EP0938375B1 - Acide polysilicique (silice) synthetique contenant du fer et de l'aluminium pour le traitement des huiles - Google Patents

Acide polysilicique (silice) synthetique contenant du fer et de l'aluminium pour le traitement des huiles Download PDF

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Publication number
EP0938375B1
EP0938375B1 EP97943828A EP97943828A EP0938375B1 EP 0938375 B1 EP0938375 B1 EP 0938375B1 EP 97943828 A EP97943828 A EP 97943828A EP 97943828 A EP97943828 A EP 97943828A EP 0938375 B1 EP0938375 B1 EP 0938375B1
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EP
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approximately
iron
polysilicic acid
bleaching
synthetic
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German (de)
English (en)
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EP0938375A1 (fr
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Norbert Schall
Max Eisgruber
Werner Zschau
Uwe Flessner
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Sued Chemie AG
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Sued Chemie AG
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/10—Refining fats or fatty oils by adsorption

Definitions

  • the invention relates to Fe and Al-containing synthetic polysilicic acid (silica), a process for their production, as well as their use in the treatment of oils and fats.
  • Vegetable and animal oils or fats are immediately after their extraction usually not for the immediate Can be used as they contain accompanying substances that Taste, smell, appearance or shelf life influence negatively. Especially vegetable oils therefore subjected to a multi-stage refining process to to remove these unwanted accompanying substances.
  • This refining process consists of an optimized combination of physical treatments such as Filtration, drying or steam distillation, with chemical treatment methods, such as. Acid or base treatment and / or treatment with adsorbents and catalysts.
  • the treatment with so-called bleaching earth is a key step of the whole oil refining process, as one Stage removes a large number of unwanted accompanying substances by adsorption or through catalytic processes into tolerable substances being transformed.
  • Silicates and silicas show good adsorption performance for metals in the oil, such as magnesium, iron or copper, and for so-called mucilages, the phospholipids.
  • metals in the oil such as magnesium, iron or copper
  • mucilages the phospholipids.
  • synthetic bleaching earths based on pure SiO 2 have no bleaching activity whatsoever, so that they, too, cannot replace the bleaching earths based on bentonite.
  • US-A-3,478,890 describes a process for the production of aluminum silicates, in which acidified metal salt solutions are reacted with alkali silicates.
  • the products consist of about 85 wt% SiO 2 , 2 wt% Al 2 O 3 in addition to small amounts of MgO and do not contain iron.
  • the products are used for the fining of juices and wines and as a catalyst carrier. The use as bleaching earth is not mentioned.
  • DE-B-20 36 819 describes a process for the preparation of silicatic adsorbents and drying agents with an alkali content of less than 0.1% by weight, a specific surface area of 300 to 600 m 2 / g and a micropore volume of at least 0 , 35 ml / g in pores ⁇ 140 ⁇ m and an ion exchange capacity of 15 to 20 mVal / 100g.
  • the materials are produced by producing precipitated products from salt solutions of the metals iron, magnesium, zinc, manganese or aluminum by adding alkali silicate solutions, washing them alkali-free and drying them at temperatures below 130 ° C.
  • the SiO 2 content of the products is 50 to 80% by weight.
  • the material can be further activated by treatment with acids.
  • EP-B-269 173 describes metal oxide silicas (metal oxide silicas) and their use in the treatment of glyceride oils.
  • the products are characterized by a typical pore distribution from at least 40% of the specific surface provided by pores with a radius of 2 to 4 nm and the pore volume in pores with a radius from 100 to 2000 nm, determined by mercury porosimetry, is at least 0.5 ml / g.
  • These product features will on the one hand through litigation, on the other hand through intensive Washing operations and redispersions of the products in ammonium carbonate solution reached.
  • the metal oxide silicas will be produced using a three-stage process at 30 ° C. To to form the products, the reaction mixture is filtered, washed and in a 10% ammonium carbonate solution redispersed to cause ion exchange. After that must filtered again and washed.
  • the ratio of metals to silicon in the metal oxide silica is between 4 and 50 mol%, preferably between 13 and 23 mol%, the amount of sodium in the product is less than 0.5 % By weight.
  • the materials produced according to EP-B-269 173 show Decolorization performance comparable to that of medium-quality bleaching earth correspond. Should oils with easy oxidizability, such as. refined highly unsaturated fish oil or soybean oil metal oxide silicas should preferably be used, which do not contain metal, which acts as a catalyst for oxidation reactions works. Iron and copper are mentioned by name. In such cases, the preferred adsorbent is a pure one Aluminum silicate.
  • EP-B-376 406 describes pure aluminosilicates for the refining of oils.
