EP2176204A1 - Procede d'hydrogenation de glycerine - Google Patents

Procede d'hydrogenation de glycerine

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Publication number
EP2176204A1
EP2176204A1 EP08784510A EP08784510A EP2176204A1 EP 2176204 A1 EP2176204 A1 EP 2176204A1 EP 08784510 A EP08784510 A EP 08784510A EP 08784510 A EP08784510 A EP 08784510A EP 2176204 A1 EP2176204 A1 EP 2176204A1
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EP
European Patent Office
Prior art keywords
reactor
propanediol
phase
hydrogen
reactors
Prior art date
Legal status (The legal status 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 status listed.)
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Application number
EP08784510A
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German (de)
English (en)
Inventor
Norbert Klein
Alfred Westfechtel
Martin BÄHR
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Emery Oleochemicals GmbH
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Emery Oleochemicals GmbH
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Application filed by Emery Oleochemicals GmbH filed Critical Emery Oleochemicals GmbH
Publication of EP2176204A1 publication Critical patent/EP2176204A1/fr
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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C269/02—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from isocyanates with formation of carbamate groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group

Definitions

  • the present invention relates to a process for producing 1,2-propanediol by hydrogenating glycerol by means of hydrogen gas, the 1,2-propanediol obtainable by this process, an apparatus for producing 1,2-propanediol, and a process for producing a compound at least one ether group, at least one ester group, at least one amino group, at least one urethane group, or at least two thereof.
  • 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, antifreeze agents, lubricants in refrigerators, as a solvent for fats , 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.
  • the hydrogenation of glycerol is also considered as a possible method for the preparation of 1,2-propanediol, although this method has not yet been able to prevail in industrial practice.
  • BESTATIGUNGSKOPIE reactors In the examples of this publication, a single, two-meter long reaction tube with the inner diameter of 25 mm is used, which is filled with copper chromite tablets. Through this reaction tube, a mixture of hydrogen gas and a glycerol phase at a pressure in a range of 50 to 250 bar and a temperature in a range of 180 to 27O 0 C out.
  • tube bundle reactors for the hydrogenation of organic compounds, such as fats, fatty acids or fatty acid methyl esters, is also known from the prior art.
  • the disadvantage of using such tube bundle reactors is that due to the relatively small cross section of the reaction tubes arranged in such a tube bundle reactor, the total catalyst volume is comparatively small. Due to the small catalyst volume of the catalyst is therefore consumed quickly, so that when using such tube bundle reactors for the hydrogenation of organic compounds, the catalyst bed must be regenerated in relatively short time intervals.
  • the object of the present invention was to overcome, or at least reduce, the disadvantages resulting from the prior art in the production of 1,2-propanediol by hydrogenation of glycerol.
  • the present invention was the object of a new process for the preparation of 1,2-propanediol by hydrogenation of glycerol in which fewer by-products are formed compared to the processes known in the art.
  • this method should have the advantage that it can be operated economically as long as possible before the device used in this process for the preparation of 1,2-propanediol for the purpose of regeneration of the catalyst must be shut down.
  • a contribution to solving the above-mentioned objects is made by a process for the preparation of 1, 2-propanediol by hydrogenation of glycerol by means of hydrogen gas, wherein the glycerol with hydrogen in at least i fluidly connected with each other, each having a hydrogenation reactor reactors Ri to R, to 1, 2-propanediol is reacted, wherein
  • n is an integer from the range of 2 to i, which formed in the above-arranged reactor R n - I , preferably liquid 1,2-propanediol-containing phase P nI and hydrogen introduced and a preferably liquid 1,2-propanediol-containing phase P n and a preferably gaseous hydrogen phase H n are formed in the reactor R n ,
  • glycerol phase P G iycenn at least 60 wt .-%, more preferably at least 80 wt .-%, still more preferably .-%, and most preferably at least 90 at least 97 wt .-%, based on the total weight of glycerol Phase P G i ycenn , glycerin. It is particularly preferred that each 1,2-propanediol-containing phase P n
  • glycerol-rich starting compositions can be hydrogenated particularly selectively in a cascade reactor, when the product mixtures leaving the reactors are cooled before they enter the subsequently arranged reactor and / or within the individual reactors , If tubular reactors are used as reactors, moreover, the process according to the invention can be operated for a very long time before the catalyst used in the reactors for the hydrogenation of the glycerol has to be regenerated.
  • a glycerol phase P d ycenn is introduced into the first reactor Ri, wherein the glycerol phase P d ycerin at least 60 wt .-%, more preferably at least 80 wt .-%, even more preferably at least 90 Wt .-%, and most preferably at least 97 wt .-%, based on the total weight of the glycerol phase P G iy c en ⁇ , glycerol.
  • the glycerol phase P dycenn may also contain further components, such as glycerol-based fatty acid esters, which are split in the hydrogenation to form fatty acids and glycerol, in which case fatty alcohols are formed in addition to 1,2-propanediol ,
  • the glycerol phase PGiyce ⁇ n less than 50 wt .-%, more preferably less than 25 wt .-%, even more preferably less than 10 wt .-%, more preferably less as 5% by weight, based in each case on the total weight of the glycerol phase P d yce-Hn, and most preferably does not include any glycerol-based fatty acid ester at all.
  • the entering the reactor Ri glycerol phase P G iy ce nn a temperature in a range from 140 to 260 0 C, particularly preferably in a range of 160 to 240 ° C and most preferably in a Range of 180 to 220 0 C.
  • solid and carrier contacts come into question, which contain metals, metal salts or metal oxides or the like of the I. and VIII. Subgroup as the main component. Other metals may be added as dopants to improve the properties.
  • a heterogeneous catalyst particularly preferably a copper-containing catalyst, and moreover preferably a heterogeneous catalyst comprising copper and chromium.
  • Such catalysts can be prepared in different ways. In particular, precipitation of the metal salts, in particular the copper salts, impregnation, ion exchange or solid-state reactions are considered, to name only a few examples.
  • Catalysts particularly preferably used according to the invention are in particular catalysts which comprise Cu chromite, Cu zinc oxide, Cu aluminum oxide or Cu silicon dioxide, whereby Cu chromite-containing catalysts are most preferred.
  • the Cu-chromite catalyst preferably used in this context contains 35 to 55 wt .-%, preferably 40 to 50 wt .-% copper, 35 to 55 wt .-%, preferably 40 to 50 wt .-% chromium, based in each case to the oxidic catalyst mass, and optionally other alkaline earth or transition metals, in particular barium and manganese, in the form of their oxides. It is advantageous if the catalyst contains 1 to 7 wt .-%, in particular 1.5 to 3 wt .-% barium, based on the oxidic catalyst composition.
