WO2008001509A1 - Agent de décoloration pour huile et graisse ou huile minérale - Google Patents
Agent de décoloration pour huile et graisse ou huile minérale Download PDFInfo
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- WO2008001509A1 WO2008001509A1 PCT/JP2007/052061 JP2007052061W WO2008001509A1 WO 2008001509 A1 WO2008001509 A1 WO 2008001509A1 JP 2007052061 W JP2007052061 W JP 2007052061W WO 2008001509 A1 WO2008001509 A1 WO 2008001509A1
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- oil
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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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
- C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
- C01B33/40—Clays
Definitions
- the present invention relates to a bleaching agent for fats and oils or mineral oils, and more particularly to a bleaching agent comprising activated clay.
- activated clay which is activated by increasing the specific surface area, etc. by acid treatment of such a hectral type smectite clay mineral, is also being used as a decolorizer for fats and oils and mineral oils.
- Patent Document 1 discloses that activated clay obtained by acid-treating a dioctahedral smectite clay mineral and having a crystallite size adjusted to a predetermined range is used as a decolorizing agent for fats and oils and minerals. Proposed.
- Patent Document 2 states that the fine pores that are obtained by acid-treating montmorillonite clay minerals belonging to the doral-type smectite clay mineral, with most of the pores in the range of 30 to 5 OA.
- An inorganic polymer having a pore distribution is disclosed.
- Permission Document 3 discloses a novel dry acid treatment method for producing activated clay or fine silica by acid-treating alumina silicate clay containing acid-soluble basic components. It is clear.
- Patent Document 1 Japanese Patent Laid-Open No. 1 1 1 1 5 7 8 2 9
- Patent Document 2 Japanese Patent Laid-Open No. 6-3 4 0 4 1 3
- decolorization and oil retention are particularly closely related. For example, if the decolorization is increased, the oil retention increases and the oil content that is adsorbed and retained on the waste clay. As a result, it is extremely difficult to satisfy both high decolorization and low oil retention at the same time.
- the above-mentioned decoloring agent proposed in Patent Document 1 has a problem that the decolorization property is high, but the irretention property is not lowered to a satisfactory level.
- the inorganic porous material having a very sharp pore distribution shown in Patent Document 2 has low oil retention but low decolorization.
- the activated clay obtained by the dry acid treatment method disclosed in Patent Document 3 also has high decolorization property, and does not have a satisfactory decrease in oil retentivity.
- an object of the present invention is to provide a bleaching agent for fats and oils or mineral oils that has excellent filterability, high decolorization properties, and low oil retention properties.
- the inventors have conducted many experiments on the decolorization and oil retention of activated clay. As a result, when performing acid treatment on the dioctahedral smectite clay mineral, adjusting the sulfuric acid treatment conditions, selectively treating the particle surface with acid, and suppressing acid treatment inside the particles, The present inventors have found a novel finding that an activated clay with high oil retention, low oil retention, and excellent filterability can be obtained, thereby completing the present invention.
- a defatting agent for fats or mineral oils comprising an activated clay obtained by acid treatment of a dioctahedral smectite clay mineral,
- the activated clay has an average particle size (D 50 ) in terms of volume by laser diffraction scattering method in the range of 20 to 30 rri and the content of fine particles of 5 m or less is 15% by volume or less, and the bulk density is 0 In the range of 60 to 0.7 O gZc c, the pore volume at a pore diameter of 17 to 3000 A is 0.35 to 0.40 c, ⁇
- a decolorizing agent characterized in that the ratio of the bulk density to the pore volume (bulk density / pore volume) is in the range of 1.55 to 1., 95. It is.
- the activated clay is 200 to 300 m 2 Zg.
- It preferably has a BET specific surface area.
- the powder obtained by pulverizing and classifying the divergent smectite clay mineral and having an average particle size (D 50 ) in the body conversion by the laser diffraction scattering method in the range of 20 to 30 / m Prepare
- the powder cake, 35 to 45 wt% sulfuric acid aqueous solution is used, the powder is added to and mixed with the sulfuric acid aqueous solution, and heated to a temperature of 85 ° C or higher, and subjected to phosphoric acid treatment,
- a method for producing a decolorizing agent which is characterized in that the resulting acid-treated product is washed and dried, is hereinafter referred to as a “wet method”.