  • the adsorbents have a specific surface area of at least 150 m 2 / g in pores with a diameter of 4 to 20 nm.
  • the pore volume provided by these pores is 0.65-1.0 ml / g, the total pore volume is 2 to 4 ml / g.
  • a three-stage process is used to produce the adsorbents.
  • the products described have adsorption properties for phospholipids, oil-soluble iron and bleaching properties of medium-quality bleaching earth.
  • DE-A-43 06 663 describes a method for environmentally friendly Recovery of acidic wastewater from the bleaching earth production process.
  • the wastewater containing metal salts is treated with water glass solutions precipitated at elevated temperature.
  • the felling material can washed out and dried at low temperatures. There is no information about the Al and Fe content of the felling material Information.
  • the materials can be used to treat oils. Are the materials e.g. up to a water content of 30-50 wt .-% dried, they are suitable as adsorbents for Phospholipids, when dried to 5 to 15 wt .-% water the materials can be used as bleach, whereby bleaching activities are also achieved here which correspond to an average quality of bleaching earth. It is mentions that these materials include metals from the oils can adsorb, a related adsorption performance is not mentioned.
  • the object of the invention was therefore to avoid the disadvantages of the prior art metal oxide silicas (silicas), which at the same time have a high adsorption and have bleaching activity and are easy to manufacture are.
  • the invention thus relates to a synthetic polysilicic acid (silica) containing the oxides of at least two metals with a valence of 2 or higher, one of which is iron and the other aluminum, for refining oils, which is characterized in that the proportion of Iron and aluminum is less than about 15 mol% (based on the sum of these metals and silicon), that the specific surface is more than 100 m 2 / g and that the water content (determined after drying at 105 ° C as loss on ignition at 1000 ° C) is less than about 5% by weight.
  • the loss on ignition is preferably about 2.5 to 3.5% by weight.
  • polysilicic acid largely coincides with that English term “silica”, i.e. it describes condensed Silicas that still contain a certain amount of bound Contain water.
  • the proportion of iron and aluminum is preferably approximately 5 to 15 mol% (based on the sum of these metals and the Silicon).
  • the iron can be in a bivalent or trivalent form.
  • iron and aluminum as the main components, but not limited to alkaline earth metals such as calcium and magnesium, as well as zinc and manganese.
  • the molar proportion of iron, based on the sum of iron and aluminum is preferably at least 2 mol%, in particular about 2 to 50 mole%.
  • The is particularly preferably Proportion of iron, based on the sum of iron and Aluminum, about 4 to 25 mol%, in particular about 5 to 10 Mole%.
  • the proportion of iron is preferably about 0.1 to 2.0 mol%, in particular about 0.4 to 1.5 mol%.
  • the metal oxides can be at least partially in the form of metal silicates are present with part of the polysilicic acid are connected. These silicates are in particular around iron aluminosilicates. The metal oxides or metal silicates are in a polysilicic acid matrix and are probably at least partially crystalline. The rest of Polysilicic acid is predominantly in amorphous form.
  • the bleaching activities of the invention Metal oxide polysilicic acids even higher than that of very good conventional bleaching earths based on bentonite. Furthermore, the adsorption capacity for metals is preserved remained.
  • the metal oxide polysilicic acids according to the invention show completely unexpected even increased adsorption rates for oil-soluble iron.
  • the metal oxide polysilicic acids according to the invention preferably have a specific surface area of approximately 250 to 500 m 2 / g; the total pore volume (determined by the method of mercury porosimetry, as explained below) is approximately 0.4 to 1.4 ml / g, the total ion exchange capacity is approximately 20 to 100 meq / 100 g and the Fe ion exchange capacity is approximately 1.0 to 10 .0 meq / 100 g.
  • the invention further relates to a method for the production the synthetic polysilicic acids specified above, which is characterized in that an alkali silicate solution, preferably a water glass solution until formation acidifies a hydrogel, the hydrogel with the solution of a or more salts of two or more metals with one Value of 2 or higher mixed, of which one iron and the other aluminum represents the pH of the mixture by adding alkali to form a precipitate increased, the precipitate is separated from the solution and washed and drying the washed precipitate and optionally calcined.
  • an alkali silicate solution preferably a water glass solution until formation acidifies a hydrogel
  • the hydrogel with the solution of a or more salts of two or more metals with one Value of 2 or higher mixed, of which one iron and the other aluminum represents the pH of the mixture by adding alkali to form a precipitate increased
  • the precipitate is separated from the solution and washed and drying the washed precipitate and optionally calcined.
  • the alkali silicate solution is first so far acidified that a pH of about 8.5 to 11 is established.
  • the pH can also be adjusted by adding an acid Metal salt solution can be obtained.