  • a catalyst which contains about 47 wt .-% CuO, 46 wt .-% Cr 2 O 3 , 4 wt .-% MnO 2 and 2 wt .-% BaO.
  • This catalyst and its method of preparation is described in detail in EP 254 189 A2.
  • the disclosure contained therein is hereby expressly referred to, and the information given there should also be part of the present application.
  • the invention is not limited to Cu-chromite catalysts.
  • Other catalysts, such as Cu / ZnO catalysts or Cu / Al 2 ⁇ 3 catalysts can be used.
  • Suitable catalysts for the process according to the invention can be obtained commercially via the companies Südchemie AG, Germany, and Engelhard Inc., USA.
  • the catalyst has a high surface area and porosity, so that a high activity and selectivity as well as a particularly long service life, which is particularly important for technical applications, are 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.
  • reactors R 1 to R j it is possible to use all reactors known to the person skilled in the art, which are designed to permit hydrogenation of glycerol by means of hydrogen gas under the pressure and temperature conditions required for this purpose, the use of tubular reactors being the most preferred. It is also conceivable to use reactors which have thermoplates as components. Both in the tube 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. It is preferred in this context if at least one of the reactors R 1 to Rj, preferably all reactors Ri to Rj, have a catalyst bed.
  • the hydrogenation is carried out in at least one of the reactors Ri to Ri, preferably in all reactors Ri to R 1 , so that the entering into the respective reactor R n phase (the glycerol phase P d ycenn for the reactor Ri or the 1,2-propanediol-containing phases P n - I in the reactors R 2 to R 1 ) in the form of liquid fluids in trickle bed in cocurrent or countercurrent with hydrogen
  • the glycerol phase entering the reactor Ri P d y ce nn and the entering into the reactors R 2 to R, 1, 2-propanediol-containing phase P n- I, where n is an integer from the range of 2 to 1, is passed back-mixing arm through the catalyst charge with a defined residence time
  • the reaction tubes are used as reactors R 1 to R 4
  • backmixing at least partially preventing measures are basically all known to those skilled and suitable for this seem appropriate measures, such as suitable pipe cross-sections or Rohrqueritess- length ratios into consideration, which are usually selected depending on the prevailing during operation of the reactor flow conditions.
  • the amount of injected gas can be regulated via the feed points or lances by means of suitable regulating means, preferably by means of a valve.
  • suitable regulating means eg constant-cycle gas pump
  • the distribution of hot gas / cold gas can be adjusted by means of valves of the respective catalyst activity and exotherm.
  • the distribution of the amount of gas fed in particular by other or further measures, such as the choice of a suitable diameter of the holes inside the reactor, through which the hydrogen gas enters be regulated.
  • the reactor Ri fed-in hydrogen gas at a temperature in a range of 140 to 26O 0 C, more preferably in a range from 160 to 240 0 C and most preferably in a range of 180 to 220 0 C.
  • a separate feed of the glycerol phase PGiyce ⁇ n and the hydrogen gas is conceivable in principle, wherein, for example, the glycerol phase is fed from above and the hydrogen gas from below, from the outside via lances or from the inside via multiple feed directly into the catalyst bed.
  • fresh hydrogen can be used as hydrogen gas in the first reactor, but preference is given to using a so-called "cycle gas.”
  • This "cycle gas” is understood as meaning hydrogen from one of the subsequently arranged reactors R 1 to R 1 , preferably from the last Reactor R 1 , as hydrogen phase H, leaked.
  • This hydrogen can, after cooling and subsequent separation of the 1,2-propanediol-containing phase P 1 , for example, after mixing with fresh hydrogen, which compensates the reaction and loss amounts, and the passage of a recycle gas pump, which compensates the pressure losses, again as hydrogen used in the first reactor.
  • a molar ratio of hydrogen to glycerol in the range of 2 to 500, more preferably 10 to 350 is set. This means that the flow rate of hydrogen gas through the first reactor, measured in moles of H 2 / hour, is 2 to 500 times higher than the flow rate of glycerol through the first reactor, measured in moles of glycerol / hour.
  • a most preferred range of the conversion ratio is 30: 1 to 200: 1.
  • the pressure in at least one of the reactors R 1 to R 1 is preferably in the range from 20 to 300 bar, in particular at 100 to 280 bar, while the temperature in at least one of the reactors.
  • Ri to Ri preferably in all reactors Ri to Ri, preferably in the range of 150 0 C to 280 0 C, in particular 200 to 250 0 C.
  • the glycerol in the first reactor Ri is preferably reacted to 40 to 80 mol%, more preferably to 45 to 65 mol%, even more preferably to about 50 mol%.
  • a preferably liquid 1,2-propanediol-containing phase Pi is formed, preferably in its composition unchanged, is introduced into the subsequent reactor R 2 . It is in principle possible and also preferred according to the invention to introduce the 1,2-propanediol-containing phase Pi together with the preferably gaseous hydrogen phase Hi into the subsequent reactor R 2 . However, it is also conceivable first to separate off the preferably liquid 1,2-propanediol-containing phase P] from the hydrogen phase Hi, this separation preferably taking place in separation devices known to the person skilled in the art, such as a separator.
  • Suitable separating devices for this purpose are described, for example, in Chapter 4.2.1 in "Basic Operations in Chemical Process Engineering", Wilhelm RA Vauck and Hermann A. Müller, Wiley-VCH Verlag, Eleventh Edition Separating the liquid 1,2-propanediol-containing phase from the hydrogen phase Hi, the preferably liquid 1,2-propanediol-containing phase Pj can then be introduced into the subsequent reactor.
  • the hydrogen required for hydrogenation is introduced into the subsequent reactor R 2 .
  • the hydrogen phase Hi exiting from the above reactor Ri which may have been previously separated from the 1,2-propanediol-containing phase Pi.
  • the use of fresh, preferably cold hydrogen, ie hydrogen gas which has not previously passed the reactor Ri, or the use of a mixture of the hydrogen phase Hi and fresh hydrogen gas.
  • the hydrogen gas can be introduced into the reactor R 2 together with the 1,2-propanediol-containing phase Pi or else separately from the 1,2-propanediol-containing phase Pi, with the joint or separate introduction of the 1,2-propanediol -containing phase Pi and the hydrogen gas in the subsequent reactor R 2 can in principle be carried out in the same manner in which the glycerol phase P d ycerin and the hydrogen gas are introduced into the first reactor Ri.
  • the 1,2-propanediol-containing phase Pi and the hydrogen gas are introduced together in a vertical arrangement of the reactor R 2 from above into the reactor.
