DE102008023016A1 - Preparing ether, useful e.g. in lacquer composition, comprises contacting aqueous phase and oily phase containing hydrocarbon compounds, and separating obtained emulsion into an aqueous phase and oil phase having ether - Google Patents

Abstract

Preparing ether comprises: (a) providing an aqueous phase containing water and as water-processing components of at least one alcohol component and a catalytically active composition; (b) providing an oily phase containing oil-processing components of hydrocarbon compound; (c) optionally providing further additives; (d) contacting the two phases and additives to form emulsion; (e) separating the emulsion into aqueous phase and oil phase having ether; and (f) separating the oil phase into first and second phases, where the first phase comprises more ether than the second phase. Method for preparing ether comprises: (a) providing an aqueous phase containing water and as water-processing components of at least one alcohol component having two or more hydroxyl groups and a catalytically active composition; (b) providing an oily phase containing oil-processing components of hydrocarbon compound having at least two conjugated double bonds; (c) optionally providing further additives; (d) contacting the aqueous phase with the oil phase and the additives to form an emulsion (unit A); (e) separating the emulsion into (unit B) an aqueous phase and oil phase, where the aqueous phase is recycled into the reactor and combined with the aqueous phase in the step (a) and the oil phase contains the ether; and (f) separating the oil phase into (unit C) first phase and second phase, where the ether content in the first phase is greater than the second phase and the second phase in the reactor is recycled into the reactor and combined with the oil phase in the step (b). Independent claims are included for: (1) a formulation comprising a formulation component based on the ether obtained by the above method and/or the ether obtained by the above method; (2) a method-2 for preparing an intermediate product I comprising: (i) providing, as intermediate component, at least one ether, prepared by the above method, (ii) providing a carboxylic acid component, and (iii) reacting the intermediate component to obtain the intermediate product I; (3) a lacquer composition comprising, as lacquer components, at least one intermediate product II, which is obtained by reacting the intermediate product I with at least one polyol having 2-6 hydroxyl groups, and a radical forming agent; and (4) a reactive diluent composition comprising, as reactive diluent components, the intermediate product I obtained by the above method, an ester of unsaturated carboxylic acid having 6-22C and polyol having 3-6 hydroxyl groups.

Description

The The present invention relates to a continuous process for Preparation of ethers in a reactor, a process for the preparation a thermoplastic composition containing at least one of the ethers according to the invention, a method for producing a shaped article, including at least one of the ethers according to the invention or the invention thermoplastic composition, a process for production a packaged goods, a process for producing at least one partially coated article, as well as uses of the invention Ester as an additive in various compositions.

It are various methods for preparing ethers from polyols and conjugated diene compounds known to undergo telomerization underlying. Often, this synthetic route can be in two steps first, an oligomerization of an ethylenic unsaturated, conjugated diene, which turns out to be a second Addition of another connection connects.

Such a method is in the DE 601 00 610 T2 described. In this case, a polyol having three or four hydroxy groups is reacted in a two-phase reaction in the presence of a transition metal compound with a dimer of a conjugated diene and then subjected to a further chemical treatment. This process is in need of improvement both in terms of product quality and process management.

Another method for telomerizing conjugated dienes with a diol, or a polyol, is known from US Pat DE 690 07 418 T2 known, which also Runaway as a two-phase reaction in the presence of a transition metal compound and is accompanied by a purification step of the crude product. Also, this method is in need of improvement, both of the product quality, as well as the process management.

• – verbesserungsfähige Rohstoffeffizienz,
• – hoher Katalysatorrückstand bzw. -austrag im Ether,
• – aufwendige Aufreinigung des Ethers zur Beseitigung von Verunreinigungen,
• – geringe Selektivität Mono-/Di-Ether, dadurch hoher Anteil an Nebenprodukten,
• – hoher Energieverbrauch,
• – hoher Anteil an Di-Ethern,
• – lange Reaktionszeiten,
• – inkonstante Produktqualität durch Batchverfahren,
• – Gesundheits- und Umweltgefährdung durch Butadienfreisetzung oder Butadienentsorgung, bspw. Verbrennung.

In view of the industrial production of ethers by telomerization, there is a need for improvement in various respects in order to reduce the effort in the production of ethers and to meet the requirements and desires of the market. The known methods have, in addition to the above, usually at least one, often more, or even all of the following sketched disadvantages:

• - improving raw material efficiency,
• High catalyst residue or discharge in the ether,
• - elaborate purification of the ether to remove impurities,
• Low selectivity mono- / di-ether, thus high proportion of by-products,
• - high energy consumption,
• High proportion of di-ethers,
• - long reaction times,
• - inconsistent product quality through batch processes,
• - Health and environmental hazards due to butadiene release or butadiene disposal, eg combustion.

Therefore There is a need for improvement of the known methods and, where appropriate, the establishment of new procedures for at least one addressed drawbacks, and overcome at best.

Furthermore There is a desire for more efficient production processes a lower energy and resource consumption with high revenues, Have yields and selectivities and post-treatment steps superfluous make, or at least simplify.

Of the Present invention was based on the object resulting from the At least partially overcome the disadvantages of the prior art.

Especially The present invention was based on the object, the consumption of raw materials in the light of increasing material costs, and reaction times because of rising energy costs.

Farther had been set to the task of safety and health risks, as well as a possible environmental impact, especially in handling with butadiene and butadiene utilization, and if possible to reduce to avoid.

A Another object of the present invention was to provide additives for the production of, as well as emulsifiers for thermoplastic To provide compositions which are suitable for the properties of Modify compositions as desired and simultaneously the high standards, as defined by the food industry or medical technology are sufficient.

a Contribute to the solution of at least one of the above Tasks perform the objects of the category-forming Claims, the dependent claims further embodiments of the invention represent.

a Contribute to the solution of at least one of the above tasks provides a continuous process in which process components, not implemented for the product of the invention were returned to the manufacturing process and thus be reused. In order to can also reduce environmental impact and / or hazard become.

a further contribution to the solution of at least one of the above mentioned tasks provides a continuous process, which a high selectivity in favor of mono-ethers in short Has reaction times.

• 1a) Bereitstellen einer wässrigen Phase, mindestens beinhaltend Wasser, sowie als w-Verfahrenskomponenten – mindestens eine Alkoholkomponente mit zwei oder mehr Hydroxygruppen, und – eine katalytisch aktive Zusammensetzung,
• 1b) Bereitstellen einer öligen Phase, mindestens beinhaltend als o-Verfahrenskomponente – eine Kohlenwasserstoffverbindung mit mindestens zwei konjugierten Doppelbindungen,
• 1c) gegebenenfalls Bereitstellen weiterer Zusatzstoffe,
• 1d) Kontaktieren der wässrigen Phase mit der öligen Phase, sowie gegebenenfalls mit den weiteren Zusatzstoffen, unter Bildung einer Emulsion in einer Einheit A,
• 1e) Teilen der Emulsion in einer Einheit B in eine wässrige Phase und eine ölige Phase, – wobei die wässrige Phase in den Reaktor zurückgeführt und mit der wässrigen Phase in Verfahrensschritt 1a) vereinigt wird, – wobei die ölige Phase einen Ether beinhaltet,
• 1f) Teilen der öligen Phase in einer Einheit C in eine erste Phase und eine weitere Phase, – wobei die erste Phase mehr Ether als die weitere Phase aufweist, – wobei die weitere Phase in den Reaktor zurückgeführt und mit der öligen Phase in Verfahrensschritt 1b) vereinigt wird.

An object of the present invention is a process for the preparation of ethers, comprising the process steps:

• 1a ) Providing an aqueous phase, at least including water, and as w-process components - at least one alcohol component having two or more hydroxy groups, and - a catalytically active composition,
• 1b ) Providing an oily phase, at least comprising as o-process component - a hydrocarbon compound having at least two conjugated double bonds,
• 1c ) optionally providing further additives,
• 1d ) Contacting the aqueous phase with the oily phase, and optionally with the further additives, to form an emulsion in a unit A,
• 1e ) Dividing the emulsion in a unit B into an aqueous phase and an oily phase, - wherein the aqueous phase is returned to the reactor and with the aqueous phase in process step 1a ), the oily phase containing an ether,
• 1f ) Dividing the oily phase in a unit C in a first phase and another phase, - wherein the first phase has more ether than the further phase, - wherein the further phase is recycled to the reactor and with the oily phase in process step 1b ) is united.

According to the invention, the process for producing an ether is carried out as a two-phase reaction. A two-phase reaction in the sense of the present invention is understood to mean a reaction which has two or more different phases. It is preferred that the first phase at most in a proportion of 0.1 to 15 wt .-%, preferably from 0.1 to 10 wt .-%, particularly preferably from 0.1 to 5 wt .-% and most preferably from 0.1 to 3 wt .-% with the further phase, in each case based on the total weight of both phases, is homogeneously miscible. Above these levels, the first phase and at least one other phase different from the first phase are immiscible. Furthermore, the first and at least one further phase is preferred, at least during a part of the method steps 1d ) 1e ) or 1f ), or a combination of two or more of them, liquid.

Under an w-process component is understood to mean all process components the solubility of at least 20 g of process component per 100 g of water, preferably of at least 25 g per 100 g of water and most preferably a solubility of more than 30 g of the process component, each in 100 g of water.

Under an o-process component understood all process components, to less than 20 g, more preferably less than 5 g preferably less than 2 g, most preferably less than 1 g, each in 100 g of water, are soluble.

When Alcohol component having two or more hydroxy groups is in principle any one skilled in the art and for carrying out the invention Process suitable appearing alcohol component with two or more hydroxy groups usable.

Of the Term "alcohol component" as used herein includes the alcohol in its protonated form, the alcohol in its partially protonated form, the alcohol in its deprotonated form Form, in particular salts of the alcohol, as well as mixtures of the alcohol in its protonated form, its partly protonated form and its deprotonated form, or mixtures of the alcohol in any of the above Forms and one or more salts of alcohol.

When Alcohol component having two or more hydroxy groups are preferred Alcohols having a number of hydroxy groups in a range of 2 to 9, more preferably 3 to 8 and most preferably 3 used to 6. The number of carbon atoms in the alcohol with Two or more hydroxy groups are preferably in one range from 3 to 30, preferably 3 to 20, more preferably 3 to 10 and most preferably 3, 4 or 5.

Farther can also be used as an alcohol component with two or more hydroxy groups an alcohol used in technical quality. "Technical Quality "means in the context of a chemical substance or a chemical composition that is the chemical substance or the chemical composition low levels of impurities having. In particular, the chemical substance or the chemical Composition in a range of 5 to 20 wt .-%, preferably from 5 to 15% by weight, more preferably from 5 to 10% by weight impurities, based on the total amount of chemical or chemical Composition. Particularly preferably, the chemical Substance or chemical composition of 1.5 to 5% by weight impurities, based on the total amount of chemical or chemical Composition on. Impurities become all parts understood by the chemical substance or the chemical composition are different. The typical amount of contamination is not the same for all alcohol components, but the proportion of Impurities in terms of classification as "technical Quality "depending on substance or composition, or also dependent on the manufacturing process. The skilled person is the classification as "technical quality" in Dependence on the substance and the manufacturing process, or the composition and the manufacturing process, common.

