DE102007027374A1 - Producing 1,2-propanediol comprises continuously hydrogenating glycerol in the presence of a heterogeneous copper catalyst and distilling the reaction mixture - Google Patents

Abstract

Producing 1,2-propanediol with a purity of at least 98% comprises continuously hydrogenating glycerol in the presence of a heterogeneous copper catalyst to give a glycerol conversion of 95% or less, and distilling the reaction mixture. Independent claims are also included for: (1) producing an ether, ester, amine or urethane compound by producing 1,2-propanediol as above and reacting it with an active hydrogen, epoxy, ester or isocyanate compound; (2) ether, ester, amine or urethane compound produced as above; (3) emulsion produced by contacting an aqueous phase with an organic phase in the presence of an ester compound produced as above; (4) cosmetic composition produced by contacting an emulsion produced as above with a cosmetic component; (5) plastic composition produced by contacting an ether, ester, amine or urethane compound produced as above with a plastic material; (6) drilling composition produced by contacting an ether, ester, amine or urethane compound produced as above with a liquid drilling fluid component; (7) producing a composition by producing 1,2-propanediol as above and contacting it with a mineral oil component, a skin or hair care agent, a nutrient, a pigment, a dye or a surfactant; (8) composition produced as above.

Description

The The invention relates to a process for the preparation of 1,2-propanediol. The invention further relates to a method for producing a Compound containing at least one ester function, a process for preparing a compound containing at least one ether function as well as the use of 1,2-propanediol.

The glycerol, which is abundantly available as an industrial raw material due to fats and oils, can serve as the basis for various syntheses. Mention should be made in this context, on the one hand dehydration (elimination of water) to acetol (see, for example DE-A-41 28 692 /Handle; Fleckenstein et al.) And on the other hand the dehydration to 1,2-propanediol.

1,2-propanediol is an industrially interesting raw material. It comes in a variety used by applications, namely in the food industry, as a solvent for dyes and flavors, as Humectants for tobacco, in cosmetics, as an ingredient brake and hydraulic fluids, antifreeze, Lubricants in refrigerators, as a solvent for greases, oils, resins, waxes, dyes etc. It also serves as a starting product for the manufacture of other products. Through esterification, and / or etherification, numerous, as a solvent, to syntheses, as a plasticizer, thickener, Emulsifiers, etc. to gain usable products. In the majority The purity of the 1,2-propanediol plays a role in these applications a role. 1,2-Propanediol is usually by hydration of propylene oxide industrially produced. The above mentioned Preparation of 1,2-propanediol by hydrogenation of glycerol Although several times described, but has in the industrial triellen Practice so far can not enforce.

The oldest patent document known to the Applicant which describes the hydrogenation of glycerol to 1,2-propanediol is the German patent DE-C-524 101 from IG Farben. According to Example 1 of this document, a hydrogen stream containing 1 to 1.5 vol .-% glycerol, passed at 200 to 210 ° C over a catalyst which is applied to glass beads. In this case, a liquid is obtained, which is fractionally distilled after removal of the water formed in the hydrogenation. The reaction of glycerol was almost complete. In the distillation, a mixture of 1,2-propanediol and propyl alcohol was obtained. The yield of 1,2-propanediol was reported as 70%.

DE-C-541 362 discloses the hydrogenation of polyoxy compounds. In this case, liquid or solid polyoxy compounds in aqueous solution or suspension are treated with hydrogen in the presence of catalysts. In Example 1, glycerin and a nickel catalyst are treated with hydrogen in a bomb at 200 to 240 ° C and a pressure of 100 atm. Thus, it is a batch process, ie a discontinuous hydrogenation, wherein the catalyst is slurried in powder form in the liquid glycerol. From the statement that after 4 hours, the calculated amount of hydrogen was taken, it will be clear to the expert that glycerol was apparently quantitatively implemented.

For a long time, the subject of glycerol hydrogenation to 1,2-propanediol was apparently broke. Only about 50 years later, it was taken up again:
Montassier et al. Report in Heterogeneous Catalysis and Fine Chemicals (1988, Elsevier, Amsterdam, pp. 165-170) in that the hydrogenation of glycerol in the presence of Ru, Ni, Rh or Ir based catalysts leads to hydrocarbons, in particular methane. With Raney copper as catalyst, however, a mixture of 1,2-propanediol, ethylene glycol and carbon dioxide is obtained.

EP-A-0 523 014 and EP-A-0 523 015 (Novamont) address the problem of the lack of selectivity of glycerol hydrogenation to 1,2-propanediol by employing specific ruthenium or zinc-copper based catalysts in very dilute aqueous media. Nevertheless, the selectivity leaves much to be desired. According to the examples of EP-A-0 523 015 (Use of a zinc-copper catalyst) namely in the hydrogenation of glycerol in addition to propylene glycol, large amounts of ethylene glycol and also formed significant amounts of lactic acid. According to the examples of EP-A-0 523 014 (Use of a sulfide-modified ruthenium catalyst) are formed in the hydrogenation of glycerol in addition to propylene glycol very large amounts of ethylene glycol. In addition, a dilution of the raw material to be used (glycerol) with water is technically unsatisfactory because this water must then be removed from the reaction mixture.

DE-A-43 02 464 from 1993 (Henkel, Fleckenstein et al.) describes the continuous hydrogenation of glycerol in the presence of a specific heterogeneous catalyst. Preferably, a copper-containing catalyst is used, in particular copper chromite. According to the embodiments, Glyce Substantially quantitatively reacted (glycerol content in the reaction mixture below 0.1%), only 3 of the total of 10 examples worked with a partial conversion of glycerol (Examples 1, 3 and 9). Although analytical data were given for all the reaction mixtures of the examples, the mixtures were not worked up. Thus, the technical teaching of DE-A-43 02 464 to be seen in that it shows the principal suitability of copper-containing heterogeneous catalysts for the hydrogenation of glycerol to 1,2-propanediol. It does not include the teaching that a partial hydrogenation of glycerol followed by distillation leads to a 1,2-propanediol with a very special profile of properties. The document noted on page 3, lines 16/17 only that would be deducted for working up the reaction mixture obtained in the hydrogenation; the purely optional possibility of "further processing steps" is mentioned only marginally, without discussing in any way how such a work-up would look like and whether there are processing steps that would be of particular relevance.

According to US-A-5,616,817 (BASF, Schuster and Eggersdorfer) of 1995, the glycerol hydrogenation is carried out such that on the one hand glycerol with a water content of up to 20 wt .-% and on the other hand special catalysts (containing 40-70% Co, 10-20% Mn, 0-10% Mo and 0-10% Cu) are used. Glycerol is completely converted. However, even with the specific catalyst disclosed here, the limits of selectivity are still encountered. This will become immediately clear to the person skilled in the art if he considers the two exemplary embodiments. In Example 1, the reaction mixture contains 95.8% 1,2-propanediol and 3.2% n-propanol, in Example 2 the reaction mixture contains 92% 1,2-propanediol and 4.3% n-propanol.

