EP1509583B1 - Paraffines microcristallines, procede de fabrication - Google Patents

Paraffines microcristallines, procede de fabrication Download PDF

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Publication number
EP1509583B1
EP1509583B1 EP03755932.5A EP03755932A EP1509583B1 EP 1509583 B1 EP1509583 B1 EP 1509583B1 EP 03755932 A EP03755932 A EP 03755932A EP 1509583 B1 EP1509583 B1 EP 1509583B1
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Prior art keywords
catalyst
paraffin
microcrystalline
paraffins
process according
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German (de)
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EP1509583A1 (fr
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Helmuth Schulze-Trautmann
Michael Matthäi
Thorsten Butz
Günter Hildebrand
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Hywax GmbH
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Sasol Wax GmbH
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Priority claimed from PCT/EP2002/005970 external-priority patent/WO2002096842A2/fr
Priority claimed from DE10256431A external-priority patent/DE10256431A1/de
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  • the invention first relates to a microcrystalline paraffin.
  • a method for producing a microcrystalline paraffin is also known.
  • microcrystalline paraffin also known as microwaxes
  • n-alkanes branched isoalkanes and alkyl-substituted cycloalkanes (naphthenes) as well as - albeit usually small - proportions of aromatics.
  • the content of iso-alkanes and naphthenes ranges between 40 and 70% as determined by the EWF Standard Test Method for Analysis of Hydrocarbon Wax by Gas Chromatography. The quantitative dominance of isoalkanes (and naphthenes) determines their microcrystalline structure.
  • the solidification range is between 50 and 100 ° C according to DIN ISO 2207.
  • the needle penetration has values between 2 x 10 -1 and 160 x 10 -1 mm according to DIN 51579.
  • the solidification point and the needle penetration are used to distinguish between the microcrystalline paraffins between plastic and hard microcrystalline paraffins.
  • Soft plastic microcrystalline paraffins (so-called petrolatum) are fast with pronounced adhesiveness and have solidification points of 65 to 70 ° C and penetration values of 45 to 160 x 10 -1 mm.
  • the oil contents are between 1 and 15%.
  • Plastic microcrystalline paraffins are readily malleable and kneadable and have solidification points between 65 and 80 ° C and penetration values of 10 to 30 x 10 -1 mm.
  • the oil contents can be up to 5%.
  • the hard microcrystalline paraffins are tough and slightly adhesive with freezing points from 80 to 95 ° C and penetration values 2 to 15 x 10 -1 mm.
  • the oil contents amount to a maximum of 2% (see Ullmann's Encyclopedia of Industrial Chemistry, VCH Verlagsgesellschaft 1996 ).
  • Microcrystalline paraffins have a high molecular weight and thus high boiling points. They are so far from the residues of vacuum distillation of petroleum and from precipitates of petroleum in its storage (bottom residue, residue wax) won, in technologically very complex and costly process with multiple stages, for example deasphalting, solvent extraction, dewaxing, de-oiling and refining.
  • the de-oiled microcrystalline paraffins contain sulfur, nitrogen and oxygen compounds as impurities. They are therefore not completely odorless and have a dark yellow to dark brown color. The refining required therefore takes place depending on the later use by bleaching (technical applications) or by hydrorefining (applications in the food and pharmaceutical industries).
  • Microcrystalline paraffins are mainly used as a mixture component in paraffin or wax mixtures.
  • the use is usually in areas up to 5%.
  • the hardness and melting point of these mixtures should be increased and flexibility and oil-binding improved.
  • Typical applications include, for example, the manufacture of waxes for impregnation, coating and laminating for the packaging and textile industries, heat seal and hot melt adhesives, and pharmaceutical and cosmetic products, including chewing gum.
  • they are used in potting and cable compounds as well as plastics in general but also in the candle, rubber and tire industries as well as in care, anti-slip and anti-corrosion agents.
  • the catalyst is based on a metal component on a porous, heat-resistant metal oxide support, in particular on 0.1 to 5 wt .-% of platinum on alumina or zeolites, such as Offretit, zeolite X, zeolite Y, ZSM -5, ZSM- 2 etc.
  • the feed to be isomerized may be any wax or waxy material, such as slack waxes or Fischer-Tropsch wax.
