WO2008020077A1 - Procédé de fabrication du propane-1,2-diol - Google Patents

Procédé de fabrication du propane-1,2-diol Download PDF

Info

Publication number
WO2008020077A1
WO2008020077A1 PCT/EP2007/058577 EP2007058577W WO2008020077A1 WO 2008020077 A1 WO2008020077 A1 WO 2008020077A1 EP 2007058577 W EP2007058577 W EP 2007058577W WO 2008020077 A1 WO2008020077 A1 WO 2008020077A1
Authority
WO
WIPO (PCT)
Prior art keywords
propanediol
group
compound
glycerol
hydrogenation
Prior art date
Application number
PCT/EP2007/058577
Other languages
German (de)
English (en)
Inventor
Alfred Westfechtel
Norbert Klein
Elke Grundt
Teresa Alexandre
Original Assignee
Cognis Oleochemicals Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from EP06017124A external-priority patent/EP1889825A1/fr
Priority claimed from DE102007027374A external-priority patent/DE102007027374A1/de
Application filed by Cognis Oleochemicals Gmbh filed Critical Cognis Oleochemicals Gmbh
Priority to EP07802687A priority Critical patent/EP2061741A1/fr
Publication of WO2008020077A1 publication Critical patent/WO2008020077A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of -OH groups, e.g. by dehydration