It is also conceivable that as alcohol component with two or more hydroxy groups not a single alcohol or an alcohol technical quality, but a mixture of several alcohols is used in the sense of the above. For example can use several forms of alcohol according to the above be used as a mixture. Preference is given to several alcohols characterized by at least one of the following features, such as different number of carbon atoms, different numbers to hydroxy groups or different structure, or alcohols, at the same time in two or more of the above features used, as for example, from large-scale Processes can be obtained as technical qualities.

According to one preferred embodiment of the invention Method are suitable as alcohol component divalent, trivalent, tetrahydric or pentahydric alcohols or a mixture from two or more of them.

Suitable alcohol components having two or more hydroxyl groups in this connection are based, for example, on the following dihydric alcohols:
1,2-etanediol, 1,2-propanediol, 1,3-propanediol, dihydroxyacetone, 2-methyl-1,3-propanediol, 2-butene-1,4-diol, 3-butene-1,2-diol, 2,3-butanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2-buten-1,4-diol, 1,2-cyclopentanediol, 3-methyl-1,3-butanediol, 2,2-dimethyl-1,3-propanediol, 4-cyclopenten-1,3-diol, 1,2-cyclopentanediol, 2,2-dimethyl-1,3-propanediol, 1,2-pentanediol, 2,4- Pentanediol, 1,5-pentanediol, 4-cyclopentene-1,3-diol, 2-methylene-1,3-propanediol, 2,3-dihydroxy-1,4-dioxane, 1,6-hexanediol, 2,5- Hexanediol, 3,4-hexanediol, 1,2-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,2-heptanediol, 1,7-heptanediol, 2,6-heptanediol, 3,4-heptanediol, 1,2-cycloheptanediol, 1,3-cycloheptanediol, 1,4-cycloheptanediol, 1,2-octanediol, 1,8-octanediol, 2,7-octanediol, 4,5-octanediol, 1,2-cyclooctanediol, 1, 3-cyclooctanediol, 1,4-cyclooctanediol, 1,5-cyclooctanediol, 1,2-nonanediol, 1,9-nonanediol, 2-methyl-1,9-octanediol, 2,2-dimethyl-1,9-octanediol, or two or more of them.

When Alcohol component based on trihydric alcohols are glycerol, 1,2,4-butanetriol, erythrose, threose, trimethylolethane, trimethylolpropane, 2-hydroxymethyl-1,3-propanediol or two or more thereof.

When Alcohol component based on tetrahydric alcohols are erythritol, Threit, pentaerythritol, arabinose, ribose, xylose, ribulose, xylulose, Lyxose, ascorbic acid glucono-γ-lactone, or two or more of them.

When Alcohol component based on pentavalent and higher Alcohols are arabitol, adonite, xylitol and dipentaerythritol.

Further are suitable as alcohol component with two or more hydroxy groups Sugar compounds such. Glucose, fructose, sucrose, galactose, Mannose, maltose, lactose, cellulose, or starch, or one Combination of two or more of them.

According to one particularly preferred embodiment is the alcohol component with two or more hydroxy groups selected from the group consisting of 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, glycerol, 1,2,4-butanetriol, glucose, fructose, sucrose, more preferred Glycerol or 1,2-ethanediol.

In In this context, the reaction products are also suitable the above-mentioned alcohol components having two or more Hydroxy groups with ethylene oxide or propylene oxide, or both, wherein at least one, preferably two or more, more preferably all hydroxy groups of the alcohol component having two or more hydroxy groups, each independently between 2 and 30 units, especially preferably, 2, 3, 4, 5, 6, 7, 8, 9 or 10 units of ethylene oxide or propylene oxide, or both. Furthermore The use of di-, tri- or tetrabutyl glycol is conceivable.

According to one another preferred embodiment, the alcohol component with two or more hydroxy groups at least one primary Hydroxy group on.

According to one another preferred embodiment, the alcohol component with two or more hydroxy groups less than 10 wt .-%, preferably less than 5% by weight of nitrogen-containing compounds, respectively based on the total weight of the alcohol component with two or more hydroxyl groups, wherein nitrogen-containing compounds both nitrogen-containing alcohol components having two or more hydroxy groups, as well as other nitrogen-containing organic compounds. Further preferably, the alcohol component has two or more Hydroxy groups do not contain nitrogen atoms (N).

According to one another preferred embodiment, the alcohol component with two or more hydroxy groups less than 10 wt .-%, preferably less than 5% by weight of aromatic cycle compounds on the total weight of the alcohol component having two or more hydroxy groups on, wherein aromatic cycle compounds have both aromatic cycles having alcohols, as well as other aromatic cycle compounds are. Further preferably, the alcohol component with two or more hydroxy groups non-aromatic cycle compounds.

According to one another preferred embodiment, the alcohol component with two or more hydroxy groups as non-metal atoms only non-metal atoms selected from the group consisting of carbon (C), Oxygen (O), nitrogen (N) or hydrogen (H), or more of which, preferably consisting of carbon (C), oxygen (O) and hydrogen (H), on.

• – Gruppe A), der Übergangsmetallverbindungen, sowie der
• – Gruppe B), der phosphororganischen Verbindungen des dreiwertigen Phosphors,

oder zwei oder mehr davon, aufweist.In principle, any catalytically active composition known to the person skilled in the art and suitable for carrying out the process according to the invention is suitable as the catalytically active composition. In particular, however, is a catalytically active composition which at least one compound selected from the

• - Group A), the transition metal compounds, as well as the
• - group B), the organophosphorus compounds of trivalent phosphorus,

or two or more thereof.

Prefers a catalytically active composition is used by Group A and Group B each independently several, more preferably two or three different Includes connections. In particular, the following are in particular Combinations of a number of compounds of group A with one Number of compounds of group B expressed as a number ratio (A: B) in the catalytically active composition is advantageous: 1: 1, 1: 2, 1: 3, 2: 1, 2: 2, 2: 3, 3: 1, 3: 2, 3: 3. Occasionally, combinations become from up to six different compounds of group A with bis to six different compounds of group B to the invention used catalytically active composition.

Preferably, the catalytically active composition is in a range of 0.01 to 10 wt .-%, more preferably from 0.05 to 4.5 wt .-%, or from 0.1 to 3.5 wt .-%, in addition preferably from 0.5 to 3.5 wt .-%, each used in relation to the total amount of all process components. Especially before The amount of the catalytically active composition used is in a range of from 0.7 to 3.2% by weight of from 1 to 3% by weight and more preferably from 1.5 to 3% by weight, more preferably from 2 to 3 percent and particularly preferably from 2.2 to 2.8 wt .-%, each based on the total amount of all process components.

According to one another preferred embodiment, the catalytic active composition a molar ratio of the compounds group B group to group A compounds in one area from 1: 1 to 50: 1, preferably from 2: 1 to 20: 1, more preferably from 4: 1 to 10: 1, more preferably from 4: 1 to 8: 1, and in particular preferably from 5: 1 to 7: 1.

When Compounds of group A of the catalytically active composition are preferably palladium, platinum, nickel or rhodium compounds, particularly preferably palladium or platinum compounds.

Suitable compounds of the group of palladium compounds are in principle all salts and complexes of palladium known to the person skilled in the art and suitable, and elemental palladium which can be used as a powder. Particular preference is given to compounds selected from the group consisting of: Pd (OAc) ₂ , PdCl ₂ , Pd (acac) 2, PdCl ₂ (pyr) ₂ , Pd (C ₃ H ₅ ) ₂ , Pd (C ₃ H ₅ ) ₂ OAc ₂ , {Pd (C ₃ H ₅ ) Cl} ₂ , or a combination of two or more thereof.

Suitable platinum compounds are, in principle, all salts and complexes of platinum which are known to the person skilled in the art and are suitable, and elemental platinum which can be used as powder. Particularly, in particular, compounds selected from the group consisting of: PtCl ₂ , PtCl ₄ , Pt (C ₃ H ₅ ) ₂ , Pt (cod) ₂ , or a combination of two or more thereof.

When In principle, compounds of group B are all suitable for the person skilled in the art known and suitable appearing organophosphorus compounds of trivalent phosphorus, as well as salts of organophosphorus Compounds of trivalent phosphorus, in particular triphenylphosphine, Triphenylphosphine derivatives, and salts thereof. Very particularly preferred are in detail: triphenylphosphine-3-sulfonic acid, Triphenylphosphine-3,3'-sulphonic acid, triphenylphosphine-3,3 ', 3'-sulphonic acid, and salts of the above-mentioned triphenylphosphine compounds, or a combination of two or more of them. As salts are preferred the alkali metal salts and ammonium salts, more preferably the Sodium and lithium salts.

Further Also preferred are organophosphorus compounds which derived from phosphonium salts, these compounds at least one point of the invention Process the organophosphorus compounds described above of the trivalent phosphorus, and then present as such. Suitable phosphonium salts are, for example: 3- (octa-2,7-dienyldiphenylphosphonium) benzenesulfonate, Trisodium mono (3,3'-octa-2,7-dienyl (3-sulfinatophenyl) phosphonodiyl) di-benzenesulfonate, trisodium mono ((E) -3,3 '- (but-2-enyl (3-sulfinatophenyl) - phosphoniodiyl) -dibenzolsulfonat).

When Hydrocarbon compound having at least two conjugated double bonds For the preparation of the ether, in principle any known in the art Hydrocarbon compound having at least two conjugated double bonds be used. These may be both hydrocarbon compounds with at least two conjugated double bonds, the others have functional groups, or those that have no further have functional groups. Preferably, the hydrocarbon compounds with at least two conjugated double bonds no further functional groups.

in principle are both hydrocarbon compounds with at least two conjugated Double bonds suitable, in addition, aromatic groups such as those further containing aliphatic hydrocarbon compounds exhibit, or both.

In this context suitable aliphatic hydrocarbon compounds with at least two conjugated double bonds are particularly suitable: 1,3-butadiene, 1,3-pentadiene, isoprene, 1,3-hexadiene, 2,4-hexadiene, 2,3-dimethylbuta-1,3-diene, 2-chloro-3-methylbutamino-1,3-diene, 2-chloro-1,3-butadiene, 2,4-octadiene, 2-methyl-2,4-pentadiene, 1,3-cyclohexadiene, 1,3-cyclooctadiene, 7-methyl-3-methylenocta-1,6-diene, or 2,6-dimethylocta-2,4,6-triene, more preferably 1,3-butadiene.

When aromatic hydrocarbon compound having at least two conjugated For example, double bonds are: (3-methylbuta-1,3-dien-2-yl) benzene, buta-1,3-dien-2-yl-benzene, particularly preferably (3-methylbuta-1,3-dien-2-yl) benzene.

According to a further preferred embodiment, further additives can be added in process step 1c ) to be provided. The addition of the optional, at least one further additive is generally carried out in a separate process step to the already provided aqueous phase, or the oily phase, or both. It is likewise possible to add a plurality of additives, each independently of one another, to one of the two phases, the aqueous phase or the oily phase, prior to contacting the two phases. It is often advantageous to mix the additives at least in part simultaneously with the aqueous or the oily phase, or both, during the preparation with stirring. Occasionally, after providing the oily and aqueous phases, optionally at least one further additive is added upon contacting.