  • the isomerization product is liquid and the starting material for the production of lubricating oil components.
  • the object of the invention is to provide a novel microcrystalline paraffin and a process for the production of microcrystalline paraffin.
  • microcrystalline paraffin preparable by catalytic hydroisomerization at temperatures above 200 ° C, from FT paraffins with a C chain length distribution in the range of 20 to 105, using a catalyst based on a beta zeolite, with a pore size between 0.5 and 0.8 nm, wherein the catalyst further comprises a hydrogenation metal of VIII.
  • Subgroup of the Periodic Table and the content of the hydrogenation metal is 0.1 to 2 MA .-%.
  • the microcrystalline paraffin produced is not liquid at 25 ° C, but at least pasty to solid with a needle penetration of less than 100 x 10 -1 , measured according to DIN 51579.
  • microcrystalline paraffin Compared to the natural micro waxes such a microcrystalline paraffin is free of naphthenes and aromatics. Despite isomerization, crystallinity has been preserved. Continuous production with defined properties is possible. The production is possible even in one process step. There is provided a microwax product in the low and high solidification point range. Continuous or discontinuous catalytic hydroisomerization of FT paraffins can be carried out. With regard to FT paraffins as such, particular reference is made to the statements made by A. kuhnle in Fette. Soap. Paint, Volume 84, pages 156 ff.
  • FT paraffins are paraffins prepared by the Fischer-Tropsch process in a known way from synthesis gas (CO and H2) in the presence of a catalyst at elevated temperature ,
  • Such FT paraffins with a high proportion of n-paraffins and a C chain length in the range of C 20 to C 105 are converted by the method described here to high-melting, microcrystalline paraffins with a high proportion of iso-paraffins.
  • the catalyst fills the reactor volume almost completely, so that instead of catalyst volume can also be spoken of reactor volume.
  • each solid hydroisomerates is> 90%, in many cases between 90 and 96% by mass, based on the particular FT paraffin used.
  • a catalyst is used which can selectively convert solid Fischer-Tropsch paraffin into microcrystalline paraffins in a single process step.
  • the surface-rich gamma-alumina has a specific surface area of 15-350 m 2 / g, based on ⁇ -Al 2 O 3 .
  • the calcined at 800 ° C combination of all catalyst components is free of water and ammonium.
  • catalyst moldings are obtained, which can be used in a heterogeneous process, wherein the catalyst is preferably used as a fixed bed, and the liquefied wax together with hydrogen at temperatures between preferably 200 and 270 ° C in trickle phase over it.
  • This combination of catalysts achieves such high isomerization activity that a Fischer-Tropsch paraffin solid at normal ambient temperature can be used directly to obtain a microcrystalline wax in a single step.
  • the properties of the microcrystalline wax can even be varied to a limited extent by choosing suitable reaction parameters.
  • Beta zeolite is a commercially available product. It is preferably used as a crystalline aluminosilicate powder in a composition Na n [Al n Si 64-n O 128 ] with n ⁇ 7 according to the invention. In place of aluminum can also Boron or gallium isomorphously entering the spatial silicate structure. As a result of its high content of SiO 2 can also expose it to an acid medium, without losing its crystalline structure, wherein a portion of the aluminum tetrahedra may be removed from the crystalline lattice.
  • the beta zeolite is preferably used as a fine powder having a particle size of in particular 0.5 to about 200 microns, as measured by laser particle size analyzer.
  • the zeolite has pores with diameters of about 0.5 to 0.8 nm.
  • the structural 12-ring openings have a width of 0.55 nm in [001] direction and a width of 0.64 and 0, respectively, 76 nm in the [100] direction of the crystal lattice.
  • the long, normally paraffinic paraffins are apparently capable of entering, at least in part, the internal structure of the zeolite with its acidic centers.
  • any alkali cations still present after the synthesis can be exchanged as quantitatively as possible by protons.
  • the replacement of the alkali cations by protons is carried out according to methods known per se, for example by exchange with water-soluble ammonium salts and subsequent calcination at 500 ° C.
  • the introduction of protons can also be carried out directly with dilute acids.