Definitions

  • the invention relates to a process for the preparation of 1,2-propanediol. Also proposed is a process for preparing a compound comprising at least one ether group, at least one ester group, at least one amino group or at least one urethane group or at least two thereof, the compound obtainable by this process comprising at least one Ether group, at least one ester group, at least one amino group or at least one urethane group or at least two thereof, a process for preparing a process for preparing a composition, the composition obtainable by this process, the use of a hydrogenation process and the Use of a connection.
  • 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 / Henkel, Fleckenstein et al.) And on the other hand, the dehydration proceeds to 1,2-propanediol with elimination of water.
  • 1,2-Propanediol is an industrially interesting raw material. It is used in a variety of applications, namely in the food industry, as a solvent for dyes and flavors, as humectants for tobacco, in cosmetics, as a component of brake and hydraulic fluids, antifreezes, lubricants in refrigerators, as a solvent for greases , Oils, resins, waxes, dyes, etc. It also serves as a starting material for the manufacture of other products. By esterification and / or etherification, it is possible to obtain numerous products which can be used as solvents, for syntheses, as plasticizers, thickeners, emulsifiers and the like.
  • 1,2- Propanediol is usually produced industrially by hydration of propylene oxide.
  • DE-C-541 362 discloses the hydrogenation of polyoxy compounds.
  • liquid or solid polyoxy compounds in aqueous solution or suspension are treated with hydrogen in the presence of catalysts.
  • glycerin and a nickel catalyst are treated in a bomb at 200 to 240 0 C and a pressure of 100 atm with hydrogen.
  • 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 the calculated amount of hydrogen was taken up after 4 hours, it will be clear to the person skilled in the art that glycerol was evidently quantitatively reacted.
  • EP-AO 523 014 and EP-AO 523 015 (Novamont) address the problem of the lack of selectivity of glycerol hydrogenation to 1,2-propanediol in that they are based on ruthenium or zinc-copper based catalysts in very dilute aqueous medium deploy. Nevertheless, the selectivity leaves much to be desired. Namely, according to the examples of EP-A-0 523 015 (use of a zinc-copper catalyst) in the hydrogenation of glycerol in addition to propylene glycol, large amounts of ethylene glycol and also significant amounts of lactic acid are formed.
  • EP-A-0 523 014 use of a sulfide-modified ruthenium catalyst
  • ethylene glycol are formed in the hydrogenation of glycerol.
  • 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.
  • glycerol was substantially quantitatively reacted (glycerol content in the reaction mixture below 0.1%), only 3 of the total of 10 examples operated 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.
  • DE-A-43 02 464 shows the basic 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 to give a 1,2-propanediol with very particular intrinsic professional profile.
  • the glycerol hydrogenation is carried out such that on the one hand glycerol having a water content of up to 20% by weight and on the other hand special catalysts (containing 40-70%) Co, 10-20% Mn, 0-10% Mo and 0-10% Cu). 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.
  • the object of the present invention was to provide a novel process for the preparation of 1,2-propanediol by hydrogenation of glycerol.
  • the 1,2-propanediol thus prepared should be distinguished by a high purity, in particular a purity of at least 98% and preferably of at least 99%.
  • 1,2-propanediol thus prepared should be of the highest possible quality, which means that it should in no case have an unpleasant and / or strong odor but at most a slight odor and should preferably be odorless.
  • the invention relates to a process for the preparation of 1,2-propanediol having a purity of at least 98%, wherein
  • glycerol in the presence of a heterogeneous copper-containing catalyst, in particular a heterogeneous copper-chromium -containing catalyst - continuously hydrogenated, glycerol being at most 95 wt .-%, preferably at most 90 wt .-%, even more preferably at most 85 wt .-%, more preferably at most 80 wt .-%, moreover even more preferred to at most 75% by weight, and most preferably to at most 70% by weight, and that in the first step, glycerol in the presence of a heterogeneous copper-containing catalyst, in particular a heterogeneous copper-chromium -containing catalyst - continuously hydrogenated, glycerol being at most 95 wt .-%, preferably at most 90 wt .-%, even more preferably at most 85 wt .-%, more preferably at most 80 wt .-%, moreover even more preferred to at most 75% by weight, and most preferably to at
  • the weight percentages used in the present invention are determined by gas chromatographic determinations by integrating the areas of the signals. For calibration and verification of the measurements, the weight percentages were confirmed by distillation and weighing of the individual components from a sample measured by gas chromatography.
  • a purity of at least 98% is understood to mean that after the process according to the invention has been carried out after passing through both steps (ie hydrogenation and distillation), a product is obtained whose content of 1,2-propanediol is at least 98%.
  • the purity is determined by gas chromatography (area percent).
  • the two steps of the process according to the invention are carried out in such a way that the purity of the target product 1,2-propanediol is at least 99%.
  • the overall process for the preparation of 1,2-propanediol according to the inventive method comprises two steps, namely • the hydrogenation of glycerol under the specified 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.
  • the following is informative: if one carries out the hydrogenation of glycerol in a quantitative manner, one obtains hydrogenation processes that almost stink. If subsequently such hydrogenation processes (ie, glycerine obtained with complete hydrogenation) are distilled, it is found that the fractions of 1,2-propanediol thus obtained still have an unpleasant odor. However, if the hydrogenation is carried out in accordance with the invention such that the glycerol used is only partially hydrogenated and then the hydrogenation processes thus obtained are distilled, fractions are obtained which have no or at least a significantly low unpleasant odor.