When other additives can in principle all those skilled in the art known and suitable compounds appear to be used. In particular, the additive is selected from the group Emulsifier, defoamer, inhibitor, phase mediator, pH regulator, or ligand reservoir such. B. phosphonium salts.

According to a preferred embodiment of the method according to the invention is in process step 1c ) at least one emulsifier added. In principle, any emulsifier known to the person skilled in the art and suitable for emulsifying the oily with the aqueous phase appears suitable emulsifier. For example, the emulsion may be given a preferred droplet size or stability.

After providing the aqueous phase, the oily phase and optionally further additives, takes place in the process step 1d ) contacting the aqueous phase with the oily phase, and optionally the further additives to form an emulsion in a unit A.

in principle can as unit A any known to the skilled person and for contacting the process components suitable appearing device used become. Particularly preferred is a mixing unit, in particular for contacting liquids, solids, or a Mixture of both is suitable. As a mixing unit is suitable, for example a reactor, a loop or jet circulation reactor, tubular reactors with static mixer, capillary reactors. Likewise, a suitable Boiler or autoclave, preferably with stirrer.

As a stirrer, in principle, any stirrer is suitable which is known to the person skilled in the art and with regard to its design and stirrer geometry for carrying out the method step 1d ) seems suitable. Particularly preferred as a stirrer, a MIG stirrer is selected. Further preferably, the reactor has a jacket heating, as well as on its inner wall baffles on.

According to a further preferred embodiment, the mixing unit is designed such that the method step 1d ) can be carried out under increased pressure. In this case, suitable measures are known to those skilled in the art. Particularly preferred is a pressure autoclave is used. This preferably has a reaction vessel of V2A or V4A steel, or a combination of both. V2A refers to steel of material numbers 1.4301, 1.4541 or 1.4307, while V4A refers to steel of material numbers 1.4401, 1.4571 or 1.4404. Also preferred is a pressure autoclave which can be operated with a pressure of 1 to 50 bar, from 1 to 100 bar, from 1 to 200 bar, or from 1 to 400 bar internal pressure. According to a further preferred embodiment, the mixing unit can be operated at a temperature of 0 up to 150 ° C, or 0 up to 250 ° C. According to a very particularly preferred embodiment, a pressure autoclave is used as the mixing unit, which is operated at an internal pressure of 1 to at least up to 50 bar and at a temperature of 0 to at least up to 150 ° C.

Occasionally the inventive method can also in a Mixing unit to be carried out, consisting of one or more Microreactors exists. Here, the contacting takes place in the one or more microreactors preferably by a merge the process components to a mass flow, wherein the contacting while mixing, in particular by guiding the mass flow against impact surfaces, deflection devices or flow dividers in the flow path of the mass flow.

According to one another preferred embodiment of the invention Method is the ratio of diameter of the stirrer to diameter of the mixing chamber of the mixing unit, in one area from 0.35 to 0.45. More preferably, this ratio in a range of 0.37 to 0.43. The preferred ratio applies here the diameter for each plane perpendicular to the rotor can be put through a stirring day.

According to a further preferred embodiment, the stirrer is at a number of revolutions operated per minute in a range of 600 to 2000. Particularly preferred is a number of revolutions per minute from 800 to 2000, or from 1000 to 2000, or from 1200 to 2000, or more preferably from 1200 to 1600 revolutions per minute. Occasionally, a higher number of revolutions per minute, for example. More than 2000 to 4000 revolutions per minute can be selected.

Occasionally is also the ratio of diameter of the stirrer to diameter of the mixing chamber of the mixing unit of larger selected as 0.45, for example from more than 0.46 to 0.7. in this connection is a contacting of the process components at a lower Number of revolutions per minute possible.

The stirrer and the reactor are preferably selected such that the liquid in the reactor is characterized by a Reynolds number Re of from 2,000 to 40,000, more preferably from 3,000 to 20,000 and most preferably from 4,000 to 10,000. The Reynolds number Re is a quantity whose calculation is known to the person skilled in the art and, for example, in the Roempp Chemistry Dictionary, 1999, Wiley-VCH, Weinheim , as a keyword can be looked up.

wobei d für den größten Durchmesser des Rührers, g für die Erdbeschleunigung (9,81 m/s²) und n für die Rührerdrehzahl steht.According to a further preferred embodiment, the reactor with the stirrer is designed such that the stirrer is characterized by a Froude number Fr in a range from 0.4 to 5, particularly preferably from 1 to 5 and very particularly preferably from 1.5 to 5 becomes. The Froude number is calculated according to formula (1),

where d is the largest diameter of the agitator, g is the acceleration due to gravity (9.81 m / s ² ) and n is the stirrer speed.

According to a further preferred embodiment, the method according to the invention, in particular the method step 1d ), in the unit A at a temperature in a range of 50 to 100 ° C, more preferably 60 to 100 ° C, or 70 to 95 ° C, or 80 to 100 ° C, and especially 85 to 95 ° C, carried out.

According to a further preferred embodiment, process step 1d ) at a pressure in a range from 12 to 25 bar, particularly preferably from 14 to 23 bar, more preferably from 15 to 21 bar and particularly preferably carried out 16 to 19 bar.

When contacting the aqueous phase with the oily phase and optionally other additives, an emulsion is formed with vigorous stirring. The emulsion may have one continuous phase and one discontinuous phase, or two discontinuous phases. The continuous phase is preferably the aqueous phase from the process step 1a ). According to another preferred embodiment, the emulsion is an oil-in-water emulsion. In such an emulsion, droplets of the oily phase are present in a usually continuous aqueous phase. Preferably, the aqueous phase to at least 90 wt .-%, based on the aqueous phase, continuously before.

Prefers At least the droplets of the oily phase have to 50% by weight, preferably at least 70% by weight, more preferably at least 80% by weight, a droplet size in a range of 20 to 1000 microns, more preferably from 50 to 500 μm, and more preferably from 100 to 400 μm, or from 150 to 400 microns, and most preferably from 180 up to 500 μm, on.

In the process step 1e ), the previously formed emulsion is divided as mass flow M0 according to the invention in a unit B into at least two mass flows M1 and M2, wherein the mass flows M1 and M2 have the same state of aggregation as the mass flow M0. Preferably, the state of matter of the mass flow M0 is liquid. It corresponds to a further preferred embodiment that an aqueous phase is obtained as the mass flow M1 and an oily phase is obtained as the mass flow M2, wherein the aqueous phase is recycled to the reactor and mixed with the aqueous phase obtained in process step 1a ) is pooled. The oily phase contains the ether.

to Division of the emulsion as mass flow M0 into a mass flow M1 and a mass flow M2 can be used in principle any method which is known to those skilled in the art and to carry out the method of the invention seems suitable. Sheath methods are preferred.

In this case, the unit B according to the invention is a separation unit T1. As a separation unit T1 is in principle any known in the art and for carrying out the method step 1e ) suitable for use, in particular one which includes a sheath unit for separating a liquid mass flow into two or more, also liquid, phases. Particularly preferred is a centrifuge, a separator, preferably horizontal or vertical separator, which are equipped with or without Koaleszierhilfen. Suitable coalescing aids are, for example, fibrous tissue, wire mesh, mesh, fillings of spherical hollow or solid bodies such as plastic rings, plastic balls, glass rings, glass beads, Raschig rings, activated carbon beds and other inert bodies with respect to the aqueous phase and the oily phase. The person skilled in the art is aware of further, customary embodiments. According to an advantageous embodiment, a standing separator, particularly preferably selected with coalescing.

The Separating unit has a separation chamber with at least one removal device on. If the separation unit has a removal device, it can be designed as a pivotable interface controller. Prefers the separation unit has two or more removal devices, particularly preferably one at the bottom of the separation chamber and at least another, with the liquid from the surface discharged from the liquid level of the separation chamber can be.

• – wobei mindestens eine Kammer einen Zustrom zur Zuführung von M0 aufweist,
• – wobei die eine oder mehreren in fluidleitender Verbindung stehenden Kammern insgesamt mindestens zwei Abströme aufweisen,
• – wobei mindestens ein erster Abstrom höher angeordnet als ein weiterer Abstrom
• – wobei dem ersten Abstrom der Massestrom M2 entnehmbar,
• – wobei dem weiteren Abstrom der Massestrom M1 entnehmbar ist.

According to a further preferred embodiment, the unit B includes a separation unit T1 for dividing the mass flow M0 into at least two mass flows M1 and M2, the separation unit T1 having one or more chambers in fluid communication,

• - wherein at least one chamber has an inlet for supplying M0,
• Wherein the one or more chambers in fluid communication have a total of at least two outflows,
• - At least a first effluent arranged higher than another effluent
• Wherein the mass flow M2 can be taken from the first outflow,
• - Wherein the further outflow of the mass flow M1 can be removed.

According to one Another preferred embodiment are in a separation unit with several chambers in each case the inflows to the chambers fluidly connected. More preferred are the effluents from the chambers which discharge the mass flow M1, fluid-conducting connected. Also preferred are the effluents from the chambers, which dissipate the mass flow M2, fluidly connected. Most preferably, both the inflows are fluid-conducting connected, as well as the effluents, the mass flow M1 remove as well as the effluents from the chambers, which dissipate the mass flow M2.

According to the invention preferred The process for dividing the emulsion into an aqueous solution Phase and an oily phase at a temperature in one Range from 0 to 100 ° C, more preferably 50 to 100 ° C, further preferably 70 to 100 ° C and particularly preferably 80 or 90 to 100 ° C performed.

According to a further preferred embodiment of the method according to the invention, the splitting of the emulsion is in process step 1e ) at a pressure in a range from 12 to 25 bar, preferably from 14 to 21 bar, and most preferably from 16 to 19 bar, for example 17 bar performed.

According to a further preferred embodiment, that in the method step 1e ) obtained oily phase less than 15 wt .-%, preferably less than 10 wt .-%, and more preferably less than 5 wt .-% to 1 wt .-%, each based on the oily phase, of water.

According to the invention, the oily phase obtained by dividing the emulsion, which contains the ether, in a further process step 1f ) in a unit C in a first phase and a further phase, wherein the first phase has more ether than the further phase, and wherein the further phase is recycled to the reactor and with the oily phase, the in process step 1b ) is pooled.

To the In principle, any of the skilled person can share the oily phase known and for the implementation of the invention Process suitable appearing unit C can be used. Especially Preferably, the unit C has a separation unit T2, in which an oily Phase as mass flow M2 in at least two mass flows M3 and M4 is shared, wherein the mass flow M4 one of the mass flows M2 and M3 has different physical state. Especially preferred is selected as a separation unit T2 a relaxation device, those skilled in the implementation of the inventive Method suitable relaxation devices are known. All particularly preferably, the expansion device has a nozzle, a valve, a diffuser, a capillary, or a combination of two or more of them.

It corresponds to a further preferred embodiment, when the mass flow M2 is released by the expansion device and directed against a baffle. Especially preferred is the distance of the baffle from the outlet of the Relaxation device 10 times to 50 times, especially preferably 10 times to 20 times the diameter of the expansion device

Further has the mass flow at the outlet of the expansion device an exit velocity whose distance per second is preferred 1000 times to 1000000 times, more preferably 10000 times up to 100,000 times, and most preferably 300,000 times to 80000 times the diameter of the expansion device is.

