METHOD FOR THE CATALYTIC CONVERSION OF GLYCEROL TO PROPANOL

Abstract

In a method, device, catalyst and a method for producing a catalyst for the catalytic conversion of a substance mixture containing glycerol to propanol in a fixed-bed reactor, substrates of the catalyst have inorganic materials and/or metal oxides. The substrates have a pore diameter at the surface of between 10 and 25 angstroms, preferably between 12 and 20 angstroms, particularly preferably 15 angstroms.

Claims

1-24. (canceled)

25. A method for the catalytic conversion of a substance mixture containing glycerol to propanols in a fixed-bed reactor, wherein substrates of the catalyst comprise inorganic materials and/or metal oxides, wherein the substrates comprise a pore diameter at the surface of between 10 and 25 angstroms, the catalyst comprising silicotungstic acid or phosphotungstic acid.

26. The method according to claim 25, wherein the substrates are extrudate pellets and preferably ceramic.

27. The method according to claim 25, wherein the reaction of the substance mixture containing glycerol takes place continuously in the fixed-bed reactor, which is preferably single-stage.

28. The method according to claim 25, wherein mixed oxides of silicon, tungsten, zirconium and/or aluminium, preferably zirconium dioxide, aluminosilicate zeolites and/or aluminophosphate zeolites, preferably VFI zeolites and/or VPI-5 zeolites, dealuminated USY zeolites and/or aluminium dioxide are used as substrate of the catalyst, the catalyst preferably comprising a platinum doping.

29. The method according to claim 25, wherein the substance mixture containing glycerol is crude glycerol, technical glycerol or purified glycerol.

30. The method according to claim 25, wherein the method comprises one or more of the following steps: removing the substance mixture containing glycerol from a storage container, filtering the substance mixture containing glycerol, preferably with undissolved solids and/or diluted accompanying substances contained therein being removed, and/or mixing the substance mixture containing glycerol with water in the mixer, the concentration of the glycerol preferably being adjusted to between 5 and 80 percent, particularly preferably to between 10 and 60 percent, even more preferably to between 15 and 50 percent.

31. The method according to claim 25, wherein the method comprises one or more of the following steps: heating the substance mixture containing glycerol with a heat exchanger, preferably an economiser, adding hydrogen to the substance mixture containing glycerol, preferably in a static mixer, returning the heat of the substance mixture reacted in the fixed-bed reactor to the heat exchanger for heat transfer to the substance mixture containing glycerol before the reaction, so that the method is adiabatic.

32. The method according to claim 25, wherein hydrogen is recovered from the substance mixture reacted in the fixed-bed reactor via a separator device, the recovered hydrogen preferably being recompressed subsequently in a compressor and added to fresh hydrogen, the hydrogen mixture being used particularly preferably in the method at an earlier point, the recovered hydrogen having a proportion of between 50 and 99 percent of the total hydrogen used in the method.

33. The method according to claim 25, wherein propanols, preferably both 1-propanol and 2-propanol, are obtained from the substance mixture reacted in the fixed-bed reactor, preferably by first removing water from the substance mixture reacted in the fixed-bed reactor via a treatment cascade and obtaining pure propanols, the separated process water being added to a fresh water in a water mixer and the water mixture being used particularly preferably in the method at an earlier point, particularly for mixing in the mixer, and the recovered process water having a proportion of between 80 and 100 percent of the total water used in the method and/or longer-chain hydrocarbons are built up, preferably oligomerised, from the substance mixture reacted in the fixed-bed reactor.

34. The method according to claim 25, wherein the reaction takes place in the fixed-bed reactor at a temperature between 150 and 300 C.

35. The method according to claim 25, wherein the reaction takes place in the fixed-bed reactor at a pressure of between 10 and 100 bar.

36. A device for the catalytic conversion of a substance mixture containing glycerol, preferably crude glycerol, to propanols in a fixed-bed reactor, wherein the device comprises a catalyst and substrates of the catalyst comprise inorganic materials and/or metal oxides, wherein the substrates comprise a pore diameter at the surface of between 10 and 25 angstroms, the substrates preferably being extrudate pellets and preferably being ceramic, the catalyst comprising silicotungstic acid or phosphotungstic acid.

37. The device according to claim 36, wherein the substrates of the catalyst comprise mixed oxides of silicon, tungsten, zirconium and/or aluminium, preferably zirconium dioxide, aluminosilicate zeolites and/or aluminophosphate zeolites, preferably VFI zeolites and/or VPI-5 zeolites, dealuminated USY zeolites and/or aluminium dioxide and preferably a platinum doping, the fixed-bed reactor preferably being suitable for continuous operation.

