EP2200959A2 - Procédé de production de propane-1,2-diol par hydrogénation de glycérine dans au moins trois réacteurs montés en série - Google Patents

Procédé de production de propane-1,2-diol par hydrogénation de glycérine dans au moins trois réacteurs montés en série

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Publication number
EP2200959A2
EP2200959A2 EP08803384A EP08803384A EP2200959A2 EP 2200959 A2 EP2200959 A2 EP 2200959A2 EP 08803384 A EP08803384 A EP 08803384A EP 08803384 A EP08803384 A EP 08803384A EP 2200959 A2 EP2200959 A2 EP 2200959A2
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EP
European Patent Office
Prior art keywords
glycerol
hydrogenation
reactor
reactors
stream
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
EP08803384A
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German (de)
English (en)
Inventor
Jochem Henkelmann
Roman Prochazka
Oliver Bey
Stephan Maurer
Jochen Steiner
Heiko Urtel
Gerhard Theis
Peter Wahl
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BASF SE
Original Assignee
BASF SE
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Application filed by BASF SE filed Critical BASF SE
Priority to EP08803384A priority Critical patent/EP2200959A2/fr
Publication of EP2200959A2 publication Critical patent/EP2200959A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

Definitions

  • the present invention relates to a process for the preparation of 1,2-propanediol in which a glycerol-containing stream, in particular a stream obtained industrially in the production of biodiesel, is subjected to hydrogenation in an at least three-stage reactor cascade.
  • vegetable oils processed in this way deviate from the technical properties of conventional diesel fuels in several ways.
  • they usually have a higher density than diesel fuel, the cetane number of rapeseed oil is lower than that of diesel fuel and the viscosity is many times higher than that of diesel fuel.
  • the use of pure vegetable oils therefore leads to coking in conventional engines, associated with increased particle emission.
  • No. 2,360,844 describes a process for producing soaps in which a crude glyceride is transesterified with C 1 -C 4 -alkanols and the glycerol released is separated off from the monoalkyl esters. The utilization of the resulting glycerol is not described.
  • DE 102 43 700 A1 describes a pressureless process for the preparation of alkyl esters of higher fatty acids, in particular biodiesel, from fatty acid triglyceride starting mixtures containing free fatty acids with a combination of acid esterification and basic transesterification.
  • the glycerol obtained during the transesterification is used in part as an entraining agent in the esterification of the free fatty acids.
  • DE-PS-524 101 describes such a method in which u. a. Glycerol undergoes a gas phase hydrogenation in the presence of a hydrogenation catalyst with hydrogen in substantial excess. Specifically, for the hydrogenation of glycerol with Cr activated copper or cobalt catalysts are used.
  • DE-PS-541 362 describes a process for the hydrogenation of Polyoxyverbindun- gene, such as.
  • Polyoxyverbindun- gene such as.
  • glycerol in the presence of catalysts at elevated temperatures above 150 0 C and under elevated pressure.
  • the hydrogenation of glycerin with a nickel catalyst at a temperature of 200 to 240 0 C and a hydrogen pressure of 100 atm is described.
  • DE 43 02 464 A1 describes a process for the preparation of 1, 2-propanediol by hydrogenation of glycerol in the presence of a heterogeneous catalyst at pressures of 20 to 300 bar, in particular at 100 to 250 bar and temperatures of 150 0 C to 320 0 C. in which glycerol is passed in vapor or liquid form over a catalyst bed.
  • Catalysts mentioned include, inter alia, Cu chromite, Cu zinc oxide, Cu aluminum oxide and Cu silicon dioxide.
  • EP 0 523 015 describes a process for the catalytic hydrogenation of glycerol for the preparation of 1, 2-propanediol and 1, 2-ethanediol in the presence of a Cu / Zn
  • the glycerol is used as an aqueous solution having a glycerol content of 20 to 60 wt .-%, the maximum glycerol content in the embodiments is 40 wt .-%.
  • WO 2005/095536 describes a low-pressure process for the conversion of glycerol into propylene glycol, in which a glycerol-containing stream having a water content of at most 50 wt .-% at a temperature in the range of 150 to 250 0 C and a pressure in the range of 1 up to 25 bar undergoes catalytic hydrogenation.
  • Different reaction parameters were tested, including the water content of the glycerol used. Although the conversion increased with decreasing water content, the highest selectivity was achieved in this low-pressure process at a water content of 20 wt .-%. No.
  • 5,616,817 describes a process for the preparation of 1,2-propanediol by catalytic hydrogenation of glycerol at elevated temperature and elevated pressure, in which glycerol having a water content of at most 20% by weight in the presence of a catalyst containing 40 to Contains 70 wt .-% cobalt, optionally manganese and / or molybdenum and a low content of copper from 10 to 20 wt .-%, reacted.
  • the temperature is in a range of about 180 to 270 0 C and the pressure in a range of 100 to 700 bar, preferably 200 to 325 bar.
  • the unpublished PCT / EP2007 / 051983 describes a process for the preparation of 1, 2-propanediol, which comprises a glycerol-containing stream of hydrogenation in the presence of a copper-containing, heterogeneous catalyst at a temperature of 100 to 320 0 C and a pressure of 100 to 325 bar.
  • the present invention is based on the object to provide an improved process for the preparation of 1, 2-propanediol available.
  • the known methods are still in need of improvement in terms of the most complete hydrogenation of glycerol with good selectivity with respect to the desired 1, 2-propanediol.
  • many processes known from the prior art require relatively large amounts of catalyst or have too low a space-time yield.
  • the process according to the invention should also be suitable, in particular, for the further processing of large-scale glycerol streams, as obtained in the transesterification of fatty acid triglycerides for the preparation of alkyl esters of higher fatty acids.
  • the invention therefore provides a process for the preparation of 1, 2-propanediol, in which
  • the hydrogenation product obtained in step b) may optionally be subjected to at least one work-up step (step c)).
  • the hydrogenation is carried out continuously in n hydrogenation reactors connected in series (in series), where n is an integer of at least 3. Suitable values for n are 3, 4, 5, 6, 7, 8, 9 and 10. Preferably, n is 3 to 6 and especially 3.
  • the reactors used for the hydrogenation in step b) can independently of one another have one or more reaction zones within the reactor.
  • the reactors may be the same or different reactors. These can be z. B. each have the same or different mixing characteristics and / or be subdivided by internals one or more times.
  • Suitable 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 as. B. tube reactors, tube bundle reactors, gas circulation reactors, bubble columns, loop apparatus, stirred tank (which can also be designed 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 in the fol lowing, z. In the form of pressed cylinders, tablets, pastilles, carriage wheels, rings, stars or extrudates, such as solid strands, poly-lobar strands, hollow strands, honeycomb bodies, etc.
  • heterogeneous catalysts are also used.
  • the heterogeneous catalysts are usually used in a finely divided state and are finely suspended in the reaction medium before.
  • 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 several catalytically active zones, for example are separated by inert beds.
  • the individual zones may also have different catalytic activity. For this purpose, various catalytically active materials can be used and / or at least one of the zones an inert material can be added.
  • the reaction medium which flows through the 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 continuous hydrogenation in step b) takes place in at least three 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 b) is generally about 150 to 250 ° C., in particular 160 to 230 ° C., in all reactors.
  • each of the reactors may have a different temperature from each other.
  • each downstream reactor is operated at a higher temperature than the previous reactor.
  • each of the reactors may have two or more different temperature reaction zones.
  • a higher temperature than in a preceding reaction zone can be set, for. B. to achieve the fullest possible conversion in the hydrogenation.
  • the first reactor about 170 to 178 0 C, the second at about 179 to 183 0 C and the third at about 184 to 190 0 C operated.
  • the reaction pressure in step b) is preferably in all reactors generally about 30 to 300 bar, more preferably 60 to 250 bar, in particular 140 to 250 bar. If desired, in the case of a hydrogenation apparatus comprising n reactors, at least two of the reactors (ie, 2 to n of the reactors) may have a different pressure from each other. In a specific embodiment, each downstream reactor is operated at a higher pressure than the previous reactor.
  • the feeding of the hydrogen required for the hydrogenation can be carried out in the first and optionally additionally in at least one other Rector.