Prefers may further for dividing the oily phase as a mass flow M2 is an arrangement of two or more, connected in parallel Relaxation devices are used.

When Example of such an advantageous embodiment, a relaxation device be considered, which includes a nozzle, wherein the diameter the nozzle in a range of 1 to 2 mm, the distance of the Baffle from the outlet of the nozzle in a range of 10 to 30 mm and the exit velocity the mass flow is between 10 and 100 m / s.

The in process step 1f ) is passed, if desired via a liquid separator or a purification plant, or both, before passing the oily phase in the process step 1b ) is supplied. In principle, any device known to the person skilled in the art and suitable for appearing, with which liquid droplets transported in a gas phase can be separated from it, is suitable as a liquid separator. Particularly preferred is a cyclone, a horizontal or vertical separator, or a combination of two or more thereof. Particularly preferably, the liquid separator is equipped with a demister insert in the outflow region of the gas. As a Demistereinsatz are suitable, for example, vortex breaker assemblies, baffles, filter fabric and -gelege, filter fleece, filter felts, metal wool, wire mesh, wire mesh, heaps of hollow or solid bodies such as plastic rings, plastic balls, glass rings, glass beads, Raschig rings, activated charcoal and other, with respect to the first and the further phase inert body, or a combination of two or more different of the aforementioned inserts, or a combination of two or more layers of the same, aforementioned inserts, or both. The person skilled in the art is aware of further, customary embodiments. According to a particularly advantageous embodiment, a standing separator, more preferably with Demistereinsatz with a bed of one of the above materials is selected.

Farther It may be beneficial to complete the further phase before combining with the oily one Phase to liquefy. Preference is given to the oily This phase is pressurized, or cooled, or both.

According to the invention includes in process step 1f ) obtained first phase more ether than the other phase. Preferably, the first phase contains greater than 70% by weight, more preferably greater than 80% by weight, and most preferably greater than 90, or greater than 95%, by weight of ether based on the total weight of the process step 1f ) and the first phase.

According to a further preferred embodiment, the method step 1f ) at a temperature in a range of from 20 to 100 ° C, more preferably from 30 to 80 ° C, more preferably from 30 to 60 ° C, and most preferably from 30 to 50 ° C.

According to a further preferred embodiment, the method step 1f ) at a pressure in a range of 0.5 to 5 bar, more preferably from 0.8 to 1.5 bar, and most preferably at 1 bar performed. Further preferred is the in process step 1f ) execution according to the pressure at the outlet of the expansion device used.

According to a further preferred embodiment, that in the method step 1f ) liquid phase less than 10 wt .-%, preferably less than 15 wt .-% and particularly preferably less than 3 wt .-% to 0.1 wt .-%, each based on the oily phase, of water.

According to a further preferred embodiment of the process according to the invention, the yield of ether is obtainable as the first phase in the process step 1f ), in a range of 30 to 99 mol%, based on the total amount of the alcohol component having two or more hydroxy groups. Particularly preferably, the yield of ether in a range of 50 to 98 mol .-%, or from 70 to 95 mol .-%, and most preferably from 80 to 95 mol .-%, each based on the total amount of used alcohol component with two or more hydroxyl groups.

According to one further preferred embodiment the yield of ether with exactly one ether group in a range from 25 to 99 mol%, particularly preferably from 35 to 95 mol%, and most preferably from 50 to 60 mol%, based in each case on the total amount of the alcohol component used with two or more hydroxy groups.

According to another preferred embodiment, the numerical ratio of ether with exactly one ether group per molecule to ether with more than one ether group per molecule, both present step as a liquid phase from process 1f ), in a range from 5: 1 to 500: 1, or from 10: 1 to 100: 1, more preferably from 10: 1 to 50: 1, and most preferably more than 15: 1, or more than 25: 1 , If, as stated above, "ether groups per molecule" are considered, these are exclusively those which were formed when carrying out the process according to the invention. If, for example, tetraethylene glycol is used as the alcohol component having two or more hydroxyl groups, the ether groups inherent in the structure of the tetraethylene glycol are not taken into account, but only those which are formed by participation of the hydroxy groups of the tetraethylene glycol in a reaction or a process.

According to another preferred embodiment of the method according to the invention, it has the liquid phase in the process step 1f ), a linearity coefficient L in a range of 10: 1 to 100: 1, preferably from 30: 1 to 100: 1, on. The linearity coefficient L is understood to mean the ratio of two or more linking patterns between an alcohol component having two or more hydroxy groups and a hydrocarbon compound having two or more double bonds, or their dimer, to the ether, the linearity coefficient L being the ratio of the hydrocarbon compound terminal (linear) means non-terminal (branching) ether linkages. Occasionally this ratio is referred to as the "n / iso ratio".

Furthermore, the inventive, in process step 1f ) Ether available as a liquid phase has a proportion of phosphorus and a proportion of transition metal, in particular palladium or platinum. According to a preferred embodiment, the proportion of transition metal, in particular palladium or platinum, of the ether according to the invention, in a range of 0 to 100 ppm, or from 0 to 50 ppm, or from 1 to 50 ppm, particularly preferably from 0.2 to 20 ppm, and most preferably from 0.2 to 10 ppm, each based on the weight of the ether. Further preferably, independently or in addition to the above, the phosphorus content is in a range of 0 to 500 ppm, or from 0 to 300 ppm, more preferably from 0.1 to 200 ppm, even more preferably from 0 to 80 ppm, based on the weight of the ether. Moreover, the phosphorus content is preferably in a range of 0 to 50 ppm, or 0.1 to 30 ppm. The proportion of phosphorus, such as the platinum or palladium content, or both, can be further reduced by suitable post-treatment processes known to those skilled in the art.

According to a further preferred embodiment, the method steps 1d ) to 1e ) in two or more parallel production units. If several devices are operated in parallel, the devices in the respective process step 1e ), and with the aqueous phase in process step 1a ), preferably before the aqueous phase from process step 1a ) and supplied to the parallel devices. The gaseous phases, each available in process step 1f ) of each device, are combined and also with the oily phase in process step 1b ), preferably before the oily phase from the process step 1b ) and supplied to the parallel devices. Thus, a continuous recycling of at least a portion of possibly unreacted process components is achieved. The parallel operation of method steps is particularly advantageous in systems that are designed as microreactors.

one According to another embodiment, two or used more combinations of the unit A with the unit B, where the combinations are arranged se riell. Particularly preferred are the Combinations of production units, arranged serially, in countercurrent process operated.

• 3a) Verfahrensschritt 1b) mindestens in der ersten Produktionseinheit durchgeführt wird, und
• 3b) Verfahrensschritt 1a) mindestens in der weiteren Produktionseinheit durchgeführt wird, und
• 3c) die ölige Phase erhältlich in dem Verfahrensschritt 1e) in der ersten Produktionseinheit als ölige Phase in Verfahrensschritt 1b) in der weiteren Produktionseinheit eingesetzt wird, und
• 3d) die weitere Phase erhältlich in dem Verfahrensschritt 1e) in der weiteren Produktionseinheit als wässrige Phase in den Verfahrensschritt 1a) in der ersten Produktionseinheit eingesetzt wird, und
• 3e) die ölige Phase erhältlich in dem Verfahrensschritt 1e) in der weiteren Produktionseinheit dem Verfahrensschritt 1f) unterzogen wird, und
• 3f) die wässrige Phase erhältlich in Verfahrensschritt 1e) in der ersten Produktionseinheit mit der wässrigen Phase in Verfahrensschritt 1a) der weiteren Produktionseinheit vereinigt wird, und
• 3g) die weitere Phase erhältlich in Verfahrensschritt 1f) in die erste Produktionseinheit zurückgeführt und mit der öligen Phase in Verfahrensschritt 1f) vereinigt wird.

According to a further preferred embodiment of the method according to the invention, therefore, at least the method steps 1d ) to 1e ) performed in a first and at least one further production unit, wherein

• 3a) process step 1b ) is performed at least in the first production unit, and
• 3b) process step 1a ) is carried out at least in the further production unit, and
• 3c) the oily phase obtainable in the process step 1e ) in the first production unit as an oily phase in process step 1b ) is used in the further production unit, and
• 3d) the further phase obtainable in the process step 1e ) in the further production unit as an aqueous phase in the process step 1a ) is used in the first production unit, and
• 3e) the oily phase obtainable in the process step 1e ) in the further production unit the process step 1f ), and
• 3f) the aqueous phase obtainable in process step 1e ) in the first production unit with the aqueous phase in process step 1a ) of the further production unit, and
• 3g) the further phase obtainable in process step 1f ) returned to the first production unit and with the oily phase in process step 1f ) is united.

This system is therefore performed in countercurrent, which is exemplary in 2 is reproduced, wherein I , and II , the first and and II , another production unit, OP the oily phase, WP the aqueous phase, (g) a mass flow in the gaseous state, (fl) a mass flow in the liquid state and P the product effluent.

According to a further preferred embodiment of the method according to the invention, the oily phase is in the process step 1b ) as a further component of a polar-protic, organic solvent. This can discharge components of the catalytically active composition from the liquid phase containing the ether in process step 1f ) are reduced, preferably avoided. Particularly preferred forms the polar-protic, organic solvent with the oily phase in process step 1b ) a single, oily phase.

According to a further preferred embodiment, the weight ratio of the polar-protic, organic solvent to the aqueous phase from the process step 1a ) in a range of 0.1 to 1, more preferably 0.3 to 0.7 to one part aqueous phase.

wobei ΔU_m die molare Verdampfungsenthalpie, und V_m das molare Flüssigkeitsvolumen des Stoffs bedeutet.According to a further preferred embodiment, the polar protic organic solvent has a solubility parameter δ in a range from 18 to 26 MPa ^0.5 . The solubility parameter δ of a substance is described by the formula (2):

where ΔU _{m is} the enthalpy of vaporization, and V _{m is} the molar volume of the substance.

The solubility parameter δ is known to the person skilled in the art and, for example, in Harris, HG and Prausnitz, JM, Thermodynamics of solutions with physical and chemical interactions - solubility of acetylenes in organic solvents, Industrial and Engineering Chemistry Fundamentals, 1969, 8 (2), pp. 180-186 described. The values for the solubility parameter δ can be calculated according to formula (2), or in tables such as Barton, AFM, Solubility parameters, Chemical Reviews, 1975, 75 (6), pp. 731-753 be looked up.

The polar protic organic solvent is particularly preferably selected from the group consisting of: alcohols of chain length C ₄ to C ₁₀ having 1 to 4 hydroxyl groups, particularly preferably alcohols of chain length C ₅ to C ₈ having 1, 2, 3 or 4 hydroxyl groups , secondary alcohols, tertiary alcohols, more preferably 2-pentanol, 2-octanol or 2-methyl-2-butanol, or a mixture of two or more thereof.