  • the first step of the process according to the invention is carried out in the presence of less than 20% by weight, more preferably less than 10% by weight, even more preferably less than 5% by weight, based on the amount by weight of used Glycerol, an organic solvent, wherein the implementation of the method 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 mass.
  • the catalyst contains from 32 to 38% by weight of copper, based on the oxidic catalyst composition, of from 26 to 30% by weight of chromium, from 1.5 to 3% by weight of barium, from 0.5 to 2% by weight. Silicon and additionally 1 to 5, preferably 2 to 3 wt .-%, manganese, zirconium and / or cerium, based on the oxidic catalyst composition.
  • the catalyst is a copper chromite catalyst containing 35 to 55 wt%, preferably 40 to 50 wt% copper, 35 to 55 wt%, preferably 40 to 50 wt% chromium, in each case based on the oxidic catalyst mass, and optionally further Erdalkali- or transition metals, in particular barium and manganese, in the form of their oxides.
  • These catalysts and their production processes are described in detail in EP-AO 254 189.
  • a suitable catalyst mention may be made of a catalyst which contains about 47% by weight of CuO, 46% by weight of Cr 2 O 3 , 4% by weight of MnO 2 and 2% by weight of BaO.
  • This catalyst and its production process are also described in detail in EP 254 189 A2.
  • 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.
  • 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.
  • 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 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 0 C to 280 0 C, in particular 180 to 220 0 C, works.
  • glycerol is passed in vapor or liquid form over a fixed catalyst bed.
  • a molar ratio of hydrogen to glycerol in the range of 2 to 500 is set, wherein excess hydrogen is optionally circulated.
  • the first step of the process according to the invention can be carried out in similar reactors used for the preparation of fatty alcohols by hydrogenation of fatty acid methyl ester or directly from triglycerides and are known and which are preferably fixed bed reactors.
  • the first step of the process according to the invention 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.
  • the reactor can optionally be cooled by using a suitable coolant, wherein with the use of tube bundle reactors this coolant flows along the reaction tube and when using reactors with thermoplates through the flow paths within the thermoplates .
  • coolant are for example water, dressingträ- gerlandaisen as ® Marlothem and salt melts.
  • the hydrogenation is carried out by passing liquid glycerol in trickle bed in cocurrent or countercurrent with hydrogen over a catalyst fixed bed.
  • the reaction tubes are used Glycerol is fed under a back-mixing at least partially inhibiting 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 h "1 and beyond Favor in a range of 0.3 to 2 h" 1 through the catalyst bed in the reaction or to the pipes.
  • LHSV Liquid Hourly Space Velocity
  • measures are in principle all measures known to the person skilled in the art and suitable for this purpose, such as suitable tube cross sections or tube cross-sectional length ratios, which are usually selected as a function of the flow conditions usually prevailing during operation of the reactor.
  • the glycerol used for the hydrogenation may be hydrous.
  • the water content should be below 15% by weight, more preferably below 10% by weight and most preferably below 5% by weight, based in each case on the total weight of water and glycerol. This has procedural economic reasons, because in the course of hydrogenation water is formed anyway, which is removed in the second process step in the course of distillation.
  • the water content of the glycerol used is less than 2% by weight. It may also be desired anhydrous Use glycerol or a glycerol whose water content is only in the trace range.
  • the reaction mixture obtained in the first step is subjected to a distillation in a second step, in which preferably the 1,2-propanediol formed in the first step is obtained as distillate.
  • distillation as used herein is understood to mean its broadest meaning, comprising the evaporation of a liquid mixture, the subsequent condensation of the effluent vapor and the removal of the condensate (distillate).
  • This distillation can be a single-phase distillation (simple distillation) or a two-phase distillation (rectification), the latter usually being able to be carried out in countercurrent.
  • the single-phase or two-phase distillation can also be carried out batchwise, semicontinuously or continuously.
  • a once used still bottling feed whose composition continuously changes during distillation is separated into a distillate and a residue.
  • the residue increasingly depleted of 1,2-propanediol as the distillation progresses.
  • the distillate is successively removed in parts separated by boiling limits (so-called "fractional distillation"), so that the feed mixture is present at the end separated into a residue and several distillate fractions.
  • the bubbler feed is continuously supplemented with preheated, to be separated still.
  • the continuous procedure which succeeds with the counter or DC distillation, the to be separated, preheated liquid mixture is continuously introduced into the apparatus, wherein the mixture is decomposed into a head and a bottom product of substantially constant composition.
  • the formulation "in which preferably the 1,2-propanediol formed in the first step is obtained as distillate” comprises both processes in which the 1,2-propanediol is obtained as the top product of a distillation step (such as in a batchwise, fractional distillation ) as well as processes in which the 1,2-propanediol is withdrawn, for example, as a side draw (such as in a continuous rectification).
  • the 1,2-propanediol obtained in the process according to the invention may be subjected to further purification steps known to those skilled in the art in order to further increase the purity of the product.
  • a further purification process for example, the filtration or the extraction may be mentioned.
  • a portion of the hydrogenation effluent (that is, the reaction mixture obtained after passing through the first step of the process of the present invention) can be used as a diluent for the continuous hydrogenation in the first process step.
  • 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.
  • glycerol is preferably fed without backmixing with a defined residence time through the catalyst bed in the reaction tube (s).