  • 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 used in a stoichiometric excess of about 2 to 25 mol%, more preferably 5 to 15 mol%. %, 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 setting of the reacted in the respective reactor glycerol content can, for. B. on the reactor volume and / or the residence time in the reactor.
  • the conversion in the first reactor, based on the glycerol contained in the glycerol-containing stream, is preferably at least 60%, more preferably at least 70%.
  • Current contained glycerol is preferably at least 97%, more preferably at least 98%, in particular at least 99%.
  • one or more of the reactors may be provided with at least one cooling device.
  • at least the first reactor is provided with a cooling device.
  • the heat of reaction can be removed by cooling an external recycle stream or by internal cooling in at least one of the reactors.
  • internal cooling it is possible to use the customary devices, generally hollow-body modules, such as field tubes, tube coils, heat exchanger plates, etc.
  • the reaction can also be carried out in a cooled tube bundle reactor.
  • the hydrogenation in step b) is preferably carried out in n hydrogenation reactors connected in series, n being an integer of at least three, and at least one reactor having an external circulation stream from the reaction zone (external recycle stream, liquid recycle, loop). driving style).
  • n stands for three.
  • the hydrogenation in step b) preferably takes place in n hydrogenation reactors connected in series, where n is preferably three, and the first to (n-1). Reactor has a guided in an external circuit current from the reaction zone.
  • step b) preferably takes place in n hydrogenation reactors connected in series, n preferably being three, and the reaction being carried out adiabatically in the nth reactor (the last reactor through which the reaction mixture to be hydrogenated is flowed).
  • the hydrogenation in step b) preferably takes place in n hydrogenation reactors connected in series, where n is preferably three, and the n. Reactor is operated in a straight pass.
  • the heat of reaction which occurs during the reaction is insufficient to maintain the desired temperature in the reactor. It may also be necessary to heat the reactor (or individual reaction zones of the second reactor). This can be done analogously to the previously described removal of the heat of reaction by heating an external circulation stream or by internal heating. In a suitable embodiment, the heat of reaction from at least one of the previous reactors can be used to control the temperature of a reactor.
  • the heat of reaction removed from the reaction mixture can be used to heat the feed streams of the reactors.
  • This can z. B. the Glycerinzulaufstrom in the first reactor at least partially mixed with an external recycle stream of this reactor and the combined streams are then fed into the first reactor.
  • the feed stream from the (m-1) -th reactor in the mth reactor can be mixed with a recycle stream from the mth reactor and the combined streams then into the mth reactor be guided.
  • the Glycerinzulaufstrom and / or another feed stream can be heated by means of a heat exchanger, which is operated with withdrawn Hydrier Creek.
  • a reactor cascade of n reactors connected in series is used, the reaction being carried out adiabatically in the nth (nth) reactor.
  • This term is understood in the context of the present invention in the technical and not in the physicochemical sense.
  • Adiabatic reaction is understood to mean a procedure in which the amount of heat liberated during the hydrogenation is taken up by the reaction mixture in the reactor and no cooling by cooling devices is used.
  • the reaction heat is removed with the reaction mixture from the second reactor, except for a residual portion which is discharged by natural heat conduction and heat radiation from the reactor to the environment.
  • the nth reactor is operated in a straight pass.
  • step b For the hydrogenation in step b), preference is given to using a three-stage reactor cascade, the first and the second hydrogenation reactor having a stream flowing out of the reaction zone in an external circuit.
  • a reactor cascade of three reactors connected in series is used, the reaction being carried out adiabatically in the third reactor.
  • additional mixing can take place in at least one of the reactors used. Additional mixing is particularly advantageous if the hydrogenation takes place at high residence times of the reaction mixture.
  • the currents introduced into the reactors are used by introducing them via suitable mixing devices, such as nozzles, in the respective reactors.
  • suitable mixing devices such as nozzles, in the respective reactors.
  • the discharge is taken from a discharge, which still contains hydrogenatable glycerol and fed into the respective downstream hydrogenation reactor.
  • the discharge is separated into a first and a second partial flow, the first partial flow being recirculated to the reactor from which it was withdrawn and the second partial flow being supplied to the downstream reactor.
  • the discharge may contain dissolved or gaseous portions of hydrogen.
  • the discharge from the first to (n-1) th reactor is a phase separation vessel fed, separated into a liquid and a gaseous phase, the liquid phase separated into the first and the second partial stream and the gas phase at least partially fed separately to the subsequent reactor.
  • the discharge from the first to (n-1) th reactor is fed to a phase separation vessel and separated into a first liquid hydrogen-depleted substream and a second hydrogen-enriched substream.
  • the first part-stream is then fed back into the reactor as a cycle stream, to which it has been taken off and the second part-stream is fed to the subsequent reactor (as a glycerol- and hydrogen-containing feed).
  • the feed of the second to nth reactor with hydrogen is not carried out via a hydrogen-containing feed taken from the upstream reactor, but with fresh hydrogen via a separate feed line.
  • b1) feeds a glycerol-containing feed and hydrogen into the first reactor of a reaction system, which consists of n-1 reactors with a current conducted in an external circuit and an n-th downstream reactor, and in the presence of a copper-containing, converts heterogeneous catalyst to a partial conversion,
  • b2) takes a discharge from each of the first to (n-1) th reactor, which contains hydrogen, glycerol and 1, 2-propanediol,
  • the process variant described above is particularly advantageous for controlling the reaction temperature and the heat transfer between the reaction medium, limiting apparatus walls and environment.
  • Another way to control the heat balance is to control the inlet temperature of the glycerol-containing feed.
  • a lower temperature of the incoming feed usually leads to an improved removal of the heat of hydrogenation.
  • the inlet temperature can be set higher to achieve a higher reaction rate and thus to compensate for the decreasing catalyst activity.
  • the service life of the catalyst used can be extended.
  • the first partial stream is generally recycled chemically unchanged into the reaction system. If desired, the temperature and / or pressure may be adjusted to the desired values prior to recycling.
  • the feed of the first partial stream into the reactor from which it was taken off can take place together with the glycerol-containing feed or separately therefrom.
  • the ratio by weight of first partial stream (recycle stream) fed into a reactor to glycerol-containing feed (feed stream) is preferably in the range from 1: 1 to 50: 1, more preferably from 2: 1 to 30: 1.
  • heat is also withdrawn from the second partial stream before it enters the subsequent reactor.
  • a conventional heat exchanger can be used, which makes it possible to use the amount of heat recovered elsewhere in the process again.
  • FIG. 1 shows the schematic representation of a three-stage reactor cascade suitable for carrying out the hydrogenation process, wherein, for reasons of clarity, the reproduction of such details is omitted which are not relevant for the explanation of the invention.
  • the plant comprises three hydrogenation reactors (1), (1 1) and (19).
  • the hydrogenation reactors (1) and (11) are designed as circulation reactors and the hydrogenation reactor (19) as an adiabatic flow tube reactor.
  • Hydrogen gas is introduced under pressure into the reactor (1) via the pipeline (2), and a glycerol-containing stream is introduced into the reactor (1) via the pipeline (3).
  • a discharge from the reactor (1) is removed, fed to the phase separation vessel (5) and separated into a liquid phase and a gaseous phase.
  • the liquid phase obtained in the phase separation vessel (5) is separated into a first and a second substream.
  • the first partial stream (6) is cooled in the heat exchanger (8) and mixed as a circulating stream with the feed stream (3) and fed back to the reactor (1).
  • the second partial stream (9) is fed to the second reactor (11).
  • the gas phase obtained in the phase separation vessel (5) is fed as stream (10) to the second reactor (11) separately.
  • Via the pipe (4a) and the pump (14) a discharge from the reactor (11) is removed, fed to the phase separation vessel (12) and separated into a liquid phase and a gaseous phase.
  • the liquid phase obtained in the phase separation vessel (12) is separated into a first and a second substream.
  • the first partial flow (13) becomes cooled in the heat exchanger (15) and mixed as a circulating stream with the feed stream (9) and fed to the reactor (1 1) again.
  • the second partial stream (16) is cooled in the heat exchanger (18) and fed to the third reactor (19).
  • the gas phase obtained in the phase separation vessel (12) is fed separately as stream (17) to the second reactor (19).