  • the mixture obtained is then acidified continue with metal salt solutions or acid, so that a Adjust pH from about 3.5 to 5.0. In case of acidification if necessary with small amounts of alkali solution the pH readjusted.
  • the washed precipitate resuspended and spray dried and the spray dried Product at about 450 to 900 ° C except for a residual water content from about 0 to ⁇ 5, in particular from about 0.5 to 2 wt .-% (determined at 105 ° C) calcined.
  • the calcination is carried out briefly (shock calcination), but not all water is removed so that when drying at 105 ° C. over a longer period of time until the weight remains constant Loss of drying occurs.
  • the loss on ignition at 1000 ° C is included about 1.5 to 5% by weight.
  • the invention furthermore relates to the use of the inventive Products for refining and bleaching Oils, especially palm oil.
  • dyes like carotenoids and chlorophylls, but also others Impurities, such as phosphatides (phospholipids), soaps, Metals and oxidation products as well as other accompanying substances that the taste, smell, appearance and shelf life affect the oil, removed.
  • Impurities such as phosphatides (phospholipids), soaps, Metals and oxidation products as well as other accompanying substances that the taste, smell, appearance and shelf life affect the oil, removed.
  • Under oils are especially vegetable and animal oils or fats too understand. These are mostly glycerides, especially triglycerides of various fatty acids, especially saturated or unsaturated fatty acids.
  • metal oxide silicas according to the invention can also for the treatment of other oils, such as mineral or silicone oils, or for the treatment of various Liquids are used in which one or more unwanted accompanying substances should be removed.
  • oils such as mineral or silicone oils
  • Liquids are used in which one or more unwanted accompanying substances should be removed.
  • alternative areas of application are cleaning, Decolorization, refining or clarification of contaminated Solutions, wine, beer, juices, whey, sugar solutions or Solvents.
  • the inventive Metal oxide silicas to remove oil-soluble Iron from oils are used because they don’t give off iron themselves, however an excellent adsorption capacity for iron have. Therefore, they are particularly suitable for refining of highly unsaturated or sensitive to oxidation Oils, such as fish oil, linseed oil or rapeseed oil or of difficult to bleach Oils like palm oil. By removing the oil-soluble Iron and other pro-oxidative accompanying substances can the shelf life of the oils can be significantly improved.
  • the invention also relates to the reuse of the used, metal oxide polysilicic acids according to the invention for Refining and bleaching oils after a thermal and / or chemical treatment.
  • the thermal treatment generally involves heating the used metal oxide polysilicic acids in an oxidizing atmosphere about 500 to 900 ° C, around adhering oil residues or at the first Bleaching treatment to remove formed polymeric products oxidatively.
  • the chemical treatment includes, for example Extraction with solvents, saponification of the adherent Oil or a treatment with acids as well as a combination of these procedures.
  • Elemental analysis The elementary analysis was determined by total digestion of the materials and subsequent determination of the element concentration by means of atomic absorption spectrometry (AAS).
  • the surface was carried out on a fully automatic nitrogen porosimeter from Micromeritics, type ASAP 2010, in accordance with DIN 66131.
  • the relative surfaces in the pores with a radius of 2 to 4 nm were obtained by evaluating the BJH data (EP Barrett, LG Joyner, PP Halenda, J. Am. Chem. Soc. 73 (1951) 373).
  • Ion exchange capacity To determine the ion exchange capacity (IUF), the dried material is reacted with a large excess of an aqueous NH 4 Cl solution under reflux for 1 hour. After standing for 16 hours at room temperature, the mixture is filtered and washed. From the combined filtrate and wash water, the metal ions dissolved (eg the iron ions as Fe-IUF) are determined using AAS. The filter cake is dried and the NH 4 content determined according to the Kjeldahl. The total IUF can be calculated from the amount of ammonium exchanged.
  • IUF ion exchange capacity
  • Water content The water content of the products at 105 ° C was determined using the DIN / ISO-787/2 method.
  • Loss on ignition corresponds to the amount of chemically bound water. It was determined by heating the material predried at 105 ° C. to a temperature of 1000 ° C. over a period of 2 hours.
  • Adsorption properties The color numbers in oils (Lovibond) were determined according to AOCS Cc 13b-45. The chlorophyll A determination was carried out according to AOCS Cc 13d-55, the phosphorus determination according to AOCS method Ca 12-55. The metal concentrations in the oil were determined according to the AOCS method Ca 18-79.
  • a kg of a 27.5% water glass solution (37/40) are mixed with B kg of water at a temperature of C.degree. C. and adjusted to a pH of about 10.5 by adding D ml of 4N sulfuric acid. The mixture is stirred for E hours until the hydrogel forms.