  • a preferably liquid 1,2-propanediol-containing phase P 2 and a preferably gaseous hydrogen phase H 2 are obtained, which if appropriate (for i> 2) are introduced jointly or separately into a further reactor R 3
  • the separation may in turn preferably be effected by means of the above-mentioned separation devices (conceivable, as already explained in connection with the reactor R 3 , also the introduction of fresh hydrogen gas or a mixture of fresh hydrogen gas and the hydrogen phase H 2 in FIG the reactor R 3 ).
  • the glycerol in the second reactor R 2 is preferably 20 to 60 mol%, preferably 30 to 50 mol%, most preferably preferably 35-40 mol%, in each case based on the total amount of glycerol used in the reactor Rl, is reacted.
  • at least five, at least six, at least seven, at least eight, at least nine or at least ten successively arranged reactors are used in the inventive method (i> 5, i> 6, i> 7, i> 8, i > 9 or i> 10). It is therefore preferred according to the invention for i to be an integer from the range from 2 to 10, particularly preferably from the range from 2 to 5.
  • each 1,2-propanediol-containing phase P n i) within each reactor R n , ii) is cooled.
  • the cooling is preferably carried out
  • the introduction of hydrogen gas according to alternative I) is preferably carried out such that the hydrogen gas is introduced through lances or tubes, which are arranged parallel to the longitudinal axis in the interior of the tube reactor according to the invention preferred and have spaced holes, and passes through these holes in the catalyst bed. It is particularly preferred that the holes are in the lower two-thirds of the reactor, more preferably in the lower half of the vertically arranged reactor (provided that the feed of the hydrogen used for the reduction (cycle gas or fresh hydrogen) and glycerol done from above ). Furthermore, it is preferred in this context that the diameter of the holes in the lance or in the tube is greater, the deeper the point at which the bore is located projects into the fixed catalyst bed.
  • the temperature of for cooling the 1,2-propanediol-containing phase inside the reactor R n introduced hydrogen quench gas is preferably in a range from 40 to 100 0 C, particularly preferably in a range of 60 to 80 0 C.
  • the cooling of the 1,2-propanediol-containing phase P n inside the reactor R n by means of a cooling device according to alternative II) is carried out, they will be inside the reactor cooling coils flowed through by cooling liquids mobleche thermo- and the like are mounted, by means of which a cooling of the 1,2-propanediol-containing phase inside the reactor can take place.
  • the cooling devices in the lower two-thirds of the reactor, particularly preferably provided in the lower half of the vertically arranged reactor (provided that the feed of the hydrogen used for the reduction (circulating gas or fresh hydrogen) and the glycerol done from above).
  • the cooling region K n Ai + 1 can comprise all devices known to the person skilled in the art by means of which liquid or gaseous fluids or mixtures of liquid and gaseous fluids can be cooled.
  • heat exchangers such as serpentine heat exchangers, double tube heat exchangers, tube bundle heat exchangers, fin heat exchangers, fin tube heat exchangers or plate heat exchangers.
  • Such heat exchangers are described in Chapter 8.1.5 in "Basic Operations in Chemical Process Engineering", Wilhelm RA Vauck and Hermann A. Müller, Wiley-VCH-Verlag, Eleventh Edition. [.
  • this cooling region K n / n + i cooling of the reactor R n exiting 1,2-propanediol-containing phase P n and / or, preferably and, the R n from the reactor leaving hydrogen-phase H n , if it is introduced into the subsequent reactor R n + i, before its entry into the reactor R n + I by 10 to 70 ° C, more preferably by 20 to 60 0 C, even more preferably by 30 to 50 ° C causes ,
  • the cooling of the 1,2-propanediol-containing phases, the hydrogen phases or the mixtures of these phases by means of the cooling regions K nM + I can in principle be such that the respective liquid 1, 2-propanediol-containing phase P n together with the gaseous hydrogen phase H n emerging from the same reactor in the cooling zone K n / n + i, however, it is also conceivable that the liquid 1,2-propanediol-containing phase P n is first of all, as described above, by means of a separator from the gaseous hydrogen phase H n to separate and then the liquid 1,2-propanediol-containing phase, the gaseous hydrogen phase or both phases separately from each other in a common cooling area or in separate cooling areas of the cooling to undergo.
  • the common cooling of the 1,2-propanediol-containing phase P n and the hydrogen phase Hn in the cooling region Kn / n + i is preferred. Furthermore, it may be advantageous according to the invention if from at least one of the 1,2-propanediol-containing phases P n , where n is an integer from the range of 2 to i-1, preferably from the 1,2-propanediol-containing phase P 1 , 1,2-propanediol is purified.
  • the 1,2-propanediol may then optionally be further purified from the resulting 1,2-propanediol-containing phase, this purification being particularly preferred by purification methods known to those skilled in the art, for example by simple distillation, by rectification, by crystallization or by extraction however, by simple distillation or by rectification.
  • the invention may be advantageous according to the invention to use different reactors for the reactors R 1 to R 1, in particular with regard to their reactor volume, wherein it is particularly preferred to choose a cascade arrangement in which the volume of the reactor R 2 to R 1 , in particular the average volume of the reactors R 2 to R 1 , by at least 30%, preferably by at least 50%, more preferably by at least 100% and most preferably by at least 150% greater than the volume of the first reactor Ri Compared to the reactors arranged below smaller volumes of the reactor Ri can be taken into account in particular the fact that the highest exothermic energy is expected in this reactor in the implementation of the glycerol phase P ⁇ yc e nn used there with hydrogen per unit volume.
  • the emerging from the reactor R preferably liquid 1, 2-propanediol-containing phase P 1 , after separating the hydrogen phase H 1 , contains a glycerine rin pollution in a range of 0.01 to 20 wt .-%, or from 0.1 to 15 wt .-%, or from 1 to 10 wt .-%, each based on the total amount of the phase P 1 .
  • a contribution to the solution of the problem mentioned at the outset is also provided by a 1,2-propanediol-containing phase P; or purified 1,2-propanediol, which is obtainable by the method according to the invention described above.
  • an apparatus for the production of 1,2-propanediol comprising at least one reactors Ri to Rj which are in fluid-conducting connection with one another and have a hydrogenation catalyst, which is preferably a tubular reactor.
  • Propandiol-containing phase P n is optionally cooled together with hydrogen before entering the reactor R n + I , and in at least one reactor R n, a cooling device is provided.
  • fluid-conducting means that the reactors Ri to Ri are fluidically interconnected so that both liquids as Also, gases from a reactor, optionally through the associated with this reactor cooling area, can be passed into the subsequently arranged reactor.