  • the phase separation vessels (5) and (12) can be made separately or, alternatively, integrated into the reactors (1) and / or (11).
  • the hydrogenation product leaves the reactor (19) via the pipeline (20).
  • FIG. 2 shows the schematic representation of an alternative embodiment of a three-stage reactor cascade suitable for carrying out the hydrogenation process.
  • the plant comprises three hydrogenation reactors (1), (10) and (17).
  • the hydrogenation reactors (1) and (10) are designed as circulation reactors and the hydrogenation reactor (17) as an adiabatic flow tube reactor.
  • Hydrogen gas is introduced into the reactor (1) via the pipeline (2) under pressure, and a glycerol-containing stream is introduced into the reactor (1) via the pipeline (3).
  • a discharge from the reactor (1) is removed and fed to the phase separation vessel (5).
  • the liquid phase obtained in the phase separation vessel (5) is cooled in the heat exchanger (8) and mixed as a circulating stream with the feed stream (3) and returned to the reactor (1).
  • phase separation vessel (5) a further stream (9) is separated, which contains gaseous and liquid components and fed via a separate line to the reactor (10).
  • a discharge from the reactor (10) is removed and fed to the phase separation vessel (11).
  • the liquid phase obtained in the phase separation vessel (11) is cooled in the heat exchanger (14) and mixed as a circulating stream with the feed stream (9) and returned to the reactor (10).
  • another stream (15) is separated, the gaseous and liquid fractions containing and fed via a separate line to the reactor (17).
  • the hydrogenation product leaves the reactor (17) via the pipe (18).
  • all glycerol-containing streams are suitable for use in the process according to the invention, including those from industrially practiced processes and with the resulting purity grades. These include in particular glycerol-containing streams from the processing of oil and / or fatty starting materials, eg.
  • the glycerol-containing stream provided in step a) is a glycerol-containing stream obtained in the production of alkyl esters of higher fatty acids by transesterification of fatty acid triglycerides, such as, in particular in the production of "biodiesel" is obtained.
  • the glycerol-containing stream used in step a) preferably has a water content of at most 30% by weight, preferably of at most 20% by weight. Particularly preferred is a water content corresponding to the glycerol monohydrate (water content 16.3 wt .-%) or less.
  • a glycerol-containing stream is used, which is essentially anhydrous.
  • substantially anhydrous in the context of the present invention, a water content of at most 3 wt .-%, particularly preferably at most 1 wt .-% understood.
  • glycerol-containing streams having a water content in the range of up to 30% by weight, in particular up to 20% by weight makes it possible to produce 1,2-propanediol in high yields and with high selectivity in the temperature and pressure range used for the hydrogenation .
  • the hydrogenation of glycerol-containing streams which are not substantially anhydrous and in particular streams which have a higher water content than the glycerol monohydrate is also possible with high yields and selectivities, but less economical due to the reduced space-time yield. Nevertheless, a water content in the range of 3 to 30 wt .-% may be advantageous for the rheological properties during the hydrogenation.
  • a specific embodiment of the process according to the invention therefore relates to the use of glycerol-containing streams having a water content in the range from 3 to 30% by weight, preferably from 5 to 20% by weight, for reducing the viscosity in the hydrogenation.
  • the glycerol-containing streams may, instead of or in addition to water, comprise at least one further, preferably glycerol-miscible (and thus as a rule also water-miscible) organic solvent.
  • the glycerol-containing streams provided in step a) preferably have a total solvent content of at most 20% by weight, more preferably at most 15% by weight, in particular at most 10% by weight and especially at most 5% by weight. If solvent mixtures are used which contain water and at least one glycerol or water-miscible organic solvent, then the proportion of the organic
  • Solvent preferably at most 50 wt .-%, more preferably at most 20 wt .-%, based on the total weight of the solvent.
  • Suitable glycerine-miscible organic solvents are C 1 -C 4 -alkanols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, polyols and mono- and dialkyl ethers thereof, cyclic ethers, such as dioxane and tetrahydrofuran, etc
  • Suitable solvents are also aromatic hydrocarbons, such as benzene, toluene or the xylenes.
  • Preferred organic solvents are C 1 -C 4 -alkanols, in particular methanol and / or ethanol, and mixtures thereof with water.
  • the glycerol-containing streams used in step a) preferably have no organic solvents.
  • the glycerol-containing streams provided in step a) may be subjected to at least one work-up step. This includes z. B. at least one cleaning step to remove unwanted components. This also includes a reduction in the content of water and / or, if present, organic solvents.
  • the glycerol-containing streams may still contain inorganic salts as an undesired component. These can be removed from the crude glycerol according to the work-up procedures described below. In particular, thermal workup is suitable for this purpose (eg using a Sambay evaporator).
  • the glycerol-containing streams may also contain catalyst poisons, i. H. Components which interfere with hydrogenation by deactivating the hydrogenation catalyst included.
  • catalyst poisons i. H. Components which interfere with hydrogenation by deactivating the hydrogenation catalyst included.
  • These include z.
  • nitrogen-containing compounds such as amines
  • sulfur-containing compounds such as sulfuric acid, hydrogen sulfide, thio alcohols, thioethers, z. Dimethylsulfide and dimethyl disulfide, carbonyl sulfide, amino acids, e.g. B. sulfur and additional nitrogen-containing amino acids, fatty acids and their salt, etc.
  • the catalyst poisons continue to include halogen compounds, traces of common extraction agents, eg. As acetonitrile or N-methylpyrrolidone, etc. and optionally organic phosphorus and arsenic compounds.
  • a catalyst poison frequently contained in glycerol-containing streams from oil and fat refinement is sulfuric acid
  • a thermal workup preferably a distillation, adsorption, ion exchange, a membrane separation process, crystallization, extraction or a combination of two or more of these methods are used.
  • Membrane separation processes using membranes of defined pore sizes are particularly suitable for reducing the water content and / or for salt removal.
  • Crystallization is also understood to mean the partial freezing of the glycerol-containing streams on cooled surfaces. Thus, impurities can be removed that accumulate in the solid phase.
  • the glycerol-containing stream in step a) is subjected to a distillation to reduce the water content and / or to remove components which impair the catalytic hydrogenation.
  • a distillation to reduce the water content and / or to remove components which impair the catalytic hydrogenation.
  • Suitable apparatus for distillative workup include distillation columns, such as tray columns, which may 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
  • Suitable separation methods are described in the following documents: Sattler, Klaus: Thermal Separation Methods, 3rd Edition, Wiley VCH, 2001; Schlünder E.U., Thurner F .: Distillation, Absorption, Extraction, Springer Verlag, 1995; Mersmann, Alfons: Thermal Process Engineering, Springer Verlag, 1980; Grassmann P., Widmer F .: Introduction to Thermal Process Engineering, de Gruyter, 1997; White S., Militzer K. -E., Grammer K .: Thermal Process Engineering, Dt. Verlag für Grundstoffindustrie, Stuttgart, Stuttgart, 1993. Reference is made to these documents.
  • the glycerol-containing stream in step a) is subjected to a reduction in the content of sulfur-containing compounds, especially sulfur-containing aromatic compounds, a catalytic desulfurization, optionally in the presence of hydrogen.
  • Suitable desulfurizing agents include a metal component, which metal is preferably selected from metals of Groups 6, 7, 8, 9, 10, 11 and 12 of the Periodic Table.
  • the metals are selected from Mo, Ni, Cu, Ag, Zn, and combinations thereof.
  • Suitable further components of the desulfurization agents are dopants.
  • the metal component may be used in oxidic form, reduced form or a mixture containing oxidized and reduced components.
  • the active component of the desulfurizing agent may be applied to a support.
  • Suitable carriers are in principle the adsorbents and catalyst carriers mentioned below.
  • the support material is selected from activated charcoal, graphite, carbon black, Al 2 O 3, Si 2 O, TiO 2, ZrO 2, SiC, silicate, zeolites, clays (eg bentonites) and combinations thereof.
  • the application of at least one metal component and optionally further components to a carrier material can be carried out by known methods, for. By (Co) precipitation or impregnation.
  • the desulfurization can be used as a molded body, z.