In US-A-6,479,713 (Battelle Memorial Institute) from 2002 describes the hydrogenation of sugars or sugar alcohols, wherein special rhenium-containing multimetal catalysts are used. As a possible raw material that can be used for hydrogenation, glycerol is mentioned in the description. Tables 2-4 summarize experimental results where glycerol is hydrogenated in the presence of such catalysts. It is striking that although 1,2-propanediol is the main product of the hydrogenation, but very large amounts of ethylene glycol and lactate are formed. Unless a base was added to the glycerin used, 1,3-propanediol was added as an additional undesirable by-product (column 11, lines 49-51). The results of glycerol hydrogenation according to the US-A-6,479,713 are therefore classified as rather unsatisfactory.

Suppes et al. deal in WO-A-2005/095536 as in Applied Catalysis A: General 281 (2005), pages 225-231 , with the hydrogenation of glycerol in "mild" conditions by 200 ° C and with the production of 1,2-propanediol in two steps, namely the production of acetol from glycerol, followed by hydrogenation of the acetol to 1,2-propanediol.

task It was the object of the present invention to provide a novel process for the preparation of 1,2-propanediol by hydrogenation of glycerin.

The 1,2-propanediol prepared in this way should be distinguished by a high purity, in particular a purity of at least 98% and preferably of at least 99%.

About that In addition, the 1,2-propanediol thus produced should be from as possible high odor quality, to understand by what is that it does not cause an unpleasant and / or strong odor, but at best have a slight smell and preferably should be odorless.

Also the present invention was based on 1,2-propanediol provide based ester or ether compounds, which also no unpleasant and / or strong smell, but at best have a slight odor and preferably be odorless should.

The This complex task has been described by the following inventive method in excellent Way solved.

• • in einem ersten Schritt Glycerin in Gegenwart eines heterogenen Kupferhaltigen Katalysators - insbesondere eines heterogenen Kupfer-Chromhaltigen Katalysators - kontinuierlich hydriert, wobei man Glycerin zu höchstens 95 Gew.-%, vorzugsweise höchstens 90 Gew.-%, noch mehr bevorzugt höchstens 85 Gew.-%, darüber hinaus bevorzugt höchstens 80 Gew.-%, darüber hinaus noch mehr bevorzugt zu höchstens 75 Gew.-% und am meisten bevorzugt zu höchstens 70 Gew.-% umsetzt, und die im ersten Schritt erhaltene Reaktionsmischung
• • in einem zweiten Schritt einer Destillation unterwirft, bei der vorzugsweise das im ersten Schritt gebildete 1,2-Propandiol als Destillat erhalten wird.

The invention relates to a process for the preparation of 1,2-propanediol having a purity of at least 98%, wherein

• In a first step, continuously hydrogenating glycerol in the presence of a heterogeneous copper-containing catalyst, in particular a heterogeneous copper-chromium-containing catalyst, glycerol being not more than 95% by weight, preferably not more than 90% by weight, more preferably not more than 85% by weight. more preferably at most 80% by weight, more preferably at most 75% by weight and most preferably at most 70% by weight, and the reaction mixture obtained in the first step
• In a second step, subjected to a distillation in which preferably the 1,2-propanediol formed in the first step is obtained as distillate.

The Weight percentages used in this case arise house Gas chromatographic determinations by integrating the surfaces the signals. For calibration and verification The measurements were weight percentages by distillation and weighing the individual components from one by gas chromatography measured sample confirmed.

Under a purity of at least 98% is understood that after after passing through the process according to the invention both steps (ie hydrogenation and distillation) receive a product whose content of 1,2-propanediol is at least 98%. The purity is determined by gas chromatography (area percent).

In a preferred embodiment leads to the two steps of the method according to the invention so by, that the purity of the target product 1,2-propanediol at least 99%.

• • die Hydrierung des Glycerins unter den angegebenen Rahmenbedingungen und
• • die Aufdestillation des im ersten Schritt erhaltenen Hydrierablaufs zur Abtrennung von Wasser sowie der Verminderung der bei der Hydrierung entstandenen Nebenprodukte.

It should be expressly stated that the overall process for the preparation of 1,2-propanediol by the process according to the invention comprises two steps, namely

• • the hydrogenation of glycerol under the given conditions and
• The distillation of the hydrogenation effluent obtained in the first step for the separation of water and the reduction of the by-products formed in the hydrogenation.

That with This combination of steps achieves such success and the above complex task can be solved is not trivial and was foreseen for the expert.

In In this context, the following is instructive: leads The hydrogenation of glycerol in a quantitative manner, so you get hydrogenation processes that stink downright. Are then distilled then such (ie at more complete Hydrogenation of glycerol obtained) hydrogenation processes, so provides it can be seen that the fractions of 1,2-propanediol obtained in this way still have an unpleasant smell. Will however the Hydrogenation according to the invention carried out in the same way, that the glycerol used is only partially hydrogenated and distilled then the hydrogenation processes thus obtained, so you get fractions that have no or at least have a significantly low unpleasant odor.

The Investigations by the applicant indicate that those Odor carrier in the inventive Process with the partial conversion of glycerol as stated above and those odorants that are complete Sales of glycerol are obtained, although partly identical, to Part, however, are different and otherwise in different Extent are formed, with the result that they are going through Remove the distillation to varying degrees. And here is the method of the invention Procedure in which glycerol is hydrogenated quantitatively and then distilled, far superior. This surprising Findings form the core of the teaching of the present invention and could not be removed from the prior art by the skilled person nor was it suggested by documents of the prior art.

Furthermore has been found that the inventive Process with the said partial hydrogenation in step 1 a lesser Content of the distillate difficult to remove and unwanted By-product ethylene glycol is achieved.

Preferably leading to the first step of the invention Process (hydrogenation) in the presence of less than 20% by weight, more preferably less than 10% by weight, even more preferably less as 5% by weight, based on the amount by weight of glycerol used, an organic solvent, wherein the implementation the process in the complete absence of an organic Solvent is most preferred.

The process according to the invention is carried out in the presence of a heterogeneous copper-containing catalyst. It is particularly preferred to use a heterogeneous copper-chromium-containing catalyst. It is particularly preferred to use a copper chromite catalyst containing preferably 30 to 40 wt .-% copper, 23 to 30 wt .-% chromium, based in each case on the oxidic catalyst composition, and, if desired, further transition metals in the form of their oxides. In one embodiment, such a copper chromite catalyst may contain from 1 to 7% by weight, in particular from 1.5 to 3% by weight, of barium, based on the oxidic catalyst composition. In one embodiment, the catalyst contains from 32 to 38 weight percent Kup fer, based on the oxidic catalyst composition, 26 to 30 wt .-% chromium, 1.5 to 3 wt .-% barium, 0.5 to 2 wt .-% silicon and additionally 1 to 5, preferably 2 to 3 wt .-%, manganese, zirconium and / or cerium, based on the oxidic catalyst composition. This catalyst and its method of preparation is described in detail in EP-A-0 254 189 described. The disclosure contained therein, in particular with regard to the catalysts and the preferred manner of their preparation is hereby incorporated by reference, and the information given there should also be part of the present application.

It is further preferred that the catalyst has a high surface area and porosity, so that a high activity and selectivity as well as a particularly long useful life for technical applications is achieved. Thus, it is advantageous if the catalyst used has a specific surface area in the range from 20 to 100 m ² / g, preferably 70 to 80 m ² / g.

