WO2010094769A1 - Procédé de production de 1,2-propandiol - Google Patents

Procédé de production de 1,2-propandiol Download PDF

Info

Publication number
WO2010094769A1
WO2010094769A1 PCT/EP2010/052136 EP2010052136W WO2010094769A1 WO 2010094769 A1 WO2010094769 A1 WO 2010094769A1 EP 2010052136 W EP2010052136 W EP 2010052136W WO 2010094769 A1 WO2010094769 A1 WO 2010094769A1
Authority
WO
WIPO (PCT)
Prior art keywords
hydrogenation
glycerol
reactor
heat exchanger
crude glycerol
Prior art date
Application number
PCT/EP2010/052136
Other languages
German (de)
English (en)
Inventor
Stephan Maurer
Roman Prochazka
Oliver Bey
Jochen Steiner
Jochem Henkelmann
Gerhard Theis
Peter Wahl
Original Assignee
Basf Se
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
Application filed by Basf Se filed Critical Basf Se
Publication of WO2010094769A1 publication Critical patent/WO2010094769A1/fr

Links

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
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation

Definitions

  • the invention relates to a process for the preparation of 1,2-propanediol by catalytic hydrogenation of glycerol and utilization of the heat of reaction released in the glycerol hydrogenation in the crude glycerol workup and a suitable apparatus for working up.
  • rapeseed oil is used as a starting material in the production of biogenic fuels.
  • Biogenic oils and fats themselves are less suitable as engine fuel, since they must first be cleaned by most expensive procedures. These include the removal of lecithins, carbohydrates and proteins, the removal of the so-called oil sludge and the removal of free fatty acids contained, for example, in rapeseed oil in large quantities. Nevertheless, vegetable oils processed in this way deviate from the technical properties of conventional diesel fuels in several points.
  • DE-PS 524 101 describes such a process in which, inter alia, glycerol is subjected to gas-phase hydrogenation in the presence of a hydrogenation catalyst in substantial excess, bromine-activated copper or cobalt catalysts being used.
  • DE 4302464 A1 describes a process for the preparation of 1, 2-propanediol by hydrogenation of glycerol in the presence of a heterogeneous catalyst, wherein glycerol is passed over a catalyst bed of copper-containing catalyst.
  • WO 2007/099161 A1 describes a process for the preparation of 1,2-propanediol in which a glycerol-containing stream is subjected to hydrogenation in the presence of a copper-containing, heterogeneous catalyst.
  • the glycerol-containing streams used here can still contain numerous undesired components, for example sulfuric acid, hydrogen sulfide, thio alcohols, thioethers, carbon dioxide sulfide and amino acids. Although it is known to remove these impurities before the hydrogenation of the glycerol, these are still partially present after the hydrogenation of glycerol in 1, 2-propanediol. Such impurities may result in the resulting 1,2-propanediol not being suitable for certain applications because of the odor emanating therefrom. In particular, impurities interfere with thiols, fatty acids, esters, aldehydes and ketones, which are already perceived as odor-intensive substances in the ppb range.
  • the glycerol-containing streams used may still contain an undesirably high content of water and / or organic solvents. It is already known from WO 2007/0991161 A1 to subject the glycerol-containing stream to a distillation in order to reduce the water content and / or to remove components which impair the catalytic hydrogenation.
  • the invention had the object of providing an energetically improved process for the preparation of 1, 2-propanediol by hydrogenation of glycerol.
  • the invention relates to a process for the preparation of 1, 2-propanediol by hydrogenation of glycerol, wherein
  • a) provides a glycerol-containing stream having substantially contaminated crude glycerol, b) purifying crude glycerol by distillation to obtain a pure glycerin c) subjecting the pure glycerol-containing stream to continuous hydrogenation to yield 1,2-propanediol in at least one hydrogenation reactor H. , preferably by means of a particular copper-containing heterogeneous catalyst, wherein d) the energy released in the hydrogenation in step c) by heat transfer in at least one heat exchanger at least partially
  • Rohglycerin in step b) is fed and e) optionally works up the hydrogenation.
  • the crude glycerol purified in step b) before the continuous hydrogenation c) is removed in a further step from still existing existing trace components, especially dyes and odors cleaned.
  • This is preferably adsorptive, in particular via activated carbon.
  • the purification can also be carried out, for example, via molecular sieves, ion exchangers, aluminum oxides and carbon black.