  • the zeolites are present in the carbonyl ion reactions active Brönstedt and Lewis acids form (acidic centers).
  • the zeolite in a preferred embodiment, in particular as a powder with a ⁇ -aluminum oxide A100H, which serves as a binder for the zeolite and as a carrier for a hydra-metal component, or contains these in substantial proportions.
  • Both powders are combined together and simultaneously or thereafter dilute acid, for example mineral acid, preferably nitric acid, or organic Acid, such as formic acid or acetic acid, as Peötisationsstoff and added so much water that during the intensive processing of the mass by kneading, a plasticizable, moldable mass is formed.
  • plasticizers in particular organic auxiliaries, for example water-soluble cellulose ethers, are added in small amounts of up to about 5% by weight, based on the powder substances.
  • This mass is extruded, for example, by means of a screw extruder through dies, through which moldings are produced in strand form with an optional diameter and profile.
  • the extrudates are then at temperatures of 80 ° C to 200 ° C, in particular 100 ° C to 200 ° C, dried, optionally still broken to a certain length, and in a further step thermally at temperatures of about 400 ° C to 600 ° C treated, in particular calcined, so that all or substantially all organic components, water and optionally present nitrate and ammonium ions escape from the moldings.
  • the alumina precursor is calcined at temperatures above about 350 ° C. in gamma-alumina over a specific surface of 150 to 350m 2 / g, based on Al 2 O 3 , and a pore volume of 0.3 to about 1.0 cm 3 / g, based on Al 2 O 3 possesses ,
  • the pores of the alumina preferably have diameters of 3 to 59 nm, by which the alumina is capable of taking up large molecules and transporting them to the zeolite crystals.
  • the calcined shaped articles are impregnated with a solution containing the compound of the metal or the metals of the 8th subgroup of the PSE, in particular of the platinum.
  • Particularly suitable for this purpose are H 2 [PtCl 6 ] and H 2 [PdCl 4 ].
  • other suitable compounds containing the noble metals in anionic form may also be used.
  • the compounds of precious metals are advantageously used in a preferred embodiment in aqueous solution.
  • the concentration of noble metals in the solution is adjusted so that their desired final concentration in the catalyst is adjusted after receiving the solution according to simple pore filling of the moldings with the solution.
  • the moldings After impregnation of the moldings with the solution of the noble metal-containing compounds, the moldings are preferably dried in a device to remove water. Subsequently, the moldings are annealed, in a dry air stream with removal of the liberated volatile compounds in the exhaust gas. If necessary, the resulting nitrous gases are to be destroyed.
  • the precious metals are then present in fine distribution as metal oxy, in particular Platinoytellen, while the zeolite crystals themselves contain no hydrogenation metal component.
  • the catalyst is reduced prior to startup in the hydrogen-containing gas stream, in particular heated to temperatures of 100 to 480 ° C, to deposit the noble metal in finely divided metallic form on the alumina.
  • the metal agglomerates are advantageously and in a preferred embodiment of the invention then present in such a form that at least 30% and at most about 70% of all metal atoms are capable of adsorbing a CO molecule.
  • the metal components act as hydrogenation-effective portions of the catalyst capable of activating the long-chain paraffins to carbonium ions.
  • the latter react at the acidic centers in the catalyst with displacement of CH 3 groups on the long chains.
  • From the zeolitic pore openings occur after conversion primarily in 2-, 3-, 4- and / or 5-beta zeolite is a commercially available product. It is preferably used as a crystalline aluminosilicate powder in a composition Nan [AlnSi 64-n O 128 ] with n ⁇ 7 according to the invention.
  • boron or gallium can also enter the spatial silicate structure isomorphically.
  • the beta zeolite is preferably used as a fine powder having a particle size of in particular 0.5 to about 200 microns, as measured by laser particle size analyzer.
  • the zeolite has pores with diameters of about 0.5 to 0.8 nm.
  • the structural 12-ring openings have a width of 0.55 nm in [001] direction and a width of 0.64 and 0, respectively, 76 nm in the [100] direction of the crystal lattice.
  • any alkali cations still present after the synthesis can be exchanged as quantitatively as possible by protons.