38. The device according to claim 36, wherein the device comprises: a storage container for the substance mixture containing glycerol, a filter device for removing undissolved solids and/or undesirable accompanying substances contained in the substance mixture containing glycerol, a first mixer for diluting the substance mixture containing glycerol with water, a heat exchanger, preferably an economiser, for heating the substance mixture containing glycerol, a preferably static second mixer for adding hydrogen to the substance mixture containing glycerol, a line for returning the substance mixture reacted in the fixed-bed reactor to the heat exchanger, a separating device for recovering hydrogen from the substance mixture reacted in the fixed-bed reactor and preferably a compressor for compressing the recovered hydrogen, and/or a treatment cascade for obtaining the pure propanol fraction and preferably for recovering the process water from the substance mixture reacted in the fixed-bed reactor for mixing with fresh water in the water mixer, the water mixture obtained in this way preferably being fed to the mixer.

39. A catalyst for the catalytic conversion of a substance mixture containing glycerol to propanols in a fixed-bed reactor, wherein substrates of the catalyst comprise inorganic materials and/or metal oxides, wherein the substrates comprise a pore diameter at the surface of between 10 and 25 angstroms, the catalyst comprising silicotungstic acid or phosphotungstic acid.

40. The catalyst according to claim 39, wherein the substrates are extrudate pellets and are preferably ceramic, wherein the substrates of the catalyst preferably comprise mixed oxides of silicon, tungsten, zirconium and/or aluminium, preferably zirconium dioxide, aluminosilicate zeolites and/or aluminophosphate zeolites, preferably VFI zeolites and/or VPI-5 zeolites, dealuminated USY zeolites and/or aluminium dioxide and preferably a platinum doping and/or the catalyst is suitable for continuous operation of the fixed-bed reactor.

41. A method for producing a catalyst for the catalytic conversion of a substance mixture containing glycerol to propanols in a fixed-bed reactor, wherein substrates of the catalyst comprise inorganic materials and/or metal oxides, wherein base materials for the production of the substrates of the catalyst comprise a pore diameter at the surface of between 10 and 25 angstroms, and wherein the substrate is provided with silicotungstic acid or phosphotungstic acid.

42. The method according to claim 41, wherein mixed oxides of silicon, tungsten, zirconium and/or aluminium, preferably zirconium dioxide, aluminosilicate and/or aluminophosphate zeolites, preferably VFI zeolites and/or VPI-5 zeolites, and/or aluminium dioxide are used as base materials for the substrates.

43. A method for producing a catalyst for the catalytic conversion of a substance mixture containing glycerol to propanols in a fixed-bed reactor, wherein substrates of the catalyst comprise inorganic materials and/or metal oxides, wherein the base material for production of the substrates of the catalyst comprises USY zeolites, the USY zeolites being dealuminated so that the substrates of the catalyst comprise a pore diameter at the surface of between 10 and 25 angstroms, and wherein the substrate is provided with silicotungstic acid or phosphotungstic acid.

44. The method according to claim 41, wherein the production of the catalyst comprises one or more of the following steps: incorporating organic binders, which are subsequently burnt out without residue, the organic binder preferably being incorporated into the base materials, which are preferably in powder form, and these then being homogeneously kneaded to form a base compound, preferably a dispersion, particularly preferably a nano-dispersion, of polymers, preferably polystyrene, and water being used as the organic binders, preferably the polymer content of the dispersion being less than 5 wt. %, extruding the pellets, preferably under a pressure of between 5 and 120 bar, to a diameter of between 1 and 8 mm, and/or a length of between 0.25 and 4 cm, and preferably conditioning the pellets at a temperature between 400 and 1000 C. for a period of time between 24 and 168 h, impregnating the extruded substrate with platinum, per 1000 g of substrate material, preferably with between 0.5 and 3 litres of aqueous solution of between 15 and 300 mmol/l of H2PtCl6.6H2O, preferably followed by drying at between 60 and 120 C., and preferably followed by calcination for between 6 and 24 hours at between 250 and 450 C., and/or impregnating the platinum-doped substrate with between 0.5 and 3 litres between 25 and 100 mmol/l of aqueous silicotungstic acid for surface fixation of the dehydration catalyst, preferably with subsequent drying at between 60 and 120 C., and preferably with subsequent calcination at between 250 and 450 C. for between 6 and 24 hours.