  • the adsorbents preferably have a specific surface area, determined by BET, in the range from 10 to 2000 m 2 / g, particularly preferably in the range from 10 to 1500 m 2 / g, in particular in the range from 800 to 1500 m 2 / g.
  • the contaminated crude glycerol indicated in step a) may, inter alia, contain residues, in particular from the bottom, which are obtained in the distillation in step b).
  • Oils and fats are generally solid, semi-solid or liquid fatty acid triglycerides, especially from vegetable and animal sources, which consist essentially of glycerol esters of higher fatty acids chemically.
  • Suitable higher fatty acids are saturated or mono- or polyunsaturated fatty acids having preferably 8 to 40, particularly preferably 12 to 30 carbon atoms. These include z.
  • N-nonanoic acid N-nonanoic acid, n-decanoic acid, n-undecanoic acid, n-tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, nonanecanoic acid, arachic acid, behenic acid, lignoceric acid, cerotic acid, melissinic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, Stearic acid, elaostearic acid, etc.
  • Vegetable fats and oils are essentially based on straight-chain fatty acids, whereas animal fats and oils may also contain odd-carbon fatty acids in free or triglyceride-bound form.
  • the unsaturated fatty acids found in vegetable fats and oils are in the cis form, while animal fatty acids are often trans-configured.
  • glycerol-containing stream in step a it is possible in principle to use used or unused, unpurified or purified vegetable, animal or industrial oils or fats or mixtures thereof. These parts of other ingredients, eg. As free fatty acids.
  • the proportion of free fatty acids is generally 0% to 50%, z. B. 0.1 to 20%, of the starting mixture used for the transesterification of fatty acid triglycerides.
  • Free fatty acids can be if desired, be removed before or after transesterification of the fatty acid triglycerides. Salts of these fatty acids (e.g., the alkali salts) may be previously purified by acidification with a strong acid, e.g. As HCl, are transferred to the free acid.
  • the separation of the free fatty acids succeeds z. B. by centrifugation.
  • the free fatty acids contained in the starting mixture are also converted into the alkyl esters. This can be done before, during or after the transesterification of the fatty acid triglycerides.
  • suitable used fats and oils are fat and / or oil-containing components which, after being obtained from corresponding biogenic starting materials, are initially used for other purposes, eg. As for technical purposes or purposes of food production, have been used and which are chemically modified or unmodified as a result of this use or additional ingredients that are particularly related to this use may have. If desired, these can be at least partially removed by transesterification prior to use for the provision of the glycerol-containing stream.
  • suitable unused fats and oils are fat or oil-containing components which, after their recovery from the corresponding vegetable or animal starting materials have not yet been put to any other purpose and which therefore have only ingredients derived from the starting materials or related to the extraction from the starting materials. Also from these starting materials, ingredients other than fatty acid triglycerides (and optionally free fatty acids) may be at least partially removed, if desired, prior to use to provide the glycerol-containing stream by transesterification.
  • the unused or used fats or oils may be subjected to removal of undesired ingredients such as lecithins, carbohydrates, proteins, oil sludge, water, etc.
  • Vegetable oils and fats are those derived predominantly from plant sources such as seeds, roots, leaves or other suitable parts of plants.
  • Animal fats or oils are predominantly derived from animal feedstocks such as animal organs, tissues or other body parts or body fluids such as milk.
  • Technical oils and fats are those obtained in particular from animal or vegetable raw materials and processed for technical purposes.
  • the used or unused, unrefined or purified oils and / or fats used according to the invention are in particular selected from the group consisting of soapstock, brown grease, YeIlow Grease, technical tallow, technical lard, frying oils, animal fat, edible tallow, vegetable crude oils, animal Crude oils or fats or mixtures thereof.
  • Soapstock is understood to mean a by-product obtained in the processing of vegetable oils, in particular a by-product of edible oil refineries based on soybean, rapeseed or sunflower oil. Soapstock has a content of free fatty acids of about 50% to 80%.
  • Brown Grease an animal fat-containing waste product having a content of free fatty acids of more than 15% to 40%.