The first step of the process according to the invention is preferably carried out by using hydrogen diluted or undiluted hydrogen for hydrogenation, preferably at pressures in the range from 20 to 300 bar, in particular at 100 to 250 bar, and at temperatures in the range of 150 ° C. to 280 ° C, especially 180 to 220 ° C, works. In the continuous mode of operation, glycerol is passed in vapor or liquid form over a fixed catalyst bed. Preferably, a molar ratio of hydrogen to glycerol in the range of 2 to 500, wherein excess hydrogen ge if desired travels in a circle. This means that the flow rate of hydrogen gas, measured in moles H ₂ / hour, 2- to 500 times higher than the flow rate of glycerol, measured in moles of glycerol / hour. A preferred range of the conversion ratio is 30: 1 to 200: 1.

The first step of the process of the invention (hydrogenation) can be carried out in similar reactors which are customary and known for the preparation of fatty alcohols by hydrogenation of fatty acid methyl esters or directly from triglycerides and which are preferably fixed bed reactors. The first step of the process according to the invention (hydrogenation) is preferably carried out in isothermally operated tubular reactors or tube bundle reactors. It is also conceivable to use reactors which have thermoplates as components. Both in the tube bundle reactors and in the reactors, which have thermoplates, the catalyst may be introduced in the form of a fixed catalyst bed or be applied as a coating on the inside of the tubes or thermoplates. The reaction parameters temperature and pressure can be adapted to the respective catalyst activity. The heat of reaction is largely dissipated via the reactor wall (in the case of use of tube bundle reactors via the walls of the reaction tubes used and in the case of use of reactors with thermoplates on the thermal sheets), so that a virtually isothermal driving is possible. If cooling of the reactor via air is not possible, then the reactor can optionally be cooled by using a suitable coolant, wherein when using tube bundle reactors this coolant flows along the reaction tube and when using reactors with thermoplates through the flow paths within the thermoplates , As a coolant, for example, water, heat transfer fluids such as Marlothem ^® or molten salts are suitable. Furthermore, it is particularly preferred that the hydrogenation is carried out by passing liquid glycerol in trickle bed in cocurrent or countercurrent with hydrogen over a catalyst fixed bed. Glycerol is further added under backmixing to at least partially preventive measures with an LHSV ("Liquid Hourly Space Velocity" expressed in m ³ / h glycerol per m ³ catalyst volume) in a range of 0.1 to 5 h ^-1 , more preferably in a range of 0.2 to 3 hr ^-1 and moreover in a range of 0.3 to 2 hr ^-1 through the catalyst bed in the reaction tube (s). As the backmixing at least partially preventing measures are in principle all known to those skilled and seem suitable for this purpose measures such as suitable pipe cross-sections or pipe cross-sectional length conditions into consideration, which are usually selected depending on the prevailing during operation of the reactor flow conditions.

Further details of an advantageous embodiment of the catalyst used for the hydrogenation include the EP-A-0 334 118 whose disclosure content, in particular with regard to the prevention of backmixing in the reactor, the advantageous volume loading of the reactor and the advantageous surface loading of the reactor is hereby incorporated by reference and forms part of the disclosure of the present invention.

In addition to the use of a single fixed bed reactor as the hydrogenation reactor and at least two interconnected fixed bed reactors can be used, in which case the hydrogen is passed through the at least two fixed bed reactors in a row, without that emerging from the reactors and gas entering the subsequent reactors is cooled. Such a method is for example in the EP-A-0 515 485 the disclosure of which is hereby incorporated by reference as part of the disclosure of the present invention with regard to the exact performance of the hydrogenation process in the case of the use of two interconnected fixed bed reactors.

The used for hydrogenation glycerol may be hydrous. Preferably However, the water content should be below 15% by weight especially preferably below 10% by weight and most preferably below 5 wt .-%, each based on the total weight of water and glycerol, lie. This has procedural economic reasons because in the course of hydrogenation water is formed anyway, which in second process step is removed in the course of the distillation. In a further embodiment, the Water content of the glycerol used less than 2% wt .-%. It may also be desired to use anhydrous glycerin or a glycerol whose water content is only in the trace range.

in the second step of the method according to the invention is the reaction mixture obtained in the first step in a second step of a distillation, preferably obtained the 1,2-propanediol formed in the first step as a distillate becomes. Here, the term "distillation" used herein is referred to as understood its broadest meaning. It includes evaporation a liquid mixture, the subsequent Condensation of the effluent steam and the running down of the condensate (distillate).

at This distillation can be a single-phase distillation (simple distillation) or a two-phase distillation (Rectification), the latter being mostly countercurrent can be. Also, the Einphasenstrom- or the two-phase distillation discontinuous, semi-continuous or continuous become.

at a discontinuous procedure is a once used Distillation bubble insert, the composition of which during The distillation continuously changed, in a distillate and a residue separated. In the case of the present distillation of 1,2-propanediol, the residue depleted in progressive Distillation increasingly to 1,2-propanediol. Preferably is at such a discontinuous distillation, the distillate successively in parts separated by boiling limits (so-called "fractionated Distillation "), so that the feed mixture ends up in a residue and several distillate fractions are present separately.

at the semi-continuous procedure becomes bladder use running with preheated, to be separated still added.

at the continuous procedure, with the counter or DC distillation succeeds, is to be separated, preheated fluid mixture continuously introduced into the apparatus, wherein the mixture in a top product and a bottoms product with substantially the same consistency Composition is decomposed.

Details of the individual distillation processes and the suitable distillation apparatuses are in particular chapters 10.4.1, 10.4.2 and 10.4.3 of the textbook "Basic Operations in Chemical Process Engineering", Wilhelm RA Vauck and Hermann A. Müller, 11th revised and expanded edition, Willey-VCH-Verlag, 2000 , refer to. The disclosure of this textbook relating to the manner of carrying out single-phase or two-phase distillations and the distillation temperatures suitable therefor is hereby incorporated by reference and forms part of the disclosure of the present application.

The Formulation "preferably at the first step formed 1,2-propanediol is obtained as a distillate "includes both according to the invention Process in which the 1,2-propanediol as the top product of a distillation step obtained (such as in a discontinuous, fractional distillation) as well as processes in which the 1,2-propanediol For example, as a side print is deducted (such as a continuous rectification).

If desired, can the obtained in the process according to the invention 1,2-Propanediol further, known in the art purification steps be subjected to further increase the purity of the product. As an example of such a further purification process, for example called the filtration or the extraction.

If desired, a part of the Hydrierablaufes (ie the reaction mixture, which after Durchlau obtained in the first step of the process according to the invention) can be used as diluent for the continuous hydrogenation in the first process step. For example, 25% of the hydrogenation process can be added to the raw material (glycerol) used in the first step of the process according to the invention in order to achieve a gentle reaction without temperature peaks on the hydrogenation catalyst in this way. However, glycerol is preferably fed without backmixing with a defined residence time through the catalyst bed in the reaction tube (s).