  • F g of FeSO 4 * 7H 2 O, dissolved in G ml of water, and H g of an aluminum sulfate solution (5% by weight of Al 2 O 3 ) are then added, and the pH is adjusted to about 4.5 using 4 N sodium hydroxide solution. After the formation of the Fe-Al-silicate precipitate, the reaction mixture is filtered and washed with water.
  • the filter cake is resuspended in 10 liters of demineralized water and filtered.
  • this resuspension is dispensed with.
  • the filter cake obtained after filtration / resuspension / filtration or filtration / washing is removed, redispersed in water, spray-dried and calcined at 700 ° C.
  • Table I explains the preparation, Table II the characterization of the products according to the invention.
  • a synthetic aluminum iron silicate was produced after the gradual precipitation described in EP-B-269 173, Example 4.
  • 2.0 kg of water glass (37/40) were diluted with 9.0 kg of water at 30 ° C., and the pH was adjusted by adding 751 ml of 4N H 2 SO 4 , containing 63.98 g of FeSO 4 * 7H 2 O, set to 10.1 within 45 seconds. This mixture was stirred for 45 minutes to form hydrogel.
  • 2.111 kg of an aluminum sulfate solution (5% by weight Al 2 O 3 ) were added, and the pH was raised to 4.3 by adding 4N sodium hydroxide solution, the temperature being kept at 30 ° C.
  • the reaction mixture was filtered and the filter cake was redispersed in water at 75 ° C. After renewed filtration, this resuspending was repeated, filtered and the filter cake was now resuspended in a 10% ammonium carbonate solution for one hour and then filtered and washed twice with hot water. This filter cake was mixed in water to a 7.5% by weight suspension and spray-dried. The product was then calcined at 700 ° C for one hour.
  • the molar aluminum fraction Al / (Al + Si) in this approach was 18%
  • the molar iron fraction Fe / (Fe + Si) was 2%.
  • the product analysis showed that the relative surface fraction in the pores with a radius of 2 to 4 nm accounted for 38% of the total surface area of 367 m 2 / g.
  • the pore volume, determined by means of mercury porosimetry, in pores with a radius of 100 to 2000 nm was 0.695 ml / g; the total Hg pore volume was 0.703 ml / g.
  • the total IUF was 46.2 meq / 100 g, the Fe IUF 6.8 mVal / 100 g.
  • Example 3 of DE-B-2 036 819 was reworked.
  • 0.15 mol of iron sulfate and 0.15 mol of magnesium sulfate are dissolved in 500 ml of water and heated to the boiling point.
  • 87.39 g of a sodium silicate solution (27.5% by weight SiO 2 ) are added dropwise to this solution within 30 minutes and the mixture is boiled under reflux for a further 4 hours.
  • the precipitate is then filtered and washed with 500 ml of water, dried at 110 ° C. and sieved through a 60 ⁇ m sieve.
  • the product analysis showed a BET surface area of 476 m 2 / g, a pore volume of 0.354 ml / g in pores of 0-140 ⁇ m (CCl 4 method), a total Hg pore volume of 1.411 ml / g, a total IUF of 29.9 mVal / 100 g and an Fe-IUF of 11.0 mVal / 100 g.
  • An aluminosilicate according to Example 1 of EP-B-376 406 was produced as follows: A dilute alkali silicate solution (5% by weight SiO 2 ) was mixed in a first reactor at 50 ° C. with vigorous stirring with 4 N sulfuric acid within 45 sec, where a pH of 10 was reached. The mixture was transferred to a second reactor and aged there for 60 minutes at a temperature of 50 ° C. without changing the pH. The mixture was then transferred to another reactor and reacted there with an aluminum sulfate solution which contained 5% by weight Al 2 O 3 . After the addition, the pH was adjusted to 5.0 with 4 N sodium hydroxide solution and the mixture was slowly stirred for a further 20 min.
  • the precipitate was then filtered, washed and redispersed in water at a solids content of 7.5% by weight.
  • the dispersion was filtered and the filter cake was redispersed in 10% ammonium carbonate solution. It was then filtered again and washed with water.
  • the filter cake was spray dried as a 7.5% by weight suspension and calcined at 700 ° C.
  • Raw linseed oil (80g) heated to 100 ° C is placed in a beaker and added the bleaching earth. Stir evenly is bleached for 30 minutes at normal pressure. After completing the The oil is bleached from the solids by filtration separated, the transmission is on a spectrophotometer determined at 460 nm against water. For this purpose, 1 cm thick Cuvettes used. The percentage transmission is a direct one Measure of bleaching success.
  • the bleaching tests on linseed oil show the high activity of the synthetic bleaching earth.
  • the products according to the invention even exceed the bleaching activity of bleaching earths Quality.
  • De-gummed rapeseed oil was bleached with the bleaching earth materials listed in Table III.
  • the bleaching was carried out at a temperature of 110 ° C., a pressure of 20 mbar and a treatment time of 30 minutes.
  • the bleaching effect was determined using the Lovibond Colourscan method. Low color numbers mean good bleaching results.
  • the results are shown in Table IV.
  • the examples demonstrate the good bleaching results with the synthetic bleaching earths according to the invention.
  • the activity is in the order of magnitude of the highly active acid-activated Bentonite.
  • the inventive ones are Products the acid activated bentonites think.
  • the products of the invention are universal usable synthetic bleaching earth. Their bleaching action, their adsorption capacity as well as their catalytic capacities are equally well developed.