  • the total yield of 1,2-propanediol from glycite can be reduced by recycling the glycerol from the bottom product or by directly recycling the bottom product itself into the first step of the process according to the invention - rin be further increased.
  • both a part of the hydrogenation processes, which were obtained in the first process step, as well as a part of the glycerol from the bottom product, which was retained in the second process step, are recycled to the first process step.
  • a contribution to achieving the abovementioned objects is also achieved 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 comprising at least one ester Group or function, including the process steps
  • the compound having at least one active hydrogen atom may be a compound having at least one hydroxyl group, so that after reaction of this compound with the 1,2-propanediol phase, a compound having at least one ether group is obtained.
  • a polyether compound can also be obtained.
  • the compound having at least one active hydrogen atom may also be a compound having at least one carboxylic acid group, so that after reaction of this compound with the 1,2-propanediol phase, a compound having at least one ester group is obtained.
  • an ester polyether compound can also 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.
  • an aminopolyether compound can also be obtained.
  • ether or polyether can likewise be obtained by reacting this compound with the 1,2-propanediol phase.
  • urethanes or polyurethanes can be obtained.
  • the use of a compound having at least one carboxylic acid group in process step b1) is particularly preferred.
  • 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, especially fatty acids, are most preferred.
  • 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.
  • the compounds having at least one carboxylic acid group is 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 in which the abovementioned monocarboxylic acids are saturated monocarboxylic acids, such as, for example, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, fish oil, palmitic acid, margaric acid, stearic acid, arachidic 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 neuronic acid, or polyunsaturated monocarboxylic acids, such as
  • this compound is a fatty acid ester, in particular a fatty acid monoester, a polyester or a polyester resin or a 1,2-propanediol-based alkyd resin
  • alkyd resins are synthetic, strongly 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 other polyhydric alcohols, in particular glycerol or pentaerythritol. to be obtained.
  • the compound having at least one carboxylic acid group is a dibasic acid which is preferably 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 acid, succinic acid, fumaric acid, adipic acid, sebacic acid, azelaic acid and maleic anhydride, with adipic acid, azelaic acid and terephthalic acid being particularly preferred and terephthalic acid being most preferred.
  • a dibasic acid which is preferably selected from the group consisting of phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, n
  • oils or oil derivatives of vegetable and animal origin are suitable in each case individually or as a mixture.
  • oils and oil derivatives of animal origin tallow as well as from tallow, in particular by fractionation, oil acids to be mentioned.
  • organic oil or fatty acids are particularly tallow, canola oil, rapeseed oil, sunflower oil, palm oil, which may optionally be present in cured or cured version, rapeseed oil, soybean oil, safflower oil, linseed oil, tall oil, coconut oil, palm kernel oil, castor oil, dehydrated castor oil, fish oil and Tungöl into consideration.
  • dry oils or semi-dry oils having iodine numbers of at least 100 are preferred, among others, soybean oil and tall oil are advantageous.
  • Suitable fatty acids which are used both to prepare the alkyd resins and to prepare the fatty acid esters are in particular 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.
  • these fatty acids those of drying oils or semi-drying oils having iodine numbers of at least 100, including those of soybean oil and tall oil, are preferable.
  • alkyd resins can be found, for example, in WO-A-01/62823, the disclosure content of which with respect to the preparation of alkyd resins is hereby introduced as a reference and which forms part of the disclosure of the present invention.
  • a contribution to the solution of the abovementioned objects is also provided by a compound comprising at least one ester function obtained by the process described above.
  • a further contribution to the solution of the abovementioned objects is afforded by a method for producing a compound comprising at least one ether function, comprising the method steps
  • 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 from DE 197 26 508 A1.
  • 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:
  • Hydraulic fluids which are preferred according to the invention are hydraulic oils which fulfill the requirements of ISO 6743/4 and are designated by the designations HL, HM, HV or, in Germany, by the designations HL, HLP, HVLP according to DIN 51524.
  • the hydraulic fluids may in particular be water-in-oil or oil-in-water emulsions which If necessary, other additives such as corrosion inhibitors, agents for improving the aging resistance, to reduce the Fressverschl foundedes mixed friction region and to improve the viscosity-temperature behavior may contain.
  • 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:
  • the cosmetic product is preferably a skin cream, a lotion, a hair care product, a shampoo or a sunscreen. Furthermore, it is preferred according to the invention that the cosmetic product in addition to the 1,2-propanediol and the skin or hair care contains other additives that are commonly 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.
  • 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:
  • the foodstuff may be a starch-containing foodstuff such as high-starch grains, seeds, tubers, cereals, potato, cassava or millet, for example, an oily food made from, for example, rapeseed, soy, sunflower, linseed , Peanut and the like, or a green feed mainly based on carbohydrates.
  • a starch-containing foodstuff such as high-starch grains, seeds, tubers, cereals, potato, cassava or millet, for example, an oily food made from, for example, rapeseed, soy, sunflower, linseed , Peanut and the like, or a green feed mainly based on carbohydrates.
  • the colorant is preferably a printing ink, this colorant, in addition to the pigment or the dye and the 1,2-propanediol, further additives known to the person skilled in the art, such as further solvents, binders, fillers and special additives, such as thixotropic agents , may contain.