- dioctahedral smectite clay mineral is further pulverized and classified, and the average particle size (D 50 ) in terms of volume by laser diffraction scattering method is 20 to 20 Prepare a powder in the range of 30 m,
- the powder By immersing the powder in an aqueous sulfuric acid solution having a concentration of 30 to 45% by weight, the powder is impregnated with the aqueous sulfuric acid solution,
- the filter cake is heated to a temperature of 80 to 1550 ° C. while maintaining a state of retaining water, thereby performing an acid treatment,
- the powder is a category having a fine particle content of 5 ⁇ m or less of 15 volume% or less prior to or after the acid treatment. It is preferable to adjust the grain size.
- the decolorizing agent of the present invention is composed of activated clay.
- the activated clay uses a raw material powder adjusted to a predetermined particle size (a powder of Joctahedral type smectite clay powder).
- the acid treatment conditions using sulfuric acid are adjusted, and the acid treatment is performed by the wet method or the semi-dry method.
- the particle surface is selectively acid-treated, and the acid inside the particles is obtained.
- the processing is suppressed. That is, the acid treatment causes an increase in pore volume and a decrease in bulk.
- the acid treatment is stopped on the particle surface and is suppressed inside the particle, so that the bulk density is 0.60.
- the pore volume at the pore diameters of 17 to 3 ⁇ ′ ⁇ and ⁇ A is 0.3.
- the ratio of the bulk density to the pore volume is in the range of 1.5 5 to 95 5
- the pore volume does not increase and the bulk density does not decrease, so the bulk density / pore volume ratio is higher than the above range. End up.
- the active clay of the present invention having the physical properties as described above exhibits excellent decoloring properties and low oil retention as well as understood from the experimental results of Examples described later. Excellent filterability. That is, in the present invention, the pores formed by the acid treatment are selectively distributed on the surface portion of the particle, and the adsorptivity to a pigment such as chlorophyll is enhanced by the pores on the surface portion of the particle. It is done. On the other hand, since such pores are suppressed inside the particles, it is possible to avoid an increase in retention of adsorbed oil, that is, oil retention. As a result, according to the present invention, it is possible to ensure excellent decolorization while retaining low oil retention.
- the fine particle content of 5 jum or less is suppressed to 1 15% by volume or less, so that excellent filterability and low oil retention are achieved. Show. Brief Description of Drawings
- Fig. 1 is a cross-sectional view of the decolorization tester. Best Mode for Carrying Out the Invention
- the activated clay used as a decoloring agent is a dioctahedral smectite clay mineral, which is pulverized and classified to obtain a powder of a predetermined particle size. It is manufactured by acid treatment with.
- Raw clay ": Doral type Sumekutai Bok clay minerals and to Jiokuta used in is believed to volcanic rock and lava is modified under the influence of sea water, S i 0 4 tetrahedral layers one A! 0 6 Octahedron layer S i 0 4 A tri-layer structure consisting of tetrahedrons and a structure in which these tetrahedrons and octahedrons are partially replaced by the same type of metal are used as the basic structure (unit layer).
- Li Between these three layers, there are cations such as Ca, K, and Na, hydrogen ions, and water molecules coordinated with them.
- a part of AI in the octahedral layer of the basic three-layer structure is replaced with Mg and F e (
- the lattice has a negative charge, and this negative charge is neutralized by metal cations and hydrogen ions present between the basic layers.
- Such smectite clays include acid clay, bennite, and fuller's earth. '' They exhibit different characteristics depending on the type and amount of metal cation existing between metal layers and the amount of hydrogen ion. .
- the amount of Na ions present between the basic layers is large, and therefore, the pH of the dispersion suspended in water is high, generally on the high alkali side, and also highly swollen with water. It also shows the property of gelling and solidifying.
- acid clay there is a large amount of hydrogen ions present between the basic layers, and therefore the pH of the dispersion suspended in water is low, and it is generally on the acidic side. Although swellable, the swelling is generally lower than bentonite and it does not gel.
- the raw clay has the following composition in terms of oxides, although it varies depending on the origin of the clay, the place of production, and the same place of production, as well as the location (face).
- the above-mentioned Joctahedral smectite clay mineral is subjected to refining operations such as stone sand separation, buoyancy beneficiation, magnetic beneficiation, elutriation, and wind drowning if necessary, and then acid treatment is performed.
- refining operations such as stone sand separation, buoyancy beneficiation, magnetic beneficiation, elutriation, and wind drowning if necessary
- acid treatment is performed prior to treatment.
- the particle size it is particularly preferable to adjust the particle size so that the coarse particle having a particle size of 104 / m or more is 5% by volume or less.