  • Unsupported desulfurizing agents may be removed by conventional methods. be formed, z. By extruding, tableting, etc.
  • the shape of supported desulfurizing agent is determined by the shape of the carrier.
  • a desulfurizing agent containing copper and zinc in an atomic ratio of 1: 0.3 to 1:10, preferably 1: 0.5 to 1: 3, more preferably 1: 0.7 to 1: 1 , 5, contains.
  • a desulphurising agent which comprises 35 to 45% by weight of copper oxide, 35 to 45% by weight of zinc oxide and 10 to 30% by weight of aluminum oxide.
  • the desulfurizing agent is a component capable of being used as a hydrogenation catalyst in step b).
  • the glycerol-containing streams are brought into contact with the desulfurizing agent in at least one desulfurization zone and then hydrogenated in at least one reaction zone.
  • the specific design and arrangement of the desulfurization and reaction zone (s) may be in any known manner. It is possible to arrange the desulfurization and reaction zone (s) spatially separated, i. H. structurally separate from one another by means of the apparatus configuration or also to be realized in one or more common desulfurization / hydrogenation zone (s).
  • the copper-zinc desulfurizing agent may, for. B. obtained by a conventional precipitation or co-precipitation and used in oxidized as well as in reduced form.
  • the copper-zinc desulfurizing agent contains at least copper, zinc and aluminum, wherein the copper: zinc: aluminum atomic ratio ranges from 1: 0.3: 0.05 to 1: 10: 2, preferably 1: 0.6: 0.3 to 1: 3: 1 and especially 1: 0.7: 0.5 to 1: 1, 5: 0.9.
  • the desulfurizing agent For conversion to the reduced form, it is possible to subject the desulfurizing agent to a hydrogen reduction. This is carried out at about 150 to 350 0 C, preferably at about 150 to 250 0 C, in the presence of hydrogen, wherein the hydrogen by an inert gas such.
  • an inert gas such as nitrogen, argon, methane, in particular nitrogen, is diluted, so that the hydrogen content is 10 vol .-% or less, preferably 6 vol .-% or less, in particular 0.5 to 4 vol .-%, is. That so obtained copper-zinc desulfurizing agent ("reduced form”) can be used in this form in the desulfurization.
  • the desulfurization of the glycerol-containing stream is carried out on the copper-zinc desulfurizing agent in oxidized form without the addition of hydrogen.
  • the desulfurization of the glycerol-containing stream is carried out on the copper-zinc desulfurizing agent in oxidized form in the presence of hydrogen.
  • the desulfurization of the glycerol-containing stream is carried out on the copper-zinc desulfurizing agent in reduced form without the addition of hydrogen.
  • the desulfurization of the glycerol-containing stream on the copper-zinc desulfurizing agent is carried out in reduced form in the presence of hydrogen.
  • the desulfurization is in a temperature range of 40 to
  • the desulfurization can in the presence of inert gases such. As nitrogen, argon or methane, are performed. In general, however, the desulfurization is carried out without the addition of inert gases.
  • hydrogen is used here with a purity of ⁇ 99.8% by volume, in particular of ⁇ 99.9% by volume, preferably of ⁇ 99.95% by volume. These degrees of purity apply analogously to the hydrogen which is used in the optionally carried out activations of the catalysts.
  • the weight ratio of glycerol-containing stream to hydrogen is in the range of 40,000: 1 to 1,000: 1, especially in the range of 38,000: 1 to 5,000: 1, in particular in the range of 37,000: 1 to 15,000: 1, preferably in the range of 36,000: 1 to 25,000: 1, especially in the range of 35,000: 1 to 30,000: 1.
  • the thus desulfurized glycerol-containing stream generally has a content of sulfur-containing impurities, especially of aromatic sulfur compounds, of at most 70 ppb, preferably of at most 50 ppb, and the total sulfur content is in total ⁇ 200 ppb, preferably ⁇ 150 ppb, in particular ⁇ 100 ppb.
  • the desulfurizing agents described above also make it possible to reduce or remove chlorine, arsenic and / or phosphorus or corresponding chlorine-, arsenic- and / or phosphorus-containing compounds from the aromatic hydrocarbon or the mixture of aromatic hydrocarbons.
  • the glycerol-containing stream is contacted with at least one adsorbent in step a) to remove components which interfere with the catalytic hydrogenation.
  • the adsorbents preferably have a specific surface area, determined by BET, in the range from 10 to 2000 m 2 / g, more preferably in the range from 10 to 1500 m 2 / g, in particular in the range from 10 to 400 m 2 / g, especially in Range from 60 to 250 m 2 / g.
  • Suitable adsorbents are z. B. active aluminas. Their preparation takes place for. B. starting from aluminum hydroxide, which is obtainable by conventional precipitation of aluminum salt solutions. Active aluminas suitable for the process according to the invention are also obtainable starting from aluminum hydroxide gels. For the preparation of such gels z. Example, precipitated aluminum hydroxide after conventional work-up steps, such as filtering, washing and drying, activated and then optionally ground or agglomerated. If desired, the resulting alumina may then be subjected to a shaping process, such as extrusion, granulation, tabletting, etc. Suitable adsorbents are preferably the Selexsorb TM grades from Alcoa.
  • Suitable adsorbents are also alumina-containing solids. These include z. As the so-called clays, which also have aluminum oxides as the main component.
  • adsorbents are aluminum phosphates.
  • adsorbents are silicas, the z. B. by dehydration and activation of silica gels are available.
  • Another method for preparing silica is the flame hydrolysis of silicon tetrachloride, wherein by suitable variations of the reaction parameters, such. As the stoichiometric composition of the educt mixture and the temperature, the desired surface properties of the resulting silica can be varied within wide ranges.
  • adsorbents are diatomaceous earth, which also have silicas as their main constituent. This includes z. As the diatomaceous earth obtained from silica sediments.
  • adsorbents are titanium dioxides and zirconium dioxides, as z. In Römpp, Chemie-Lexikon, 9th edition (paperback), Vol. 6, p. 4629f. and pp. 5156f. and the literature cited therein. This is hereby fully incorporated by reference.
  • adsorbents are phosphates, in particular condensed phosphates, such as. As melting or annealing phosphates, which have a large active surface area.
  • Suitable phosphates are, for. In Römpp, Chemie-Lexikon, 9th edition (paperback), Vol. 4, p. 3376f. and the literature cited therein. This is hereby fully incorporated by reference.
  • adsorbents are carbonaceous adsorbents, preferably activated carbon.
  • Activated carbon is generally understood to mean carbon with a porous structure and a high internal surface area.
  • plant, animal and / or mineral carbonaceous raw materials eg. B. with dehydrating agents such as zinc chloride or phosphoric acid, heated or charred by dry distillation and then activated by oxidation. This can be z. B. treat the charred material at elevated temperatures of about 700 to 1000 0 C with water vapor, carbon dioxide and / or mixtures thereof.
  • the adsorbents are preferably selected from titanium dioxides, zirconium dioxides, silicium dioxides, diatomaceous earth, aluminas, alumina-containing solids, aluminum phosphates, natural and synthetic aluminosilicates, phosphates, carbonaceous adsorbents and mixtures thereof.
  • the adsorbents generally have a specific surface area, determined by BET, in the range of about 10 to 2000 m 2 / g, in particular in the range of 10 to 1500 m 2 / g and especially in the range of 20 to 600 m 2 / g ,
  • the glycerol-containing stream is brought into contact with at least one adsorption agent in step a) in an adsorption zone.
  • an adsorbent which contains at least one component which is also capable of being used as hydrogenation catalyst in step b).
  • the hydrogenation catalysts described in more detail below are hereby incorporated by reference in their entirety.
  • Combinations of two or more than two adsorbents are also suitable for use as adsorbents. In this case, both exclusively as hydrogenation catalysts capable components, not suitable as hydrogenation adsorbents and combinations thereof are used exclusively.
  • the same component is used as adsorbent and as hydrogenation catalyst. If appropriate, one additionally uses one or more further conventional adsorbents other than the hydrogenation catalyst, as described above.
  • the glycerol-containing streams are brought into contact with the adsorbent in at least one adsorption zone and then hydrogenated in at least one reaction zone.
