EP0938375A1 - 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

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Publication number
EP0938375A1
EP0938375A1 EP97943828A EP97943828A EP0938375A1 EP 0938375 A1 EP0938375 A1 EP 0938375A1 EP 97943828 A EP97943828 A EP 97943828A EP 97943828 A EP97943828 A EP 97943828A EP 0938375 A1 EP0938375 A1 EP 0938375A1
Authority
EP
European Patent Office
Prior art keywords
polysilicic acid
approximately
aluminum
bleaching
synthetic
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.)
Granted
Application number
EP97943828A
Other languages
German (de)
English (en)
Other versions
EP0938375B1 (fr
Inventor
Norbert Schall
Max Eisgruber
Werner Zschau
Uwe Flessner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sued Chemie AG
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Sued Chemie AG
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Publication of EP0938375A1 publication Critical patent/EP0938375A1/fr
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Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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 and their use in the treatment of oils and fats.
  • Vegetable and animal oils or fats are generally not suitable for immediate use as soon as they are obtained, since they contain accompanying substances that negatively influence the taste, smell, appearance or shelf life. Vegetable oils in particular are therefore subjected to a multi-stage refining process in order 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.
  • Treatment with so-called bleaching earth is a key step of the entire oil refining process, since a large number of unwanted accompanying substances are removed by adsorption or converted into tolerable substances by catalytic processes.
  • bleaching earth In the case of bleaching earth, a distinction must be made between synthetic bleaching earth and bentonite-based bleaching earth.
  • Bleaching earths which are produced by activating bentonite, are currently mainly used worldwide.
  • Bentonite stands here as a typical representative of the montmorillonite group. Bentonite in its original form mainly consists of the mineral montmorillonite in addition to the gait, e.g. Quartz, lime, feldspar or the like.
  • the raw clay is cleaned and by slurry activation in inorganic acids, e.g. Hydrochloric acid or sulfuric acid, modified at elevated temperatures.
  • Silicates and silicas show good adsorption performance for metals in the oil, e.g. Magnesium, iron or copper and for so-called mucilages, the phospholipids.
  • metals in the oil e.g. Magnesium, iron or copper
  • mucilages the phospholipids.
  • These materials and their applications are e.g. in European Patent Specifications EP-B-185 182, EP-B-234 221 and EP-B-295 418, EP-B-361 622 and EP-B-389 057.
  • 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 approximately 85% by weight SiC ⁇ 2/2% by weight Al2O3 in addition to small amounts of MgO and contain no 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 production of silicate 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, a micropore volume of at least 0.35 ml / g in pores ⁇ 140 ⁇ m and an ionum - exchangeability from 15 to 20 mVal / lOOg.
  • 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 SiC> 2 content of the products is 50 to 80% by weight.
  • the material can be further activated by treatment with acids.
  • the iron content of a refined oil has a significant influence on its shelf life. It is now generally accepted that iron, in addition to copper as a prooxidative element, promotes the oxidative decomposition of the oil. The aim of today's refining processes is therefore to remove these pro-oxidants from the oil (see, for example, AJ Dijkstra et al, J. Am. Oil Soc. Vol. 66, no. 7 (1989) 1002-1009 or GR List et al, J Am. Oil Soc. Vol. 55, No. 2 (1978) 277-284 or US-A-4,089,880).
  • EP-B-269 173 describes metal oxide silicas and their use for the treatment of glyceride oils.
  • the products are characterized by a typical pore distribution, with at least 40% of the specific surface area of pores having a radius of 2 to 4 nm being prepared. are set, and the pore volume in pores with a radius of 100 to 2000 n, determined by mercury porosimetry, is at least 0.5 ml / g.
  • These product properties are achieved on the one hand through process control, and on the other through intensive washing operations and redispersion of the products in ammonium carbonate solution.
  • the metal oxide silicas are produced in a three-stage process at 30 ° C. After the formation of the products, the reaction mixture is filtered, washed and redispersed in a 10% ammonium carbonate solution in order to bring about an ion exchange. Then it must be filtered and washed again.
  • 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 below 0.5% by weight.
  • EP-B-269 173 show decolorization performances which correspond to those of an average quality of bleaching earth.
  • oils with easy oxidizability e.g. highly unsaturated fish oil or soybean oil
  • metal oxide silicas that do not contain any metal that acts as a catalyst for oxidation reactions should preferably be used. Iron and copper are mentioned by name.
  • the preferred adsorbent is a pure 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 a medium quality bleaching earth.
  • DE-A-43 06 663 describes a process for the environmentally friendly recycling of acidic wastewater from the bleaching earth production process.
  • the wastewater containing metal salts is precipitated with water glass solutions at elevated temperature.
  • the felling material can be washed out and dried at low temperatures.
  • AI and Fe content of the precipitated material can be used to treat oils.