  • 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:
  • liquid heavy-duty detergents are preferred as detergents which, in addition to the 1,2-propanediol and the at least one surfactant, are 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 carboxymethyl cellulose coated cotton fibers, core soaps, defoamers, such as silicones, fragrances, stabilizers and preservatives may contain.
  • a process for the preparation of an emulsion in which an aqueous phase and an organic phase in the presence of a compound according to the invention have at least one ester group, preferably in the presence of a monofatty acid ester according to the invention, with formation of an emulsion contributes to the solution of the abovementioned objects be brought into contact with each other.
  • organic phases are particularly preferably based on synthetic, vegetable or animal oils.
  • oils here come, for example liquid at room temperature fatty acid triglycerides, 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. However, they are used in the chemical industry (eg lubricating oils, soap) or in mechanical engineering (lubricants).
  • Suitable synthetic oils are, for example, silicone oils.
  • Hydrocarbon-based organic phases may also be included in the emulsions. Here in particular paraffins come into consideration.
  • the emulsion according to the invention may be a water-in-oil or an oil-in-water emulsion.
  • the amount of the compound according to the invention having at least one ester group, preferably the amount of a monofatty acid ester according to the invention, in the emulsion according to the invention is preferably in a range from 50 to 0.1% by weight, more preferably in a range from 20 to
  • aqueous phase and organic phase can vary widely and is particularly dependent on whether a water-in-oil or a
  • Oil-in-water emulsion should be obtained.
  • the preparation of the emulsion according to the invention is preferably carried out by the methods known in the art for the preparation of emulsions.
  • the individual components of the emulsion according to the invention are combined and converted into an emulsion by means of a suitable homogenizer, for example by means of a rapid stirrer, a high-pressure homogenizer, a shaker, a vibration mixer, an ultrasonic generator, an emulsifying centrifuge, a colloid mill or an atomizer.
  • the invention in another embodiment, relates to a cosmetic composition
  • a cosmetic composition comprising an emulsion according to the invention.
  • Cosmetic composition according to the invention an emulsion being prepared by a process according to the invention and having at least one cosmetic composition 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.
  • one or more of these emulsions 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 most preferably in the range of 0.15 to 5 wt .-%, each based on the cosmetic composition used.
  • the invention relates to a plastic composition
  • 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 including at least one ester group according to the invention.
  • 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.
  • 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 (Gumbleter / Müller, Kunststoff-Additive, Carl Hanser Verlag 1989).
  • polyesters and polyolefins are PET, PBT, PLA or PHB.
  • Preferred polyolefins are PE, PP, PVC, SAN, with PVC being particularly preferred.
  • the invention in another embodiment, relates to a drilling composition
  • a drilling composition comprising at least one liquid rinsing component and a compound comprising at least one ether group obtainable according to the invention, at least one ester group obtainable according to the invention, at least one amino group obtainable according to the invention or at least one urethane available according to the invention.
  • 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 % By weight, based in each case on the flushing component.
  • a further embodiment of the present invention relates to a 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 one ester group, or else at least two thereof are prepared by a process according to the invention and are brought into contact with at least one liquid rinsing component.
  • Liquid flushing systems for drilling rock drilled holes while applying the detached drill cuttings are known to be limited to thickened, flowable systems which can be assigned to one of the following three classes: Purely aqueous drilling fluids, oil drilling fluids commonly used as invert emulsion slurries, and water based O / W emulsions containing a heterogeneous finely dispersed oil phase in the closed aqueous phase.
  • 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.
  • Drilling fluids based on water-based O / W emulsion systems occupy an intermediate position in their performance properties between the purely aqueous systems and the oil-based invert fluids.
  • Detailed factual information can be found here in the relevant specialist literature, reference is made, for example, to the specialist book George R. Gray and HCH Darley, "Composition in Properties of Oil Well Drilling Fluids", 4th edition, 1980/81, Guild Publishing Company , Houston and the extensive technical and patent literature cited therein, and the handbook "Applied Drilling Engineering", Adam T. Bourgoyne, Jr. et al., First Printing Society of Petroleum Engineers, Richardson, Texas (USA).
  • the use of the hydrogenation processes obtained in the first step of the process according to the invention and / or the 1,2-propanediol obtained after passing through both steps of the process according to the invention also contributes to the solution of the abovementioned processes as a refrigerant, for producing a compound comprising at least one Ester function, preferably for Preparation of a polyester or of an alkyd resin, for producing a compound comprising at least one ether function, preferably for producing a polyether, as heat transfer medium, as hydraulic fluid or as component for a hydraulic fluid, for lowering the freezing point of aqueous phases, as solvent or plasticizer Coloring agents, in particular in printing inks, as a solvent or as an excipient in preferably liquid detergents, as an additive in feeds, as humectants in food and tobacco products, as a formulation component in cosmetic products, as an additive or base or both in pumping agents or lubricants or both, especially in the Exploration of oil deposits, or as a formulation component of corrosion inhibitors.