  • the specific configuration and arrangement of the adsorption and reaction zone (s) may be in any known manner. It is preferable to arrange the adsorption and reaction zone (s) spatially separated from each other, that is, to separate the adsorption and reaction zones (n). H. structurally separated from each other by the apparatus design.
  • z. B a first adsorption zone in a first reactor, which contains a first adsorbent, and separately, so separated by equipment, z. B. in a second reactor, a second adsorption zone containing a second adsorbent.
  • the first and / or the second adsorbent may contain at least one component capable of being used as a hydrogenation catalyst.
  • a conventional adsorbent is combined with an adsorbent capable of hydrogenation in a single embodiment
  • Adsorption zone, z. B. in layered form, mixed in the form of a random distribution or in the form of a gradient bed.
  • the use in mixed form optionally allows better control of the temperature.
  • linear and non-linear gradients can be used. It may be advantageous in this case to carry out the distribution within the bed such that the glycerol-containing stream to be hydrogenated is first brought into contact with the conventional adsorbent before it is brought into contact with the adsorbent capable of hydrogenation.
  • At least two adsorption zones will be arranged so that the glycerol-containing stream to be hydrogenated in the first adsorption zone is contacted with a conventional adsorbent and contacted in the second adsorption zone with an adsorbent containing at least one component capable of use as a hydrogenation catalyst becomes.
  • the glycerol-containing streams provided in step a) of the process according to the invention are preferably derived from the production of biodiesel.
  • biodiesel is understood as meaning a mixture of fatty acid monoalkyl esters which can be obtained from biogenic oil and / or fat-containing starting mixtures and used as fuel in diesel engines.
  • 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, nonadecanoic acid, arachidic 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 transconfigured.
  • the proportion of free fatty acids is generally 0% to 50%, z. B.
  • free fatty acids can be removed before or after the transesterification of the fatty acid triglycerides.
  • Salts of these fatty acids 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 their extraction from corresponding biogenic starting materials 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 may be at least partially removed by transesterification prior to use to provide 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. From these starting materials, too, ingredients other than fatty acid triglycerides (and optionally free fatty acids) may, if desired, be at least partially removed by transesterification prior to use to provide the glycerol-containing stream.
  • the unused or used fats or oils may be subjected to the removal of undesired ingredients such as lecithins, carbohydrates, proteins, oil sludge, water, etc.
  • Vegetable oils and fats are those which are predominantly derived from vegetable raw materials such as seeds, roots, leaves or other suitable plants. parts of the origin. 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, yellow grease, technical tallow, technical lard, frying oils, animal fat, edible tallow, vegetable crude oils, animal crude oils or greases 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 number, 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 recovery of poultry, beef, pork, fish and marine mammal bodies sloping fatty products, such as solar stearin, a solid residue that remains 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, ie of liquid or solid compositions consisting of vegetable raw materials such. B. obtained by pressing, where they have not undergone treatment other than settling in common time periods and centrifuging or filtering, in which for the separation of the oil of solid components only mechanical forces such as gravity, centrifugal force or pressure are used.
  • 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 for example, raffinates or semi-refined, of the abovementioned vegetable oils can also be 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 can 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:
  • a2) transesterifying the fatty acid triglycerides present in the starting mixture with at least one C 1 -C 9 -monoalcohol and optionally esterifying the free fatty acids contained in the starting mixture to form an esterification mixture, a3) separating the esterification mixture to obtain at least one fraction enriched in biodiesel and at least one fraction enriched in the esterification of released glycerol,
  • the provision of the biogenic fat and / or oil-containing starting mixture in step a1) comprises in a preferred embodiment at least one purification step.
  • the fat and / or oil-containing starting mixture at least one commonly used cleaning method for fats and oils, such as clarification, filtration, treatment with bleaching earths or treatment with acids or alkali to remove interfering impurities such as proteins, phosphatides and mucilage and a combination of at least be subjected to two of these purification steps.
  • fatty acid triglycerides is preferably at least one
  • Ci-Cg monoalcohol in particular at least one Ci-C4 monoalcohol used. Preference is given to the use of methanol or ethanol.
  • the transesterification of the fatty acid triglycerides can be catalyzed acidic or preferably catalytically.
  • Suitable acids are, for example, mineral acids such as HCl, H 2 SO 4 or H 3 PO 4 .
  • At least one base is used as the catalyst.
  • This is preferably selected from among alkali hydroxides, such as NaOH and KOH, alkaline earth hydroxides, such as Ca (OH) 2 , alkali metal and alkaline earth d-Ce alkoxaten, such as NaOCH 3 , KOCH 3 ,
  • the amount of base used is usually in the range from 0.1 to 10% by weight, in particular from 0.2 to 5% by weight, based on the amount of fatty acid triglycerides used.
  • the base is preferably used in the form of an aqueous or alcoholic, particularly preferably alcoholic, solution.
  • aqueous or alcoholic particularly preferably alcoholic, solution.
  • a NaOCH3 solution in methanol is used for transesterification.
  • the transesterification is preferably carried out at a temperature of about 20 to 150 0 C, in particular 30 to 95 0 C.
  • the transesterification takes place in customary, known to those skilled devices. After a suitable execution, the transesterification takes place continuously.
  • the transesterification preferably takes place in at least one column, the resulting transesterification mixture being simultaneously subjected to a separation. In this case, a higher-boiling phase is generally obtained, which is enriched in the basic catalyst, unreacted monoalcohol and the glycerol formed in the transesterification and obtains a lower-boiling phase which is enriched in the transesterification product. If the transesterification product does not contain transesterified triglycerides, these can likewise be separated off and subjected to renewed transesterification in the first or a further transesterification stage.
  • the last transesterification mixture is transferred to a drying plant, again removing residual amounts of water.
  • the desired end product is biodiesel in purified form and can be used directly as a fuel.
  • the fat and / or oil-containing starting mixture used to provide the glycerol-containing stream in step a) contains free fatty acids, these may preferably be subjected to esterification for conversion into biodiesel-suitable esters.
  • the free fatty acids are preferably transesterified with the same d-Cg monoalcohol used to transesterify the fatty acid triglycerides.
  • the esterification of free fatty acids can take place before, during or after the transesterification of the fatty acid triglycerides. In a preferred embodiment, the esterification of free fatty acids takes place before the transesterification of the fatty acid triglycerides.
  • the esterification of the free fatty acids can be basic or preferably acid catalysed. Suitable acids are the aforementioned mineral acids, such as HCl, H 2 SO 4 or H 3 PO 4, p-toluenesulfonic acid, etc.
  • the esterification is preferably carried out at a temperature of about 20 to 95 0 C, in particular 40 to 80 0 C.
  • the esterification takes place in customary, known to those skilled devices. These include stirred tank and / or columns, which are optionally connected to cascades.
  • the esterification of the free fatty acids takes place in at least one esterification unit designed as a column, the resulting esterification mixture being simultaneously subjected to a separation.
  • the esterification is carried out in the presence of an entraining agent to facilitate the separation.
  • the esterification mixture is subjected to separation to obtain at least one fraction enriched in d-Cg monoalkyl esters and at least one fraction enriched in glycerol released in the transesterification.
  • the separation is preferably carried out by distillation according to customary methods known to the person skilled in the art. Suitable distillation apparatuses are those mentioned above.
  • the glycerol-enriched fraction obtained after separating the esterification mixture in step a3) may optionally be subjected to at least one work-up step.
  • work-up step include, for example, the removal of undesired components, such as salts, as well as components which impair the catalytic hydrogenation or the separation of water and, if present, organic solvent.
  • the catalysts used in the process according to the invention may be unsupported catalysts or supported catalysts. They can be used in the form of uniformly composed catalysts, impregnated catalysts, coated catalysts and precipitation catalysts.
  • a plurality of copper-containing catalysts are suitable, which additionally at least one further element of the I., II., III., IV or V. main group, the I., II., IV., V., VI., VII VIII.
  • Subgroup and the lanthanides may contain (IUPAC: groups 1 to 15 and the lanthanides), in particular Ca, Mg, Al, La, Ti, Zr, Cr, Mo, W, Mn, Ni, Co, Zn and combinations thereof.