- the surface portion of the particles is selectively acid-treated and activated, and the acid treatment does not penetrate into the particles, and will be described later. It becomes possible to obtain particles having characteristics. For example, when particles having an average particle size larger than the above range are subjected to acid treatment, even if the surface portion is selectively acid-treated, when the acid-treated product is atomized, acid treatment is not performed at all. In this case, a large amount of particles are generated, and as a result, physical properties such as a desired pore volume can be confirmed, and decolorization performance and the like are deteriorated.
- the particle size of the raw clay can be measured by a laser diffraction scattering method in which the raw clay is suspended and dispersed in a non-aqueous dispersion medium such as ethanol.
- the degree adjustment as described above can be performed by pulverizing the raw clay, pulverizing it with a ball mill or the like, and classifying it with a sieve.
- the above-mentioned raw clay powder can be further adjusted in particle size, and the content of fine particles having a particle size of 5 / m or less can be adjusted to 15 / volatilizer 0/0 or less.
- the fine particle content can be adjusted to a certain level or less, it is possible to avoid the deterioration of the filterability and the oil retention of the obtained acid substance as well as the fine particle content has been eliminated in the same way. This is also advantageous for lowering.
- Such removal of fine particles can also be performed after the acid treatment described below.
- the raw clay powder whose particle size is adjusted as described above is subjected to an acid treatment.
- acid treatment is performed by a wet method or a semi-solid method described below.
- the concentration is 35 to 45% by weight, preferably 37 to 43% by weight.
- the sulfuric acid aqueous solution is used, and the above-mentioned raw clay powder is put into such a sulfuric acid aqueous solution for acid treatment. That is, conventionally, acid treatment was performed using sulfuric acid having a concentration lower than the above range. However, when such low concentration sulfuric acid is used, the acid treatment time becomes longer, and therefore the present invention is particularly effective. Thus, when the raw clay is powdered and acid-treated, the sulfuric acid penetrates into the inside of the particles, making it difficult to selectively neutralize the surface portion of the particles by acid treatment. This is because it becomes impossible to obtain particles having the characteristics described later. In addition, when a high concentration of sulfuric acid exceeding 45% by weight is used, even the layered structure peculiar to the raw clay has been destroyed, or the equipment is loaded and the life of the equipment is reduced. There is also a risk.
- the treatment using the sulfuric acid having a relatively high concentration as described above is performed at a temperature of 85 ° C. or more to _fc, particularly 85 to 95 ° C. That is, when the acid treatment is performed at a low temperature, it takes a long time until the predetermined pores are formed and activated, and as a result, the sulfuric acid penetrates into the inside of the particles, and the bulk density and fineness described later are increased. This is because it becomes impossible to obtain activated particles having physical properties such as child L volume, bulkiness Z pore volume ratio, and the like. Also, if the temperature is higher than necessary, the activation proceeds rapidly, and it may be difficult to limit the activation to the particle surface. Therefore, the upper limit of the temperature is It is preferable that the temperature is 95 ° C. as myself.
- the acid treatment as described above must be limited to the surface of the particle so that the acid penetrates into the inside of the particle and the inside of the particle is not activated. Therefore: Such acid treatment is very short. Such acid treatment time depends on the amount of raw clay powder, acid concentration, and acid treatment temperature to be treated, and is generally specified; ⁇ cannot be obtained, but in general, it takes 1 to 3 hours. Yes, for each condition, measure the physical properties of the active soot particles obtained; It is preferable to set in advance.
- the acid treatment as described above is performed by pouring a sulfuric acid aqueous solution of a predetermined concentration into a treatment tank, pouring the raw clay powder into the treatment tank, and stirring at a predetermined temperature. At the same time, the water can be washed by supplying a large amount of room temperature water to the treatment equipment and washing it.
- this method uses the minimum amount of soot sulfuric acid and acid treatment with sulfuric acid that has penetrated into the interstices of particles in the filter cake (some of which also penetrates into the pores of the particles). By doing so, the surface of the particles is selectively acidified and the acid treatment inside the particles is suppressed.
- the raw material powder when the raw material powder has a low water content, it is preferable to perform a moisture absorption process prior to the dipping process and adjust the water content of the powder to 10% by weight or more. As a result, the interlayer of the basic layer structure of the smear is expanded, and sulfuric acid is uniformly permeated into the powder particles.
- Such moisture absorption treatment is not particularly limited.
- the moisture absorption treatment is performed by leaving the powder in the atmosphere at room temperature for an appropriate time (usually 10 hours or more). Of course, when left in an atmosphere with high relative humidity, this time can be reduced.