Farther It may be advantageous according to the invention at least one part, preferably at least 20% by weight, more preferably at least 30% by weight, moreover preferably at least 40% by weight, and most preferably at least 50 wt .-% of the retained during distillation in the bottom product Attributed glycerol in the first step. In this connexion, it may be particularly advantageous when at least one part, preferably at least 20% by weight, more preferably at least 30% by weight, moreover preferably at least 40% by weight, and most preferably at least 50 wt .-% of the bottom product without prior purification in the first step is traced back. Since that at the bottom product obtained from the distillation of the hydrogenation processes is relatively rich in glycerol, can be due to the recycling of the glycerol from the bottom product or by the immediate return of the bottom product itself in the first step of the invention Continue the overall yield of 1,2-propanediol from glycerol be increased.

Next the immediate repatriation of at least one Part of the bottom product obtained in the distillation in the However, it can also be advantageous for the first method step prove, at least part of the bottom product in the distillation retained glycerol first by distillation or filtration of the bottom product to purify and then in to take the first step back. In this way can be an entry of larger amounts of by-products be prevented in the hydrogenation reactor. For purification of the glycerin from the bottom product can basically those Be used distillation processes, the above in connection with the second step of the method according to the invention have been described.

According to one particular embodiment of the invention Process can be both a part of the hydrogenation processes, which obtained in the first step, as well as a part of Glycerol from the bottom product, which in the second step was returned to the first step of the process become.

• a1) Herstellung von 1,2-Propandiol durch das erfindungsgemäße Verfahren, sowie
• b1) Umsetzung des 1,2-Propandiols mit einer Verbindung aufweisend mindestens ein aktives Wasserstoffatom, mindestens eine Epoxid-Gruppe, mindestens eine Ester-Gruppe oder mindestens eine Isocyanat-Gruppe.

A contribution to the solution of the abovementioned objects is also provided by a process for preparing a compound comprising ether group, at least one ester group, at least one amino group or at least one urethane group or at least two thereof, preferably having at least one ester group or function, including the method steps

• a1) Preparation of 1,2-propanediol by the process according to the invention, and
• b1) reacting the 1,2-propanediol with a compound having at least one active hydrogen atom, at least one epoxide group, at least one ester group or at least one isocyanate group.

at the compound having at least one active hydrogen atom it may be a compound having at least one hydroxyl group act, so after reacting this compound with the 1,2-propanediol phase a compound having at least one ether group becomes. Depending on the molar ratio in which the compound having at least one hydroxyl group in the 1,2-propanediol phase 1, 2-propanediol is reacted, may also be a polyether compound to be obtained.

at the compound having at least one active hydrogen atom it may also be a compound having at least one Carboxylic acid group act, so after implementation of this Compound having the 1,2-propanediol phase having a compound at least one ester group is obtained. Depending on the molar ratio, in which the compound has at least one carboxyl group reacted with the 1,2-propanediol contained in the 1,2-propanediol phase is also an ester polyether compound can be obtained.

The compound having at least one active hydrogen atom may also be a compound having at least one amino group, so that after reaction of this compound with the 1,2-propanediol phase, a compound having at least one amino group and at least one hydroxyl group is obtained. Depending on the molar ratio in which the compound having at least one amino group is reacted with 1,2-propanediol contained in the 1,2-propanediol phase, a Amino polyether compound can be obtained.

Becomes in process step b1) a compound has at least one Epoxide group used, so can by the implementation this compound with the 1,2-propanediol phase also ether or Polyether can be obtained.

Becomes in process step b1) a compound has at least one Isocyanate group used, so can by the reaction this compound with the 1,2-propanediol phase urethanes or polyurethanes to be obtained.

Particularly preferred according to the invention is the use of a compound having at least one carboxylic acid group in process step b1). In this case, the compound having at least one carboxylic acid group may be a monocarboxylic acid, a dicarboxylic acid or a tricarboxylic acid, mono- and dicarboxylic acids being particularly preferred and monocarboxylic acids, in particular fatty acids, being most preferred. Further, it is preferred that the compound having at least one carboxylic acid has 5 to 30, more preferably 10 to 25, and most preferably 15 to 20 carbon atoms per molecule. In this connection it is particularly preferred that the compounds having at least one carboxylic acid group a C ₅ to C ₃₀ monocarboxylic acid, moreover preferably a C ₁₀ to C ₂₅ monocarboxylic acid, and most preferably a C ₁₅ to C ₂₀ Monocarboxylic acid, wherein the monocarboxylic acid mentioned above are saturated monocarboxylic acids, such as caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, fish oil, palmitic acid, margaric acid, stearic acid, arachic acid, behenic acid, lignoceric acid or cerotic acid, monounsaturated Monocarboxylic acids such as undecylenic acid, oleic acid, elaidic acid, vaccenic acid, icosenoic acid, cetoleic acid, erucic acid or nervonic acid, or polyunsaturated monocarboxylic acids such as linoleic acid, linolenic acid, arachidonic acid, timnodonic acid, clupanodonic acid or cervonic acid.

According to one preferred embodiment of the invention Process for preparing a compound comprising at least an ester function is this compound is a Fatty acid esters, in particular a fatty acid monoester, to a polyester or a polyester resin or a 1,2-propanediol based alkyd resin. Such alkyd resins are synthetic, strong hydrophobic polymers obtained by condensation of 1,2-propanediol with polybasic acids with the addition of organic oils or Fatty acids (to modify the properties of the resin) and further, polyhydric alcohols, in particular glycerol or Pentaerythritol, to be obtained. In this case it is special preferred that the compound having at least one carboxylic acid group is a dibasic acid, which is preferably selected is selected from the group consisting of phthalic anhydride, isophthalic acid, Terephthalic acid, tetrahydrophthalic anhydride, Hexahydrophthalic anhydride, naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, Succinic acid, fumaric acid, adipic acid, Sebacic acid, azelaic acid and maleic anhydride, being adipic acid, azelaic acid and terephthalic acid most preferred are terephthalic acid and most is preferred.

It come as organic first oils or oil derivatives of plant and animal origin each for themselves or as a mixture into consideration. As oils or oil derivatives of animal origin are tallow as well as tallow, in particular by Fractionation to name recovered oil acids. As organic oil or fatty acids come in particular Tallow, canola oil, rapeseed oil, sunflower oil, Palm oil, which may also be in hardened or cured version, Poppy oil, soybean oil, thistle oil, flaxseed oil, tall oil, Coconut oil, palm kernel oil, castor oil, dehydrated Castor oil, fish oil and tung oil. In particular, dry oils or semi-dry oils with iodine numbers of at least 100 preferred, among others are soybean oil and tall oil beneficial. As fatty acids, both for the preparation of the alkyd resins as well as for the preparation of the fatty acid esters are used, especially those of soybean oil, Thistle oil, linseed oil, tall oil, coconut oil, Palm kernel oil, castor oil, dehydrated castor oil, Fish oil and tung oil are considered. Of these fatty acids are those drying oils or semi-drying oils with iodine numbers of at least 100, including those of soybean oil and tall oil, preferred.

The preparation of alkyd resins is for example the WO-A-01/62823 , the disclosure of which with respect to the preparation of alkyd resins is hereby incorporated by reference and which forms part of the disclosure of the present invention.

a Contribute to the solution of the above-mentioned tasks also a compound containing at least one ester function, obtained by the method described above.