  • Yellow Grease contains about 5% to 15% free fatty acids.
  • “Technical tallow” and “technical lard” are animal fats that are manufactured for technical purposes and obtained by the dry or wet-melt process, for example, from slaughterhouse waste. Technical tallow are evaluated and traded according to their acid value, the content of free fatty acids depending on the origin z. B. between 1 and 20 wt .-%, such as in the range of 1 to 15 wt .-% is. However, the content of free fatty acids may be more than 20 wt .-%.
  • the "animal fats” include in particular in the utilization of poultry, beef, pork, fish and marine mammal bodies sloping fatty products, such as solar stearin, a solid residue remaining after pressing lard oil from lard.
  • the provision of the glycerol-containing stream in step a) is preferably carried out from vegetable crude oils as starting material.
  • This can be based on unrefined vegetable crude oils, d. H. of liquid or solid compositions derived from vegetable starting materials e.g. B. are obtained by pressing, where they have experienced no other treatment than settling in common periods and centrifuging or filtering, are used in the separation of the oil from solid components only mechanical forces such as gravity, centrifugal force or pressure.
  • Such unrefined vegetable crude oils may also be obtained by extraction of vegetable oils, if their properties are not or only slightly different from the corresponding obtained by pressing vegetable oils.
  • the proportion of free fatty acids in unrefined vegetable fats and oils is different and is z. B. at about 0 to 20%, such as. B. 0.1 to 15%.
  • the vegetable oils may be subjected to one or more workup steps prior to their use for transesterification, as described in more detail below.
  • purified vegetable oils such as Example, raffinates or semi-refined, the above vegetable oils are used as starting materials.
  • a vegetable oil or fat is used, which is preferably selected from rapeseed oil, palm oil, rapeseed oil, soybean oil, sunflower oil, corn oil, cottonseed oil, palm kernel and coconut fat and mixtures thereof. Particular preference is given to using rapeseed oil or a rapeseed oil-containing mixture.
  • Suitable for providing the glycerol-containing stream in step a) is also animal oil or fat, which is preferably selected from milk fat, wool fat, beef tallow, lard, fish oils, fish oil, etc., and mixtures thereof. These animal fats or oils may also be subjected to one or more processing steps before they are used for transesterification, as described in more detail below.
  • the provision of the glycerol-containing stream in step a) comprises the following steps:
  • the glycerol-containing stream, a part of the resulting in the following distillation step b), purified from low boilers product can be added.
  • the glycerol-containing stream is in step b) a distillation in an apparatus A to
  • Suitable apparatus for working up by distillation comprise distillation columns, such as tray columns, which can be equipped with bells, sieve plates, sieve trays, packings, random packings, valves, side draws, etc., evaporators, such as thin film evaporators, falling film evaporators, forced circulation evaporators, Sambay evaporators, etc. and combinations thereof.
  • the removal of sulfuric acid is already possible by a simple distillation, in particular a short path distillation.
  • the hydrogenation reactor H is preferably a single reactor or continuously connected in series hydrogenation reactors. Hydrogenation reactors may independently have one or more reaction zones within the reactor. Preferred pressure-resistant reactors for the hydrogenation are known to the person skilled in the art. These include the commonly used reactors for gas-liquid reactions, such. Tube reactors, tube bundle reactors, gas recycle reactors, bubble column, loop apparatuses, stirred tanks (which may also be configured as stirred tank cascades), air lift reactors, etc.
  • the process according to the invention using heterogeneous catalysts can be carried out in fixed bed or suspension mode.
  • the fixed bed mode can be z. B. in sump or in trickle run.
  • the catalysts are preferably used as shaped bodies, as described below, for. In the form of pressed cylinders, tablets, pastilles, carriage wheels, rings, stars or extrudates, such as solid strands, polylobal strands, hollow strands, honeycomb bodies, etc.
  • heterogeneous catalysts are also used.
  • the heterogeneous catalysts are usually used in finely divided state and are finely suspended in the reaction medium before. Suitable heterogeneous catalysts and processes for their preparation are described in more detail below.