  • the materials e.g. Dried up to a water content of 30-50% by weight, they are suitable as adsorbents for phospholipids. When dried to 5 to 15% by weight of water, the materials can be used as bleaching agents, with bleaching activities also being achieved here correspond to those of an average quality of bleaching earth.
  • these materials can also adsorb metals from the oils, an adsorption performance in this regard is not mentioned.
  • silicas have high adsorption capacities, but no bleaching activities.
  • pure aluminum oxides show certain bleaching activities, but have a large number of undesirable side reactions.
  • 15 to 50 mol% of polyvalent metals, based on metals and silicon are usually incorporated into the silicas. This increases the bleaching activity of the materials, but the adsorption capacity falls.
  • pure aluminum silicates are preferably used, or the bleaching materials are specially pretreated, for example by intensive washing of the filter cake or by the one mentioned in EP-B-361 622 Complexation of the iron content in the silicate with EDTA.
  • the invention was therefore based on the object, while avoiding the disadvantages of the prior art, of providing metal oxide silicas (silicas) which at the same time have high adsorption and bleaching activity and which are simple to prepare.
  • the invention thus relates to a synthetic polysilicic acid (silica) containing the oxides of at least two metals with a valency of 2 or higher, of which one is iron and the other aluminum, for refining oils, which is characterized in that the The proportion of egg and aluminum is less than about 15 mol% (based on the sum of these metals and silicon), that the specific surface area is more than 100 m 2 / g and that the water content (determined after drying at 105 ° C. as an annealing agent) - lust at 1000 ° C) is less than about 5 wt .-%.
  • the loss on ignition is preferably about 2.5 to 3.5% by weight.
  • polysilicic acid largely coincides with the English term “silica”, i.e. it describes condensed silica which still contains a certain proportion of bound water.
  • the proportion of iron and aluminum is preferably about 5 to 15 mol% (based on the sum of these metals and silicon).
  • the iron can be in a bivalent or trivalent form.
  • alkaline earth metals such as calcium and magnesium, as well as zinc and manganese can also be present, but are not limited to these.
  • 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 mol%.
  • the proportion of egg, based on the sum of iron and aluminum is particularly preferably approximately 4 to 25 mol%, in particular approximately 5 to 10 mol%.
  • 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 which are connected to part of the polysilicic acid.
  • these silicates are iron aluminosilicates.
  • the metal oxides or metal silicates are present in a polysilicic acid matrix and are probably at least partially crystalline. The rest of the polysilicic acid is predominantly in amorphous form.
  • the bleaching activities of the metal oxide polysilicic acids according to the invention are even higher than that of very good conventional bleaching earths based on bentonite.
  • the adsorption capacity for metals has also been retained.
  • the metal oxide polysilicic acids according to the invention even show 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 mercury porosimetry method, as explained below) is about 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 mVal / 100 g.
  • the invention further relates to a process for the preparation of the synthetic polysilicic acids specified above, which is characterized in that an alkali silicate solution, preferably a water glass solution, is acidified until a hydrogel is formed, the hydrogel with the solution of one or more salts of two or more metals mixed with a valence of 2 or higher, one of which is iron and the other aluminum, increases the pH of the mixture by adding alkali to form a precipitate, separates the precipitate from the solution and washes and the washed precipitate dries and optionally calcined.
  • an alkali silicate solution preferably a water glass solution
  • the alkali silicate solution is first acidified to such an extent that a pH of approximately 8.5 to 11 is established.
  • the pH can also be obtained by adding an acidic metal salt solution.
  • the addition of the water glass solution to the acid or to the acidic metal salt solution is also possible.
  • the mixture obtained is then acidified further with metal salt solutions or acid, so that a pH of about 3.5 to 5.0 is established.
  • the pH value is readjusted with small amounts of alkali solution.
  • the washed precipitate is resuspended and spray-dried and the spray-dried product at approximately 450 to 900 ° C. to a residual water content of approximately 0 to ⁇ 5, in particular approximately 0.5 to 2% by weight (determined at 105 ° C) calcined.
  • the calcination is carried out briefly (shock calcination), not all of the water being removed, so that drying at 105 ° C. over a longer period of time leads to a loss of weight until constant weight.
  • the loss on ignition at 1000 ° C is included about 1.5 to 5 wt. -%.
  • the invention furthermore relates to the use of the products according to the invention for refining and bleaching oils, in particular palm oil.
  • This removes not only colorants such as carotenoids and chlorophylls, but also other contaminants such as phosphatides (phospholipids), soaps, metals and oxidation products as well as other accompanying substances that negatively affect the taste, smell, appearance and shelf life of the oil.
  • Oils are to be understood in particular as vegetable and animal oils or fats. These are predominantly glycerides, in particular triglycerides of a wide variety of fatty acids, in particular saturated or unsaturated fatty acids.