  • Preferred reactors, hydrogenation catalysts and cooling regions are those reactors, hydrogenation catalysts and cooling regions which have already been mentioned in the introduction in connection with the process according to the invention for preparing 1,2-propanediol as preferred reactors, hydrogenation catalysts or cooling regions.
  • at least one of the reactors R 1 to R 1 comprises a heterogeneous catalyst comprising copper or chromium, in particular a heterogeneous copper chromite catalyst.
  • cooling device which may be provided in the interior of the reactor according to variants b) and c), on the one hand, those cooling devices come into consideration, which have already been described above in connection with the variant II) of the method according to the invention as a suitable cooling device.
  • Conceivable and inventively particularly preferred as a cooling device is also the pipe already described at the outset in connection with the process according to the invention, which has bores and via which hydrogen can be introduced as quench gas directly into the catalyst bed in the interior of the reactor. It is also conceivable, however, to supply quench gas from below or through lances entering the reactor laterally, which can be individually controlled with respect to the amount of hydrogen by means of external valves.
  • this further comprises a fluid splitter with at least one of the reactors Ri to R 1 , preferably connected to the reactor Ri Fettpalter so that the obtained in the fat splitter, glycerol-containing reaction phase, optionally after previous cooling and / or purification, as the glycerol phase PGiyc e ⁇ n in min. at least one of the reactors Ri to R 1 , preferably in the reactor Ri can be introduced.
  • a contribution to achieving the abovementioned objects is also made by a process for the preparation of 1,2-propanediol by hydrogenation of glycerol by means of hydrogen gas, in which the device described above is used.
  • a further contribution to achieving the abovementioned objects is afforded by a process for preparing a compound having at least one ether group, at least one ester group, at least one amino group, at least one urethane group, or at least two thereof, preferably having at least one Ester group, including the process steps:
  • the i) - 1, 2-propanediol-containing phase P 1 prepared in process step i) and containing the process according to the invention contains a glycerol impurity in a range from 0.01 to 20% by weight. , or from 0.1 to 15 wt .-%, or from 1 to 10 wt .-%, each based on the total amount of the phase P 1 , and in step ii) used ii) -l, 2-propanediol-containing Phase P 1 at least 70 up to 100% by weight of the glycerol impurity of the i) -l, 2-propanediol-containing phase P 1 provided in process step i).
  • the i) -l, 2-propanediol-containing phase P 1 obtained in process step i) can be used essentially without intermediate treatment or purification steps in process step ii) as ii) -l, 2-propanediol-containing phase P 1 .
  • the ratio of glycerol to 1,2-propanediol in the 1,2-propylene glycol prepared in process step i) is Propandiol-containing phase Pj in a range from 1: 3 to 1:99, preferably from 1: 3 to 1:50, or from 1: 2.5 to 1: 8.
  • a compound having at least one active hydrogen atom is preferably understood as meaning a compound which has at least one hydrogen atom which is bonded to an atom other than carbon, preferably to an oxygen atom, a nitrogen atom or a sulfur atom, particularly preferably to an oxygen atom or a nitrogen atom and most preferably attached to an oxygen atom.
  • These compounds having at least one active oxygen atom therefore preferably have an OH group, a COOH group, an NH 2 group, an NRH group (wherein R is a further organic radical such as an alkyl or alkenyl group) or a SH group on.
  • the compound having at least one active hydrogen atom is a compound having at least one hydroxyl group
  • a compound having at least one ether group after reaction of this compound with the 1,2-propanediol-containing phase Pi or the purified 1,2-propanediol a compound having at least one ether group.
  • a polyether compound can be obtained.
  • the compound having at least one active hydrogen atom is a compound having at least one carboxylic acid group
  • reaction of this compound with the 1,2-propanediol-containing phase P; or with the purified 1,2-propanediol having a compound having at least one ester group.
  • an ester polyether compound can also be obtained.
  • the compound having at least one active hydrogen atom is a compound having at least one amino group
  • the compound having at least one active hydrogen atom is a compound having at least one amino group
  • the purified 1,2 Propanediol having a compound having at least one amino group and at least one hydroxyl group are reacted with the 1,2-propanediol contained in the 1,2-propanediol-containing phase P 1 or with the purified 1,2-propanediol.
  • a Amino polyether compound can be obtained.
  • 1,2-propanediol-containing phase P 1 or with the purified 1,2-propanediol also ether or polyether can be obtained.
  • Compound having at least one isocyanate group used can be obtained by reacting this compound with the 1,2-propanediol-containing phase P 1 or with the purified 1, 2-propanediol urethanes or polyurethanes.
  • 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.
  • 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 a C 5 - to C30 monocarboxylic acid, moreover preferably a C 10 - to C 2 s monocarboxylic acid and most preferably a C 15 - to C 2 o monocarboxylic acid, wherein it is in the abovementioned monocarboxylic acids to 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, 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 neuronic acid, or poly
  • the fatty acids mentioned above can be obtained, for example, from vegetable oils, hydrogenated vegetable oils, marine oils and animal fats and oils.
  • Preferred vegetable oils include corn oil, canolaol, olive oil, cottonseed oil, soybean oil, coconut oil, palm kernel oil, sunflower oil, rapeseed oil, especially high erucic rapeseed oil, partially or fully hydrogenated soybean oil, partially or fully hydrogenated canolaol, partially or fully hydrogenated sunflower oil, partially or fully hydrogenated high erucic rapeseed oil, partially or fully hydrogenated cottonseed oil, palm oil or palm stearin.
  • a dicarboxylic acid compounds selected in particular 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, of which terephthalic acid is most preferred.
  • the compound having at least one carboxylic acid group is reacted in process step ii) of the process according to the invention as acid component with 1,2-propanediol as alcohol component to give an ester.
  • 1,2-propanediol as the sole alcohol component, but additionally to use at least one further alcohol component, so that a compound having at least two different ester groups is obtained.
  • This at least one other alcohol component can be a trivalent or higher alcohol, such as diglycerol, triglycerol, polyglycerol, pentaerythritol, dipentaerythritol or sorbitol, or a tri-, di- or monohydric alcohol, such as trimethylolpropane, trimethylolethane a dihydric alcohol such as ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,4-dimethylolcyclohexane, methanol.
  • a trivalent or higher alcohol such as diglycerol, triglycerol, polyglycerol, pentaerythritol, dipentaerythritol or sorbitol
  • Ethanol, 1-propanol or 2-propanol If at least one further alcohol component is used, however, it is preferred that the proportion of this further alcohol component in the total amount of 1,2-propanediol and further alcohol component is at most 50% by weight, particularly preferably at most 25% by weight, above In addition, preferably at most 10 wt .-% and most preferably at most 5 wt .-% is.