  • the use of the compound obtained by the erfmdungswashe method for producing a compound containing at least one ester function containing at least one ester function contributes to solve the problems mentioned above.
  • the present invention relates to a process for the preparation of a compound comprising at least one ether group, at least one ester group, at least one amino group or at least one urethane group or at least two thereof, including the process steps,
  • the present invention relates to a process for preparing a compound comprising at least one ether group, at least one ester group, at least one amino group or at least one urethane group or at least two thereof, comprising the process steps al) and bl), wherein the method comprises the further step of contacting the 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 one ester group, with at least one plastic to form a Kunsstoffzusammena.
  • the present invention relates to a process for preparing a compound comprising at least one ether group, at least one ester group, at least one amino group or at least one urethane group or at least two thereof, comprising the process steps al) and bl), wherein the method comprises the further step of contacting the 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 one ester group with at least one liquid rinse component to form a drilling composition.
  • the invention also relates to an emulsion obtainable by the process described above, a cosmetic composition obtainable by the process described above, a Kunsstoffzusammen arrangement available by the method described above and a drilling composition obtainable by the method described above.
  • the present invention also relates to a process for the preparation of a composition comprising the process steps:
  • B1 contacting the 1,2-propanediol with the at least one component selected from the group consisting of a mineral oil component, a skin and / or hair care agent, a nutrient, a pigment, a dye or a surfactant.
  • the composition is a hydraulic fluid containing at least one mineral oil component and 1,2-propanediol, wherein in process step B2) the 1,2-propanediol is brought into contact with at least one mineral oil component.
  • the composition is a cosmetic product comprising at least one skin and / or hair care product and 1,2-propanediol, wherein in process step B2) the 1,2-propanediol with at least one skin and / or hair care product is brought into contact.
  • the composition is a feed comprising at least one nutrient and 1,2-propanediol, wherein in process step B2) the 1,2-propanediol is brought into contact with at least one nutrient.
  • the composition is a pigment or dye and 1,2-propanediol, and in process step B2) the 1,2-propanediol is brought into contact with at least one pigment or dye.
  • the composition is a detergent comprising at least one surfactant and 1,2-propanediol, wherein in process step B2) the 1,2-propanediol is brought into contact with at least one surfactant.
  • the invention also relates to the composition obtainable by the methods described above.
  • the hydrogenation effluent was 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. By-products could only be observed as small impurities in the GC.
  • the hydrogenation effluent had a faint odor and was almost clear.
  • the hydrogenation effluent was distilled in the laboratory: fractionation with attached 20 cm Vigreux column, distillation at atmospheric pressure, amount used: 1000 g.
  • fraction IV 505.4g colorless, clear liquid. This fraction is the target product.
  • Example 1 was repeated but glycerol was hydrogenated almost completely (and not partially as in Example 1). This was done by raising the temperature to 230 0 C and reducing the throughput to 441 g / h. To monitor the degree of conversion of glycerol, the hydrogenation sequence was analyzed, but not completely, but only with respect to 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 effluent had an extremely strong odor and was cloudy. Several small peaks could be detected in the GC, but these could not be qualified.
  • Example 1 was repeated except that the glycerol used in a ratio of 4: 1 was mixed with the hydrogenation procedure obtained in Example 1 (4 parts by weight of pure glycerol and 1 part by weight of the hydrogenation procedure from Example 1).
  • the hydrogenation sequence was analyzed, but not completely, but only with respect to 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 and was almost clear.
  • the hydrogenation effluent was distilled in the laboratory: fractionation with attached 20 cm Vigreux column, distillation at atmospheric pressure, amount used: 1000 g.
  • fraction IV (630.7 g colorless, clear liquid, odorless) is the decisive fraction. This is the target product product. In this fraction could be identified by gas chromatography no further by-products.
  • 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 0 C, using a copper silicate (Cu-SiO 2 / Kata Leuna) and choice of a throughput of 441 g / h.
  • a copper silicate Cu-SiO 2 / Kata Leuna
  • the hydrogenation effluent (yellow, floating droplets, very unpleasant odor) was distilled: fractionation with attached column as in Table 1, distillation at atmospheric pressure, amount used: 1000 g.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de fabrication du propane-1,2-diol avec une pureté d'au moins 98%, suivant lequel dans une première étape, on hydrogène en continu du glycérol en présence d'un catalyseur contenant du cuivre, hétérogène, en particulier un catalyseur contenant du cuivre et du chrome, hétérogène, le glycérol étant converti à au plus 95%, et le mélange réactionnel obtenu dans la première étape étant soumis à une distillation dans deuxième étape. L'invention concerne également un procédé de fabrication d'un composé contenant au moins un groupe éther, au moins un groupe ester, au moins un groupe amino ou au moins un groupe uréthane ou au moins deux parmi ceux-ci, le composé pouvant être obtenu par ce procédé comportant au moins un groupe éther, au moins un groupe ester, au moins un groupe amino ou au moins un groupe uréthane ou au moins deux parmi ceux-ci, un procédé de fabrication d'une composition, la composition pouvant être obtenue par ce procédé, l'utilisation d'un écoulement de sortie d'hydrogénation ainsi que l'utilisation d'un composé.
PCT/EP2007/058577 2006-08-17 2007-08-17 Procédé de fabrication du propane-1,2-diol WO2008020077A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP07802687A EP2061741A1 (fr) 2006-08-17 2007-08-17 Procédé de fabrication du propane-1,2-diol