According to a further preferred embodiment, the aqueous phase in the process step 1a ) as further component at least one cyclodextrin compound. According to the invention, the ratio of the molar amount of cyclodextrin compound to the molar amount of catalytically active composition is preferably in the range from 1: 1 to 30: 1, more preferably from 5: 1 to 20: 1, and most preferably from 5: 1 to 15: 1.

According to one Another preferred embodiment is the cyclodextrin compound selected from the group consisting of: α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin and modified α-cyclodextrin, modified β-cyclodextrin, modified γ-cyclodextrin, such as and in particular preferably methyl-β-cylcodextrin or 2-hydroxypropyl-γ-cyclodextrin, or a combination of two or more of them.

According to a further, preferred embodiment of the method according to the invention, the oily phase comprises in process step 1b ) at least one further aliphatic or aromatic hydrocarbon compound.

in principle are all known to the skilled and suitable appearing aliphatic or aromatic hydrocarbon compounds.

It corresponds to an advantageous embodiment, when the further aliphatic or aromatic hydrocarbon compound has a solubility parameter δ according to Hildebrandt in a range of 16 to 23 MPa ^0.5 , more preferably from 18 to 21.5 MPa ^0.5 .

Especially preferred is the further aliphatic or aromatic hydrocarbon compound selected from the group consisting of: toluene, cyclohexane, Cyclohexanol, or ethyl acetate, or a combination of two or more of that. Particularly preferred is cyclohexanol or cyclohexane selected.

According to one another preferred embodiment of the invention Process becomes at least one, preferably all process components provided as a liquid. This may require to pressurize the process component. Likewise, or In addition, it may be preferable to cool the component or to liquefy by cooling. According to one Another preferred embodiment, the process components each subjected to a treatment with which the Reduced proportion of oxygen in the respective liquid becomes. In principle, all known to those skilled in and under Consideration of the chemical compounds used appear suitable method for reducing the oxygen content suitable. In particular, it is preferred that as a liquid present process component via a copper bed respectively. For example, as a bed of copper (II) oxide, which is preferably finely distributed on magnesium silicate particles, be used before, after, or before and after use must be regenerated to elemental copper. A suitable bed is available, for example, from BASF AG as "R3-11G", in which the copper is present before use as CuO .. Furthermore, can the bed preferably as a heatable bed, for example, in a column. According to one Another preferred embodiment, all process components subjected to a treatment for reducing the oxygen content.

• M41: ein Verhältnis des Gewichts der Alkoholkomponente zu Gewicht des Wassers in der wässrigen Phase 1a) in einem Bereich von 1:2 bis 2:1, bevorzugt 0,6:1 bis 1,8:1;
• M42: ein Verhältnis des Gewichts der Verbindung aus Gruppe A) zu Gewicht der Kohlenwasserstoffverbindung mit mindestens zwei konjugierten Doppelbindungen in einem Bereich von 0,0005:1 bis 0,005:1, insbesondere von 0,001 bis 0,003;
• M43: ein Verhältnis der Molzahl von Kohlenwasserstoffverbindung mit mindestens zwei konjugierten Doppelbindungen zu Alkoholkomponente in einem Bereich von 1,5:1 bis 5:1, insbesondere von 1,5:1 bis 2,5:1, oder besonders bevorzugt von 1,8:1 bis 2,2:1.
• M44: ein Verhältnis der Molzahl von Verbindungen der Gruppe B) zur Verbindungen der Gruppe A) in einem Bereich von 1:1 bis 50:1, insbesondere von 2:1 bis 20:1, oder besonders bevorzugt von 4:1 bis 10:1.

According to a further embodiment, the method according to the invention is carried out such that at the beginning of the method step 1d ) at least one, preferably each, of the following features is fulfilled:

• M41: a ratio of the weight of the alcohol component to the weight of the water in the aqueous phase 1a ) in a range from 1: 2 to 2: 1, preferably 0.6: 1 to 1.8: 1;
• M42: a ratio of the weight of the compound of Group A) to the weight of the hydrocarbon compound having at least two conjugated double bonds in a range of 0.0005: 1 to 0.005: 1, especially 0.001 to 0.003;
• M43: a ratio of the number of moles of hydrocarbon compound having at least two conjugated double bonds to alcohol component in a range from 1.5: 1 to 5: 1, especially from 1.5: 1 to 2.5: 1, or more preferably from 1.8 : 1 to 2.2: 1.
• M44: a ratio of the number of moles of compounds of group B) to compounds of group A) in a range from 1: 1 to 50: 1, in particular from 2: 1 to 20: 1, or particularly preferably from 4: 1 to 10: 1.

It also corresponds to embodiments of the invention, if at the beginning of the process step 1d ) several of the above features are met. In detail, the following combinations of features result from the combinations of numbers: M41M42, M41M43, M41M44, M42M43, M42M44, M43M44, M41M42M43, M41M42M44, M41M43M44, M42M43M44.

• 34a) Bereitstellen – der flüssigen Phase beinhaltend den Ether, sowie – ein Adsorbens,
• 34b) In Kontakt bringen der flüssigen Phase und des Adsorbens unter Bildung eines Gemischs,
• 34c) gegebenenfalls Teilen des Gemischs unter Abtrennen einer festen Phase, wobei die feste Phase mindestens einen Teil des Adsorbens beinhaltet,
• 34d) Zugabe eines Monoalkohols zu dem Gemisch, unter Bildung einer weiteren feste Phase,
• 34e) Teilen des Gemischs in mindestens eine feste Phase und eine flüssige Phase, wobei die flüssige Phase mehr Ether beinhaltet als die feste Phase,
• 34f) Entfernen des Monoalkohols aus der flüssigen Phase.

According to a further embodiment of the method according to the invention, the liquid phase is from the process step 1f ) containing the ether after treatment, including the following post-treatment steps:

• 34a) providing - the liquid phase containing the ether, and - an adsorbent,
• 34b) contacting the liquid phase and the adsorbent to form a mixture,
• 34c) optionally dividing the mixture to remove a solid phase, the solid phase containing at least a portion of the adsorbent,
• 34d) adding a monoalcohol to the mixture to form another solid phase,
• 34e) dividing the mixture into at least one solid phase and one liquid phase, the liquid phase containing more ether than the solid phase,
• 34f) removing the monoalcohol from the liquid phase.

Aftertreatment is understood to mean all conceivable steps and methods which are familiar to the person skilled in the art and which can be undertaken in the process step 1f ) of by-products, impurities, components of the catalytically active composition, as well as other additives to purify, or such processes, with which the ether is further processed to another end product.

For this In particular, distillation, sorpbtion, filtration, bleaching, Centrifugation, crystallization or drying process as well further implementation, or a combination of two or more of it, understood. Preference is given here to processes which involve treatment with an adsorbent.

In principle, any adsorbent known to the person skilled in the art and suitable for after-treatment may be used as the adsorbent. Likewise, a mixture of two or more adsorbents can be used. In the context of the invention, adsorbents are understood as meaning, in particular, substances which contribute to improving the physical properties or the purity of the ether prepared according to the invention, in this case in the liquid phase from the process step 1f ), or both, without altering the identity of the crude ether of the invention by, for example, a chemical reaction. According to the invention, the adsorbent is introduced into the crude ether as a particulate solid.

According to a preferred embodiment of the method according to the invention of the adsorbent in a range of 10 to 400 parts to 100 parts of liquid phase containing the ether from the process step 1f ) brought in. Further preferred are from the adsorbent in a range from 25 to 250 parts, very particularly preferably from 40 to 250 parts, in each case to 100 parts of the liquid phase from the process step 1f ). Occasionally, less than 10 parts, for example, 5 parts to 100 parts of liquid phase from process step 1f ).

When Particle size of the particulate Solid introduced adsorbent come basically all known in the art and for the purpose of the present Invention suitable appearing particle sizes into consideration. As a particulate, the solid in particular then designates if there is at least a portion of its particles Particle size of 8 microns to 5 mm. According to the above, preferably at least 70 Wt .-%, in particular at least 80 wt .-%, more preferably at least 90% by weight and most preferably in a range of at least 95 wt .-% to 99.5 wt .-% of the particles, each based on the Total weight of the adsorbent, one particle size in a range of 8 microns to 0.1 mm. Likewise apply the weight percentages given in the preceding sentence in each case for the following particle size ranges: from 400 μm to 5 mm, or preferably from 500 μm up to 700 μm, or from 1 to 5 mm, in each case based on the Total weight of the active component.

The as a particulate solid present adsorbent can Have particles of a single particle size or particles of several particle sizes, the one Form particle size distribution. Is a particle size distribution before, one is close to or corresponding to a bell curve Distribution preferred. Furthermore, it is also possible that Agglomerates of particles occur when two or more particles stick to each other. Such agglomerates are also by the invention Particle concept regardless of their composition and includes their emergence.

According to a further preferred embodiment of the present invention, the active component detects a BET surface area DIN 66131 in a range of 50 to 1500 m ² per g. Often, active components having a BET surface area in a range of 50 to 250 m ² per g or of 100 to 200 m ² per g, or more preferably of 120 to 190 m ² per g are preferred. Likewise, active components having a BET surface area of 500 to 700 μm are preferably used.

When Adsorbents are, for example, substances selected from the categories: inorganic, oxidic compounds, activated carbon, Ion exchangers, or two or more of them. Preference is given to inorganic, oxidic compounds and ion exchangers.

The term activated carbon in the context of the present invention also includes activated carbon black, activated carbon coke and graphite. Occasionally, however, activated carbon molecular sieve is not used as the activated carbon. According to the invention, the activated carbon selected is preferably one which consists of more than 80% by weight, or more than 90% by weight, or more than 95 to 99% by weight of carbon, particularly preferably of elemental carbon. Such an activated carbon is designed particularly advantageous if it has a BET surface area in a range of 50 to 1500 m ² / g, in particular from 500 to 700 m ² / g. Furthermore, the par Particle size of an advantageously designed activated carbon to 75 wt .-% or more, in particular 85 wt .-%, each based on the total weight of the activated carbon, in a range of 1 to 5 mm. The particle size is particularly preferably 85% by weight or more, in particular 90% by weight, in each case based on the total weight of the activated carbon, in a range from 1.5 to 4.75 mm.

Also suitable as the adsorbent is an inorganic, oxidic compound, preferably an oxide compound of aluminum, zeolites, clays, or two or more thereof. The inorganic oxide compound advantageously has a BET surface area in a range of from 50 to 1500 m ² / g, more preferably from 100 to 500 m ² / g, and most preferably from 135 to 190 m ² / g. Furthermore, the particle size of an advantageously configured inorganic, oxidic compound is 70% by weight or more, in particular more than 85% by weight, in each case based on the total weight of the inorganic, oxidic compound, in a range from 0.1 to 2 mm, more preferably from 0.5 to 1.5 mm.

When Inorganic oxide compound is preferably one or more Compounds used, selected from the group consisting made of: alumina, silica, zeolite, bentonite. Especially preferred is an inorganic, oxidic compound alumina, in particular acid-activated, or acid-activated calcium bentonite, used.