  • esterification catalysts acids such as sulfuric acid or p-toluenesulfonic acid, or metals and their compounds are used. Suitable examples are tin, titanium, zirconium, which are used as finely divided metals or expediently in the form of their salts, oxides or soluble organic compounds.
  • the metal catalysts are unlike prototype nen yarnren high-temperature catalysts, achieving their full activity usually only at temperatures above 180 0C. However, they are preferred according to the invention because they provide less by-products, such as olefins, compared to proton catalysis.
  • Particularly preferred esterification catalysts according to the invention are one or more divalent tin compounds or tin compounds or elemental tin, which can react with the educts to form divalent tin compounds.
  • Particularly preferred tin catalysts are tin (II) oxalate and tin (II) benzoate.
  • the carrying out of the esterification reaction can be carried out by methods known to the person skilled in the art. It may be particularly advantageous to remove the water formed during the reaction from the reaction mixture, wherein this removal of the water is preferably carried out by distillation, optionally by distillation with 1,2-propanediol used in excess. Also, after carrying out the esterification reaction, unreacted 1,2-propanediol can be removed from the reaction mixture, and this removal of 1,2-propanediol preferably also takes place by means of distillation. Furthermore, after completion of the esterification reaction, in particular after the separation of unreacted 1,2-propanediol, the catalyst remaining in the reaction mixture, if appropriate after treatment with a base, can be separated off by filtration or by centrifuging.
  • esterification reaction at a temperature in a range of 50 to 300 0 C, more preferably in a range of 100 to
  • the optimum temperatures depend on the alcohol (s) used, the reaction progress, the type of catalyst and the catalyst concentration. They can easily be determined by experiment for each individual case. Higher temperatures increase the reaction rates and promote side reactions, such as dehydration from alcohols or formation of colored by-products.
  • the desired temperature or the desired temperature range can be adjusted by the pressure in the reaction vessel (slight overpressure, atmospheric pressure or optionally negative pressure).
  • Alkyd resins are synthetic, highly hydrophobic polymers obtained by condensation of diols (in the present case of 1,2-propanediol) with polybasic acids with the addition of organic oils or fatty acids (to modify the properties of the resin) and optionally other polyhydric alcohols, in particular glycerol or pentaerythritol.
  • 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 'Biphenyl-dicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, succinic acid, fumaric acid, adipic acid, azelaic acid, sebacic acid and maleic anhydride, with terephthalic acid being most preferred.
  • Tallow canola oil, rapeseed oil, sunflower oil, palm oil, optionally also in hardened or hardened form, are used as organic oil or fatty acids Execution can be present, soybean oil, thistle oil, linseed oil, tall oil, coconut oil, palm kernel oil, castor oil, dehydrated castor oil, fish oil and tung oil into consideration.
  • dry oils or semi-dry oils with iodine numbers of at least 50 are preferred, among others soybean oil, tall oil and, in particular, tallow are also advantageous.
  • Suitable fatty acids which are used both for preparing the alkyd resins and for preparing 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 , Of these fatty acids, those of drying oils or semi-drying oils having iodine numbers of at least 100, among others, 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 regard to the preparation of alkyd resins is hereby introduced as a reference and which forms part of the disclosure of the present invention.
  • a compound having at least one hydroxyl group in process step ii). It may be in the compound having at least one hydroxy group to a monool, a diol, a triol or an alcohol more than three OH groups.
  • especially preferred compounds having at least one OH group are fatty acid alcohols which have been obtained by reduction of fatty acid esters, for example with sodium, in a Bouveault-Blanc reaction.
  • Suitable fatty alcohols in this context are, for example, hexanol, octanol, decanol, dodecanol, tetradecanol, hexadecanol, heptadecanol, octadecanol, eicosanol, behenyl alcohol, delta-9-cis-hexadecenol, delta-9-octadecenol, trans-delta-9-octadecenol , cis-delta-11-octadecenol or octadecatrienol.
  • the preparation of ethers from fatty alcohols and 1,2-propanediol, in particular the production of polyethers by the polypropoxylation of fatty alcohols 1,2-propanediol is likewise preferably carried out by means of suitable catalysts, such as calcium and strontium hydroxides, alkoxides or phenoxides (EP-A-0 092 256, calcium alkoxide (EP-AO 091 146), barium hydroxide (EP-B-0 115 083) ), basic magnesium compounds, such as alkoxides (EP-A-0 082 569), magnesium and calcium fatty acid salts (EP-AO 085 167), antimony pentachloride (DE-A-26 32 953), aluminum isopropylate / sulfuric acid (EP-A No.
  • suitable catalysts such as calcium and strontium hydroxides, alkoxides or phenoxides (EP-A-0 092 256, calcium alkoxide (EP-AO 091 146), bar
  • the compound having at least one amino group may in particular be a fatty amine which can be obtained from triglycerides by treatment with ammonia and subsequent hydrogenation.
  • the propoxylation of amines with 1,2-propanediol is also described in EP-A-0 361 083, to which reference is hereby made.
  • compounds such as ethylene oxide, propylene oxide
  • a transesterification is carried out by the reaction with 1,2-propanediol, esters of the abovementioned monofatty acids preferably being used as the ester having at least one ester group.
  • diisocyanates such as, for example, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI) or mixtures of diphenylmethane diiso
  • a suitable process for preparing polyurethanes is disclosed, for example, in DE-A-IO 2004 041 299, the disclosure of which is incorporated herein by reference for the production of polyurethanes from diols and polyisocyanates and forms part of the disclosure of the present invention.
  • the 1,2-propanediol-containing phase Pj obtained in process step i), preferably the 1,2-propanediol-containing phase P 2 obtained in a process with i 2 , before the Reaction in process step ii) not, preferably at least not by thermal separation processes, such as distillation or rectification, purified.
  • the 1,2-propanediol-containing phase is thus supplied directly to the reaction with a compound of 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.
  • this separation is preferably carried out by non-thermal separation methods, that for example by filtration, sedimentation or Zentrif ⁇ igation.
  • a contribution to achieving the abovementioned objects is also achieved by a compound having at least one ether group, at least one ester group or at least one urethane group, preferably having at least one ester group which is obtainable by the process according to the invention described above, was preferably obtained.
  • FIG. 1 shows a particular embodiment of the method according to the invention or of the device according to the invention, in which two reactors with a cooling region connected between them are provided.
  • FIG. 2 shows a further, particular embodiment of the method according to the invention or the apparatus according to the invention with two tubular reactors connected in series, in which the hydrogen gas leaving the last reactor is introduced as quench gas into the reactors R 1 and R 2 and as gas for the hydrogenation is returned to the reactor Ri.