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP06017124 2006-08-17
EP06017124A EP1889825A1 (fr) 2006-08-17 2006-08-17 Procédé pour la synthèse du 1,2-propanediol
DE102007027374A DE102007027374A1 (de) 2007-06-11 2007-06-11 Verfahren zur Herstellung von 1,2-Propandiol
DE102007027374.8 2007-06-11

Publications (1)

Publication Number Publication Date
WO2008020077A1 true WO2008020077A1 (fr) 2008-02-21

Family

ID=38645790

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2007/058577 WO2008020077A1 (fr) 2006-08-17 2007-08-17 Procédé de fabrication du propane-1,2-diol

Country Status (2)

Country Link
EP (1) EP2061741A1 (fr)
WO (1) WO2008020077A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2038243A1 (fr) * 2006-10-27 2009-03-25 Archer-Daniels-Midland Company Procédés d'isolement ou de purification de propylène glycol et d'éthylène glycol, et produits dérivés de ces derniers
WO2009145691A1 (fr) * 2008-05-30 2009-12-03 Perstorp Specialty Chemicals Ab Production de 1,2-propanediol
WO2010084118A1 (fr) * 2009-01-21 2010-07-29 Basf Se Procédé de production de 1,2-propanediol désodorisé

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE524101C (de) * 1926-01-13 1931-05-11 I G Farbenindustrie Akt Ges Verfahren zur UEberfuehrung von hoeherwertigen Alkoholen in niedrigerwertige
EP0523015A2 (fr) * 1991-07-10 1993-01-13 NOVAMONT S.p.A. Méthode d'hydrogénation du glycérol
DE4302464A1 (de) * 1993-01-29 1994-08-04 Henkel Kgaa Herstellung von 1,2-Propandiol aus Glycerin
US5616817A (en) * 1994-11-26 1997-04-01 Basf Aktiengesellschaft Preparation of 1,2-propanediol
WO2005095536A2 (fr) * 2004-03-25 2005-10-13 Suppes Galen J Procede de production d'alcools inferieurs a partir de glycerol

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE524101C (de) * 1926-01-13 1931-05-11 I G Farbenindustrie Akt Ges Verfahren zur UEberfuehrung von hoeherwertigen Alkoholen in niedrigerwertige
EP0523015A2 (fr) * 1991-07-10 1993-01-13 NOVAMONT S.p.A. Méthode d'hydrogénation du glycérol
DE4302464A1 (de) * 1993-01-29 1994-08-04 Henkel Kgaa Herstellung von 1,2-Propandiol aus Glycerin
US5616817A (en) * 1994-11-26 1997-04-01 Basf Aktiengesellschaft Preparation of 1,2-propanediol
WO2005095536A2 (fr) * 2004-03-25 2005-10-13 Suppes Galen J Procede de production d'alcools inferieurs a partir de glycerol