Description

[0080] The invention is further explained below on the basis of a preferred embodiment shown in the drawing, to which the invention should by no means be limited, however. The drawing shows, specifically:

[0081] FIG. 1 a preferred embodiment of the method and of the device for the catalytic conversion of a substance mixture containing glycerol to propanols in a fixed-bed reactor.

[0082] FIG. 1 shows a preferred embodiment of the device 1 for the catalytic conversion of a substance mixture containing glycerol to propanols in a fixed-bed reactor 2. In particular, crude glycerol that is removed from a storage container 3 is used as starting material. The substance mixture containing glycerol is then fed, preferably by means of a pump, to a filter device 4, in which it is filtered in order to remove any undissolved solids and undesirable accompanying substances which may be contained therein, depending on the quality of the substance mixture containing glycerol. In the specific embodiment, the filter device consists of two redundantly arranged, back-flushable filters, a control valve preferably being arranged upstream of each back-flushable filter. The filtered substance mixture containing glycerol is then mixed with water in a mixing vessel 5 and diluted, the resulting glycerol content preferably being between 10 and 60 percent. The mixing vessel 5 is equipped with a safety valve (pressure relief valve).

[0083] The filtered and diluted substance mixture containing glycerol is then heated via an economiser heat exchanger 6, to which the substance mixture containing glycerol has been fed via a pump, and then hydrogen is added in the static mixer 7, and the mixture is advantageously then passed through a cooler. This mixture is then fed to the continuous, catalytic fixed-bed reactor 2, which in turn preferably comprises a safety valve. The reacted substance mixture is fed via the line 8 for heat input in the heat exchanger 6. The energy of the process waste heat is sufficient to preheat the filtered and mixed substance mixture containing glycerol, and usually no external reaction energy needs to be supplied. Thus, the reaction is adiabatic. An exception to this is, of course, during the switch-on process.

[0084] The converted substance mixture is then fed via a flash valve to a separation device 9, in particular a vapour-liquid separator or flash drum, for the recovery of hydrogen from the substance mixture converted in the fixed-bed reactor. The hydrogen recycling gas stream is passed through an air cooler, and highly volatile organic accompanying components recondense in the separator vessel. Subsequently, a part of the hydrogen recycling gas stream is flared downstream of a control valve for the discharge of by-product gases (in particular predominantly propane), the proportion of the flared hydrogen recycling gas stream being less than 0.5%, and particularly preferably less than 0.1%. The recovered hydrogen is then recompressed in a compressor 10 and added to the fresh hydrogen with which the substance mixture containing glycerol is mixed in the static mixer 7, the proportion of recycled hydrogen in the hydrogen input in one cycle preferably being between 70 and 97 percent. The pure propanols can then be obtained from the reacted substance mixture in a treatment cascade 11, to which the reacted substance mixture is fed via a heat exchanger and a cooler, and the extraction agents for the extraction circuit can be recovered in the same treatment cascade, and the process water for reuse in the production of a diluted substance mixture containing glycerol is also recovered, the recovered process water being mixed with fresh water in a water mixer 12 and then added to the substance mixture containing glycerol in the mixer 5. Preferably, the proportion of recovered process water makes up between 80 and 100 percent of the total water input of a cycle, even more preferably between 90 and 100 percent.

[0085] The reacted substance mixture fed to the treatment cascade 11 first passes through a control valve and is supplied to a separating device, to which toluene is fed as an extraction agent and in which the process water is separated from the reacted substance mixture, which is then fed to the water mixer 12 via a control valve, as already explained, with dirty water being removed via a further control valve. Furthermore, a mixture of propanols and toluene is fed from the separating device to a first extraction column, to which N-methyl-2-pyrrolidone (NMP) is added as an extraction agent. In this extraction column the top product containing the target fraction (propanols) is extracted at 108 C., and then the propanols are obtained via a condensation column at 30 C. Furthermore, a mixture of toluene and NMP is separated from the first extraction column, for example at a temperature of 160 C., via an evaporation column and fed to a second extraction column, for example at 134 C. In this second extraction column, the bottom product is drawn off and the residual toluene is distilled off and fed back to the second extraction column for energy input, and subsequently the unevaporated NMP is fed back again to the first extraction column at about 232 C. via a pumpmixed with fresh NMP in a static mixerfor precipitation of the propanols. In the second extraction column, the top product is also drawn off and the toluene is condensed out at below 125 C. and fed via a pump and in a static mixer mixed with fresh toluene from the separation device as an extraction agent.

[0086] The embodiment shown in the drawing and explained in conjunction with it serves to explain the invention and does not limit the invention. The temperatures stated in the embodiment are only to be understood as examples; other temperatures are possible.