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Microbiology (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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Claims (12)

  1. Acide polysilicique synthétique (silice), contenant les oxydes d'au moins deux métaux ayant une valence de deux ou plus, dont l'un est le fer et l'autre l'aluminium, pour le raffinage d'huiles, caractérisé en ce que la proportion du fer et de l'aluminium est inférieure à environ 15 % en mole (par rapport à la somme de ces métaux et du silicium), que l'aire spécifique est supérieure à 100 m2/g, et que la teneur en eau (déterminée après séchage à 105°C par la perte à la calcination à 1000°C) est inférieure à environ 5 % en poids.
  2. Acide polysilicique synthétique selon la revendication 1, caractérisé en ce que la proportion du fer et de l'aluminium est d'environ 5 à 15 % en mole (par rapport à la somme de ces métaux et du silicium).
  3. Acide polysilicique synthétique selon la revendication 1 ou 2, caractérisé en ce que la proportion molaire du fer, rapportée à la somme du fer et de l'aluminium, est d'au moins environ 2 % en mole et de préférence d'environ 2 à 50 % en mole.
  4. Acide polysilicique synthétique selon la revendication 3, caractérisé en ce que la proportion molaire du fer, rapportée à la somme du fer et de l'aluminium, est d'environ 4 à 25 % en mole, de préférence d'environ 5 à 10 % en mole.
  5. Acide polysilicique synthétique selon l'une des revendications 1 à 4, caractérisé en ce que les oxydes métalliques sont au moins partiellement liés sous forme de silicates métalliques à une partie de l'acide polysilicique.
  6. Acide polysilicique synthétique selon l'une des revendications 1 à 5, caractérisé en ce qu'il se présente essentiellement sous forme amorphe.
  7. Acide polysilicique synthétique selon l'une des revendications 1 à 6, caractérisé en ce que l'aire spécifique est d'environ 250 à 500 m2/g, le volume total des pores, mesuré par la technique au mercure, est d'environ 0,4 à 1,4 ml/g, la capacité totale d'échange d'ions est d'environ 20 à 100 mVal/100 g, et la capacité d'échange de l'ion Fe est d'environ 1 à 10,0 mVal/100 g.
  8. Procédé de préparation de l'acide polysilicique synthétique selon l'une des revendications 1 à 7, caractérisé en ce qu'on acidifie une solution d'un silicate d'un métal alcalin, de préférence une solution de silicate de sodium, jusqu'à formation d'un hydrogel, on mélange l'hydrogel à la solution d'un ou plusieurs sels de deux métaux ou plus ayant une valence de deux ou plus, dont l'un est le fer et l'autre est l'aluminium, on élève le pH du mélange par addition d'une base jusqu'à formation d'un dépôt, on sépare le dépôt de la solution et on le lave, et on sèche le dépôt lavé, et éventuellement on le calcine.
  9. Procédé selon la revendication 8, caractérisé en ce qu'on acidifie d'abord la solution du silicate d'un métal alcalin jusqu'à ajuster un pH d'environ 8,5 à 11, après quoi on soumet le mélange ainsi obtenu à une acidification plus poussée, de façon à arriver à un pH d'environ 3,5 à 5,0.
  10. Procédé selon la revendication 8 ou 9, caractérisé en ce qu'on remet en suspension le dépôt lavé et on le sèche par atomisation, et on calcine à une température d'environ 450 à 900°C le produit séché par atomisation, jusqu'à arriver à une teneur en eau résiduelle d'environ 0,5 à 2 % en poids (déterminée à 105°C).
  11. Utilisation de l'acide polysilicique synthétique selon l'une des revendications 1 à 7 pour raffiner et blanchir des huiles, en particulier de l'huile de palme.
  12. Réutilisation de l'acide polysilicique synthétique usé, contaminé par des résidus d'huile adhérents ou des produits polymères, selon l'une des revendications 1 à 7, pour raffiner et blanchir des huiles après un traitement thermique et/ou chimique.
EP97943828A 1996-09-03 1997-09-02 Acide polysilicique (silice) synthetique contenant du fer et de l'aluminium pour le traitement des huiles Expired - Lifetime EP0938375B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19635730A DE19635730A1 (de) 1996-09-03 1996-09-03 Fe- und Al-haltige synthetische Polykieselsäure (silica) zur Behandlung von Ölen
DE19635730 1996-09-03
PCT/EP1997/004782 WO1998009723A1 (fr) 1996-09-03 1997-09-02 Acide polysilicique (silice) synthetique contenant du fer et de l'aluminium pour le traitement des huiles