- the raw material powder whose water content has been adjusted as described above is immersed in the sulfuric acid aqueous solution having the predetermined concentration described above, and then filtered by a conventional method to obtain a filter cake in which sulfuric acid is impregnated with water.
- Such immersion is preferably performed at a temperature of 40 ° C. or lower (usually room temperature). If it is carried out at a temperature higher than this, acid treatment proceeds with a large amount of sulfuric acid at this stage, and the acid treatment proceeds to the inside of the particles, making it difficult to obtain an activated clay with physical properties to be described later. Increase retention.
- Such immersion is performed until a sufficient amount of sulfuric acid and water penetrate into the pores of the particles and the pores of the particles, and is usually performed for 1 hour or more. Ion exchange such as Na ions is carried out, but the acid treatment is not carried out so as to elute the metal components constituting the three-layer structure.
- filtration under reduced pressure or pressure filtration may be performed as necessary.
- the amount of sulfuric acid impregnated (sulfuric acid + water) by such immersion and filtration can be reduced to 1 OO g (dry) As a thing), it is about 70-95 mI.
- the filter cake obtained as described above is subjected to an acid treatment.
- This acid treatment is performed at a temperature of 80 to 150 ° C, preferably 85 to 150 ° C. Under the condition that water existing in the interstices is retained.
- the sulfuric acid is gradually permeated from the surface of the particles to the inside to carry out the acid treatment.
- sulfuric acid does not migrate from the particle surface to the inside, resulting in insufficient acid treatment. It becomes difficult to obtain, and for example, the decolorization performance is lowered.
- the acid treatment proceeds to the inside of the particle by heating in a state where water is retained.
- the amount of sulfuric acid is limited to the particle gap (partially in the pores), so The acid treatment is performed only on the surface portion, and the acid treatment to the inside of the particles is effectively suppressed.
- the heating in the state of holding water is specifically performed by heating the filter cake to a predetermined temperature in a closed container such as an oven clave.
- a closed container such as an oven clave.
- water evaporates with heating (in this case, it becomes the same as drying), and as a result, sufficient acid treatment is not performed. As a result, the decolorization is reduced.
- the liquefied water may come into contact again with the superheated particles and may not effectively migrate to the particle gap, resulting in no retention of water. This is not very suitable because there is a risk of decolorization as well as heating in the state.
- the heating temperature is higher than the above range, the equipment is burdened and a special pair for preventing volatilization of water is required.
- the heating temperature is lower than the above range, it takes a long time for activation, which is extremely disadvantageous industrially.
- the acid treatment as described above is carried out until the sulfuric acid present in the interstices of the cake is completely consumed, and is usually about 1 to 20 hours.
- Such an acid treatment time can usually be set by conducting a laboratory experiment in advance, measuring unreacted sulfuric acid by a titration method or the like, and grasping the time when it becomes d.
- the filter cake is suspended and dispersed in a dilute acid, washed, then washed with water, and then subjected to filtration and drying.
- the target activated clay of the present invention is obtained. I can get it.
- the resulting activated clay is a cake, readily Hogusuko: and can become a powder having a particle size distribution described above.
- the obtained activated clay is left to stand in a state of being suspended and dispersed in water, and then watered, and the above-mentioned particle size is 5%. It is preferable to remove fine particles so that the content of fine particles of m or less is 15% by volume or less. No. That is, the removal of such fine particles can be performed prior to the acid treatment, but after the acid treatment, the fine particles can be removed easily by the elutriation (since the fine particles float, Fine particles are easily removed by sedimentation), which is extremely advantageous in terms of productivity. Since the raw clay swells before acid treatment, it is not possible to use chickenpox, but after acid treatment, the obtained activated clay does not have water swellability, so it is possible to use chickenpox. Is possible.
- the activated clay obtained by the above method is generally dried at a temperature of 80 to 50 ° C., particularly at a temperature of 100 to 300 ° C. as in the case of conventional activated clay. This is carried out for about 0 hours, especially about 0.7 to 5 hours, whereby the concentration of the surface silanol groups is reduced, the hygroscopicity, the swelling property, etc. are reduced, and the filterability can be further enhanced.
- the activated clay obtained by the above acid treatment has a mean particle size (D 5 0 ) in the range of 20 to 3 O jU m in terms of volume and 5 im, as with the raw clay powder.
- the following content of fine particles is 15% by volume or less (in the range of 3 ⁇ 4, and more preferably, coarse particles having a particle size of 104 m or more are in the range of 5% by volume or less.
