are arranged equidistantly (500 mm distance). The Thormann floors are designed in such a way that about the arrangement of the drive slots in the hoods the Thormannn bottoms in successive in the cross-flow direction Troughs each one ent ent opposite flow direction the liquid is generated. The aperture ratio (on the cross-section related gas passage area) is 14%.

Above of the last soil is still a bed (height 400 mm, Pall rings of metal, 25 × 25) as a drip catcher.

Below the lowermost dual-flow tray 13000 Nm ³ / h of compressed residual gas (pressure ~ 2.9 bar, temperature ~ 160 ° C) are fed into the first stripping column, where it rises in countercurrent to the running in the stripping column extract.

At the top of the first stripping column, 17424 kg / h of first laden gas are taken out (temperature = 82.2 ° C.) and fed to the second stripping column. The temperature in the bottom of the first stripping column is about 155 ° C. 49311 kg / h bottoms liquid are withdrawn continuously from the bottom of the first stripping column. 5987 kg / h of the bottoms liquid withdrawn from the first stripping column are cooled to 50 ° C. by two-stage indirect heat exchange (the first stage in a plate heat exchanger heat-integrated against extract) and recycled to the top of the extraction column. 43324 kg / h on from the ers th stripping column withdrawn bottom liquid are heated in an external forced circulation tube bundle expansion evaporator to 160 ° C and recycled to the bottom of the first stripping.

Comparative example

It is executed as the example. The extracted in the example However, sour water is not extracted, but as in the state of Technology burned.

The Extraction column and the first stripping omitted. To stripping the bottoms taken from the condensation column the appropriate amount of compressed residual gas is used. The stream taken from the first side draw raw Acrylic acid is 87307 kg / h and contains 96.863 Wt .-% of acrylic acid.

The the amount of pure acrylic acid to be supplied to the storage tank is 16994 kg / h. Its purity is 99.736 wt .-% Acrylic acid.

Example 2

Into a jacketed stirred vessel (thermostated with water) with an internal volume of 1.3 l, stirred at 50 ° C., were added 498 g of non-inhibited acid water at a temperature of 50 ° C., which had the following contents: 2.19% by weight formaldehyde, is obtained, 82.00% by weight Water, 4.01% by weight Acetic acid, 11.09% by weight Acrylic acid, 0.69% by weight Formic acid, and 0.01% by weight Diacrylate.

Under Stirring was then 499 g of dimethyl phthalate added, which also had 50 ° C. At constant temperature of 50 ° C, the resulting mixture was during Stirred for 10 min at a speed of 250 revolutions / min. After switching off the stirrer, the mixture became 50 ° C leave it to itself, within a short time phase separation occurred. The mass of the organic phase was 565 g, the mass the aqueous phase was 432 g. Gas chromatographic Analysis of the aqueous phase revealed that these were still 20.26 g of acrylic acid and 13.0 g of acetic acid.

Example 3

For the extraction of acrylic acid from sour water, an extraction column made of glass was used. The non-inhibited acid water had the following contents: 2.36% by weight formaldehyde, is obtained, 83.12% by weight Water, 3.98% by weight Acetic acid, 9.70% by weight Acrylic acid, 0.68% by weight Formic acid, and 0.01% by weight Diacrylate.

The Extraction column was thermostated via a double jacket (with 60 ° C warm water). As separating internals contained the extraction column structured stainless steel sheet packs (stainless steel from Type 1.4404, perforated packages of the company Montz type B1-350). The inner diameter of the extraction column was packed Part 40 mm. In the bottom of the column were 10 kg / h of the aqueous Solution (temperature = 60 ° C) out. At the Head of the extraction column were in countercurrent as disperse phase (drop size: 4 to 5 mm) 10 kg / h of diethyl phthalate added (temperature = 60 ° C). The aqueous led out at the top of the column Raffinate still contained 0.8% by weight of acrylic acid and 2.9% by weight Acetic acid. The content of acrylic acid in sour water could thus (based on the original weight content) be depleted by 93.3 wt .-% and that of acetic acid by 41% by weight.

in the Raffinate was 0.2 wt .-% diethyl phthalate dissolved.