  • the exchange of the alkali metal ions by protons is carried out according to methods known per se, for example by exchange with water-soluble ammonium salts and subsequent calcination at 500 ° C.
  • the introduction of protons can also be carried out directly with dilute acids.
  • the zeolites are present in the carbonyl reactions active Brönstedt or respectively Lewis acids form (acidic centers).
  • the zeolite in a preferred embodiment, in particular as a powder with a ⁇ -aluminum oxide A100H, which at the same time as a binder for the zeolite and as a carrier for a hydro-metallic component serves, or contains these in substantial proportions.
  • dilute acid for example, mineral acid, preferably nitric acid, or organic acid, such as formic acid or acetic acid, is added as a peptizer and enough water to form, by plasticizing, a plasticizable, plasticized material Mass arises.
  • plasticizers in particular organic auxiliaries, for example water-soluble cellulose ethers, are added in small amounts of up to about 5% by weight, based on the powder substances.
  • This mass is extruded, for example, by means of a screw extruder through dies, through which moldings are produced in strand form with an optional diameter and profile.
  • the extrudates are then at temperatures of 80 ° C to 200 ° C, in particular 100 ° C to 200 ° C, dried, optionally still broken to a certain length, and in a further step thermally at temperatures of about 400 ° C to 600 ° C treated, in particular calcined, so that all or substantially all organic components, water and optionally present nitrate and ammonium ions escape from the moldings.
  • the alumina precursor is calcined at temperatures above about 350 ° C. in gamma-alumina over a specific surface of 150 to 350m 2 / g, based on Al 2 O 3 , and a pore volume of 0.3 to about 1.0 cm 3 / g, based on Al 2 O 3 possesses ,
  • the pores of the alumina preferably have diameters of 3 to 59 nm, by which the alumina is capable of taking up large molecules and transporting them to the zeolite crystals.
  • the calcined shaped articles are mixed with a solution, the compound of the metal or of the metals of the 8th subgroup of the PSE, in particular of the platinum, contains, impregnated.
  • Particularly suitable for this purpose are H 2 [PtCl 6 ] and H 2 [PdCl 4 ].
  • other suitable compounds containing the noble metals in anionic form may also be used.
  • the compound of the noble metals are advantageously used in a preferred embodiment in aqueous solution.
  • the concentration of noble metals in the solution is adjusted so that their desired final concentration in the catalyst is adjusted after receiving the solution according to simple pore filling of the moldings with the solution.
  • the moldings After impregnation of the moldings with the solution of the noble metal-containing compounds, the moldings are preferably dried in a device to remove water. Subsequently, the moldings are annealed, in a dry air stream with removal of the liberated volatile compounds in the exhaust gas. If necessary, the resulting nitrous gases are to be destroyed.
  • the precious metals are then present in fine distribution as metal oxy, in particular Platinoytellen, while the zeolite crystals themselves contain no hydrogenation metal component.
  • the catalyst is reduced prior to startup in the hydrogen-containing gas stream, in particular heated to temperatures of 100 to 480 ° C, to deposit the noble metal in finely divided metallic form on the alumina.
  • the metal agglomerates are advantageously and in a preferred embodiment of the invention then present in such a form that at least 30% and at most about 70% of all metal seeds are capable of adsorbing a CO molecule.
  • the metal components act as hydrogenation-effective portions of the catalyst capable of activating the long-chain paraffins to carbonium ions.
  • the latter react at the acidic centers in the catalyst under displacement of CH 3 groups on the long chains.
  • the catalyst can be used, for example, in the form of extrudates, cylinders, granules, spheres, tablets or powders.
  • the catalyst can preferably be used in the presence of hydrogen at an H 2 partial pressure of from 5 to 180 bar.
  • the catalyst can be used at a H 2 : feed ratio of 100: 1 to 2000: 1 Nm 3 / m 3 feed.
  • the catalyst may be used at a loading of 0.1 to 1 volume feed / volume of catalyst per hour.
  • the catalyst can be used at a temperature of 200 ° to 270 °.
  • the catalyst may be further suspended in the form of small particles suspended in the feed at temperatures of preferably 200 ° C to 270 ° C and elevated pressure in the presence of hydrogen to convert Fischer-Tropsch paraffin to microcrystalline wax.