- the particle size distribution can be measured by suspending and dispersing this activated clay powder in water and using a laser diffraction scattering method, that is, the obtained activated clay is non-swellable and therefore can be used as a dispersion medium. T can be measured using water.
- the activated clay with such a particle size distribution has very fine filterability because fine particles are removed.
- the activated clay of the present invention obtained by the acid treatment described above generally has the following chemical composition in terms of oxide.
- AI a O 2 ; 8 to 1 3 weight 0 / o
- Such activated clay has a fine L volume (by a nitrogen adsorption method) in a pore diameter of 17 to 3000 A in a range of 0.35 to 0.40 c cZg and a bulk density.
- the volume density Z fines L volume ratio is ⁇ .55 to 1.95, especially
- the bulk density Z pore volume ratio should be within the above range. If the acid treatment is not performed effectively and a sufficient amount of pores are not formed on the surface of the particle, the bulk density pore volume ratio is larger than the above range. .
- the activated clay of the present invention having the physical properties as described above exhibits excellent filterability and, at the same time, exhibits excellent characteristics as a decoloring agent having excellent decolorization properties and low oil retention properties.
- pigments such as chlorophyll are present in a state where molecules are associated in fats and oils. Therefore, it is adsorbed and held in relatively large pores in the particle surface portion formed by acid treatment. In the present invention, such pores are selectively formed in the particle surface portion. Therefore, as shown in the examples described later, it exhibits excellent decolorization.
- the pores are limitedly distributed on the surface of the particle, and there are few pores inside the particle.
- the oil retention property is very low.
- the activated clay (Comparative Example 4) as described in Patent Document 1 described above has pores formed to the inside of the particles, so its bulk density is small, from 17 to 300 A.
- the pore volume at the pore diameter is large, so the oil retention is extremely high.
- the active clay of the present invention has a relatively large BET specific surface area in connection with the above-mentioned particle size and pore volume, and generally falls within the range of 200 to 300. In addition, such a large specific surface area contributes to excellent decolorization.
- the activated clay described above is excellent in decoloring property and low in oil retention, so it is used as a bleaching agent for oils or mineral oils, particularly as a bleaching agent for fats and oils. Is done.
- the oils and fats to be color-treated include at least one of vegetable oils, animal fats and mineral oils.
- the fats and oils of the raw materials are widely present in the celestial fauna and flora and are mainly composed of fatty acids and glycerides.
- various lubricating oils such as spindle oil, refrigerating machine oil, dynamo oil, turbine oil, machine oil, marine internal combustion engine lubricating oil, gasoline engine lubricating oil, diesel engine lubricating oil, cylinder oil, marine engine oil.
- the active white having the above-mentioned particle size distribution in the oil or mineral oil to be decolorized;
- the powder of: and stirring both of them uniformly the coloring components and impurity components contained in the oil or mineral oil are adsorbed in the clay particles.
- an amount of oil or mineral oil close to the oil absorption of the white clay used is retained. In the present invention, this oil retention can be reduced.
- Decolorization treatment of fats and oils or mineral oils (or conditions known per se, such as adding a bleaching agent of 5 o / o or less on a weight basis per fat or mineral oil,
- the decolorization treatment can be completed by stirring both compositions for 5 to 30 minutes at a temperature.
- the mixture after the decolorization treatment is supplied to a vacuum filter or a pressure filter such as a filter press, a belt filter, an olive filter, an American filter, a centrifugal filter, etc. Or used with mineral oil
- Measurement was performed by laser diffraction scattering method using Mastersizer 2000 manufactured by Malvern.
- the raw clay was measured using ethanol as the solvent, and the decolorizing agents shown in the present invention (Examples) and Comparative Examples were measured using water as the solvent.
- Micromer measured the nitrogen adsorption method using Tri Star 3000 made by ics, and obtained the pore volume from the desorption data up to a pore diameter of 17 300 OA by BJH method.
- Fig. 1 See Chemistry and Industry 4, 1 26 (1 951) for more details.
- Eight hard glass large test tubes (capacity: ft 2 OOml) can be set in the oil bath. Each test tube has a rounded bottom.
- a stirring blade that stirs the oil bath is attached under the central master gear to keep the temperature in the oil bath uniform. A maximum of 8 decoloring tests can be performed.
- each test tube Take 50 g of rapeseed oil that has been deoxidized into each test tube, add 0.5 g of each decolorizer sample (1 ⁇ 1 ⁇ 2 to oil) and mix well with a stir bar for decolorization test.