  • a reactor In the hydrogenation on a fixed bed, a reactor is used, in the interior of which a fixed bed is arranged, through which the reaction medium flows.
  • the fixed bed can be formed from a single or multiple beds.
  • Each bed may have one or more zones, wherein at least one of the zones contains a material active as a hydrogenation catalyst.
  • Each zone can have one or more different catalytically active materials and / or one or more different inert materials. Different zones may each have the same or different compositions. It is also possible to provide a plurality of catalytically active zones, which are separated from each other, for example, by inert beds. The individual zones may also have different catalytic activity.
  • reaction medium which flows through the fixed bed contains according to the invention at least one liquid phase.
  • the reaction medium may also contain a gaseous phase in addition.
  • loop apparatuses such as jet loops or propeller loops
  • stirred tank which can also be configured as ROWkesselkaskaden, bubble columns or air-lift reactors are used.
  • the glycerol and the resulting 1, 2-propanediol are preferably in liquid form.
  • the temperature in the hydrogenation is preferably 150 to 250 0 C, in particular 160 to 230 0 C.
  • the usual devices can be used, such as hollow body modules, field tubes, pipe rods, heat exchanger plates.
  • the heat withdrawn from the hydrogenation reactor H is transferred in the context of heat integration in a suitable exchanger directly or indirectly to the still to be purified crude glycerol, which is supplied to the apparatus A.
  • the withdrawal of the energy from the hydrogenation reactor takes place in a preferred embodiment in that a product stream comprising substantially 1,2-propanediol and still residues of unhydrogenated glycerol is withdrawn from the hydrogenation reactor, in a heat exchanger gives off the energy and cooled is fed back to the hydrogenation reactor.
  • the transfer of energy in the exchanger can be done directly or indirectly.
  • Step d1) Direct energy transfer
  • the product stream originating from the hydrogenation reactor H enters a heat exchanger at a temperature T1, leaves it at a temperature T2 which is less than T1, and is fed to the hydrogenation reactor together with glycerol and hydrogen to be hydrogenated.
  • the energy is transferred to crude glycerol, which enters the heat exchanger at the temperature T3 and, after transferring the energy from the hydrogenation reactor, leaves the temperature T4, which is greater than T3.
  • the crude glycerol heated to the temperature T4 is supplied to the apparatus A.
  • the heat exchange takes place indirectly, d. H. the product stream from the hydrogenation reactor is not mixed with the crude glycerine.
  • Heat exchangers suitable according to the invention are, in particular, double pipe, tube bundle, finned tube, spiral or plate heat exchangers.
  • Double tube heat exchangers consist of two tubes lying one inside the other. Several of these double pipes can be connected to pipe walls.
  • the inner tube may be smooth or treaded to enhance heat transfer.
  • a tube bundle represent the inner tube.
  • the heat exchanging fluids move in cocurrent or, preferably, in countercurrent. In a preferred embodiment, this proviso is worked in the following temperature ranges:
  • T1 150 ° C. to 250 ° C.
  • T2 130 ° C to 230 0 C.
  • T3 20 ° C to 150 ° C
  • T4 50 ° C to 180 ° C
  • the transfer of the heat originating from the hydrogenation reactor H does not take place directly on the crude glycerol stream, but indirectly.
  • the energy originating from the hydrogenation reactor is transferred into a heat exchanger to a fluid heat carrier (preferably hot water condensate) and transfers this energy into a further exchanger indirectly to the crude glycerol to be purified. It is also possible to switch several heat exchangers. workup
  • the hydrogenation effluent leaving the hydrogenation reactor consists essentially of 1,2-propanediol, preferably at least 50% by weight, in particular greater than 60% by weight.
  • Other components are u. a. Methanol, ethanol, n-propanol, isopropanol, 1, 3-propanediol, glycerol, ethylene glycol and water.
  • the hydrogenation discharge can be worked up by customary processes; for this purpose, for example, thermal processes, preferably distillative processes, adsorption, ion exchange, membrane separation processes, crystallization, extraction or a combination thereof are suitable.
  • the hydrogenation product is passed into at least one further hydrogenation reactor.
  • the hydrogenation effluent leaving the further hydrogenation reactor is preferably at least 60% by weight, in particular at least 70% by weight, of 1,2-propanediol.
  • the continuous hydrogenation in step c) takes place in two fixed bed reactors connected in series (in series).