  • the Figure 1 of hydrogen gas and a glycerol phase P G are introduced iycerin via a feed line 1 to the first reactor Ri (2).
  • this reactor Ri (2) is preferably a tubular reactor containing a catalyst charge based on a Cu-chromite catalyst.
  • the glycerol phase PGiyce ⁇ n in trickle bed (trickle bed ') is passed in cocurrent or countercurrent with hydrogen through the reactor Ri.
  • the 1,2-propanediol-containing phase Pi is cooled by hydrogen quenching gas, which passes into the reactor Ri (2) via a pipe (3) which has bores.
  • cooling may also be provided by other suitable cooling means, such as by cooling coils and the like.
  • a liquid 1, 2-propanediol-containing phase Pj and a gaseous hydrogen phase Hi are obtained, which are then passed together through a cooling zone Ki / 2 (4).
  • a separator from the hydrogen phase Hi and then separate the 1,2-propanediol-containing phase Pi from the hydrogen phase Hi by the cooling region Kj / 2 to lead.
  • the cooling area is a cooling device, such as a heat exchanger, particularly a coiled tube heat exchanger, a double tube heat exchanger, a shell and tube heat exchanger, a fin heat exchanger, a finned tube heat exchanger, or a plate heat exchanger.
  • a heat exchanger particularly a coiled tube heat exchanger, a double tube heat exchanger, a shell and tube heat exchanger, a fin heat exchanger, a finned tube heat exchanger, or a plate heat exchanger.
  • the reactor R 2 there is also a cooling of the 1,2-propanediol-containing phase P 2 formed there by hydrogen quenching gas, which likewise passes into the interior of the reactor via a tube (3) provided with bores.
  • the 1,2-propanediol-containing phase is preferably in the downflow Pi ⁇ "trickle bed") passed in cocurrent or counter-current with hydrogen.
  • FIG. 2 shows a particular embodiment of the procedure described in FIG. According to FIG.
  • the mixture of the glycerol phase P d ycerin and the hydrogen gas used as educt composition is first passed through a heat exchanger 6 and in this way already preheated. Then, the educt composition is heated by means of a heater 7 to a temperature in a range of 180 to 220 0 C and introduced into the reactor (2). There, the glycerol is converted to about 50 mol%. After leaving the reactor Ri (1), the 1,2-propanediol-containing phase Pi is passed together with the hydrogen phase Hi through a cooler Ky 2 (4), which heats the composition to a temperature in the range of 180 Cools to 220 0 C.
  • the composition is introduced into the reactor R 2 (5), in which the remaining glycerol is converted to about 35 mol%.
  • a 1,2-propanediol-containing phase P 2 and a hydrogen phase H 2 is obtained, which are initially passed together through the heat exchanger 6 the.
  • Then follows a further cooling of the 1,2-propanediol-containing phase P 2 and the hydrogen phase H 2 in the cooling zone K 2/2 (8).
  • the composition cooled in this way is then transferred to a separator 9, in which the 1,2-propanediol-containing phase P 2 is separated from the hydrogen phase H 2 .
  • the hydrogen in the hydrogen phase H 2 can then be recycled as recycle gas after filling with hydrogen and pressure increase in the reactor Ri.
  • part of the hydrogen gas is introduced as quenching gas via the bored tubes (3) into the reactors Ri and R 2 .
  • 2-propanediol-containing phase P 2 can be used after Ent voltage without further purification directly for the production of secondary products, such as for the production of fatty acid esters.

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Abstract

La présente invention concerne un procédé de production de 1,2-propanediol par hydrogénation de glycérine à l'aide de gaz hydrogène, procédé selon lequel on fait réagir la glycérine avec l'hydrogène dans au moins i réacteurs R1 à Ri en communication fluidique, présentant chacun un catalyseur d'hydrogénation, pour obtenir le 1,2-propanediol, le gaz hydrogène et une phase glycérique PGlycerin étant introduits dans le premier réacteur R1 et une première phase P1, de préférence liquide, contenant le 1,2-propanediol, ainsi qu'une première phase hydrogène H1, de préférence gazeuse, étant formées dans le réacteur R1, la phase Pn-1, de préférence liquide, contenant le 1,2-propanediol, formée dans le réacteur Rn-1 précédent, et l'hydrogène étant introduits dans chacun des réacteurs suivants Rn, n étant un nombre entier compris entre 2 et i, et une phase Pn, de préférence liquide, contenant le 1,2-propanediol, ainsi qu'une phase hydrogène, de préférence gazeuse, étant formées dans le réacteur Rn, la phase glycérique PGlycerin présentant au moins 60 % en masse de glycérine, par rapport à la masse totale de la phase glycérique PGlycerin. L'invention concerne également le 1,2-propanediol pouvant être obtenu au moyen de ce procédé, un dispositif permettant de produire le 1,2-propanediol ainsi qu'un procédé de production d'un composé renfermant au moins un groupe éther, au moins un groupe ester, au moins un groupe amino, au moins un groupe uréthane ou au moins deux desdits groupes.