Example 4

The procedure was as in Example 3. As extracting agent and disperse phase, 27.5 kg / h of dimethyl phthalate (T = 60 ° C.) were introduced at the top of the extraction column (drop size: 4 to 5 mm). The sour water, which was also fed as a continuous stream 27.5 kg / h at a temperature of 60 ° C in the bottom of the column as a continuous phase, had the following contents: 2.77% by weight formaldehyde, is obtained, 82.82% by weight Water, 4.02% by weight Acetic acid, 9.53% by weight Acrylic acid, 0.63% by weight Formic acid, and 0.05% by weight Diacrylate.

The At the top of the extraction column effluent aqueous raffinate contained 0.2% by weight of acrylic acid and 2.4% by weight of acetic acid. The content of acrylic acid in the sour water could thus (based to the original weight content) depleted by 98.3 wt .-% and acetic acid by 51.5 wt .-%. In the raffinate 0.9% by weight of dimethyl phthalate was dissolved.

Example 5

It The procedure is as in Example 1. In addition to the return fluid (Sour water) are shared with the same and with the same Temperature 1000 kg / h of water (additional absorbent) led into the condensation column. The furfural content the second capture bottom as the first side draw from the condensation column led out crude acrylic acid drops thereby from 0.1642% by weight (value in Example 1) to 0.1225% by weight.

Example 6

It The procedure is as in Example 1. In addition to the return fluid (Sour water) are shared with the same and with the same Temperature 5000 kg / h of water (additional absorbent) led into the condensation column. The furfural content the second capture bottom as the first side draw from the condensation column led out crude acrylic acid drops thereby from 0.1642% by weight (value in Example 1) to 0.1125% by weight.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

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Claims (25)