  • the metal oxide silicas according to the invention can also be used for the treatment of other oils, such as mineral or silicone oils, or also for the treatment of various liquids in which one or more undesired accompanying substances are to be removed.
  • oils such as mineral or silicone oils
  • examples of such alternative fields of application are the cleaning, decolorization, refining or clarification of contaminated solutions, wine, beer, juices, whey, sugar solutions or Solvents.
  • the metal oxide silicas according to the invention can be used to remove oil-soluble iron from oils since they do not give off iron themselves, but have an excellent adsorption capacity for iron. They are therefore particularly suitable for refining highly unsaturated or oxidation-sensitive oils, such as fish oil, linseed oil or rapeseed oil, or oils which are difficult to bleach, such as palm oil.
  • highly unsaturated or oxidation-sensitive oils such as fish oil, linseed oil or rapeseed oil, or oils which are difficult to bleach, such as palm oil.
  • the storage stability of the oils can be considerably improved by removing the oil-soluble iron and other pro-oxidative accompanying substances.
  • 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 comprises heating the used metal oxide polysilicic acids in an oxidizing atmosphere at about 500 to 900 ° C. in order to oxidatively remove adhering oil residues or polymer products formed during the first bleaching treatment.
  • the chemical treatment comprises, for example, extraction with solvents, saponification of the adhering oil or treatment with acids and a combination of these processes.
  • 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 measured on a fully automatic nitrogen porosimeter from Micromeritics, type ASAP 2010, carried out according to 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 capability To determine the ion exchange capability (IUF), the dried material is reacted with a large excess of an aqueous NH 4 C1 solution under reflux for 1 hour. After standing for 16 hours at room temperature, the mixture is filtered and washed. The metal ions (eg the iron ions as Fe-IUF) are determined from the combined filtrate and wash water using AAS. The filter cake is dried and the H4 content determined according to Kjeldahl. The total IUF can be calculated from the amount of ammonium exchanged.
  • IUF ion exchange capability
  • 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 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 ° 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 is formed. Then F g FeS0_ ⁇ * 7H2 ⁇ , dissolved in G ml of water, and H g of an aluminum sulfate solution (5 wt .-% Al2O3) are added and the pH is adjusted to about 4.5 with 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. In example 5, this suspension is dispensed with.
  • the filter cake obtained after filtration / suspension / filtration or filtration / washing is removed, redispersed in water, spray-dried and calcined at 700.degree. 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 within 45 seconds by adding 751 ml of 4N H2SO, containing 63.98 g of FeSO4 * 7H2 ⁇ set to 10.1. 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 stirred in water to give 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 / (A1 + Si) at. 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.
  • Example 3 of DE-B-2 036 819 was reworked.
  • the product analysis showed a BET surface area of 476 m / g, a pore volume of 0.354 ml / g in pores of 0-140 ⁇ m (CCI4 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 stirred in a first reactor at 50 ° C. with 4 N sulfuric acid within 45 seconds added, 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 there with an aluminum sulfate solution which contained 5% by weight of Al 2 O 3. brought to reaction. 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 with a solids content of 7.5% by weight.
  • the dispersion was filtered and the filter cake was redispersed again 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 the bleaching earth is added.
  • the mixture is bleached at normal pressure for 30 minutes with uniform stirring.
  • the oil is separated from the solids by filtration, and the transmission is determined on a spectrophotometer at 460 nm against water. 1 cm thick cuvettes were used for this.
  • the percentage transmission is a direct measure of the success of the bleaching. The results are shown in Table III.
  • 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 of the highest quality. Bleaching of rapeseed oil
  • 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 color scan method. Low color numbers mean good bleaching results.
  • the results are shown in Table IV.
  • ERSWZBLATT (RULE 26)
  • the examples demonstrate the good bleaching results with the synthetic bleaching earths according to the invention.
  • the activity is of the order of magnitude of the highly active acid-activated bentonites.
  • chlorophyll A adsorption the products according to the invention are superior to the acid-activated bentonites.
  • SUBSTITUTE SHEET (RULE 6 ) This example demonstrates the excellent bleaching activity of the products according to the invention even with palm oil which is difficult to bleach. Also to be emphasized is the extraordinarily high adsorption capacity for oil-soluble iron. The prior art materials have lower bleaching activities and poor iron adsorption values. The product according to DE-B-2036 819 (Comparative Example 2) even releases iron into the oil.
  • the products according to the invention thus represent synthetic bleaching earths which can be used universally. Their bleaching action, their adsorption capacity and 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)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Fats And Perfumes (AREA)
  • Silicon Compounds (AREA)