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DASARI M A ET AL: "Low-pressure hydrogenolysis of glycerol to propylene glycol", APPLIED CATALYSIS A: GENERAL, ELSEVIER SCIENCE, AMSTERDAM, NL, vol. 281, no. 1-2, 18 March 2005 (2005-03-18), pages 225 - 231, XP004771366, ISSN: 0926-860X *
DOW CHEMICAL: "Propylene glycols", 3 May 2006 (2006-05-03), XP002457845, Retrieved from the Internet <URL:http://web.archive.org/web/20060503054658/http://www.dow.com/propyleneglycol/prod/pguspep.htm> [retrieved on 20071107] *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2038243A1 (fr) * 2006-10-27 2009-03-25 Archer-Daniels-Midland Company Procédés d'isolement ou de purification de propylène glycol et d'éthylène glycol, et produits dérivés de ces derniers
WO2009145691A1 (fr) * 2008-05-30 2009-12-03 Perstorp Specialty Chemicals Ab Production de 1,2-propanediol
WO2010084118A1 (fr) * 2009-01-21 2010-07-29 Basf Se Procédé de production de 1,2-propanediol désodorisé
CN102325744A (zh) * 2009-01-21 2012-01-18 巴斯夫欧洲公司 生产祛臭的1,2-丙二醇的方法
CN102325744B (zh) * 2009-01-21 2014-06-18 巴斯夫欧洲公司 生产祛臭的1,2-丙二醇的方法
US8809596B2 (en) 2009-01-21 2014-08-19 Basf Se Method for producing deodorized 1,2-propanediol
US9145347B2 (en) 2009-01-21 2015-09-29 Basf Se Process for preparing deodorized 1,2-propanediol

Also Published As

Publication number Publication date
EP2061741A1 (fr) 2009-05-27

Similar Documents

Publication Publication Date Title
WO2008151785A1 (fr) Procédé de production d&#39;un composé renfermant au moins un groupe ester
EP3492446B1 (fr) Procédé d&#39;obtention d&#39;alcools à partir d&#39;aldéhydes
EP3492445A1 (fr) Procédé d&#39;obtention d&#39;alcools à partir d&#39;aldéhydes
EP2188236B1 (fr) Procede continu en une etape pour l&#39;hydroformylation d&#39;olefines ou de melanges olefiniques superieurs
EP3492447A1 (fr) Procédé d&#39;obtention d&#39;alcools à partir d&#39;aldéhydes
WO2008049470A1 (fr) Procédé de fabrication de 1,2-propanediol par hydrogénolyse de glycérine
EP3170828A1 (fr) Procede de preparation de composes a squelette de 16-oxabicycloo[10.3.1]pentadecen et leurs produits secondaires
WO2010000382A2 (fr) Procédé de préparation de néopentylglycol
DE60214168T2 (de) Verfahren zur herstellung einer in hohem grade linearen alkoholzusammensetzung
WO2008151784A1 (fr) Procédé d&#39;hydrogénation de glycérine
WO2009080395A1 (fr) Procédé continu en plusieurs étapes pour l&#39;hydroformylation d&#39;oléfines ou de mélanges oléfiniques supérieurs
DE102008013474B4 (de) Katalytisches Verfahren zur Gewinnung von chemischen Grundstoffen aus nachwachsenden Rohstoffen
EP2358851B1 (fr) Utilisation de l&#39;acide méthanesulfonique pour la fabrication d&#39;esters d&#39;acide gras
EP2111386A1 (fr) Procédé pour la préparation de 1,2-propanediol par hydrogénolyse de glycérine
WO2008020077A1 (fr) Procédé de fabrication du propane-1,2-diol
EP1318970B1 (fr) Procede pour preparer des alcools de guerbet
WO2012116775A2 (fr) PROCÉDÉ POUR LA MISE EN OEUVRE DE RÉACTIONS DE CONDENSATION D&#39;ALDOLS MULTIPHASIQUES EN ALDÉHYDES α,β-INSATURÉS
DE4203077C2 (de) Verfahren zur Herstellung hydroxylierter Fettsäureverbindungen
EP2448892B1 (fr) Procédé de production de n-butane peu odorant
EP2373601B1 (fr) Procédé de préparation de 1,6-hexanediol
DE102007027374A1 (de) Verfahren zur Herstellung von 1,2-Propandiol
EP1294667A1 (fr) Procede de production d&#39;aldehydes
DE69608105T2 (de) Verfahren zur herstellung von einem alkohol
EP1889825A1 (fr) Procédé pour la synthèse du 1,2-propanediol
EP0538686B1 (fr) Procédé de préparation de 2,2-bis-hydroxyméthyl-butanédiol-(1,4)

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07802687

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2007802687

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: RU