- Each test tube is set in the above-mentioned decoloring tester maintained at 110 ° C., stirred for 20 minutes and then removed from the decoloring tester, and the mixed slurry of oil and decoloring agent is filtered. Get each decolorized oil.
- the white light transmittance (relative value when the transmittance of distilled water is 1 ⁇ %) of each decolorized oil was measured with a photoelectric colorimeter 2 C type manufactured by Hirama Rika Laboratory Co., Ltd. Of decoloring ability. The higher the transmittance value, the higher the decolorizing ability of the decoloring agent used.
- Soybean oil 1 50 g ⁇ 0.1 g is weighed into a 30 Om I beaker. Beaker
- the fine particle content of 5 Um or less was 12.5% by volume, and the coarse particle content of 104 jUm or more was 3.2% by volume.
- a beaker take 40 ml of sulfuric acid aqueous solution 800 ml, disperse 3 60 g of this raw clay powder under stirring, and perform acid treatment at 90 ° C for 2 hours with stirring on a heater. It was. After completion of the acid treatment, water was added to the acid-treated product, washed by a decantation method and filtered, and the filter cake was dried at 11 ° C. to obtain an activated clay powder.
- Example 2 An activated clay powder was obtained in the same manner as in Example 1 except that instead of the 40 wt% sulfuric acid aqueous solution in Example 1, a 45 wt% sulfuric acid aqueous solution was used. The physical properties were measured and the results are shown in Table 1.
- Example 1 The same procedure as in Example 1 was carried out except that a 3.5% by weight sulfuric acid aqueous solution was used instead of the 40% by weight sulfuric acid aqueous solution in Example 1, and the acid treatment was performed at 90 ° C for a long time. It was. Table 1 shows the results of physical property measurement.
- Example 2 The same octahedral smectite clay mineral as in Example 1 was roughly crushed, kneaded and granulated to a diameter of 5 mm. This granulated product was dried at 110 ° C. and then pulverized by a ball mill, and only coarse particles were removed by a sieve. The raw clay powder obtained was obtained using ethanol as the solvent. The average particle size (D 50 ) measured was 21.3 m, the content of fine particles of 5 m or less was 16.4% by volume, and the coarse particle content of 10 or more was 2.0. . In a beaker
- a 40 wt% sulfuric acid aqueous solution 8 O Om I was taken, and 360 g of this raw clay powder was dispersed with stirring, and acid-treated at 90 ° C. for 2 hours with stirring on a turret. After the acid treatment was completed, water was added to the acid-treated product and allowed to stand, and fine particles were removed with a water tank. The acid-treated product from which the fine particles had been removed was washed by a decantation method and then filtered, and the filter cake was dried at 11 ° C to obtain a t-activated clay powder. The physical properties were measured and the results are shown in Table 1.
- the same octahedral smectite clay mineral as in Example 1 was roughly crushed and kneaded to establish a diameter of 5 mm.
- the granulated product was dried at 110 ° C., pulverized with a pole mill, and classified by combining a sieve and a windmill.
- the obtained raw clay powder has an average particle size (D 50 ) of 26.9) Um and a fine particle content of 5 m or less of 10.1% by volume and 10 4 rr> or more as measured using ethanol as a solvent.
- the coarse content was 0.8% by volume and the water content was 10.5%.
- Example 5 Instead of the oven 1 20 ° C and are in Example 5, except that for 2 hours fermentation process at 1 20 0 C in the autoclave, to obtain a powdery active clay was in the same manner as in Example 5. Physical properties were measured and the results are shown in Table 1.
- Example 5 Odor ⁇ 1 Change to 20 ° C on, 1 in oven at 50 ° C 90
- An activated clay powder was obtained in the same manner as in Example 5 except that the acid treatment was performed for a minute. The physical properties were measured and the results are shown in Table 1.
- Example 5 An activated clay powder was obtained in the same manner as in Example 5 except that in Example 5, the oven was changed to an oven at 120 ° C. and the acid treatment was carried out in an oven at 85 ° C. for 20 hours. Physical properties were measured and the results are shown in Table 1.
- Example 5 except that 35% by weight sulfuric acid aqueous solution was used instead of 45% by weight sulfuric acid aqueous solution and acid treatment was carried out in an oven at 85 ° C for 20 hours. A white clay powder was obtained. The physical properties were measured and the results are shown in Table 1.