  • Optionally occurring slight fractions can be aborted by means of steam distillation (stripping).
  • the catalyst is incorporated as a fixed bed in a reactor through which the feed can flow slowly together with hydrogen at temperatures of preferably 200 ° C to 270 ° C.
  • the catalyst can be used in a continuous, semi-continuous or batchwise procedure.
  • a solution of 1.636 g of H 2 PcCl 6 in 242 ml of water is sprayed onto 220 g of the moldings with agitation.
  • the moldings are dried with agitation until the bulk of liquid has evaporated and the individual moldings are not stick more together.
  • the impregnated moldings are dried at 120 ° C in a drying oven in air.
  • the dried moldings are heated in a vertical oven at 100 ° C / h to 450 ° C in the stream of dry air and held at 450 ° C for one hour.
  • the moldings are cooled in the oven to ambient temperature, the air flow is replaced by pure nitrogen until the oxygen content in the outflowing gas is less than 0.5 vol .-% and then switched from nitrogen to hydrogen.
  • the furnace is again heated at 100 ° C / h to 450 ° C, and the catalyst is treated for three hours at this temperature in the flowing hydrogen, that is reduced. Thereafter, the catalyst is allowed to cool in a nitrogen stream and can be removed.
  • the resulting catalyst A according to the invention is stable in air.
  • the platinum content is 0.8% by weight, based on the combination of all components annealed at 800 °.
  • the catalyst A prepared above was comminuted to a particle size of 160 to 315 ⁇ m and 4 g of this comminuted catalyst were stirred into 180 g of a Fischer-Tropsch-prefin ("feed") at a temperature of 120 ° C.
  • feed a Fischer-Tropsch-prefin
  • the mixture was poured into an autoclave. After completion of the autoclave, a hydrogen pressure of 50 bar was pressed and with stirring, the mixture was heated to 250 ° C and further treated with stirring for seven hours. Thereafter, the autoclave was again cooled to 120 ° C, and the product was taken out of the autoclave, the catalyst was separated and examined. The product characteristics were compared with those of the feed (see table).
  • the hydroisomerizate clearly shows different properties from the starting material, which correspond to a microcrystalline wax.
  • the proportion of I-paraffins is significantly increased compared to the feed.
  • the catalytic hydroisomerization of the FT paraffins is carried out continuously in a flow-through reactor with a fixed catalyst, in particular in the form of extrudates, spheres or tablets, the reactor, when it is, as preferred, oriented vertically both from top to bottom and from bottom to top can be flowed through.
  • the process can also be carried out batchwise or semi-continuously in, for example, a stirred autoclave in a batch process, the catalyst being contained in a permeable network or being finely divided is used as granules or powder in FT paraffin.
  • the process parameters of the continuous as well as the discontinuous process are the same.
  • the solid microcrystalline paraffins obtained according to the invention have the following properties:
  • n-alkanes Compared with the FT paraffins used, they have somewhat lower solidification points and, in addition to n-alkanes, contain a high, in particular higher, weight fraction of iso compared to or as to n-alkanes.
  • the proportion of n- or iso-alkanes is determined by gas chromatography.
  • the increased degree of isomerization achieved by the hydroisomerization finds expression in increased penetration values, a reduced degree of crystallization and a reduced enthalpy of fusion.
  • the products were firm, white, pak and sticky in consistency. The strength was in any case given at ambient temperature (20 ° C).
  • the degree of crystallinity is determined by an X-ray diffraction analysis. It denotes the crystalline content in the product obtained relative to the amorphous content. The amorphous portions lead to a different diffraction of the X-rays than the crystalline portions.
  • the needle penetration at 25 ° C in the products of the invention is in the range of 20 to 100, measured according to DIN 51579.
  • the crystalline fraction is reduced in particular as follows: While the starting material, a crystalline content in a range of 60 to 75% occurs, is observed in the hydroisomerizate such from 30 to 45%. Especially in the range of 35 to 40%. This crystalline fraction then lies midway between the petroleum-based microcrystalline paraffin and that of the starting product, the FT paraffins. the crystalline proportion of these synthetic microparaffins accordingly also closes a gap in the performance properties of such products. For the physical and material properties of such products are usually an expression of crystallinity.