  • the reactors are preferably operated in direct current.
  • the feeding of the feed streams can be done both from above and from below.
  • the glycerol and the resulting 1, 2-propanediol are preferably in the liquid phase.
  • the temperature in the hydrogenation in step c) is in two reactors in general mean about 150 to 250 0 C, in particular 170 to 230 0 C.
  • a different temperature can be set in the second reactor than in the first reactor.
  • the second reactor is operated at a higher temperature than the first reactor.
  • the first and / or second reactor may have two or more reaction zones of different temperature.
  • another, preferably a higher, temperature than in the first reaction zone or in each subsequent reaction zone can be set to a higher temperature than in a preceding reaction zone, for. B. to achieve the fullest possible conversion in the hydrogenation.
  • the reaction pressure in step c) is preferably about 30 to 300 bar, particularly preferably 60 to 250 bar, in particular 140 to 250 bar.
  • a different pressure can be set in the second reactor than in the first reactor.
  • the second reactor is operated at a higher pressure than the first reactor.
  • the feeding of the hydrogen required for the hydrogenation can be carried out in the first and optionally in the second reactor.
  • the feed of hydrogen takes place only in the first reactor.
  • the amount of hydrogen fed to the reactors results from the amount of hydrogen consumed in the hydrogenation reaction and the amount of hydrogen optionally discharged with the exhaust gas.
  • the molar ratio of hydrogen to glycerol is preferably 1: 1 to 500: 1, especially 1: 1: 1 to 100: 1.
  • the hydrogen is in a stoichiometric excess of about 2 to 25 mol%, more preferably 5 to 15 MoI-%, based on glycerol used.
  • the catalyst loading in continuous operation is preferably 0.05 to 1, particularly preferably 0.1 to 0.5 kg, in particular 0.1 to 0.3 kg of glycerol to be hydrogenated per kg (catalyst) per h.
  • the conversion in the first reactor is preferably at least 85%, particularly preferably at least 90%, in particular at least 92%.
  • the regulation of the reacted in the first reactor glycerol content can, for. B. on the reactor volume and / or the residence time in the first reactor.
  • the total glycerol in step b), based on the glycerol contained in the glycerol-containing stream is preferably at least 97%, more preferably at least 98%, in particular at least 99%.
  • the invention further relates to a device suitable for carrying out the method according to the invention from a hydrogenation reactor H, at least one heat exchanger W and an apparatus A for low boiler removal, characterized in that
  • the hydrogenation reactor H has product inlets for glycerol HE1 and hydrogen HE2 and a product outlet HA1 for substantially propanediol and also an outlet HA2 for recycling the reactor contents, which is connected via a pipe connection K to the inlet HE3, the pipe joint K preferably a Has pump for product delivery and is passed through an indirect heat exchanger W, in which a heat transfer to the product contained in the tube R1 Rohglycerin takes place, the tube R1 is introduced by side entry AF in an apparatus A and wherein 2.
  • the apparatus A has a trigger AK for low boilers and in the sump AS a deduction for purified from low boilers crude glycerol, which is conveyed via a pipe R2, preferably pumped by a pump to the manifold V, via which it back into pipe R1 and in the heat exchanger W and / or via the pipe R4 for further product workup or directly to the hydrogenation reactor H is performed.
  • Figure 1 shows the schematic representation of the device according to the invention.
  • crude glycerol is purified and hydrogenated, the heat obtained in the hydrogenation being fed via the heat exchanger W to the crude glycerol.
  • the glycerol withdrawn from the apparatus A via R4 is fed to the hydrogenation reactor after working up in a further distillation column and after absorptive fine cleaning via activated carbon via HE1.
  • the transfer of the heat produced during the hydrogenation to the crude glycerol takes place directly in the heat exchanger W.
  • the energy savings in the low boiler removal in the crude glycerol distillation is when using the heat of hydrogenation at more than 50%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé d'utilisation de la chaleur de réaction libérée an cours de l'hydrogénation de glycérine pour le traitement de glycérine brute, ainsi que le dispositif nécessaire à cet effet.
PCT/EP2010/052136 2009-02-20 2010-02-19 Procédé de production de 1,2-propandiol WO2010094769A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP09153357 2009-02-20
EP09153357.0 2009-02-20