- Example 2 Instead of 40 wt% sulfuric acid aqueous solution in Example 1, 25 wt% sulfuric acid aqueous solution was used.
- An activated clay powder was obtained in the same manner as in Example 1 except that 800 mI was used. The physical properties were measured and the results are shown in Table 2.
- Comparative Example 2 Active activated clay powder in the same manner as Comparative Example 2, except that 35% by weight sulfuric acid aqueous solution was used instead of 35% by weight sulfuric acid aqueous solution and acid treatment was performed at 70 ° C for 9 hours. The Obtained. The physical properties were measured and the results are shown in Table 2.
- Example 2 The same octahedral smectite clay mineral as in Example 1 was coarsely kneaded and kneaded to granulate to a diameter of 5 mm, and 150 g of this granulated product was filled into a treatment tank. 30% by weight sulfuric acid aqueous solution 2 O O O m I was circulated there for acid treatment. The treatment temperature at that time was 90 ° C, and the treatment time was 5 hours. After completion of the acid treatment, washing water was circulated through the acid-treated product, followed by washing with water, followed by drying, pulverization and classification at 110 ° C. to obtain an activated clay powder. The physical properties were measured and the results are shown in Table 2.
- Example 2 The same octahedral smectite clay mineral as in Example 1 is roughened to obtain raw clay. Add 980/0 sulfuric acid 1 3 8 g to raw material viscosity +/- 600 g containing moisture 36%, knead well and granulate to 5 mm diameter. This granulated product was put in a glass container, covered gently, and acid-treated in an oven at 1'20 ° C for 2 hours. After the acid treatment is completed, acid is added to the acid-treated product to extract soluble salts (at this time, the granulated product is not suspended and dispersed), then water is added and the product is washed with water and dried at 110 ° C. After pulverization and classification, an activated clay powder was obtained. The physical properties were measured and the results are shown in Table 2.
- Example 5 use 35% by weight sulfuric acid solution instead of 2% by weight sulfuric acid solution! The others were carried out in the same manner as in Example 5 to obtain activated clay powder. The physical properties were measured and the results are shown in Table 2. [0080]
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ES07708113.1T ES2685421T3 (es) | 2006-06-28 | 2007-01-31 | Agente decolorante para aceite y grasa o aceite mineral |
PL07708113T PL2034006T3 (pl) | 2006-06-28 | 2007-01-31 | Środek odbarwiający do oleju i tłuszczu lub oleju mineralnego |
DK07708113.1T DK2034006T3 (en) | 2006-06-28 | 2007-01-31 | Decolorizing oil and grease or mineral oil |
EP07708113.1A EP2034006B1 (en) | 2006-06-28 | 2007-01-31 | Decoloring agent for oil-and-fat or mineral oil |
KR1020087030255A KR101321266B1 (ko) | 2006-06-28 | 2007-01-31 | 유지류 또는 광유류의 탈색제 |
AU2007264603A AU2007264603A1 (en) | 2006-06-28 | 2007-01-31 | Decoloring agent for fats and oils or mineral oils |
Applications Claiming Priority (4)
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JP2006177841 | 2006-06-28 | ||
JP2006-177841 | 2006-06-28 | ||
JP2007015807A JP4912168B2 (ja) | 2006-06-28 | 2007-01-26 | 油脂類もしくは鉱油類の脱色剤 |
JP2007-015807 | 2007-01-26 |
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WO2008001509A1 true WO2008001509A1 (fr) | 2008-01-03 |
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PCT/JP2007/052061 WO2008001509A1 (fr) | 2006-06-28 | 2007-01-31 | Agent de décoloration pour huile et graisse ou huile minérale |