  • the crystalline fractions and the amorphous fractions are indicated by the aforementioned X-ray diffraction analysis in each case in MA.%.
  • the medium hard product became a very hard product when compared to the petroleum type.
  • the de-oiled hydroisomerate is the hardest type comparable to petroleum.
  • the microcrystalline hydroisomerate prepared according to the invention and the corresponding deoiled microcrystalline hydroisomerizate, such as a microwax can be used (see introduction).
  • the resulting hydroisomerizate can also be oxidized.
  • oxidized products that can be different by melting range and degree of oxidation and are used mainly as a base for corrosion inhibitors and as a cavity and underbody protection for motor vehicles. They are also used in emulsions as care and release agents and as an additive for printing and carbon paper colorants.
  • the acid and ester groups which are statistically distributed over hydrocarbon chains, can be reacted with inorganic or organic bases to form water-dispersible formulations (emulsifying waxes) and lead to products with very good metal adhesion.
  • sunscreen waxes for the tire industry electrical insulation materials scaffolding and model waxes for the investment casting industry and wax formulation for the explosives, ammunition and propellant technology.
  • such products are suitable as release agents in the pressing of wood, chipboard and fibreboard in the manufacture of ceramic parts and because of their retention capacity for the preparation of solvent-based care products, grinding and polishing pastes and matting agents for paints.
  • these products can be used for the formulation of adhesive waxes, cheese waxes, cosmetic preparations, chewing gum bases, cast and cable compounds, sprayable pesticides, vaselines, artificial chimney logs, lubricants and hot melt adhesives.
  • the synthetic microwaxes are food safe.
  • the test is carried out according to FDA, ⁇ 175. 250.
  • the catalyst had 0.8 MA% platinum on ⁇ - zeolite and a SIO 2 to Al 2 O 3 mole ratio of 23: 1 and a high surface area alumina.
  • the catalyst was in acid form. It contained less than 0.02% alkali oxide based on dry matter.
  • the resulting hydroisomerate was solid, white-opaque, odorless, slightly sticky and thus differed significantly from the brittle-hard feedstock.
  • the isoalkane content was increased by about 5-fold, which is evidenced by the increased penetration value, the reduced crystalline content and the reduced enthalpy of fusion.
  • the synthetic, microcrystalline paraffin thus prepared is classified according to its characteristics between a plastic and a hard microwax based on petroleum. With the hydroisimerizate thus a paraffin was obtained with pronounced microcrystalline structure whose C-chain length distribution on the basis of carbon atoms with 23 to 91 in about that of the starting material with 27 to 95, thus slightly shifted towards smaller chain lengths out. The chain length was determined by gas chromatography. a corresponding gas chromatogram is attached as FIG.
  • An FT paraffin having a solidification point of 71.5 ° C was catalytically isomerized in an autoclave under a hydrogen pressure of 5 MPa (50 bar) and a temperature of 250 ° C.
  • the structural transformation that has occurred is substantiated by the key figures in the table.
  • the obtained hydroisomerizate was solid, white-opaque and odorless as well as pasty and slightly sticky.
  • the isoalkane content was increased approximately 5-fold.
  • the high degree of isomerization finds expression in the significantly increased penetration value, the reduced crystalline content and the reduced enthalpy of fusion.
  • the microcrystalline paraffin thus obtained has a similar but slightly reduced C chain length as the FT paraffin, which is clear from the carbon atoms: 23 to 42 in the hydroisomerate and 25 to 48 in FT paraffin.
  • the resulting synthetic microcrystalline paraffin is comparable to a petroleum based soft plastic microcrystalline paraffin according to its characteristics.
  • Examples 1 and 2 show that the FT-paraffins, which consist predominantly of n-alkanes and have a finely crystalline structure and a brittle-hard consistency, have been converted into non-flowing, pasty or solid paraffins by the process according to the invention, the lower melting temperatures as the feedstock.
  • These paraffins are characterized by a high content of branched alkanes and consequently have a microcrystalline structure with a significantly reduced degree of crystallization (compared to the starting material) and a plastic to slightly sticky consistency.