Process for the preparation of acrylic acid, in which by heterogeneously catalyzed gas phase partial oxidation of at least one C ₃ precursor of acrylic acid with molecular oxygen to solid state catalysts at elevated temperature produces an acrylic acid, water vapor and minor components containing product gas mixture, the temperature of the acrylic acid, Water vapor and secondary components containing product gas mixture optionally reduced by direct and / or indirect cooling, and the acrylic acid, water vapor and secondary components containing product gas mixture then passes into a equipped with separation internals condensation column, within the condensation column can rise in itself and thereby fractionally condensed and a first , Above the feed point of the product gas mixture located in the condensation column, side draw contains a total of water and secondary components de-enriched End crude acrylic acid as the target product and a second, located above the first side draw, liquid phase still acrylic acid and secondary components containing acidic water and at the top of Kondensationsationskolonne a lower water than boiling secondary components containing residual gas mixture and from the bottom space of the condensation column still acrylic acid and heavier than acrylic acid leading from the condensation column containing boiling secondary products and secondary components bottoms liquid, a portion of the withdrawn acidic water as such and / or after cooling thereof as reflux liquid in the condensation column and the crude acrylic acid optionally subjected to at least one further thermal separation process for the purpose of their further purification, characterized that in at least a subset of acidic water not recycled to the condensation column in this acrylic acid contained by E extraction with an organic solvent to form an acrylic acid-containing organic extract from the acidic water out into the organic solvent, subsequently separating the acrylic acid from the organic extract using at least one thermal separation process and extracting acrylic acid separated from the extract into the condensation column, or further purification the crude acrylic acid feeds and / or receives in the aqueous solution of a metal hydroxide. A method according to claim 1, characterized in that the C ₃ precursor is propylene, or acrolein, or a mixture of propylene and acrolein. Method according to claim 1 or 2, characterized that at least 25 wt .-% of not in the condensation column recycled acid water contained in this Acrylic acid by extraction with an organic solvent to form an acrylic acid-containing organic extract in the organic solvent, hereinafter the Acrylic acid from the organic extract using separated at least one thermal separation process and the of the Extract separated acrylic acid either in the condensation column returns, or the further purification of the raw Acrylic acid feeds and / or into the aqueous Solution of a metal hydroxide absorbs. Method according to one of claims 1 to 3, characterized in that the extraction of acrylic acid carried out from the sour water in an extraction column is used as separating internals packings and / or sieve plates contains. Method according to claim 4, characterized in that that the organic solvent at the top of the extraction column and give the acid water in the bottom region of the extraction column is and the organic solvent as dispersed Phase descends in the continuous acid water phase, or thereby characterized in that the sour water at the top of the extraction column and the organic solvent in the bottom region of the extraction column is abandoned, and the organic solvent as dispersive distributed phase rises in the continuous acid water phase. Method according to one of claims 1 to 5, characterized in that the organic solvent at least one ester of an aliphatic containing 5 to 20 C atoms or aromatic monocarboxylic acid and 1 to 8 carbon atoms containing alcohol. Method according to one of claims 1 to 5, characterized in that the organic solvent at least one diester containing from 5 to 20 C atoms aliphatic or aromatic dicarboxylic acid and a Containing 1 to 8 carbon atoms containing alcohol. Method according to one of claims 1 to 5 or claim 7, characterized in that the organic solvent dimethyl phthalate, diethyl phthalate, dimethyl isophthalate, diethyl isophthalate, dime ethyl terephthalate and / or diethyl terephthalate. Method according to one of claims 1 to 8, characterized in that the boiling point of the organic solvent at atmospheric pressure ≥ 200 ° C. Method according to one of claims 1 to 9, characterized in that the acrylic acid from the separating organic extract by stripping with a first stripping gas and the acrylic acid loaded first stripping gas into the Condensation column returns and / or in the first loaded stripping gas contained acrylic acid in the aqueous solution of a metal hydroxide absorbs. Method according to one of claims 1 to 9, characterized in that the acrylic acid from the separating organic extract by stripping with a first stripping gas and the resulting incurred with acrylic acid first Stripping gas is used as a second stripping gas to get out of the Condensation column led out bottoms liquid to freeze any remaining acrylic acid while doing so resulting with acrylic acid loaded second stripping gas in the condensation column is recycled and / or the in the second stripping gas contained acrylic acid in the aqueous Solution of a metal hydroxide absorbs. Method according to claim 11, characterized in that that the stripping of led out of the condensation column Sump liquid in one with separating internals provided stripping column is performed, and the temperature in the bottom of the stripping 150 to 190 ° C. Method according to claim 11 or 12, characterized that is loaded with acrylic acid second stripping a Subjecting countercurrent rectification before reacting with acrylic acid loaded in the condensation column recycled and / or the acrylic acid contained in it in the aqueous Solution of a metal hydroxide is added. Method according to one of claims 10 to 13, characterized in that the first stripping gas is air, N ₂ , CO ₂ and / or water vapor is used. Method according to one of claims 10 to 13, characterized in that the first stripping gas residual gas mixture is used. Method according to one of claims 1 to 16, characterized in that the crude acrylic acid crystallizes is further cleaned up. Method according to claim 17, characterized in that that of the crude acrylic acid in advance of the crystallisative further purification a subset of not recycled to the condensation column acidic water is supplied. Method according to claim 16 or 17, characterized that the crystallisative further purification of crude acrylic acid or their mixture with acidic water by suspension crystallization he follows. Method according to claim 18, characterized that for separation of remaining in the suspension crystallization Mother liquor and formed suspension crystals a wash column is used. Method according to one of claims 17 to 19, characterized in that a method of radical Polymerization connects, in which molten Acrylsäurekristallisat and / or its metal salt miteinpolymerisiert becomes. Method according to one of claims 10, 11, 13, characterized in that a method of radical Polymerization connects, in which from loaded first and / or second stripping gas in the aqueous solution copolymerized with a metal hydroxide incorporated acrylic acid becomes. Method according to one of claims 1 to 21, characterized in that a subset of the residual gas mixture recycled as recycle gas into the gas phase partial oxidation becomes. Method according to one of claims 1 to 22, characterized in that the organic solvent has a mass density which differs under the conditions of extraction of that of water by ≥ 25 kg / m ³ . Method according to one of claims 1 to 23, characterized in that the aqueous solution of a metal hydroxide NaOH, KOH, Ca (OH) ₂ and / or Mg (OH) ₂ dissolved. Method according to one of claims 1 to 24, characterized in that the condensation column is fed via a located between its first side draw and its second side draw feed a liquid absorbent whose boiling temperature T _S at a pressure of 1 atm greater than or equal to the boiling temperature T _W. of water at a pressure of 1 atm.