When Ion exchangers come in principle all known to those skilled and suitable appearing ion exchange resins into consideration. Prefers are polymer resin-based ion exchangers, in particular acid cation exchange resins wherein the replacement resin is preferably styrene-vinylbenzene copolymer based, and particularly preferably with sulfonic acid groups or carboxylic acid groups, or both, functionalized is. Furthermore, the particle size is advantageous designed ion exchanger to 75 wt .-% or more, in particular 85 wt .-%, each based on the total weight of the ion exchanger, in a range of 100 to 1000 μm, preferably 300 to 800 microns, and most preferably from 500 to 700 microns.

Further may also be a combination of two or more adsorbents, in particular a combination of two or more adsorbent different Categories, are used. Will such a combination of at least one adsorbent of the category inorganic, oxidic Connection and the category activated carbon, will be beneficial a ratio of inorganic, oxidic compound to activated carbon in a range of 10: 1 to 1:10, or 5: 1 to 1: 5, or from 5: 1 to 1: 1, preferably from 4: 1 to 1.5: 1 used.

According to one Another preferred embodiment is the treatment with an adsorbent, or a mixture of two or more Adsorbents, designed for continuous operation. In this case, preferably two or more adsorption columns, in which the adsorbent is present, parallel angeord net and fluid-conducting over Separating valves so connected to the inflow and outflow that a change of the columns is possible. The respectively non-operating adsorption can a regenerating Treated or filled with new adsorbent become. As measures to carry out a regenerating Treatment of the adsorbent are those considered by those skilled in the art are known and appear suitable for this purpose.

After this the liquid phase and the adsorbent according to process step 5b) as embodiment preferred according to the invention is contacted and a mixture is formed, if desired Mixture divided with the separation of a solid phase, wherein the solid Phase includes at least a portion of the adsorbent. To the division The mixture may be any method suitable to those skilled in the art appears. Particularly preferred are filtration, pressure filtration, Sedimentation or centrifugation. Especially preferred Here are filtration or pressure filtration. Become filtration processes is selected, then to be filtered mixture in a filter unit divided on a filter surface, with a fixed and a liquid phase is obtained. In a pressure filtration process the mixture to be filtered is additionally added before the filtration process subjected to a pressure.

the One skilled in the art is the design of a suitable filtration process as well as a suitable pressure filtration method. According to the invention preferred the mixture is divided in a pressure filtration process, wherein pressurized the mixture to be filtered and in the filter device is shared on a filter surface, for example from a tight mesh, a filter paper, a tissue or a Clutch is formed. Preferably, the filter device is a filter press designed. The inventively preferred Druckfiltrierverfahren can at a pressure in a range of 0.5 to 20 bar, preferably from 1 to 10 bar, more preferably carried out from 1.5 to 8 bar. Often the Druckfiltrierverfahren is also at a pressure in a range of 1 to 3 bar performed.

According to one another embodiment of the invention is considered a particularly simple device for dividing the mixture a funnel with a filter paper selected.

in the As part of the filtering process described above, the mixture on a filter surface in a solid and a liquid Divided phase, taking place during the division of the mixture in the separator often a solid phase on at least which forms a filter surface. The solid phase is preferred a thickness in a range of 1 to 20 mm, preferably from 20 to 18 mm, and more preferably from 3 to 10 mm. The solid phase preferably contains the adsorbent, preferably in an amount ranging from 30 to 90% by weight, more preferably from 50 to 80 wt .-%, based on the total amount of solid phase.

Further it is preferred according to the invention, the division in the separator at a temperature of 0 to 100 ° C, preferably from 10 to 50 ° C, and most preferably from 10 to 30 ° C perform. The remaining one liquid phase is fed to process step 5d).

According to one Another preferred embodiment is liquid Phase in process step 5d) with a monoalcohol to a mixture united, whereby a solid phase is formed. In terms of the preferred approach to unifying the liquid Phase with a monoalcohol is on the section regarding the Contacting the process components referenced.

When Monoalcohol is in principle any alcohol, the expert is known and to carry out the inventive Embodiment seems appropriate. Especially preferred are suitable as mono-alcohols compounds selected from the group consisting of: methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2,2-dimethylpropanol, 1-pentanol, 2-pentanol, Neopentyl alcohol, or a combination of two or more thereof. Occasionally it may also be advantageous to use monoalcohols of 6 or more To use carbon atoms.

Especially Preferably, the weight fraction is in the process step 5d) formed solid phase in a range of 0.01 to 1 wt .-%, more preferably from 0.1 to 0.8 wt .-%, each based on the total amount on liquid phase and added monoalcohol. Farther Preferably, the solid phase includes parts of the invention in the Method used catalytically active composition, their salts or reaction products, or a combination of two or more from that.

Embodiment will become the mixture in process step 5e) into at least one solid phase and divided at least one liquid phase, wherein the liquid Phase contains more ether than the solid phase. Regarding the Dividing the mixture is applied to the previously described filtering, in particular pressure filtration method referenced. Preferably includes the liquid phase more than 50 wt .-%, more preferably more as 70% by weight, more preferably more than 80% by weight, and especially preferably more than 90% by weight of ether, based on the total amount on liquid and solid phase.

The liquid phase from process step 5e) is in process step 5f) by at least partially removing the monoalcohol. In principle, all those skilled in the art are suitable for removing the monoalcohol known and to carry out this measure suitable appearing process, in particular distillation process. In this case, it may be preferable to remove the monoalcohol from the liquid Phase, which includes the ether to remove by distillation, and to remove the ether from the monoalcohol by distillation. According to a further preferred embodiment the removal of the monoalcohol, or ether, from the liquid Phase at reduced pressure, more preferably less than 500 mbar to 1 mbar, even more preferably less than 200 mbar to 1 mbar and most preferably less than 100 mbar to 1 mbar pressure, or carried out based on the ambient pressure.

in the The following is an example of a device for carrying out the inventive method, wherein the device still has optional features and in no way a limitation of what has been said so far, on the basis of drawings explained.

In 1 is a production unit with various devices which are suitable and preferred for carrying out the inventive method. Production unit ( 1d ) 1e )) is over the inlet 1a ) an aqueous phase, via an inlet 1b ) an oily phase and optionally via the inlet 1c ) supplied further additives. In the process step 1d ) is used for contacting the two phases, for example, a mixer or a stirrer, before the resulting mixture in process step 1e ) is divided into an aqueous phase (WP) and an oily phase (OP). The aqueous phase (WP) from the production unit ( 1d ) 1e )) is sent to the production unit via the inlet 1a ), or a separate inlet, returned. The oily phase (OP) from the production unit ( 1d ) 1e )) is in one process step 1f ), for example in a flash column, or other suitable separator, into an oily phase containing the ether and a gaseous phase (g). The gaseous phase (g) is, optionally via a device for liquefying a gaseous phase (g) as a liquid phase (fl) with the oily phase, as the process step 1b ) is supplied to the production unit, combined. The oily phase containing the ether becomes a process step 1f ) as product (P).

In 2 a plant is shown in which two production units are connected so that the execution form according to preferred method is carried out in countercurrent principle. The aqueous phase (WP) is supplied to the production unit II ., providing the oily phase (OP) to production unit I .. The effluent of the oily phase (OP) of the production unit I , becomes as a procedural step 1b ) of the further production unit II , supplied and the effluent of the aqueous phase (WP) of the further production unit II , as a process step 1a ) of the production unit I , fed. The process step 1 ) is applied to the oily phase effluent (OP) from the production unit II , carried out, wherein the thereby obtainable gaseous phase (g), optionally via a device for liquefying a gaseous phase (g) as a liquid phase (fl), with the oily phase, as the process step 1b ) of the production unit I , is fed, is united.

In 3 exemplifies a production unit, as in 1 or 2 described, shown. Such a production unit includes a heatable mixing unit (A) and, fluidly connected, a, also heatable, separation unit (D). The mixing unit (A) equipped with a stirrer B is fed via the feeder 1a ) an aqueous phase and the feed 1b ) an oily phase, and optionally via a further feed 1a ' ) is fed to a further aqueous phase (WP). On the surface of the liquid level in the mixing unit (A), the mixture produced in the mixing unit (A) is taken off via a guide, which serves as a supply line for the separation unit (C) in fluid-conducting connection. In the separation unit D, which is equipped as a separator, the aqueous phase (WP) is removed via a guide located at the bottom of the separation unit (D), and at the surface of the liquid level of the separated phases, the oily phase (OP) via a discharge line the process step 1f ).

Farther The invention relates to formulations, preferably, in each case as separate embodiment, fibers, films, moldings, molding compounds, Paint, textile auxiliaries, defoamers, adhesives, cleaning, Plastic additive, ointment, drilling fluid, lubricating, soil stabilization, Food, preservation or well cleaning compositions, each including one on the by the inventive Method available ether-based formulation component or obtainable by the process according to the invention Ether or a mixture of both. Preferably, the ether components or the ether or both in the above formulations in an amount in a range of 0.0001 to 70% by weight, preferably from 0.001 to 50% by weight, and more preferably from 0.01 to 30 Wt .-%, in each case based on the total processing included.

Further the invention relates to the use of a on by the inventive Method available ether-based formulation component or one obtainable by the process according to the invention Ethers or a mixture of both as a formulation component in formulations, in particular, each as separate embodiments, in fibers, films, moldings, molding compounds, paint, textile auxiliaries, Defoamer, Adhesive, Cleaning, Detergent, Plastic Additive, Ointment, Drilling Rinse, Lubrication Soil Hardening, Food, Preservative or well cleaning compositions, as well in hair and body care products, as low-foaming Wetting agent in cleaning compositions, or as an emulsifier. Preferably is the ether components or the ether or both in the above Formulations in an amount ranging from 0.0001 to 70 Wt .-%, preferably from 0.001 to 50 wt .-% and particularly preferably from 0.01 to 30 wt .-%, in each case based on the total processing, used.

formulation components are then based on the by the invention Method available ethers, if this ether as a Starting material in the preparation, preferably chemical reaction, this formulation component is used. Furthermore, the above formulations apart from those obtainable according to the invention Ether-based formulation components and the inventively available Ether itself the expert from relevant textbooks known.

The The present invention will now be described by way of example by way of drawings and examples are explained.

measurement methods

Provided not expressly stated otherwise, all done Measurements according to the relevant ISO standards. If there Unless otherwise specified, the temperature was 23 ° C, an air pressure of 1 bar and a relative humidity of 50% elected.

Composition of a mixture of several, liquid ingredients; Determination of the phase relationships

mixtures or phases with multiple liquid components, as they are For example, in a two-phase system, can by means of Gas chromatography (GC) or high pressure liquid chromatography (HPLC) can be determined. The Ge weight shares are in wt .-%, based on the total weight of the sample supplied.

Determination of particle size, Grain size distribution, fine dust content

The particle size or grain size is determined by means of laser diffractometry ISO 13320-1 (1999) Can be determined on a Coulter 230 LS.

water content

The water content is determined using a commercial coulometer ^®, type 652/01, Metrohm AG, Herisau, Switzerland.