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EP0938375A1 EP0938375A1 (fr) 1999-09-01
EP0938375B1 true EP0938375B1 (fr) 2000-06-07

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JP (1) JP3996199B2 (fr)
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DE10324561A1 (de) * 2003-05-30 2004-12-16 Süd-Chemie AG Semi-synthetische Bleicherde
US7553416B2 (en) * 2007-06-27 2009-06-30 J.M. Huber Corporation Caustic silica gel manufacturing method and gels made thereby
DE102009043418A1 (de) * 2009-09-29 2011-04-07 Süd-Chemie AG Alumosilikat-basierte Adsorbentien zur Aufreinigung von Triglyceriden
CN109321356B (zh) * 2018-10-30 2024-01-16 新疆维吾尔自治区分析测试研究院 一种沙棘油精炼设备

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FR2481257B1 (fr) * 1980-04-25 1986-01-10 Eparco Sa Produit et procede de lutte contre la pollution de l'eau
JPS57115495A (en) * 1980-11-20 1982-07-17 Unilever Nv Purification of fat
DE3775008D1 (de) * 1986-11-24 1992-01-16 Unilever Nv Metall-oxid-siliziumdioxid enthaltendes sorbentmittel und dessen verwendung zur oelraffinierung.
WO1989006637A1 (fr) * 1988-01-13 1989-07-27 E.I. Du Pont De Nemours And Company Procede de production et composition d'un microgel de polyaluminosilicate
US5079208A (en) * 1988-12-30 1992-01-07 Van Den Bergh Foods Co., Division Of Conopco, Inc. Synthetic, macroporous, amorphous alumina silica and a process for refining glyceride oil
AU3115693A (en) * 1992-02-28 1993-09-02 W.R. Grace & Co.-Conn. Process for removal of chlorophyll and color bodies from glyceride oils using amorphous silica alumina

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WO1998009723A1 (fr) 1998-03-12
DE19635730A1 (de) 1998-03-05
DE59701863D1 (de) 2000-07-13
EP0938375A1 (fr) 1999-09-01
JP2000517241A (ja) 2000-12-26
JP3996199B2 (ja) 2007-10-24

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