• a2) Herstellung von 1,2-Propandiol durch das erfindungsgemäße Verfahren zur Herstellung von 1,2-Propandiol, sowie
• b2) Umsetzung des 1,2-Propandiols mit einer Verbindung aufweisend mindestens eine Epoxid- oder Hydroxyl-Gruppe oder beide, unter Erhalt eines Ethers.

A further contribution to the solution of the abovementioned objects is provided by a method for producing a compound comprising at least one ether function, comprising the method steps

• a2) Preparation of 1,2-propanediol by the process according to the invention for the preparation of 1,2-propanediol, and
• b2) reacting the 1,2-propanediol with a compound having at least one epoxide or hydroxyl group, or both, to give an ether.

The compound containing at least one ether function is preferably a polyether, more preferably a polytheric polyalcohol. The preparation of polyethers and polyether polyalcohols is known from the prior art, for example DE 197 26 508 A1 , known.

• a3) Herstellung von 1,2-Propandiol oder dessen Ether, oftmals als Ethoxylierungs- und/oder Propoxylierungsprodukte, oder beide, vorzugsweise 1,2-Propandiol, durch das erfindungsgemäße Verfahren zur Herstellung von 1,2-Propandiol, sowie
• b3) In Kontakt bringen des 1,2-Propandiols mit der mindestens einen Mineralölkomponente.

A contribution to the solution of the abovementioned objects is also provided by a method for producing a hydraulic fluid comprising at least one mineral oil component and 1,2-propanediol, comprising the method steps:

• a3) Preparation of 1,2-propanediol or its ethers, often as ethoxylation and / or propoxylation products, or both, preferably 1,2-propanediol, by the process according to the invention for the preparation of 1,2-propanediol, and
• b3) contacting the 1,2-propanediol with the at least one mineral oil component.

Hydraulic fluids which are preferred according to the invention are hydraulic oils which meet the requirements ISO 6743/4 and by the designations HL, HM, HV or, in Germany, by the designations HL, HLP, HVLP according to DIN 51524 Marked are. The hydraulic fluids may be in particular water-in-oil or oil-in-water emulsions, which may also contain other additives, such as corrosion inhibitors, agents for improving the aging resistance, to reduce the Fressverschleißes in Mischreibungsgebiet and to improve may contain the viscosity-temperature behavior.

• a4) Herstellung von 1,2-Propandiol durch das erfindungsgemäße Verfahren zur Herstellung von 1,2-Propandiol, sowie
• b4) In Kontakt bringen des 1,2-Propandiols mit dem mindestens einen Haut- und/oder Haarpflegemittel.

A further contribution to the solution of the abovementioned objects is provided by a process for the production of a cosmetic product comprising at least one skin and / or hair care product and 1,2-propanediol, comprising the process steps:

• a4) Preparation of 1,2-propanediol by the process according to the invention for the preparation of 1,2-propanediol, and
• b4) contacting the 1,2-propanediol with the at least one skin and / or hair care product.

at the cosmetic product is preferably a skin cream, a lotion, a hair care product, a shampoo or a Suncream. Furthermore, it is preferred according to the invention that the cosmetic product in addition to the 1,2-propanediol and the skin or Haircare product contains other additives, usually used for the production of cosmetic products, such as Preservatives, perfumes, emulsifiers, other solvents, such as water and / or ethanol, antioxidants, oils, Fats and the like.

• a5) Herstellung von 1,2-Propandiol durch das erfindungsgemäße Verfahren zur Herstellung von 1,2-Propandiol, sowie
• b5) In Kontakt bringen des 1,2-Propandiols mit dem mindestens einen Nährmittel.

A further contribution to the solution of the abovementioned objects is provided by a method for producing a feed comprising at least one nutrient and 1,2-propanediol, comprising the method steps:

• a5) Preparation of 1,2-propanediol by the process according to the invention for the preparation of 1,2-propanediol, and
• b5) contacting the 1,2-propanediol with the at least one nutrient.

at The food may be a starch-containing Foods, such as starchy grains, Seeds, tubers, cereals, potatoes, manioc or millet, to an oily Food, for example, from the oilseed of rape, soy, sunflower, linseed, peanut and the like can be obtained, or to trade in a green feed, which is mainly based on carbohydrates.

• a6) Herstellung von 1,2-Propandiol durch das erfindungsgemäße Verfahren zur Herstellung von 1,2-Propandiol, sowie
• b6) In Kontakt bringen des 1,2-Propandiols mit dem mindestens einen Pigment oder Farbstoff.

A further contribution to the solution of the abovementioned objects is afforded by a process for the preparation of a coloring agent comprising at least one pigment or dye and 1,2-propanediol, comprising the process steps:

• a6) Preparation of 1,2-propanediol by the process according to the invention for the preparation of 1,2-propanediol, and
• b6) contacting the 1,2-propanediol with the at least one pigment or dye.

at the coloring agent is preferably one Printing ink, this coloring agent being in addition to the pigment or the dye and the 1,2-propanediol further, the expert known additives, such as other solvents, Binders, fillers and specialty additives such as thixotropic agents, may contain.

• a7) Herstellung von 1,2-Propandiol durch das erfindungsgemäße Verfahren zur Herstellung von 1,2-Propandiol, sowie
• b7) In Kontakt bringen des 1,2-Propandiols mit dem mindestens einen Tensid.

A further contribution to the solution of the abovementioned objects is made by a process for producing a detergent comprising at least one surfactant and 1,2-propanediol, comprising the process steps:

• a7) Preparation of 1,2-propanediol by the process according to the invention for the preparation of 1,2-propanediol, and
• b7) contacting the 1,2-propanediol with the at least one surfactant.

When Detergents are especially liquid heavy duty detergents preferred, which in addition to the 1,2-propanediol and the at least one Surfactant preferably further additives, such as water softeners, for example, zeolite A and also phyllosilicates, wash alkalis, Enzymes, for example amylases, lipases, proteases or cellulases, Dirt carriers, such as carboxymethylcellulose Coated cotton fibers, core soaps, defoamers, such as For example, silicones, perfumes, stabilizers and preservatives can contain.

a Contribute to the solution of the above-mentioned tasks in particular also a process for the preparation of an emulsion, wherein an aqueous phase and an organic phase in Presence of a compound of the invention at least one ester group, preferably in the presence of an inventive Monofatty acid ester to form an emulsion with each other be brought into contact.

When organic phase come here basically all with water immiscible, organic solvents into consideration. However, organic phases are particularly preferably based on synthetic, vegetable or animal oils. Come as oils fatty acid triglycerides which are liquid at room temperature, for example, especially vegetable oils such as rapeseed oil, Sunflower oil, thistle oil, olive oil, linseed oil, Pumpkin seed oil, hemp oil or mustard oil, or animal oils such as tallow, fish oil or claw oil are used less frequently as food. But they are used in the chemical industry (eg lubricating oils, Soap) or in mechanical engineering (lubricants). As synthetic oils For example, silicone oils come into consideration. On too Hydrocarbon-based organic phases can be included in the emulsions. Paraffins come here in particular in consideration.