EP08784510A 2007-06-11 2008-06-11 Procede d'hydrogenation de glycerine Withdrawn EP2176204A1 (fr)

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DE102007027372A DE102007027372A1 (de) 2007-06-11 2007-06-11 Verfahren zur Hydrierung von Glycerin
PCT/EP2008/004666 WO2008151784A1 (fr) 2007-06-11 2008-06-11 Procédé d'hydrogénation de glycérine

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Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1918354A1 (fr) * 2006-10-13 2008-05-07 Cognis Oleochemicals GmbH Compositions de combustible comprenant de la glycérine
US8293951B2 (en) 2007-08-31 2012-10-23 Basf Se Method for producing 1,2-propandiol by hydrogenation in at least three successive reactors
PL2200958T3 (pl) 2007-08-31 2016-04-29 Basf Se Sposób wytwarzania 1,2-propanodiolu drogą uwodorniania glicerolu w dwustopniowej kaskadzie reaktorów
PL2200960T3 (pl) 2007-08-31 2016-04-29 Basf Se Sposób wytwarzania 1,2-propanodiolu przez niskociśnieniowe uwodornianie glicerolu
JP5612806B2 (ja) * 2008-01-30 2014-10-22 花王株式会社 多価アルコールの水素化分解物の製造方法
DE102008008251A1 (de) * 2008-02-08 2009-08-20 Cognis Oleochemicals Gmbh Vernetzte Glycerin- oder Oligoglycerinester und deren Verwendung als Additiv in Bohrspülungen
JP5350059B2 (ja) * 2008-04-22 2013-11-27 三井化学株式会社 プロピレングリコールの製造方法
US8071820B2 (en) * 2008-12-23 2011-12-06 Uop Llc Method for converting glycerol to propanol
US9447011B2 (en) 2012-11-21 2016-09-20 University Of Tennessee Research Foundation Methods, systems and devices for simultaneous production of lactic acid and propylene glycol from glycerol
WO2014134733A1 (fr) * 2013-03-07 2014-09-12 University Of Saskatchewan Procédé pour l'hydrogénolyse de glycérol
DE102015219306A1 (de) * 2015-10-06 2017-04-06 Hydrogenious Technologies Gmbh Reaktor-Vorrichtung zum Beladen und/oder Entladen eines Trägermediums mit bzw. von Wasserstoff sowie Anlage mit einer derartigen Reaktor-Vorrichtung
RU2663419C1 (ru) * 2017-04-06 2018-08-06 Вадим Алексеевич Меньщиков Способ получения 1,2-пропиленгликоля из глицерина

Family Cites Families (72)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2441540A (en) * 1943-06-19 1948-05-11 Wyandotte Chemicals Corp Production of allyl alcohol
GB807697A (en) * 1956-07-02 1959-01-21 Dow Chemical Co Polyhydric alcohol esters of 2,2,3-trichloropropionic acid
IT581918A (fr) * 1956-10-23
DE1595662A1 (de) * 1966-08-01 1970-01-22 Bayer Ag Verfahren zur Herstellung von Polyestern
US3940432A (en) * 1973-06-19 1976-02-24 Union Carbide Corporation Process for making ethylene glycol
GB1553561A (en) * 1975-07-24 1979-09-26 Chem Y Alkylether sulphate detergent compositions containing them
CA1185993A (fr) 1981-12-23 1985-04-23 Shell Canada Limited Alcoxylation d'alcanols
EP0085167A1 (fr) 1981-12-24 1983-08-10 Conoco Phillips Company Alcoxylation avec des sels de calcium et de magnésium
US4396779A (en) 1982-04-07 1983-08-02 Shell Oil Company Alkanol alkoxylate preparation
US4453022A (en) 1982-04-21 1984-06-05 Union Carbide Corporation Process for preparing nonionic surfactants-oxyalkylation with calcium and/or strontium catalysts
CA1247649A (fr) 1982-12-30 1988-12-28 James H. Mccain Catalyseurs a base d'hydroxyde de baryum et d'alcool inferieur pour les reactions d'oxyalcoylation
DE3437453A1 (de) * 1984-10-12 1986-04-17 Hoechst Ag, 6230 Frankfurt Photopolymerisierbares aufzeichnungsmaterial und verfahren zu seiner herstellung
DE3574370D1 (en) 1984-10-29 1989-12-28 Shell Int Research Alkoxylation process using bimetallic oxo catalyst
DE3516345C1 (de) * 1985-05-07 1986-07-24 Daimler-Benz Ag, 7000 Stuttgart Positioniereinrichtung fuer eine mit dem Aufbau eines Kraftwagens verklebbare Scheibe
US4721816A (en) 1985-12-23 1988-01-26 Shell Oil Company Preparation of nonionic surfactants
DE3776997D1 (de) 1986-07-23 1992-04-09 Henkel Kgaa Verfahren zur direkthydrierung von glyceridoelen.
US4721817A (en) 1986-12-31 1988-01-26 Shell Oil Company Preparation of nonionic surfactants
GB8702654D0 (en) * 1987-02-06 1987-03-11 Davy Mckee Ltd Process
DE3829751A1 (de) 1988-09-01 1990-03-15 Henkel Kgaa Verwendung von metallacetylacetonaten als katalysatoren fuer die ethoxylierung bzw. propoxylierung
DE4018228A1 (de) * 1990-06-07 1991-12-12 Henkel Kgaa Fliessfaehige bohrlochbehandlungsmittel auf basis von kohlensaeurediestern
DE4204369C2 (de) * 1992-02-14 1994-08-25 Forschungszentrum Juelich Gmbh Verfahren zur Qualitätsbestimmung eines einzelnen supraleitenden Filmes und Vorrichtung zur Durchführung dieses Verfahrens
DE4208484C2 (de) * 1992-03-14 1998-09-17 Ald Vacuum Techn Gmbh Magnetisches Ablenksystem für einen Hochleistungs-Elektronenstrahl
DE4209953A1 (de) * 1992-03-27 1993-09-30 Freudenberg Carl Fa Dichtungsanordnung
DE4218074A1 (de) * 1992-06-01 1993-12-02 Henkel Kgaa Verfahren zur Entwässerung von feinteiligen Feststoffsuspensionen
DE4224141A1 (de) * 1992-07-22 1994-01-27 Hoechst Ag Vorrichtung zum Vorformen von plastifiziertem Kunststoffmaterial
US5509667A (en) * 1992-11-04 1996-04-23 Firma Carl Freudenberg Radial lip seal for a shaft in a housing
DE4237965A1 (de) * 1992-11-11 1994-05-19 Henkel Kgaa Polyurethan-Dispersionen und ihre Verwendung als Bindemittel in Einbrennlacken
DE4302464A1 (de) 1993-01-29 1994-08-04 Henkel Kgaa Herstellung von 1,2-Propandiol aus Glycerin
DE4316245A1 (de) * 1993-05-14 1994-11-17 Henkel Kgaa Polyalkylenglykol
DE4335233C1 (de) * 1993-10-15 1994-09-15 Bundesrep Deutschland Reaktionskammer zur Dekontamination von Bekleidungs- und Ausrüstungsgegenständen