  • a specific embodiment of catalysts which are particularly advantageously suitable for use in the process according to the invention are skeletal or metal sponge catalysts, which are referred to as "Raney catalysts". These include especially Raney copper and copper-containing metal alloys in the form of a Raney catalyst.
  • Raney catalysts whose metal component consists of at least 95%, in particular at least 99%, of copper.
  • Methods for the preparation of Raney catalysts are known in the art and z.
  • Raney copper can be prepared in a manner known per se by treating copper-aluminum alloys with alkali metal hydroxides.
  • a suitable for use in the process according to the invention Raney catalyst is z. B.
  • the catalyst alloy comprises copper and optionally at least one further catalytically active catalyst metal and a leachable alloy component, optionally with the addition of humectants and / or additives such as shaping aids, lubricants , Plasticizers and / or pore formers, homogenizing this mixture and shaping to the desired shaped body, calcining the shaped body and activating the catalyst precursor thus obtained by partial or complete leaching of the leachable alloy component and optionally final washing of the finished catalyst.
  • humectants and / or additives such as shaping aids, lubricants , Plasticizers and / or pore formers
  • a further specific embodiment of catalysts which are particularly advantageous for use in the process according to the invention are catalysts which contain copper in oxidic form and optionally additionally in elemental form.
  • the hydrogenation catalyst used in step b) then preferably contains at least 23 wt .-%, more preferably at least 35 wt .-%, copper in oxidic and / or elemental form, based on the total weight of the catalyst.
  • a frequently used process for the preparation of such catalysts is the impregnation of support materials with solutions of the catalyst components, which are then converted by thermal treatment, decomposition or reduction in the catalytically active state.
  • Another suitable method for the preparation of catalysts comprises the precipitation of a catalyst component or the co-precipitation of two or more than two catalyst components.
  • a copper compound, optionally at least one further Metal compound and / or an additive can be precipitated and then subjected to drying, quenching and shaping.
  • the precipitation can be carried out in the presence of a carrier material.
  • Suitable starting materials for the precipitation are metal salts and metal complexes.
  • all known Cu (I) and / or Cu (II) salts which are soluble in the solvents used for application to the support can be used as copper compounds for the precipitation. These include z.
  • nitrates carbonates, acetates, oxalates or ammonium complexes.
  • copper nitrate is used.
  • the catalytic active component of the catalyst apart from a copper compound, further elements as additives, for.
  • metals non-metals and their compounds. These are preferably metals of groups 4 to 15 and the lanthanides. Particularly preferred metals are La, Ti, Zr, Cu, Mo, W, Mn, Re, Co, Ni, Cu, Ag, Au, Zn, Sn, Pb, As, Sb and Bi.
  • an aqueous medium is used for the precipitation ,
  • Suitable aqueous media are substances or mixtures which are liquid under the process conditions and which contain at least 10% by weight, particularly preferably at least 30% by weight, in particular at least 50% by weight, of water.
  • the portion other than water is preferably selected from inorganic or organic compounds which are at least partially soluble in water or at least partially miscible with water.
  • the compounds other than water are selected from organic solvents, such as C 1 -C 20 -alkanols, in particular methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, penthanols and hexanols, C 8 -cycloalkyl ethers, such as tetrahydrofurans, pyrans, dioxanes and trioxanes, C 1 -C 12 -dialkyl ethers, such as dimethyl ether, dibutyl ether and methyl butyl ether.
  • the aqueous medium preferably contains less than 40% by weight, more preferably less than 30% by weight and in particular less than 20% by weight of organic solvents. In a preferred embodiment of the process according to the invention, the aqueous medium is substantially free of organic solvents.
  • the precipitation may be carried out by known methods, e.g. B. cooling a saturated solution, adding a precipitant, etc. induced. Suitable precipitants are for. As acids, bases, reducing agents, etc.
  • the precipitate may be induced by adding an acid or a base to the aqueous medium containing the copper compound and optionally further compounds.
  • Suitable acids are mineral acids such as HCl, H2SO4 and H3PO4.
  • the base is preferably selected from metal oxides, metal hydroxides, in particular in particular alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide, metal carbonates, in particular alkali metal and alkaline earth metal carbonates, such as lithium carbonate, sodium carbonate, potassium carbonate, magnesium carbonate and calcium carbonate, nitrogen bases, in particular ammonia and primary, secondary and tertiary amines.
  • suitable reducing agents are carboxylic acids, such as formic acid, citric acid, lactic acid, tartaric acid and especially salts of carboxylic acids, preferably the alkali metal, alkaline earth metal, ammonium and C 1 -C 10 -alkylammonium salts, phosphorous or hypophosphorous acid, the salts of phosphorous or hypophosphorous acid, in particular the alkali metal or alkaline earth metal salts, C 1 -C 10 -alkanols, such as methanol, ethanol and isopropanol, sugars, such as aldoses and ketoses in the form of monosaccharides, disaccharides and oligosaccharides, in particular glucose, fructose and lactose, aldehydes, such as For aldehyde, boron-hydrogen compounds, such as borohydrides, boranes, metal borohydrates and borane complexes, such as diborane, sodium borohydride and aminobora
  • catalysts containing on a support of silica nickel and copper among other metals as active ingredients.
  • Such catalysts are z. B. in DE-A 26 28 987 described.
  • the active material of these catalysts contains specifically 40 to 80 wt .-% nickel, 10 to 50 wt .-% copper and 2 to 10 wt .-% manganese.
  • EP-A-0 434 062 describes hydrogenation catalysts obtainable by reduction of a precursor of oxides of copper, aluminum and at least one other metal selected from magnesium, zinc, titanium, zirconium, tin, nickel and cobalt.
  • the hydrogenation catalysts described in DE 102 18 849 which contain 0.1 to 10% by weight of chromium, calculated as Cr 2 O 3 , 0.1 to 10% by weight of calcium, calculated as CaO x and 5 to 20 wt .-% copper, calculated as CuO, deposited on a silica support material and in each case based on the total weight of the calcined catalyst included.
  • Copper-zirconium oxide catalysts are known from DE-A-40 21 230, the ratio of copper atoms to zirconium atoms, expressed as a weight ratio, being 1: 9 to 9: 1.
  • DE-A-4 028 295 describes copper-manganese hydrogenation catalysts.
  • EP-A-552463 describes in a first embodiment hydrogenation catalysts, wherein the oxidic form substantially corresponds to the composition Cu a AlbZr c MndO ⁇ , wherein the following relationships apply: a>0;b>0; c ⁇ 0; d>0;a> b / 2; b> a / 4; a>c;a>d; and x denotes the number of oxygen ions required to maintain electroneutrality per formula unit.
  • the catalyst according to the invention contains a smaller proportion of aluminum oxide.
  • the catalyst according to this embodiment essentially corresponds to the composition Cu a AlbZr c MndO ⁇ , the following relationships apply: a>0; a / 40 ⁇ b ⁇ a / 4; c>0;d>0;a>c; 0.5d ⁇ a ⁇ 0.95d and x denotes the number of oxygen ions required to maintain electroneutrality per formula unit.
  • WO 2006/005505 describes shaped catalyst bodies which are particularly suitable for use in the process according to the invention. These can be produced by a process in which
  • an oxide material comprising copper oxide, alumina and at least one of the oxides of lanthanum, tungsten, molybdenum, titanium or zirconium, wherein the oxides of lanthanum and / or tungsten are to be preferred, is provided,
  • powdered metallic copper, copper flakes, powdered cement or mixtures thereof or a mixture thereof with graphite may be added to the oxidic material, and
  • lanthanum oxide is preferred.
  • the composition of the oxide material is generally such that the proportion of copper oxide is in the range of 40 to 90 wt .-%, the proportion of oxides of lanthanum, tungsten, molybdenum, titanium or zirconium in the range of 0 to 50 wt .-% and the proportion of aluminum oxide in the range up to 50 wt .-%, each based on the total weight the sum of the abovementioned oxidic constituents, wherein these three oxides together represent at least 80% by weight of the oxidic material after calcination, whereby cement is not attributed to the oxidic material in the above sense.