  • the branched alkanes are predominantly methylalkanes, with the methyl groups preferably occurring in the 2, 3, 4 or 5 position. To a lesser extent methyl branched alkanes were formed several times.
  • FIG. 2 An example 2 corresponding gas chromatogram is in FIG. 2 shown.
  • Example 2 The starting material of Example 2 was then isomerized in a flow reactor again with the same catalyst, and a hydroisomerate with somewhat different but comparable parameters (cf. also Table 1) was obtained as in the autoclave experiment (Example 2) clear lowered process temperature of 220 ° C.
  • a reactor experiment is a large-scale one Carrying out the hydroisomerization much closer than an autoclave experiment. The thus proven possible reduction of the process temperature in comparison to the autoclave experiment can be expected the same in the case of Example 1, but at least in large-scale implementation.
  • the lowering of the process temperature is also associated with the significant advantage that the concurrently cracking reaction occurring in such a hydroisomerization is decisively suppressed (see FIGS. 1 to 3 ).
  • a gas chromatograph corresponding to Example 3 is known as FIG. 3 attached.
  • the fully synthetic microcrystalline paraffins produced by the hydroisomerization according to the invention contain no strongly branched isoalkanes, no cyclic hydrocarbons (naphthenes) and in particular no aromatics and also sulfur compounds. They therefore meet the highest purity requirements for microcrystalline paraffins, making them ideally suited for use in the cosmetics and pharmaceutical industries as well as for packaging and preservation in the food industry.
  • Table 1 Characteristics of starting materials and reaction products unit Measurement Method example 1
  • Example 2 Example 3 FT paraffin (H8) Hydroisomerate (HDI-8) FT paraffin (FT 70) Hydroisomerate (HDI 70-A) FT paraffin (FT70) Hydroisome-risat (HDI 70-R) Freezing point ° C DIN ISO 2207 97.0 86.5 71.5 61.5 71.5 64.5 Penetration N at 25 ° C 0.1 mm DIN 51579 2 42 13 98 13 79 melting enthalpy J / g ASTM D4419 221 127 195 120 195 142 crystalline parts MA .-% X-ray diffraction analysis 70.7 43.5 62.4 38.8 62.4 41.2 isoalkanes % gas chromatography 12 47 9 47 9 40 MIBK-soluble MA .-% ASTM D721-87 (modified) 0.66 14.6 0.4 23.1 0.4 15.0 Viscosity (100 ° C) cSt 12 (120 °

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Claims (13)

  1. Paraffine microcristalline à l'état solide, susceptible d'être fabriquée par hydroisomérisation catalytique à des températures au-dessus de 200°C à partir de de paraffine Fischer-Tropsch en C20 à C105, sur un catalyseur basé sur une zéolithe béta avec une taille de pores entre 0,5 et 0,8 nm, dans lequel le catalyseur présente en outre un composant métallique d'hydrogénation du sous-groupe VIII de la classification périodique des éléments et la teneur du métal d'hydrogénation est de 0,1 à 2 % en rapport massique par rapport au catalyseur calciné à 800°C, dans lequel la paraffine microcristalline fabriquée n'est pas liquide à 25°C mais au moins pâteuse à solide avec une pénétrabilité à l'aiguille inférieure à 100x10-1 mm mesurée selon DIN 51579.
  2. Paraffine microcristalline selon la revendication 1, caractérisé en ce que la fraction massique d'isoalcanes est plus grande que celle des n-alcanes.
  3. Procédé de fabrication d'une paraffine microcristalline par hydroisomérisation catalytique, qui n'est pas liquide à 25°C, mais au moins pâteuse à solide, avec une pénétrabilité à l'aiguille inférieure à 100x10-1 mm mesurée selon DIN 51579, en utilisant, comme produit de départ, de la paraffine Fischer-Tropsch sur un catalyseur, basé sur une zéolithe béta, avec une taille de pores entre 0,5 et 0,8 nm, dans lequel le catalyseur présente en outre un composant métallique d'hydrogénation du sous-groupe VIII de la classification périodique des éléments et la teneur du métal d'hydrogénation est de 0,1 à 2 % en rapport massique, dans le cas du platine préférentiellement 0,4 à 1 % en rapport massique, par rapport au catalyseur calciné à 800°C, avec utilisation d'une température de procédé de plus de 200°C et par application d'une pression en présence d'hydrogène.