Farther it may be in the emulsion according to the invention a water-in-oil or an oil-in-water emulsion act.

The Amount of the compound of the invention having at least one ester group, preferably the amount of an inventive Monofatty acid ester, in the inventive Emulsion is preferably in a range of 50 to 0.1% by weight, particularly preferably in a range of 20 to 0.5 wt .-% and on most preferably in a range of 5 to 1 wt .-%, each based on the total weight of the emulsion. The volume ratio of aqueous phase and organic phase can in wide Range varies and is particularly dependent on it, whether a water-in-oil or an oil-in-water emulsion to be obtained.

The Preparation of the emulsion according to the invention takes place preferably by the process known to those skilled in the production process of emulsions. Preferably, the individual components of the combined emulsion of the invention and by means of a suitable homogenizing device, for example by means of a fast stirrer, a high-pressure homogenizer, a shaker, a vibratory mixer, an ultrasonic generator, an emulsifying centrifuge, a colloid mill or a Atomizer, converted into an emulsion.

a Contribute to the solution of the above-mentioned tasks furthermore an emulsion obtained by the process described above is available. Compared to those of the prior art This emulsion is recognizable by better known emulsions Storage stability.

In another embodiment, the invention relates to a cosmetic composition comprising an emulsion according to the invention. Cosmetic composition according to the invention, wherein an emulsion is prepared by a process according to the invention and having at least one cosmetic Component is brought into contact. Suitable cosmetic components are all those skilled in the art for various cosmetic products such as ointments, pases, creams, lotions, powders, waxes or gels and shampoos, soaps, scrubs, sunscreen or make-up known ingredients. Often, one or more of these emulsions will be present in amounts ranging from 0.01 to 15 weight percent, preferably in a range of from 0.1 to 15 weight percent, and more preferably in a range of from 0.15 to 5 % By weight, based in each case on the cosmetic composition.

In a further embodiment, the invention relates to a plastic composition comprising at least one plastic and a compound comprising at least one ether group according to the invention, at least one ester group according to the invention, at least one amino group according to the invention or at least one urethane group according to the invention, preferably containing at least one inventive ester group. Often, one or more of these compounds will be present in amounts ranging from 0.01% to 15% by weight, preferably in the range of from 0.1% to 15% by weight, and more preferably in the range of from 0.15 to 5 Wt .-%, each based on the plastic, used. A contribution to the present invention is also made by a process for producing a plastic composition, wherein a compound comprising at least one ether group according to the invention, at least one ester group according to the invention, at least one amino group according to the invention or at least one urethane group according to the invention, preferably comprising at least one Inventive ester group, which is prepared in each case by a process according to the invention and brought into contact with at least one plastic. In principle, all plastics which are familiar to the person skilled in the art may be considered as plastics, thermoplastics being preferred whose workability, in particular their demoldability and wall adhesion, can be improved ( Gächter / Müller, plastic additives, Carl Hanser Verlag 1989 ). Of these, preferred are polyesters and polyolefins. Preferred polyesters are PET, PBT, PLA or PHB. Preferred polyolefins are PE, PP, PVC, SAN, PVC being particularly preferred.

In In another embodiment, the invention relates to a drilling composition including at least one liquid rinse component and a compound containing at least one obtainable according to the invention Ether group, at least one obtainable according to the invention Ester group, at least one obtainable according to the invention Amino group or at least one obtainable according to the invention Urethane group, preferably containing at least one obtainable according to the invention Ester group. Often, one or more of these compounds in an amount ranging from 0.01 to 15% by weight, preferably in a range of 0.1 to 15 wt%, and more preferably in one Range from 0.15 to 5% by weight, based in each case on the flushing component, used.

One Another embodiment of the present invention relates to a method for making a drilling composition, wherein a compound containing at least one ether group, at least one ester group, at least one amino group or at least one urethane group, preferably containing at least one ester group, or also at least two of them according to an inventive Process is prepared and with at least one liquid Rinse component is brought into contact.

When In principle, drilling compositions all come to the skilled person especially for the drilling of rock boreholes known compositions, in particular liquid rinsing systems, drilling fluids on closed oil basis as well as drilling fluid based on water-based O / W emulsion systems into consideration.

liquid Rinsing systems for sinking rock boreholes under Applying the detached cuttings are known to be limited thickened, flowable systems that are one of the three following Classes can be assigned: Pure watery Drilling fluids, Drilling fluids oil-based, usually as so-called invert-emulsion sludge be used as well as the water-based O / W emulsions, the in the closed aqueous phase, a heterogeneous finely dispersed oil phase contain.

Closed-oil drilling fluids are generally constructed as a three-phase or multi-phase system: oil, water and finely divided solids. The aqueous phase is distributed heterogeneously finely dispersed in the closed oil phase. A plurality of additives are provided, in particular emulsifiers, fluid-loss additives, alkali reserves, viscosity regulators and the like. For details, reference is made to the publication, for example PA Boyd et al. "New Base Oil Used in Low-Toxicity Oil Muds" Journal of Petroleum Technology, 1985, 137-142 such as RB Gennett "New Drilling Fluid Technology Mineral Oil Mud" Journal of Petroleum Technologist, 1984, 975-981 and the literature cited therein.

Drilling fluids based on water-based O / W emulsion systems are in use It features an intermediate position between the purely aqueous systems and the oil-based invert fluids. Detailed factual information can be found here in the relevant specialist literature, reference may be made, for example, to the textbook George R. Gray and HCH Darley, "Composition in Properties of Oil Well Drilling Fluids", 4th Edition, 1980/81, Gulf Publishing Company, Houston and the extensive factual and patent literature cited therein as well as the manual "Applied Drilling Engineering", Adam T. Bourgoyne, Jr. et al., First Printing Society of Petroleum Engineers, Richardson, Texas (USA) ,

a Contribute to the solution of the above-mentioned tasks Furthermore, the use of in the first step of the invention Process obtained hydrogenation and / or after Going through both steps of the invention Method obtained 1,2-propanediol as a refrigerant, for preparing a compound containing at least one ester function, preferably for the preparation of a polyester or an alkyd resin, for producing a compound comprising at least one ether function, preferably for the preparation of a polyether, as a heat transfer agent, as a hydraulic fluid or as a component for a hydraulic fluid, to lower the freezing point aqueous phases, as a solvent or plasticizer in colorants, in particular in printing inks, as a solvent or as an excipient in preferably liquid detergents, as an additive in feedingstuffs, as humectants in foodstuffs and Tobacco, as a formulation ingredient in cosmetic products, as an additive or base or both in pumping agents or lubricants or both, in particular in the exploration of oil deposits, or as a formulation component of corrosion inhibitors.

Especially also makes use of the by the invention A process for preparing a compound comprising at least an ester functional compound containing at least an ester function, in particular the use of one by this Method obtained fatty acid monoester, as an emulsifier or as a formulation ingredient for PVC extrusions Contribution to the solution of the aforementioned tasks.