Publications (1)

Publication Number Publication Date
WO2010094769A1 true WO2010094769A1 (fr) 2010-08-26

Family

ID=42289283

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2010/052136 WO2010094769A1 (fr) 2009-02-20 2010-02-19 Procédé de production de 1,2-propandiol

Country Status (1)

Country Link
WO (1) WO2010094769A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103833513A (zh) * 2012-11-26 2014-06-04 中国科学院大连化学物理研究所 一种以菊芋为原料直接催化转化制备1,2-丙二醇的方法
CN116589342A (zh) * 2023-07-17 2023-08-15 万华化学集团股份有限公司 一种对粗1,2-丙二醇进行催化脱除气味杂质的方法

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
DE4302464A1 (de) 1993-01-29 1994-08-04 Henkel Kgaa Herstellung von 1,2-Propandiol aus Glycerin
WO2007053705A2 (fr) * 2005-10-31 2007-05-10 University Of Missouri Board Of Curators Procede de fabrication d'alcools inferieurs a partir de glycerol
WO2007099116A2 (fr) 2006-03-03 2007-09-07 Widex A/S Dispositif d'aide auditive et procede de compensation de son direct dans des dispositifs d'aide auditive
WO2007099161A1 (fr) 2006-03-03 2007-09-07 Basf Se Procédé de synthèse du 1,2-propanediol

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
DE4302464A1 (de) 1993-01-29 1994-08-04 Henkel Kgaa Herstellung von 1,2-Propandiol aus Glycerin
WO2007053705A2 (fr) * 2005-10-31 2007-05-10 University Of Missouri Board Of Curators Procede de fabrication d'alcools inferieurs a partir de glycerol
WO2007099116A2 (fr) 2006-03-03 2007-09-07 Widex A/S Dispositif d'aide auditive et procede de compensation de son direct dans des dispositifs d'aide auditive
WO2007099161A1 (fr) 2006-03-03 2007-09-07 Basf Se Procédé de synthèse du 1,2-propanediol

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
GRASSMANN P.; WIDMER F., EINFÜHRUNG IN DIE THERMISCHE VERFAHRENSTECHNIK, DE GRUYTER, 1997
MERSMANN; AIFONS: "Thermische Verfahrenstechnik", 1980, SPRINGER VERLAG
SATTLER; KLAUS: "Thermische Trennverfahren", 2001, WILEY VCH
SCHLÜNDER E. U.; THURNER F.: "Destillation, Absorption, Extraktion", 1995, SPRINGER VERLAG
WEISS S.; MILITZER K.-E.; GRAMLICH K.: "Thermische Verfahrenstechnik", 1993, DT. VERLAG FÜR GRUNDSTOFFINDUSTRIE