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EP (1) | EP2034006B1 (ja) |
JP (1) | JP4912168B2 (ja) |
KR (1) | KR101321266B1 (ja) |
AU (1) | AU2007264603A1 (ja) |
DK (1) | DK2034006T3 (ja) |
ES (1) | ES2685421T3 (ja) |
MY (1) | MY151451A (ja) |
PL (1) | PL2034006T3 (ja) |
TW (1) | TWI411466B (ja) |
WO (1) | WO2008001509A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2017088414A (ja) * | 2015-11-02 | 2017-05-25 | 水澤化学工業株式会社 | 脱色剤及び脱色剤の製造方法 |
CN112649555A (zh) * | 2019-10-10 | 2021-04-13 | 句容康泰膨润土有限公司 | 一种膨润土蒙脱石含量自动检测设备及检测方法 |
CN113265296A (zh) * | 2021-05-11 | 2021-08-17 | 广州明创生物科技有限公司 | 一种山茶油冷榨及物理精炼方法 |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4393579B1 (ja) | 2008-09-18 | 2010-01-06 | 水澤化学工業株式会社 | 新規な活性白土及び動植物の油脂類もしくは鉱物油の脱色剤 |
CN103706322B (zh) * | 2013-12-11 | 2015-04-08 | 中国铝业股份有限公司 | 一种油脂脱色剂 |
JP6473661B2 (ja) * | 2014-08-12 | 2019-02-20 | 水澤化学工業株式会社 | Rbdパーム油の脱色方法 |
JP6910136B2 (ja) * | 2016-01-28 | 2021-07-28 | 水澤化学工業株式会社 | プリン体用吸着剤 |
WO2017195121A1 (es) * | 2016-05-10 | 2017-11-16 | Universidad Eafit | Proceso para obtener arcillas activadas |
KR102320285B1 (ko) | 2021-01-27 | 2021-11-02 | 케이지케미칼 주식회사 | 나프탈렌계 분산제 조성물 및 그 제조방법 |
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JPH06340413A (ja) | 1993-05-28 | 1994-12-13 | Nittetsu Mining Co Ltd | 無機質多孔体及びその製造方法 |
JPH11157829A (ja) | 1997-12-02 | 1999-06-15 | Mizusawa Ind Chem Ltd | 活性白土、その製造方法及びその用途 |
JP2000344513A (ja) * | 1999-06-01 | 2000-12-12 | Mizusawa Ind Chem Ltd | 活性白土定形粒子、その製造方法及びその用途 |
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US3787330A (en) * | 1968-10-01 | 1974-01-22 | Mizusawa Industrial Chem | Refining agent for oily substances |
WO2002022693A1 (fr) * | 2000-09-13 | 2002-03-21 | Japan Polychem Corporation | Catalyseur pour polymerisation d'olefines |
KR100585823B1 (ko) * | 2003-08-19 | 2006-06-01 | 주식회사 대일화학 | 입상수율이 향상되는 활성 백토의 제조방법 |
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2007
- 2007-01-26 JP JP2007015807A patent/JP4912168B2/ja active Active
- 2007-01-31 AU AU2007264603A patent/AU2007264603A1/en not_active Abandoned
- 2007-01-31 WO PCT/JP2007/052061 patent/WO2008001509A1/ja active Application Filing
- 2007-01-31 MY MYPI20084735 patent/MY151451A/en unknown
- 2007-01-31 ES ES07708113.1T patent/ES2685421T3/es active Active
- 2007-01-31 EP EP07708113.1A patent/EP2034006B1/en active Active
- 2007-01-31 KR KR1020087030255A patent/KR101321266B1/ko active IP Right Grant
- 2007-01-31 DK DK07708113.1T patent/DK2034006T3/en active
- 2007-01-31 PL PL07708113T patent/PL2034006T3/pl unknown
- 2007-03-28 TW TW096110750A patent/TWI411466B/zh active
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JPH06340413A (ja) | 1993-05-28 | 1994-12-13 | Nittetsu Mining Co Ltd | 無機質多孔体及びその製造方法 |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2017088414A (ja) * | 2015-11-02 | 2017-05-25 | 水澤化学工業株式会社 | 脱色剤及び脱色剤の製造方法 |
CN112649555A (zh) * | 2019-10-10 | 2021-04-13 | 句容康泰膨润土有限公司 | 一种膨润土蒙脱石含量自动检测设备及检测方法 |
CN113265296A (zh) * | 2021-05-11 | 2021-08-17 | 广州明创生物科技有限公司 | 一种山茶油冷榨及物理精炼方法 |
Also Published As
Publication number | Publication date |
---|---|
EP2034006B1 (en) | 2018-07-04 |
JP4912168B2 (ja) | 2012-04-11 |
PL2034006T3 (pl) | 2018-12-31 |
ES2685421T3 (es) | 2018-10-09 |
AU2007264603A1 (en) | 2008-01-03 |
KR101321266B1 (ko) | 2013-10-25 |
KR20090021275A (ko) | 2009-03-02 |
EP2034006A4 (en) | 2012-09-26 |
EP2034006A1 (en) | 2009-03-11 |
JP2008031411A (ja) | 2008-02-14 |
MY151451A (en) | 2014-05-30 |
DK2034006T3 (en) | 2018-09-03 |
TWI411466B (zh) | 2013-10-11 |
TW200800382A (en) | 2008-01-01 |
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