The Invention will now be closer by way of non-limiting examples explains:

EXAMPLES

Example 1:

A 2 m long reaction tube with an internal diameter of 25 mm (continuous hydrogenation) was charged with a copper-chromium type catalyst (type G99 BO 3 × 3 from Südchemie). Pure glycerol was hydrogenated continuously under the following conditions: temperature = 220 ° C; 250 bar; 13 Nm ³ / h of hydrogen; Throughput = 882 g / h.

To the Monitoring the degree of conversion of glycerol was the Hydrierablaufs analyzed by GC, but not completely, but only in terms of its content of glycerol, 1,2-propanediol and Ethylene glycol. Result: 34.2% glycerol, 65.3% 1,2-propanediol, 0.5% Ethylene glycol. Byproducts could only as small impurities be observed in the GC. The hydrogenation process showed only weak Smell up and was almost clear.

Of the Hydrogenation effluent was distilled in the laboratory: fractionation with attached 20 cm Vigreux column, distillation at atmospheric pressure, Amount used: 1000 g.

Upon fractionation, the four fractions I to IV were obtained. The associated data are shown in Table 1. In this table, in column 1, "Fr" means the respective fraction and "R" the distillation residue. In columns 2 and 3, the bottom and the broth temperatures of the respective fractions are combined. Column 4 gives the amount (in grams) of fractions obtained. Column 5 indicates the fractions closer. Table 1 Fr. swamp vapors amount Remarks ° C ° C G I 117-178 77-106 114.8 Water, cloudy II 178-187 106-170 5.5 Water, clear, smells like ether III 188-189 170-176 4.2 colorless, clear, odorless IV 189-215 177-187 505.4 colorless, clear, odorless (99.5% 1,2-propanediol, 0.5% ethylene glycol) R 367.3 yellow, slightly cloudy 21.0% 1,2-propanediol, 0.7% ethylene glycol and the like. 79.0% glycerol

in the The sense of the process according to the invention is fraction IV (505.4 g colorless, clear liquid). In this faction it is the target product.

Comparative Example 1

example 1 was repeated, but glycerol was almost complete (and not partially hydrogenated as in Example 1). This happened through Increase the temperature to 230 ° C and by reducing the throughput to 441 g / h.

To the Monitoring the degree of conversion of glycerol was the Hydrierablaufs analyzed, but not completely, but only in terms of its content of glycerol, 1,2-propanediol and Ethylene glycol. Result: 0.5% glycerol, 98.7% 1,2-propanediol, 0.8% Ethylene glycol. The hydrogenation process had an extremely strong Smell up and was cloudy. Several small peaks could be found in the GC which could not be qualified.

The hydrogenation effluent was distilled in the laboratory: fractionation with attached 20 cm Vigreux column, distillation at atmospheric pressure, amount used: 1000 g In fractionation, the four fractions I to IV were obtained. The associated data are shown in Table 2. Table 2 Fr. swamp vapors amount Remarks ° C ° C G I 113-175 77-105 214.8 Water, cloudy II 178-187 106-170 26.5 cloudy, smells like ether III 188-189 170-176 4.2 colorless, smells intense IV 189-215 177-189 705.4 colorless, clear, smells of ether, (95.5% 1,2-propanediol, 1.2% ethylene glycol, 3.3% unknown by-products) R 47.3 brown, cloudy 22.0% 1,2-propanediol, 0.7% ethylene glycol and the like. 77.0% glycerol

end product of the comparative experiment is fraction IV (705.4 g colorless liquid, Smell of ether).

Example 2:

example 1 was repeated but the glycerin used was in proportion 4: 1 with the Hydrierablaufs obtained in Example 1 (4 Parts by weight of pure glycerol and 1 part by weight of the hydrogenation from Example 1).

To the Monitoring the degree of conversion of glycerol was the Hydrierablaufs analyzed, but not completely, but only in terms of its content of glycerol, 1,2-propanediol and Ethylene glycol. Result: 13.8% glycerol, 85.6% 1,2-propanediol, 0.6% Ethylene glycol. The hydrogenation effluent had a faint odor up and was almost clear.

Of the Hydrogenation effluent was distilled in the laboratory: fractionation with attached 20 cm Vigreux column, distillation at atmospheric pressure, Amount used: 1000 g.

Upon fractionation, the four fractions I to IV were obtained. The associated data are shown in Table 3. Table 3 Fr. swamp vapors amount Remarks ° C ° C G I 117-178 77-106 167.7 Water, cloudy, ether smell II 178-187 106-167 10.5 Water, clear, smells like ether III 188-189 168-176 9.2 colorless, clear, slight smell IV 189-215 177-187 630.7 colorless, clear, odorless (99.4% 1,2-propanediol, 0.6% ethylene glycol) R 181.3 yellow, slightly hazy 34.0% 1,2-propanediol, 0.7% ethylene glycol and the like. 64.0% glycerol

in the The sense of the process according to the invention is fraction IV (630.7 g colorless, clear liquid, odorless) the decisive faction. This is the target product Product. In this fraction could by gas chromatography no further By-products are identified.

Comparative Example 2:

Example 1 was repeated but glycerol was fully hydrogenated (and not partially as in Example 1). This was done on the one hand by increasing the temperature to 250 ° C, using a copper silicate (Cu-SiO ₂ / Kata Leuna) and choosing a throughput of 441 g / h.

Of the Hydrogenation process (yellow, floating droplets, very unpleasant Odor) was distilled: fractionation with attached column as in Table 1, distillation at atmospheric pressure, amount used: 1000 G.

In the fractionation, the five fractions I to V were obtained. The associated data are shown in Table 4. Table 4 Fr. swamp vapors amount Remarks ° C ° C G I 113-175 80-105 211.4 Water, contains 8 g org. phase II 175-191 104-181 28.5 slightly cloudy, very unpleasant smell III 191-192 181-187 305.8 almost colorless, clear, slight smell IV 192-205 182-188 405.4 colorless, clear, slight smell V 205-230 188-189 19.4 colorless, clear, slight smell R 29.2 dark brown, cloudy, 27.7% 1,2-propanediol, 6% ethylene glycol, 12.1% glycerol, many by-products

The Fractions III to V were combined to give 730.6 g of a clear Liquid with a slight smell. Composition according to GC: 93.5% 1,2-propanediol, 4.0% ethylene glycol, 2.5% unknown by-products.

These Total fraction had virtually the same Brüdentemperatur as described in Tables 1 to 3 fraction IV, d. H. the distillation behavior was identical.

When Comparative product here is the total fraction (fractions III to V). It is clear that the quality of Total fraction is classified as very bad (purity only 93.5%, with 4% very much ethylene glycol and further 2.5% of others By-products). The total fraction also had an inherent odor and showed slight turbidity on addition of water.