Determination of the proportion of transition metal and / or phosphorus impurities, for example in an ether by means of ICP-AES

a) Digestion and sample preparation

0.1 to 0.25 g of the sample substance to be examined, for example of the ether are placed in a Teflon beaker. Subsequently, the sample is mixed with 2 ml of HNO ₃ (conc.) And with 3 ml of H ₂ SO ₄ (conc.) And digested in the microwave. The temperature program was heated at 140 ° C. for 3.5 minutes, then at 200 ° C. for 3.5 minutes, then at 250 ° C. for 6 minutes, and the temperature was maintained at 250 ° C. for a further 15 minutes. Subsequently, 1.5 g of distilled water. and 0.8 g of H ₂ O ₂ (30% by weight) was added and the thus treated sample allowed to stand for 12 hours.

b) Determining the content of P, Pd or Pt. a.

Subsequently, the sample was detected by ICP-AES (Inductively Coupled Plasma - Atomic Emission Spectroscopy) in a "Thermo Elemental Iris Intrepid" device DIN EN ISO 11885 measured. To determine the transition metal content, in particular palladium or platinum, the procedure was analogous. For calibration, standard solutions from Acros Organics in Geel, Belgium, were used.

Determination of droplet size in the reactor

The determination of the droplet size present in the emulsion is determined in the mixing unit as follows: Through a viewing window arranged in a side wall of the mixing unit, the mixture is recorded with a high-speed 100 K camera from LaVision GmbH, Göttingen, at 10,000 images per second. To improve the images, the mixture was illuminated by another viewing window arranged in the opposite side wall. To control the software DaVis 7.2, also used by LaVision. The evaluation was performed using the software ImageJ, version 1.38 of Wayne Rasband, National Institute of Health (NIH), Bethesda (MD), USA ( http://rsb.info.nih.gov/ij/ ) carried out.

Other methods

The following parameters are determined according to published standards: characteristic value standard comment BET surface area DIN 66131 with nitrogen Glass transition temperature (T _g ), melting point (T _m ) DIN 53765 see above Particle size, particle size by laser diffractometry ISO 13320-1

Examples

commodity list raw material specification Manufacturer / Supplier Brand / product name palladium pure Umicore, Hanau Triphenylphosphine-3,3 ', 3''- sulfonic acid sodium salt 31 wt .-%, aqueous solution OXEA, Oberhausen glycerin 99.5% Cognis Oleo-Chemicals argon techn. Ait Liquide, Dusseldorf 1,3-butadiene 2.5 Air Liquide, Dusseldorf 2-methyl-2-butanol 99% Acros, Geel, Belgium alumina Grain size: 1 mm, pore size: 160 nm Sasol, Hamburg alumina spheres 1.0 / 160 activated carbon 4-12 mesh Sigma-Aldrich (see below) DARCO ^® ion exchanger Dow Chemicals Inc., Michigan, USA DOWEX ^TM Marathon ^TM C isopropanol 99.50% Acros, Geel, Belgium β-cyclodextrin Wacker, Burghausen Cavamax ^® W7

Further Raw materials that were not separately noted are available at Cognis Oleo-Chemicals Deutschland GmbH, Dusseldorf, or Sigma-Aldrich Chemie GmbH, Steinheim.

EXAMPLE 1: Preparation of an ether

According to the in 1 schematically shown construction and in 3 As explained embodiment of the production unit is as a process step 1a ) an aqueous phase containing 15 g of water, 1.25 g of a saturated aqueous solution (31% by weight) of triphenylphosphine-3,3 ', 3 "-sulfonic acid sodium salt, 0.0375 g of Pd (acac) ₂ and 15 g of glycerol under argon in a 300 ml pressure reactor to carry out the process step 1d ) submitted. As a process step 1b ) was cooled to -30 ° C and liquefied butadiene (17.6 g) fed to the pressure reactor and intensively mixed at 90 ° C for 6 hours. After these 6 hours, the mixture formed in the pressure reactor was fed to a separator for dividing the mixture into an aqueous phase and an oily phase. The resulting oily phase (OP) was depressurized and thereby divided into a liquid phase containing the ether and a gaseous phase.

At the End of the reaction was the conversion, based on the used Amount of glycerol 70 mol .-%, the yield of ether based on the used alcohol was 65 mol .-%, and the molar ratio from Monoether to Diether 19: 1. The ICP-AES analysis showed a palladium content in the product of 50 ppm and a phosphorus content of 560 ppm.

EXAMPLE 2: Preparation of an ether under Addition of a polar protic organic solvent

The reaction was carried out as in Example 1 except that the process component 1c ) were additionally introduced 15 g of 2-methyl-2-butanol under argon in the pressure reactor.

To 3 h reaction time was the conversion, based on the used Amount of glycerol 42 mol .-%, the yield of ether based on the used alcohol was 39 mol .-%, and the molar ratio from Monoether to Diether 19: 1. The ICP-AES analysis showed a palladium content in the product of 8 ppm and a phosphorus content of 77 ppm.

EXAMPLE 3: Preparation of an ether under Addition of cyclodextrin

The experiment of Example 1 was repeated, wherein additionally as an additive according to process step 1c ) β-cyclodextrin (1.686 g).

To 3 h reaction time was the conversion, based on the used Amount of glycerol 55 mol .-%, the yield of ether based on the used alcohol was 51 mol .-%, and the molar ratio from monoether to diether 20: 1. The ICP-AES analysis showed a palladium content in the product of 50 ppm and a phosphorus content of 200 ppm.

Example 4: Post-treatment of after Example 1 prepared ether

One An experiment corresponding to Example 1 was carried out. Part of the product phase containing the ether was subsequently added for post-treatment with a portion of alumina ("alumina spheres 1.0 / 160 "). The mixture thus formed was over a filter into a solid phase (the filter cake) and a liquid Phase (containing the product) separately. The palladium content of thus obtained liquid phase was 10 ppm. Subsequently this liquid phase was on with a portion of i-propanol 10 parts of the liquid phase are added and mixed. there the formation of a solid phase was observed. After separation the same was the phosphorus content of the remaining liquid Phase containing the ether, the product, below the detection limit for phosphorus.

EXAMPLE 5: Continuous Preparation an ether

According to the in 1 schematically shown construction and in 3 As explained embodiment of the production unit is as a process step 1a ) an aqueous phase containing 100 g of water, 8.3 g of a saturated aqueous solution (31% by weight) of triphenylphosphine-3,3 ', 3 "-sulfonic acid sodium salt, 0.25 g of Pd (acac) ₂ and 100 g of glycerol under argon in a template. As a process step 1b ) is cooled to -20 ° C and liquefied butadiene (117.3 g) provided in another template. The reaction takes place in a 1000 ml pressure reactor (unit A), with butadiene as the process component 1b ) are fed to the pressure reactor in a continuous feed of 30 g per hour and glycerol in a continuous feed of 26 g per hour and are intensively mixed at a residence time of 4 h at 90 ° C. The mixture formed in the pressure reactor was continuously passed to a separator (unit B) for carrying out the process step 1e ), wherein the aqueous phase (WP) obtained in the separation was fed again to the pressure reactor. The oily phase (OP) additionally obtained was used to carry out the process step 1f ) was fed to a flash vessel (unit C) in which the oily phase (OP) was expanded through a 1.5 mm diameter die and directed against a baffle spaced 20 mm apart. The oily phase (OP) was divided into a liquid phase containing the ether and a gaseous phase, the gaseous phase, possibly via a compression or Einkondensiereinheit in which it is liquefied again as a process step 1b ) was returned to the pressure reactor.

At the End of the reaction was the conversion, based on the used Amount of glycerol 61.6 mol .-%, the yield of ether based on the alcohol used was 56 mol%, and the molar ratio from monoether to diether 10: 1. The ICP-AES analysis showed a palladium content in the product of 15 ppm and a phosphorus content of 13 ppm.

EXAMPLE 6: Preparation of an ether under Addition of a polar protic organic solvent

The reaction was carried out as in Example 5, but as a process component 1c ) in addition 2-methyl-2-butanol under argon in a continuous flow of 26 g per hour is fed to the pressure reactor.

To 3 hours, the conversion, based on the amount of used Glycerol 55 mol .-%, the yield of ether based on the used Alcohol was 50 mol%, and the molar ratio of Monoether to Diether 10: 1. The ICP-AES analysis showed a palladium content in the product of 8 ppm and a phosphorus content of 25 ppm.

EXAMPLE 7: Preparation of an ether under Addition of cyclodextrin

The experiment of Example 5 was repeated, wherein additionally as an additive according to process step 1c ) β-cyclodextrin (11 wt .-%, based on the Glycerineinwawa), combined with the Verfahrenskomp onente 1a ).

To 3 hours, the conversion, based on the amount of used Glycerol 68 mol .-%, the yield of ether based on the used Alcohol was 62 mol%, and the molar ratio of Monoether to Diether 10: 1. The ICP-AES analysis showed a palladium content in the product of 15 ppm and a phosphorus content of 15 ppm.

EXAMPLE 8 Post-treatment of an after Example 5 prepared ether

One An experiment corresponding to Example 5 was carried out. Two parts of the product phase, including the ether, were subsequently added for post-treatment with a portion of alumina ("alumina spheres 1.0 / 160 "). The mixture thus formed was over a filter into a solid phase (the filter cake) and a liquid Phase (containing the product) separately. The palladium content of thus obtained liquid phase was 6 ppm. Subsequently this liquid phase was on with a portion of i-propanol 10 parts of the liquid phase are added and mixed. there the formation of a solid phase was observed. After separation the same was the phosphorus content of the remaining liquid Phase containing the ether, the product, below the detection limit for phosphorus.

1a

Zuführung der wässrigen Phase

1b

Zuführung der öligen Phase

1c

Zuführung weiterer Zusatzstoffe

1d

Produktionseinheit beinhaltend Mischeinheit

1e

Trenneinheit fl/fl

1f

Entspannungsvorrichtung

P

Produktvorlage

WP

wässrige Phase

OP

ölige Phase

g

Massestrom, gasförmig

fl

Massestrom, flüssig

I

Produktionseinheit I.

II

Produktionseinheit II.

To 1 and 2 :

1a

Feeding the aqueous phase

1b

Feeding the oily phase

1c

Supply of other additives

1d

Production unit including mixing unit

1e

Separation unit fl

1f

relief device

P

product template

WP

aqueous phase

operating room

oily phase

G

Mass flow, gaseous

fl

Mass flow, liquid

I

production unit I ,

II

production unit II ,

1a

Zuführung der wässrigen Phase

1b

Zuführung der öligen Phase

1d

beheizbare Mischeinheit

B

Rührer

D

Trenneinheit fl/fl

C

Leitung von Mischeinheit zu Trenneinheit

OP

ölige Phase

WP

wässrige Phase

1f

Abführung ölige Phase zur Entspannungsvorrichtung

E

Rückführung wässrige Phase von der Trenneinheit zur Mischeinheit

F

Förderpumpe

1a'

Zuführung der rückgewonnenen wässrigen Phase

To 3 :

1a

Feeding the aqueous phase

1b

Feeding the oily phase

1d

heatable mixing unit

B

stirrer

D

Separation unit fl

C

Line from mixing unit to separation unit

operating room

oily phase

WP

aqueous phase

1f

Dissipation of oily phase to the expansion device

e

Recycling aqueous phase from the separation unit to the mixing unit

F

feed pump

1a '

Supply of the recovered aqueous phase

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.