DE4407015C2 (de) * 1994-03-03 1996-01-25 Henkel Kgaa Kosmetische und/oder pharmazeutische Zubereitungen
DE4420310A1 (de) * 1994-06-10 1995-12-14 Henkel Kgaa Verwendung von Dimerdiol in Polyurethan-Formkörpern
DE4422858C1 (de) * 1994-06-30 1995-07-27 Henkel Kgaa Ungesättigte Fettalkohole mit verbessertem Kälteverhalten
DE4425180C2 (de) * 1994-07-16 1997-05-07 Henkel Kgaa Verfahren zur Herstellung ungesättigter Fettalkohole oder deren veresterte, alkoxylierte und/oder sulfatierte Derivate mit verbessertem Kälteverhalten
US6610811B1 (en) * 1994-08-18 2003-08-26 Henkel Kommanditgesellschaft Auf Aktien Polyurethanes with improved tear propagation resistance
DE4432168A1 (de) * 1994-09-09 1996-03-14 Rueggeberg August Lamellenschleifscheibe
DE4436764A1 (de) * 1994-10-14 1996-04-18 Henkel Kgaa Verwendung von Guanidiniumsalzen ungesättigter Fettsäuren als Korrosionsschutzwirkstoff
DE4442124A1 (de) * 1994-11-26 1996-05-30 Basf Ag Verfahren zur Herstellung von Propandiol-1,2
DE4444137A1 (de) * 1994-12-12 1996-06-13 Henkel Kgaa Synthetische Ester aus Alkoholen und Fettsäuregemischen aus ölsäurereichen, stearinsäurearmen Pflanzenölen
DE19503061A1 (de) * 1995-02-01 1996-08-08 Henkel Kgaa Dimeralkohol-bis- und Trimeralkohol-tris-sulfate und -ethersulfate
DE19623359A1 (de) * 1995-08-17 1997-02-20 Leybold Ag Vorrichtung zum Beschichten eines Substrats
FI100535B (fi) * 1996-03-05 1997-12-31 Neste Oy Menetelmä öljytisleiden dearomatisoimiseksi
DE19617698C1 (de) * 1996-05-03 1997-10-16 Forschungszentrum Juelich Gmbh Dual-mode-Zweipolfilter
DE19621681C2 (de) * 1996-05-30 1999-06-24 Henkel Kgaa Wäßrige Perlglanzkonzentrate
DE19646424A1 (de) * 1996-11-11 1998-05-14 Henkel Kgaa Verwendung von Polyolen für Isocyanat-Gießharze und -Beschichtungsmassen
DE19730993B4 (de) * 1997-07-18 2008-04-03 Ald Vacuum Technologies Ag Vakuumbeschichtungsvorrichtung zum allseitigen Beschichten von Substraten durch Rotation der Substrate im Partikelstrom
DE19745771B4 (de) * 1997-10-16 2005-12-22 Unaxis Deutschland Holding Gmbh Verfahren für den Betrieb eines Hochleistungs-Elektronenstrahls
DE19747923C2 (de) * 1997-10-30 2002-09-12 Leybold Systems Gmbh Sputterkathode
DE19750800C2 (de) * 1997-11-17 2001-04-26 Cognis Deutschland Gmbh Verfahren zur Herstellung ungesättigter Palmfettalkohole
DE19754986C2 (de) * 1997-12-11 2002-09-12 Leybold Systems Gmbh Sputterkathode
DE59813552D1 (de) * 1997-12-24 2006-06-29 Eberspaecher J Gmbh & Co Verfahren zur Herstellung eines Absorptions-Schalldämpfers
DE19829593A1 (de) * 1998-07-02 2000-01-05 Henkel Kgaa Verfahren zur Herstellung von Verbindungen mit terminalen OH-Gruppen
DE19841078C1 (de) * 1998-09-09 2000-05-18 Forschungszentrum Juelich Gmbh Abstimmbarer Hohlraumresonator
KR20020010934A (ko) * 1999-06-25 2002-02-06 추후제출 분지형의 실질적으로 불포화된 지방 알콜
DE19939538A1 (de) * 1999-08-20 2001-02-22 Cognis Deutschland Gmbh Verzweigte, weitgehend ungesättigte Fettalkoholpolyglycolether
DE19939566C1 (de) * 1999-08-20 2001-04-05 Cognis Deutschland Gmbh Verzweigte, weitgehend ungesättigte Esteröle, Verfahren zu ihrer Herstellung und ihre Verwendung zur Herstellung von kosmetischen und/oder pharmazeutischen Zubereitungen
DE19939565A1 (de) * 1999-08-20 2001-02-22 Cognis Deutschland Gmbh Verzweigte, weitgehend ungesättigte Fettalkoholsulfate
DE19944524A1 (de) * 1999-09-17 2001-03-22 Cognis Deutschland Gmbh Verfahren zur Herstellung von Alkyl-substituierten Butenolen
KR100461221B1 (ko) 2000-02-23 2004-12-10 간사이 페인트 가부시키가이샤 알키드 수지의 제조방법
DE50110583D1 (de) * 2000-04-14 2006-09-14 Eberspaecher J Gmbh & Co Abgas-Schalldämpfer in Mehrkammerbauweise
DE10057421B4 (de) * 2000-11-20 2006-01-12 Trw Automotive Electronics & Components Gmbh & Co. Kg Luftaustritt für Belüftungsanlagen
DE10104468A1 (de) * 2001-02-02 2002-08-29 Eberspaecher J Gmbh & Co Platine für ein Abgas-Gehäuseteil eines Kraftfahrzeugs sowie Verfahren zur Herstellung des Abgas-Gehäuseteils
DE10106559A1 (de) * 2001-02-13 2002-08-29 Eberspaecher J Gmbh & Co Abgas-Gehäuseteil eines Kraftfahrzeuges
DE10115300A1 (de) * 2001-03-28 2002-10-02 Cognis Deutschland Gmbh Verwendung von Fett(meth)acrylaten zur Pigmentdispergierung
DE10143534B4 (de) * 2001-09-06 2005-03-24 Cognis Deutschland Gmbh & Co. Kg Verfahren zur Herstellung von konjugierten Fettsäureestern
DE10155769A1 (de) * 2001-11-14 2003-05-22 Cognis Deutschland Gmbh Kosmetische und/oder pharmazeutische Emulsionen
DE10236086A1 (de) * 2002-08-07 2004-02-19 Cognis Deutschland Gmbh & Co. Kg Verfahren zur Herstellung von konjugierter Linolsäure
BRPI0403236A (pt) * 2003-10-01 2005-05-24 Cognis Deutschland Gmbh Aplicação de ésteres de ácido graxo à base de ácidos graxos ramificados como solventes para tintas de impressão
DE10358826A1 (de) * 2003-12-16 2005-07-14 Cognis Deutschland Gmbh & Co. Kg Verfahren zur Herstellung von Triglyceriden konjugierter Linolsäure
ES2501391T3 (es) * 2004-03-25 2014-10-01 Galen J. Suppes Procedimiento para producir una composición anticongelante que contiene alcoholes inferiores y glicerol a través de alcohólisis de un glicérido
DE102004041299A1 (de) 2004-08-25 2006-03-09 Basf Ag Verfahren zur Herstellung von Polyurethan-Weichschaumstoffen
GB0614823D0 (en) * 2006-07-26 2006-09-06 Davy Process Techn Ltd Process

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2008151784A1 *

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CN101687742A (zh) 2010-03-31
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JP2010529154A (ja) 2010-08-26
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