  4. Procédé selon la revendication 3, caractérisé en ce que la température de procédé est de 200 à 270°C.
  5. Procédé selon une des revendications 2 et 4, caractérisé en ce que la pression est de 2 à 20 MPa.
  6. Procédé selon la revendication 5, caractérisé en ce que la pression est de 3 à 8 MPa.
  7. Procédé selon la revendication 6, caractérisé en ce que la température de procédé est de 230 à 270 °C.
  8. Procédé selon une des revendications 3 à 7, caractérisé en ce que le rapport d'alimentation en hydrogène par rapport à la paraffine Fischer-Tropsch est 100 :1 à 2000 :1 Nm3 par m3.
  9. Procédé selon une des revendications 3 à 8, caractérisé en ce que le rapport d'alimentation en hydrogène par rapport à la paraffine Fischer-Tropsch est 250 :1 à 600 :1 Nm3 par m3.
  10. Procédé selon une des revendications 3 à 9, caractérisé en ce que l'on travaille avec une vitesse volumétrique horaire de 0,1, à 2,0 v / vh, préférentiellement 0,2 à 0,8 v / vh.
  11. Procédé selon une des revendications 3 à 10, caractérisé en ce que le catalyseur à une taille de pores entre 0,55 à 0,76 nm.
  12. Procédé selon une des revendications 3 à 11, caractérisé en ce qu'on fait intervenir la paraffine Fischer-Tropsch dans un point de ramollissement allant de 70 à 105°C, préférentiellement avec des points de ramollissement à 70, 80, 95 ou 105°C.
  13. Procédé selon une des revendications 3 à 12, caractérisé en ce que paraffine microcristalline est fabriquée à partir de la paraffine Fischer-Tropsch en une seule étape, éventuellement avec élimination des parties à chaînes courtes.
EP03755932.5A 2002-05-31 2003-05-19 Paraffines microcristallines, procede de fabrication Expired - Lifetime EP1509583B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP03755932.5A EP1509583B1 (fr) 2002-05-31 2003-05-19 Paraffines microcristallines, procede de fabrication

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
WOPCT/EP02/05970 2002-05-31
PCT/EP2002/005970 WO2002096842A2 (fr) 2001-05-30 2002-05-31 Paraffine microcristalline
DE10237651 2002-08-13
DE10237651 2002-08-13
DE10256431 2002-12-02
DE10256431A DE10256431A1 (de) 2002-05-31 2002-12-02 Mikrokristallines Paraffin, Verfahren zur Herstellung von mikrokristallinen Paraffine und Verwendung der mikrokristallinen Paraffine
PCT/EP2003/005236 WO2003102115A1 (fr) 2002-05-31 2003-05-19 Paraffines microcristallines, procede de fabrication et utilisation de celles-ci
EP03755932.5A EP1509583B1 (fr) 2002-05-31 2003-05-19 Paraffines microcristallines, procede de fabrication

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EP1509583A1 EP1509583A1 (fr) 2005-03-02
EP1509583B1 true EP1509583B1 (fr) 2014-06-04

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114702984A (zh) * 2022-04-12 2022-07-05 上海玖宜聚合物技术有限公司 一种合成微晶蜡的生产方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4010451A1 (fr) 2019-08-08 2022-06-15 Shell Internationale Research Maatschappij B.V. Cire microcristalline
CN111830166A (zh) * 2020-07-22 2020-10-27 济宁齐鲁检测技术有限公司 一种微晶蜡中正构烷烃的检测方法及应用

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002096842A2 (fr) * 2001-05-30 2002-12-05 Sasol Wax Gmbh Paraffine microcristalline

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002096842A2 (fr) * 2001-05-30 2002-12-05 Sasol Wax Gmbh Paraffine microcristalline

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114702984A (zh) * 2022-04-12 2022-07-05 上海玖宜聚合物技术有限公司 一种合成微晶蜡的生产方法
CN114702984B (zh) * 2022-04-12 2023-11-28 上海玖宜聚合物技术有限公司 一种合成微晶蜡的生产方法

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