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103833513A (zh) * 2012-11-26 2014-06-04 中国科学院大连化学物理研究所 一种以菊芋为原料直接催化转化制备1,2-丙二醇的方法
CN116589342A (zh) * 2023-07-17 2023-08-15 万华化学集团股份有限公司 一种对粗1,2-丙二醇进行催化脱除气味杂质的方法
CN116589342B (zh) * 2023-07-17 2023-10-17 万华化学集团股份有限公司 一种对粗1,2-丙二醇进行催化脱除气味杂质的方法

Similar Documents

Publication Publication Date Title
EP1542960A1 (fr) Procede et dispositif pour produire du biodiesel
DE60110073T2 (de) Verfahren und Vorrichtung zur Herstellung von Fettsäureestern
EP2200960B1 (fr) Procédé de production de propane-1,2-diol par hydrogénation à basse pression de glycérine
EP1910267B1 (fr) Procede de production d'alkylesters d'acide carboxylique
EP2432756B1 (fr) Procédé de production d'alcools gras par hydrogénation de triglycérides d'acide gras en présence d'un catalyseur hétérogène contenant du cuivre
WO2009027501A2 (fr) Procédé de production de propane-1,2-diol par hydrogénation de glycérine dans au moins trois réacteurs montés en série
EP1448750B1 (fr) Procede de fabrication de carburants a partir de graisses acides et dispositif correspondant
DE3512497A1 (de) Verfahren zur herstellung von carbonsaeurealkylestern, insbesondere fettsaeurealkylestern, und deren verwendung als dieselkraftstoff
EP2069282B1 (fr) Procede de production continue d'ester methylique d'acide gras ou d'ester ethylique d'acide gras
EP2200958B1 (fr) Procédé de production de propane-1,2-diol par hydrogénation de glycérine dans une cascade de réacteurs à deux étages
EP2175012B1 (fr) Procédé et installation destinés à la fabrication de biodiesel
WO2009056230A1 (fr) Procédé d'estérification à catalyse hétérogène d'acides gras
CN102102049A (zh) 在固定床热纯化条件下由植物或动物油和脂肪族一元醇制备烷基酯的方法
EP2172442B1 (fr) Procédé et dispositif destinés à la séparation d'acides carboniques ou d'ester d'acide carboniques
EP2389347B1 (fr) Procédé de production de 1,2-propanediol désodorisé
WO2009133066A1 (fr) Procédé d'hydrogénolyse de polyols
WO2010094769A1 (fr) Procédé de production de 1,2-propandiol
DE102018004940A1 (de) Verfahren zur Herstellung von Fettsäuremethylester
WO2009056231A1 (fr) Procédé en continu d'estérification catalysée hétérogène des acides gras
DE102007052064A1 (de) Verfahren zur heterogen katalysierten Veresterung von Fettsäuren
DE102007037067A1 (de) Verfahren zur Aufbereitung und/oder Reinigung eines mit Wasser zwei Phasen bildenden flüssigen Mediums und Anlage dafür
DE19803053C1 (de) Verfahren zur Herstellung von C¶1¶¶2¶-C¶1¶¶8¶-Fettsäureniedrigalkylestern
DE102008059924A1 (de) Verfahren zur Herstellung von Fettsäuremethylestern aus Palmfettsäuredestillat
FI20216371A1 (en) Heat treatment with adsorption purification of organic material of biological origin
DE10059084A1 (de) Verfahren und Anlage zur Herstellung von Fettsäuremonoalkylestern aus Fetten und Fettsäuren oder deren Mischungen

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: 10711621

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10711621

Country of ref document: EP

Kind code of ref document: A1