  • the oxide material comprises
  • alumina having a content in the range of 15 ⁇ y ⁇ 35 wt%, preferably 20 ⁇ y ⁇ 30 wt%, and
  • Preferred catalysts include the following metals in oxidic form, reduced form (elemental form) or a combination thereof. Metals that are stable in more than one oxidation state can be used completely in one of the oxidation states or in different oxidation states:
  • Cu, Al at least one other metal selected from La, W, Mo, Mn, Zn, Ti, Zr, Sn, Ni, Co
  • Particularly preferred catalysts include the following metals:
  • support materials of the prior art As an inert support material for the catalysts of the invention, virtually all support materials of the prior art, as they are advantageously used in the preparation of supported catalysts, for example SiC "2 (quartz), porcelain, magnesium oxide, tin dioxide, silicon carbide, TiO 2 (rutile, anatase) Al2O3 (alumina), aluminum silicate, steatite (magnesium silicate), zirconium silicate, cerium silicate or mixtures of these support materials are preferred support materials are aluminum oxide and silicon dioxide.
  • pyrogenic silicas or wet-chemically prepared silicas, such as silica gels, aerogels or precipitated silicas, are used for catalyst preparation (for the preparation of the various SiO 2 starting materials see: W. Buchner, R. Sch Kunststoffs, G. Winter, KH Buchel: Industrial Inorganic Chemistry, 2nd ed., Pp. 532-533, VCH Verlagsgesellschaft, Weinheim 1986).
  • the catalysts can be used as shaped bodies, for. B. in the form of spheres, rings, cylinders, cubes, cuboids or other geometric bodies.
  • Unsupported catalysts can be formed by conventional methods, e.g. By extruding, tableting, etc.
  • the shape of supported catalysts is determined by the shape of the support.
  • the support may be subjected to a molding process before or after application of the catalytically active component (s).
  • the catalysts may, for. B. in the form of pressed cylinders, tablets, pastilles, carriage wheels, rings, stars or extrudates, such as solid strands, polylobd strands, hollow strands and honeycomb bodies or other geometric bodies are used.
  • the catalyst particles generally have an average of the (largest) diameter of 0.5 to 20 mm, preferably 1 to 10 mm.
  • These include z. Eg cat lysatoren in the form of tablets, z. B. with a diameter of 1 to 7 mm, preferably 2 to 6 mm, and a height of 3 to 5 mm, rings with z. B. 4 to 7 mm, preferably 5 to 7 mm, outer diameter, 2 to 5 mm in height and 2 to 3 mm hole diameter, or strands of different lengths of a diameter of z. B. 1, 0 to 5 mm.
  • Such forms can in a known per se manner
  • the catalyst composition customary auxiliaries, for.
  • lubricants such as graphite, polyethylene oxide, celluloses or fatty acids (such as stearic acid), and / or molding aids and reinforcing agents, such as fibers of glass, asbestos or silicon carbide, are added.
  • a specific embodiment of supported catalysts are shell catalysts.
  • Shell catalysts are also particularly suitable for the process according to the invention.
  • Shelled catalysts comprise a cup-shaped catalytic mass applied to a carrier. They can be in the form of spheres, rings, cylinders, cubes, cuboids or other geometric bodies.
  • the provision of coated catalyst particles can in principle be accomplished by contacting the support with a liquid binder and the catalytically active composition, thereby applying a layer of the composition to the support, and then optionally the binder partially removed.
  • the catalytically active material is already applied in its finished catalytically active form, for example as a calcined mixed oxide.
  • Suitable processes for the preparation of coated catalysts are, for.
  • the support is first moistened with the liquid binder, then adhered to the surface of the moistened support body by contacting with dry, finely divided, active catalyst mass a layer of active catalyst mass and then optionally partially removed the liquid binder.
  • the steps of wetting the carrier, contacting the catalyst mass and removing the liquid binder are repeated one or more times until the desired layer thickness of the coated catalyst is reached.
  • aqueous salt solutions of the components for.
  • aqueous solutions of their halides, sulfates, nitrates, etc. applied to the support material.
  • the copper component may, for. Example, in the form of an aqueous solution of their amine complex salts, for example as [Cu (NH 4 ) 4 ] SO 4 - or as [Cu (NH3) 4] (NO3) 2 solution, optionally in the presence of sodium carbonate, onto the support material.
  • amine complex salts for example as [Cu (NH 4 ) 4 ] SO 4 - or as [Cu (NH3) 4] (NO3) 2 solution, optionally in the presence of sodium carbonate, onto the support material.
  • other copper amine complexes may be used with equal success for catalyst preparation.
  • the impregnation of the support material with the precursor compounds of the catalytically active components can in principle be carried out in one or more stages.
  • the impregnation can be carried out in conventional impregnating devices, e.g. Impregnated drums.
  • the finished catalyst is then obtained.
  • the drying of the impregnated catalyst form body can continuously or batchwise, for. B. in band or Hordenöfen done.
  • the drying can be carried out at atmospheric pressure or reduced pressure.
  • the drying in a gas stream for. As an air stream or a stream of nitrogen, take place.
  • the drying is generally carried out at temperatures of 50 to 200 0 C, preferably 80 to 150 0 C.
  • the calcination of the optionally previously dried catalyst is generally carried out at temperatures of 200 to 800 0 C, preferably 500 to 700 0 C.
  • the calcination like the drying, continuously or batchwise, z. B. in band or Hordenöfen performed.
  • the calcination may be carried out at atmospheric or reduced pressure and / or in a gas stream, e.g. B. in an air or a hydrogen stream.
  • Pre-treatment with hydrogen or hydrogen-containing gases generally under conditions which correspond to the hydrogenation conditions serves to pre-reduce / activate the hydrogenation catalyst.
  • the catalyst can also be reduced in situ under the conditions predetermined during the hydrogenation, preferably under pressure (for example at a hydrogen pressure of about 100 to 325 bar).
  • the hydrogenation discharge consists essentially of 1,2-propanediol.
  • Other ingredients include methanol, ethanol, n-propanol, isopropanol, 1, 3-propanediol, glycerol, ethylene glycol and water.
  • the hydrogenation discharge can then be worked up by customary methods known to the person skilled in the art. For example, thermal processes, preferably distillative processes, adsorption, ion exchange, membrane separation processes, crystallization, extraction or a combination of two or more of these processes are suitable for this purpose.
  • the hydrogenation is worked up by distillation. Suitable for this purpose are customary distillation processes known to the person skilled in the art.
  • Suitable apparatus for the work-up by distillation comprise distillation columns, such as tray columns, which may be provided with bells, sieve plates, sieve trays, packings, internals, valves, side draws, etc. Particularly suitable are dividing wall columns which are equipped with side drawers, return ments, etc. may be provided. For distillation, a combination of two or more than two distillation columns can be used. Also suitable are evaporators, such as thin film evaporators, falling film evaporators, Sambay evaporators, etc., and combinations thereof. Glycerol still present in the hydrogenation effluent can, if appropriate after distillative separation, be recycled to the hydrogenation stage.
  • FIG. 2 shows the schematic representation of the three-stage reactor cascade used for carrying out the hydrogenation process according to Example 1, wherein for the sake of clarity, the reproduction of such details is omitted, which are not relevant for the explanation of the invention.
  • the catalyst is an oxidic material comprising CuOo, 6-o, 85 (AbOs) O, 1-0.34 (La2 ⁇ 3) o, oi-o, 2 and which, based on the total weight of the oxide Materials, up to 20% may contain adjuvants.
  • the reactor (1) contains 100 ml, the reactor (10) 75 ml and the reactor (17) 70 ml of catalyst.
  • the catalyst is reduced in the hydrogen stream before the hydrogenation reaction.
  • pure glycerin is mixed with water in a mass ratio of glycerol to water of 9: 1.
  • the reaction parameters are shown in Table 1.
  • Carrier gas helium

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Abstract

La présente invention concerne un procédé de production de propane-1,2-diol, caractérisé en ce qu'un flux contenant de la glycérine, en particulier un flux produit à l'échelle industrielle lors de la production de biodiesel, est soumis à une hydrogénation dans une cascade de réacteurs à au moins trois étages.