Cited patent literature

• - DE 60100610 T2 [0003]
• - DE 69007418 T2 [0004]

Cited non-patent literature

• - Roempp Chemistry Lexicon, 1999, Wiley-VCH, Weinheim [0060]
• - Harris, HG and Prausnitz, JM, Thermodynamics of solutions with physical and chemical interactions - solubility of acetylenes in organic solvents, Industrial and Engineering Chemistry Fundamentals, 1969, 8 (2), pp. 180-186 [0099]
• Barton, AFM, Solubility parameters, Chemical Reviews, 1975, 75 (6), pp. 731-753 [0099]
• - DIN 66131 [0117]
• - ISO 13320-1 (1999) [0145]
• - DIN EN ISO 11885 [0148]
• - http://rsb.info.nih.gov/ij/ [0149]
• - DIN 66131 [0150]
• - DIN 53765 [0150]
• - ISO 13320-1 [0150]

Claims (43)

A process for producing ethers, comprising the process steps: 1a ) Providing an aqueous phase, at least including water, and as w-process components - at least one alcohol component having two or more hydroxy groups, and - a catalytically active composition, 1b ) Providing an oily phase, at least comprising as o-process component - a hydrocarbon compound having at least two conjugated double bonds, 1c ) optionally providing further additives, 1d ) Contacting the aqueous phase with the oily phase, and optionally with the further additives, to form an emulsion in a unit A, 1e ) Dividing the emulsion in a unit B into an aqueous phase and an oily phase, - wherein the aqueous phase is returned to the reactor and with the aqueous phase in process step 1a ), the oily phase containing an ether, 1f ) Dividing the oily phase in a unit C in a first phase and another phase, - wherein the first phase has more ether than the further phase, - wherein the further phase is recycled to the reactor and with the oily phase in process step 1b ) is united. The method of claim 1, wherein said contacting is in process step 1d ) is carried out so that an ether is formed from the at least one alcohol component and the hydrocarbon compound having at least two conjugated double bond. The method of claim 1 or 2, wherein at least the method steps 1d ) to 1e ) in a first and at least one further device, wherein 3a) method step 1b ) is performed at least in the first production unit, and 3b) method step 1a ) is carried out at least in the further production unit, and 3c) the oily phase obtainable in the process step 1e ) in the first production unit as oily phase in process step 1b ) is used in the further production unit, and 3d) the further phase obtainable in the method step 1e ) in the further production unit as an aqueous phase in the process step 1a ) in the first production unit, and 3e) the oily phase obtainable in the process step 1e ) in the further production unit the process step 1f ) and 3f) the aqueous phase obtainable in process step 1e ) in the first production unit with the aqueous phase in process step 1a ) of the further production unit, and 3g) the further phase obtainable in process step 1f ) returned to the first production unit and with the oily phase in process step 1f ) is united. The method of claim 1 or 2, wherein at least the method steps 1d ) to 1e ) in two or more parallel production units. The method according to one of the preceding claims, wherein the unit B comprises a separation unit T1 in which a mass flow M0 is divided into at least two mass flows M1 and M2, wherein the mass flows M1 and M2 the same state of matter as the mass flow M0 have. The method of claim 5, wherein the unit C has a separation unit T2, in which the mass flow M2 in at least two mass flows M3 and M4 is shared, with the mass flow M4 a different from the mass flows M3 and M2 state of aggregation having. The method according to any preceding claim, wherein unit A is a pressurizable mixing unit including at least one kettle and one stirrer, preferably a MIG stirrer. The method of claim 7, wherein the ratio from diameter of the stirrer to diameter of the boiler in a range of 0.35 to 0.45. The method of claim 7 or 8, wherein the agitator at a number of revolutions per minute in a range of 600 operated until 2000. The method according to one of the preceding claims, where the Reynolds number Re of the liquid in the unit A is in a range of 2000 to 40,000. The method according to one of the claims 7 to 9, wherein at least 50% of the droplets of the emulsion in Unit A, based on the total number of droplets of the emulsion, a droplet size of oily Phase in the aqueous phase in a range of 20 to 1000 microns. The method of any one of the preceding claims, wherein the method step 1d ) is carried out at a temperature in a range of 50 to 100 ° C. The method of any one of the preceding claims, wherein the method step 1d ) is carried out at a pressure in a range of 12 to 25 bar. The method according to one of the preceding claims, wherein the unit B is a separation unit T1 for dividing a mass flow M0 in at least two mass flows M1 and M2, in which the separation unit T1 via one or more in fluidleitender Connecting chambers, - where at least a chamber has an inlet for feeding M0, - in which the one or more fluidly communicating chambers have at least two outflows in total, - in which at least a first downstream arranged higher than a further outflow - Wherein the first outflow of the mass flow M2 removable, - Wherein the further outflow of the mass flow M1 is removable. The method of claim 14, wherein in step 1e ) contained less than 15% by weight, based on the weight of the oily phase, of water. The method of claim 14 or 15, wherein the method step 1e ) is carried out at a temperature in a range of 0 to 100 ° C. The method of any of claims 14 to 16, wherein the method step 1e ) is carried out at a pressure in a range of 12 to 25 bar. The method according to one of the preceding claims, wherein the unit C is a separation unit T2 for releasing liquids under release of dissolved gases, wherein the unit C at least one nozzle, one valve, one diffuser, one Capillary, or a combination of two or more thereof. The method of claim 18, wherein the method step 1f ) is carried out at a temperature in a range of 20 to 100 ° C. The method of claim 18 or 19, wherein the method step 1f ) is carried out at a pressure in a range of 0.5 to 5 bar. The method according to one of the preceding claims, wherein two or more combinations of the unit A with the unit B are used, with the combinations arranged in parallel are. The method according to one of the claims 1 to 20, wherein two or more combinations of the unit A with the Unit B are used, with the combinations arranged serially are. The method according to one of the preceding claims, wherein as the catalytically active composition at least one compound selected from the group A) and B): A) of the transition metal compounds, in particular selected from the group consisting of: Pd (OAc) ₂ , PdCl ₂ , Pd (acac) ₂ , PdCl ₂ (pyr) ₂ , Pd (C ₃ H ₅ ) ₂ , Pd (C ₃ H ₅ ) ₂ OAc ₂ , {Pd (C ₃ H ₅ ) Cl} ₂ , or a combination of two or more of these, and B) the organophosphorus compounds of trivalent phosphorus, in particular selected from the group consisting of triphenylphosphine, triphenylphosphine derivatives, salts thereof; Triphenylphosphine-3-sulfonic acid, triphenylphosphine-3,3'-sulfonic acid, triphenylphosphine-3,3 ', 3 "-sulfonic acid, salts thereof; or a combination of two or more thereof. The method of any one of the preceding claims, wherein the alcohol component having two or more hydroxy groups is selected from the group consisting of: 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, glycerol, 1,2,4-butanetriol, glucose, fructose, sucrose, more preferably glycerol or ethylene glycol. The method according to one of the preceding claims, wherein the hydrocarbon compound is conjugated with at least two Double bonds is selected from the group consisting from: 1,3-butadiene, 1,3-pentadiene, isoprene, 2,3-dimethylbuta-1,3-diene, 1,3-hexadiene, 2,4-hexadiene, (3-methylbuta-1,3-dien-2-yl) benzene, 2-Chloro-3-methylbuta-1,3-diene, 2-chloro-1,3-butadiene, 2,4-octadiene, 2-methyl-2,4-pentadiene, 1,3-cyclohexadiene, 1,3-cyclooctadiene, 7-methyl-3-methyleneocta-1,6-diene, or 2,6-dimethylocta-2,4,6-triene, more preferably 1,3-butadiene. The method according to any one of the preceding claims, wherein the oily phase is in process step 1b ) contains at least one further aliphatic or aromatic hydrocarbon compound. The process of claim 26, wherein the further aliphatic or aromatic hydrocarbon compound has a Hildebrandt solubility parameter δ in a range of 16 to 23 MPa ^0.5 . The method of claim 26 or 27, wherein the another aliphatic or aromatic hydrocarbon compound is selected from the group consisting of: toluene, cyclohexane, Cyclohexanol, or ethyl acetate, more preferably cyclohexanol or cyclohexane. The method according to one of the preceding claims, wherein the yield of ether ranges from 30 to 99% by weight is based on the total amount of the alcohol component used with two or more hydroxy groups. The method according to one of the preceding claims, wherein the yield of ether with exactly one ether group in one Range of 25 to 99 mol .-%, based on the total amount the alcohol component used with two or more hydroxyl groups. The method according to any one of the preceding claims, wherein the oily phase is in process step 1b ) has as a further component a polar-protic, organic solvent. The method of claim 31, wherein the weight ratio of the polar protic organic solvent to the aqueous Phase is in a range of 0.1 to 1. The method of claim 31 or 32, wherein said polar protic organic solvent has a solubility parameter d of Hildebrandt in a range of 18 to 26 MPa ^0.5 , said solvent being in particular selected from the group consisting of alcohols of chain length C4 to C10 with one or more hydroxy groups, more preferably 2-pentanol, 2-octanol, 2-methyl-2-butanol, or a mixture of two or more thereof. The method according to any one of the preceding claims, wherein the first phase consists of process step 1f 34a) providing - the liquid phase containing the ether, and - an adsorbent, 34b) contacting the liquid phase and the adsorbent to form a mixture, 34c) optionally dividing the 34d) adding a monoalcohol to the mixture to form another solid phase, 34e) dividing the mixture into at least one solid phase and a liquid phase, wherein the liquid phase contains more ether than the solid phase, 34f) removing the monoalcohol from the liquid phase. The method of claim 34, wherein of the adsorbent in a range of 10-400 parts, preferably 40-250 Parts of 100 parts of the liquid phase containing the Ether is introduced into the liquid phase. The method of claim 34 or 35, wherein the adsorbent is selected from the group consisting of Inorganic oxidic compound, such as alumina, silica, zeolite, bentonite. - Ion exchanger based on systyrene-vinylbenzene copolymers, - activated carbon, preferably alumina or ion exchanger. The method according to any one of the preceding claims, wherein the aqueous phase is in process step 1a ) has as further component at least one cyclodextrin compound. The method of claim 37, wherein the cyclodextrin compound is selected from the group consisting of α-, β-, or γ-cyclodextrin and modified α-, β-, or γ-cyclodextrin, more preferably methyl-β-cyclodextrin or 2-hydroxypropyl-β-cyclodextrin. The method of claim 37 or 38, wherein said Ratio of the amount of substance to cyclodextrin compound to the amount of catalytically active compound in a range from 1: 1 to 30: 1, preferably from 5: 1 to 20: 1. The method according to one of the preceding claims, wherein the ether has a proportion of transition metal in one Range of 0 to 100 ppm, based on the ether. The method according to one of the preceding claims, wherein the ether has a content of phosphorus in a range of 0 to 500 ppm, preferably from 0 to 50 ppm, based on the ether, having. A wording that includes one on one the method according to any one of the preceding claims obtainable Ether-based formulation component or by the method obtainable according to one of the preceding claims Ether or a mixture of both. A use of an on the by the method according to any one of claims 1 to 31 available ethers based formulation component or one by the method according to one of claims 1 to 31 available Ether or a mixture of both in one formulation.