Abstract

L'invention concerne un acide polysilicique (silice) synthétique contenant les oxides d'au moins deux métaux avec une valence égale ou supérieure à 2, dont l'un représente le fer et l'autre l'aluminium, pour le raffinage des huiles, caractérisé en ce que la proportion du fer et de l'aluminium est inférieure à 15 % en moles par rapport à la somme de ces métaux et du silicium), en ce que la surface spécifique est supérieure à 100 m2/g et en ce que la teneur en eau (déterminée aprés séchage à 105 °C sous forme de perte par calcination à 1000 °C) est inférieure à environ 5 % en poids.
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

Publications (2)

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

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP97943828A Expired - Lifetime EP0938375B1 (fr) 1996-09-03 1997-09-02 Acide polysilicique (silice) synthetique contenant du fer et de l'aluminium pour le traitement des huiles

Country Status (4)

Country Link
EP (1) EP0938375B1 (fr)
JP (1) JP3996199B2 (fr)
DE (2) DE19635730A1 (fr)
WO (1) WO1998009723A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004105936A1 (fr) * 2003-05-30 2004-12-09 Süd-Chemie AG Terre decolorante semi-synthetique
CN109321356A (zh) * 2018-10-30 2019-02-12 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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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

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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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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004105936A1 (fr) * 2003-05-30 2004-12-09 Süd-Chemie AG Terre decolorante semi-synthetique
CN109321356A (zh) * 2018-10-30 2019-02-12 新疆维吾尔自治区分析测试研究院 一种沙棘油精炼设备
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

Also Published As

Publication number Publication date
JP3996199B2 (ja) 2007-10-24
DE59701863D1 (de) 2000-07-13
WO1998009723A1 (fr) 1998-03-12
JP2000517241A (ja) 2000-12-26
DE19635730A1 (de) 1998-03-05
EP0938375B1 (fr) 2000-06-07

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