EP08803384A 2007-08-31 2008-08-29 Procédé de production de propane-1,2-diol par hydrogénation de glycérine dans au moins trois réacteurs montés en série Withdrawn EP2200959A2 (fr)

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EP08803384A EP2200959A2 (fr) 2007-08-31 2008-08-29 Procédé de production de propane-1,2-diol par hydrogénation de glycérine dans au moins trois réacteurs montés en série

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EP07115461 2007-08-31
EP08803384A EP2200959A2 (fr) 2007-08-31 2008-08-29 Procédé de production de propane-1,2-diol par hydrogénation de glycérine dans au moins trois réacteurs montés en série
PCT/EP2008/061386 WO2009027501A2 (fr) 2007-08-31 2008-08-29 Procédé de production de propane-1,2-diol par hydrogénation de glycérine dans au moins trois réacteurs montés en série

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Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BRPI0918489A2 (pt) 2008-09-08 2015-12-01 Basf Se processo integrado para produzir polpa e pelo menos um material de valor de baixo peso molecular
EP2379482B1 (fr) 2008-12-16 2015-08-26 Basf Se Production d'esters d'acide carboxylique par strippage avec de la vapeur d'alcool
WO2010084118A1 (fr) * 2009-01-21 2010-07-29 Basf Se Procédé de production de 1,2-propanediol désodorisé
KR101742749B1 (ko) 2009-05-20 2017-06-01 바스프 에스이 구리 함유 불균일한 촉매 상에서 지방산 트리글리세라이드의 수소화에 의한 지방 알콜의 제조 방법
WO2010146117A2 (fr) * 2009-06-19 2010-12-23 Basf Se Procédé d'hydrogénation de glycérine en 1,2-propanediol, avec désulfuration par hydrogénation sur lit sacrificiel
CN103657730B (zh) * 2012-09-20 2016-03-02 中国石油化工股份有限公司 甘油加氢制备1，2－丙二醇的催化剂及其制备方法
US8580119B1 (en) * 2012-11-27 2013-11-12 Menlo Energy Management, LLC Transesterification of biodiesel feedstock with solid heterogeneous catalyst
US8545703B1 (en) * 2012-11-27 2013-10-01 Menlo Energy Management, LLC Production of glycerin from feedstock
US8545702B1 (en) * 2012-11-27 2013-10-01 Menlo Energy Management, LLC Production of biodiesel from feedstock
US8540880B1 (en) * 2012-11-27 2013-09-24 Menlo Energy Management, LLC Pretreatment of biodiesel feedstock
US8540881B1 (en) * 2012-11-27 2013-09-24 Menlo Energy Management, LLC Pretreatment, esterification, and transesterification of biodiesel feedstock
CN103245678B (zh) 2013-04-26 2015-12-09 深圳市华星光电技术有限公司 一种异物检测装置
US10710949B2 (en) 2015-07-15 2020-07-14 Archer Daniels Midland Company Copper-containing multimetallic catalysts, and method for using the same to make biobased 1,2-propanediol
US10472592B1 (en) 2016-10-06 2019-11-12 Smisson-Mathis Energy, Llc Systems and methods for purification of fats, oils, and grease from wastewater
CA3043696C (fr) * 2016-11-16 2022-06-28 Archer Daniels Midland Company Procede de production de 1,2-propanediol a partir de glycerol

Family Cites Families (30)

* 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
DE541362C (de) 1927-10-25 1932-01-11 I G Farbenindustrie Akt Ges Verfahren zur Hydrierung von Polyoxyverbindungen
US2360844A (en) * 1941-11-26 1944-10-24 Du Pont Preparation of detergents
DE2628987C3 (de) 1976-06-28 1981-10-22 Basf Ag, 6700 Ludwigshafen Verfahren zur Herstellung von C↓3↓-C↓5↓-Alkanolen
DE2909671A1 (de) 1979-03-12 1980-10-02 Basf Ag Verfahren zur herstellung von schalenkatalysatoren
JPH03128334A (ja) 1989-07-04 1991-05-31 Ube Ind Ltd アルコールの製造方法
GB8917862D0 (en) * 1989-08-04 1989-09-20 Davy Mckee London Process
US5008235A (en) 1989-12-21 1991-04-16 Union Carbide Chemicals And Plastics Technology Corporation Catalysts of Cu-Al-third metal for hydrogenation
DE4028295A1 (de) 1990-09-06 1992-03-12 Henkel Kgaa Cupfer-mangan-katalysatoren
IT1249955B (it) 1991-07-10 1995-03-30 Menon S R L Procedimento di idrogenazione della glicerina
DE4141199A1 (de) 1991-12-13 1993-06-17 Sued Chemie Ag Chromfreier katalysator fuer die hydrierung von organischen verbindungen, die die carbonylfunktionen enthalten
DE4209779C1 (fr) * 1992-03-26 1993-07-15 Oelmuehle Leer Connemann Gmbh & Co., 2950 Leer, De
DE4302464A1 (de) 1993-01-29 1994-08-04 Henkel Kgaa Herstellung von 1,2-Propandiol aus Glycerin
DE4345265A1 (de) 1993-10-16 1995-09-21 Degussa Katalysatorvorstufe für einen aktivierten Metall-Festbettkatalysator nach Raney
DE4442124A1 (de) * 1994-11-26 1996-05-30 Basf Ag Verfahren zur Herstellung von Propandiol-1,2
DE4442346A1 (de) 1994-11-29 1996-05-30 Basf Ag Verfahren zur Herstellung eines Katalysators, bestehend aus einem Trägerkörper und einer auf der Oberfläche des Trägerkörpers aufgebrachten katalytisch aktiven Oxidmasse
DE4446907A1 (de) 1994-12-27 1996-07-04 Basf Ag Verfahren zur Herstellung eines Hydrierkatalysators
DE19643126A1 (de) * 1996-10-18 1998-04-23 Basf Ag Metall-Festbettkatalysator nach Raney, Verfahren zu seiner Herstellung sowie ein Verfahren zur Hydrierung von Polymeren unter Verwendung dieses Katalysators
US8017816B2 (en) 2002-04-22 2011-09-13 The Curators Of The University Of Missouri Method of producing lower alcohols from glycerol
DE10218849A1 (de) 2002-04-26 2003-11-06 Basf Ag Katalysator und Verfahren für die Hydrierung von Aldehyden zu Alkoholen
DE10243700A1 (de) 2002-09-20 2004-04-01 Oelmühle Leer Connemann Gmbh & Co. Verfahren und Vorrichtung zur Herstellung von Biodiesel
EP2298721B1 (fr) 2004-03-25 2014-06-04 Galen J. Suppes Procédé pour préparer une composition antigel contenant d'alcools inférieurs et du glycérol par alcoolyse d'une glycéride
DE102004033556A1 (de) 2004-07-09 2006-02-16 Basf Ag Katalysatorformkörper und Verfahren zur Hydrierung von Carbonylverbindungen
GB0514593D0 (en) * 2005-07-15 2005-08-24 Davy Process Techn Ltd Process
EP1993985B1 (fr) 2006-03-03 2017-10-04 Basf Se Procédé de synthèse du 1,2-propanediol
GB0614823D0 (en) 2006-07-26 2006-09-06 Davy Process Techn Ltd Process
DE102006050751A1 (de) 2006-10-27 2008-05-08 Clariant International Limited Verfahren zur Herstellung von 1,2-Propandiol durch Hydrogenolyse von Glycerin
DE102007003188B3 (de) * 2007-01-22 2008-06-05 Clariant International Ltd. Verfahren zur Herstellung von 1,2-Propandiol durch Hydrogenolyse von Glycerin
CN100432034C (zh) 2007-02-07 2008-11-12 南京工业大学 甘油催化加氢连续制备1,2-丙二醇的方法
DE102007027372A1 (de) * 2007-06-11 2008-12-18 Cognis Oleochemicals Gmbh Verfahren zur Hydrierung von Glycerin

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2009027501A2 *

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BRPI0815783A2 (pt) 2015-02-24
US8293951B2 (en) 2012-10-23
US20100312023A1 (en) 2010-12-09
CN101848884B (zh) 2013-05-01
WO2009027501A2 (fr) 2009-03-05
WO2009027501A3 (fr) 2009-05-07
CN101848884A (zh) 2010-09-29

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