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 4128692 A [0002]
• - DE 524101 C [0004]
• - DE 541362 C [0005]
• - EP 0523014 A [0007, 0007]
• - EP 0523015 A [0007, 0007]
• - DE 4302464 A [0008, 0008]
• US 5616817A [0009]
• - US 6479713A [0010, 0010]
• WO 2005/095536 A [0011]
• EP 0254189A [0027]
• - EP 0334118 A [0031]
• - EP 0515485 A [0032]
• WO 01/62823 A [0055]
• DE 19726508 A1 [0058]

Cited non-patent literature

• - Montassier et al. report in Heterogeneous Catalysis and Fine Chemicals (1988, Elsevier, Amsterdam, pages 165-170). [0006]
• - Applied Catalysis A: General 281 (2005), pages 225-231 [0011]
• - "Basic Operations in Chemical Process Engineering", Wilhelm RA Vauck and Hermann A. Müller, 11th revised and expanded edition, Willey-VCH-Verlag, 2000 [0039]
• - ISO 6743/4 [0060]
• - DIN 51524 [0060]
• - Gächter / Müller, plastic additives, Carl Hanser Verlag 1989 [0076]
• - PA Boyd et al. "New Base Oil Used in Low-Toxicity Oil Muds" Journal of Petroleum Technology, 1985, 137-142 [0081]
• RB Gennett "New Drilling Fluid Technology Mineral Oil Mud" Journal of Petroleum Technologists, 1984, 975-981 [0081]
• - George R. Gray and HCH Darley, "Composition in Properties of Oil Well Drilling Fluids" 4th Edition, 1980/81, Gulf Publishing Company, Houston [0082]
• Applied Drilling Engineering, Adam T. Bourgoyne, Jr. et al., First Printing Society of Petroleum Engineers, Richardson, Texas (USA) [0082]

Claims (32)

Process for the preparation of 1,2-propanediol having a purity of at least 98%, characterized in that in a first step, glycerol is continuously hydrogenated in the presence of a heterogeneous copper-containing catalyst, wherein glycerol is reacted to at most 95%, and in the first step, subjected to distillation in a second step. The method of claim 1, wherein one is a heterogeneous Copper-chromium catalyst used. The method of claim 1, wherein one is a heterogeneous Copper chromite catalyst used. Process according to claims 1 to 3, wherein the hydrogenation in isothermally operated tubular reactors or tube bundle reactors performs. Process according to claim 4, wherein the hydrogenation performs so that you liquid glycerin in trickle mode ("Trickle bed") in cocurrent or countercurrent with hydrogen a catalyst fixed bed passes. Process according to claim 5, wherein glycerin is used without Backmixing with a defined residence time through the catalyst bed in the or the reaction tubes leads. Method according to one of claims 1 to 6, wherein the hydrogenation at a temperature in the range of 180 to 220 ° C performs. Method according to one of claims 1 to 7, wherein the water content of the glycerol used below 2% lies. Method according to one of claims 1 to 8 wherein glycerol is reacted in the first step to a maximum of 90%. Method according to one of claims 1 to 9, wherein at least part of the distillation in the bottom product retained glycerol returned in the first step becomes. The method of claim 10, wherein at least one Part of the bottom product without prior purification in the first Step is traced back. The method of claim 10, wherein at least one Part of the glycerol obtained in the bottom product in the distillation first by distillation or filtration of the bottom product cleaned up and then returned to the first step becomes. A method of preparing a compound at least one ether group, at least one ester group, at least an amino group or at least one urethane group or at least two thereof, including the method steps, comprising the method steps a1) Preparation of 1,2-propanediol by a process according to one of Claims 1 to 12, as well b1) reaction of 1,2-propanediol having a compound having at least one active hydrogen atom, at least one epoxy group, at least one ester group or at least one isocyanate group. The method of claim 13, wherein the compound includes at least one ester group. The method of claim 14, wherein the compound containing at least one ester function a fatty acid monoester, a polyester resin or a polyalkyd resin. A method of preparing a compound at least one ether function, comprising the process steps a2) Preparation of 1,2-propanediol by a process according to one of Claims 1 to 12, as well b2) reaction of 1,2-propanediol having a compound having at least one epoxy or hydroxyl group or both, obtaining an ether. Compound containing at least one ester function, obtainable by a method according to claim 14. Process for producing a hydraulic fluid including at least one mineral oil component and 1,2-propanediol or its ether or both, comprising the process steps: a3) Preparation of 1,2-propanediol by a process according to one of Claims 1 to 12, as well b3) Contacting the 1,2-propanediol with the at least one mineral oil component. Process for the preparation of a cosmetic product including at least one skin and / or hair care product as well 1,2-propanediol, comprising the process steps: a4) Preparation of 1,2-propanediol by a method according to any one of claims 1 to 12, as well b4) bringing the 1,2-propanediol into contact with the at least one skin and / or hair care product. Method for producing a feed comprising at least one nutrient and 1,2-propanediol comprising the process steps: a5) Preparation of 1,2-propanediol by a method according to any one of claims 1 to 12, such as b5) contacting the 1,2-propanediol with the at least a nutrient. Process for the preparation of a coloring agent containing at least one pigment or dye and 1,2-propanediol, comprising the method steps: a6) Preparation of 1,2-propanediol by a method according to any one of claims 1 to 12, such as b6) contacting the 1,2-propanediol with the at least a pigment or dye. Process for producing a detergent containing at least one surfactant and 1,2-propanediol, comprising the process steps: a7) Preparation of 1,2-propanediol by a process according to one of Claims 1 to 12, as well b7) Contacting the 1,2-propanediol with the at least one surfactant. Process for the preparation of an emulsion, wherein an aqueous phase and an organic phase in the presence a compound containing at least one ester group according to claim 13 or 17 are brought into contact with each other to form an emulsion become. Emulsion obtainable by a process according to claim 23. Cosmetic composition containing an emulsion according to claim 24. Process for the preparation of a cosmetic composition, wherein an emulsion according to claim 24 is prepared and having at least a cosmetic component is brought into contact. Plastic composition containing at least a plastic and a compound including at least one Ether group, at least one ester group, at least one amino group or at least one urethane group, preferably including at least an ester group obtainable according to claim 13. Process for producing a plastic composition, wherein a compound comprising at least one ether group, at least one ester group, at least one amino group or at least one urethane group, preferably containing at least an ester group prepared by a process according to claim 13 and is brought into contact with at least one plastic. Drilling composition comprising at least one including liquid rinse component and a compound at least one ether group, at least one ester group, at least an amino group or at least one urethane group, preferably containing at least one ester group, obtainable according to Claim 13. Method for producing a drilling composition, wherein a compound comprising at least one ether group, at least one ester group, at least one amino group or at least one urethane group, preferably containing at least an ester group prepared by a process according to claim 13 and with at least one liquid rinse component is brought into contact. Use of the hydrogenation processes obtained in the first step of the process according to any one of claims 1 to 12 and / or of the 1,2-propanediol obtained as a refrigerant after passing through both steps of the process according to any one of claims 1 to 12, for the preparation of a compound comprising at least one ester Function, to produce a compound containing at least one ether function, as a heat transfer support means, as a hydraulic fluid or as a component for a hydraulic fluid, to reduce the freezing point of aqueous phases, as a solvent or plasticizer in colorants, especially in printing inks, as a solvent or as an adjuvant in preferably liquid detergents, as an additive in feed, as a humectant in food and tobacco , as a formulation component in cosmetic products, as an additive or base or both in pumping agents or lubricants or both, or as a formulation component of corrosion inhibitors. Use of the compound including at least an ester group according to claim 17 as an emulsifier or as a formulation component for PVC extrusions.