WO2010032568A1 - 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 - Google Patents
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 Download PDFInfo
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- WO2010032568A1 WO2010032568A1 PCT/JP2009/064194 JP2009064194W WO2010032568A1 WO 2010032568 A1 WO2010032568 A1 WO 2010032568A1 JP 2009064194 W JP2009064194 W JP 2009064194W WO 2010032568 A1 WO2010032568 A1 WO 2010032568A1
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- 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
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
- A23D9/00—Other edible oils or fats, e.g. shortenings, cooking oils
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28071—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being less than 0.5 ml/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28073—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being in the range 0.5-1.0 ml/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
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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 present invention relates to a bleaching agent for animal or plant oils or mineral oils having a novel structure, and more particularly to a bleaching agent comprising activated clay.
- activated clay that has been activated by increasing the specific surface area by acid treatment of clays mainly composed of dioctahedral smectite as a decolorizer for animal and plant oils and mineral oils.
- an activated clay obtained by acid treatment of a dioctahedral smectite clay mineral and having a crystallite diameter adjusted to a predetermined range is used as a bleaching agent for animal and plant oils and mineral oils.
- a dioctahedral smectite clay mineral and having a crystallite diameter adjusted to a predetermined range is used as a bleaching agent for animal and plant oils and mineral oils.
- Patent Document 2 discloses that most of pores obtained by acid treatment of montmorillonite clay mineral belonging to dioctahedral smectite clay mineral have a pore diameter of 30 to 50 mm (3.0 to 5.0 nm). An inorganic porous body having a sharp pore distribution is disclosed.
- an object of the present invention is to provide a novel activated clay having an excellent decolorization performance as compared with conventionally known activated clay, and a bleaching agent for animal or plant fats and oils or mineral oil comprising the activated clay.
- the present inventors can obtain a novel activated clay with significantly improved decolorization performance by subjecting it to an appropriate alkali treatment followed by acid washing. As a result, the present invention has been completed.
- the pore volume at a pore diameter of 1.7 to 100 nm is in the range of 0.40 to 0.60 cm 3 / g as measured by the nitrogen adsorption method, and 1.7 to 11.
- the pore volume ratio (B / A) between the pore volume (A) at a pore diameter of 5 nm and the pore volume (B) at a pore diameter of more than 11.5 nm and not more than 100 nm is 0.75 to 1.5
- an activated clay is provided in which the solid acid amount of Ho ⁇ ⁇ 3.0 is in the range of 0.15 to 0.40 mmol / g.
- a decolorizing agent for animal and plant oils or mineral oils comprising activated clay.
- the pH (25 ° C.) in a 5% by weight aqueous suspension is in the range of 2.5 to 5.0, (2) having a BET specific surface area of 150 to 300 m 2 / g, Is preferred.
- the activated clay of the present invention has a pore volume in the range of 0.40 to 0.60 cm 3 / g at a pore diameter (pore diameter) of 1.7 to 100 nm, and has such a pore volume.
- the activated clay is known from the past.
- the present invention has such a pore volume and at the same time has a pore volume (A) with a pore diameter of 1.7 to 11.5 nm and a fine volume of more than 11.5 nm and less than 100 nm.
- the pore volume ratio (B / A) to the pore volume (B) in the pore diameter is in the range of 0.75 to 1.5, and the solid acid amount of Ho ⁇ ⁇ 3.0 is 0.15 to 0.00. It has a remarkable feature in that it is in the range of 40 mmol / g.
- the activated clay of the present invention has a large pore volume like the conventionally known activated clay, but contains many pores having a larger diameter than the conventionally known activated clay, In addition, since it contains a lot of relatively strong solid acid, both the physical adsorption performance by the pores and the chemical adsorption performance by the solid acid are enhanced with respect to the dye. As shown in Fig. 5, the color removal performance is remarkably superior to that of conventionally known activated clay.
- conventionally known activated clay simply increases the pore volume by acid treatment, resulting in a decrease in the amount of solid acid.
- the pore volume ratio (B / Even if A) is satisfied, the amount of solid acid is lower than that of the activated clay of the present invention. Therefore, even if the dye adsorption performance by the pores is enhanced, the dye adsorption performance by the solid acid is lowered. Therefore, it does not show the excellent decolorization performance as in the present invention.
- the activated clay of the present invention has a markedly improved decolorization performance, and is therefore suitably used as a decolorizing agent for fats and oils and mineral oils.
- the activated clay of the present invention uses an acid-treated clay (corresponding to a conventionally known activated clay) mainly composed of dioctahedral smectite as a starting material, which is alkali-treated and then adhered by acid washing. Is obtained.
- An acid-treated product of clay used as a raw material is produced by acid-treating the clay under known conditions.
- Clay mainly composed of the above-mentioned dioctahedral smectite, volcanic rock and lava, etc. are believed to have modified under the influence of sea water, from SiO 4 tetrahedral sheets -AlO 6 octahedral sheet -SiO 4 tetrahedral sheet
- This unit layer is the basic structure. Since a part of Al in the octahedron sheet of the basic structure is replaced with Mg or Fe (II) and a part of Si in the tetrahedron sheet is isomorphously replaced with Al, the unit layer has a negative charge.
- the negative charges are neutralized by metal cations such as Ca, K, Na, and hydrogen ions existing between the stacked layers of the unit layer.
- metal cations such as Ca, K, Na, and hydrogen ions existing between the stacked layers of the unit layer.
- Such smectite clays include acid clay, bentonite, fuller's earth, and the like, and exhibit different characteristics depending on the kind and amount of cations existing between the layers and the amount of hydrogen ions.
- bentonite has a large amount of Na ions present between the basic layers, and therefore, the pH of the dispersion suspended in water is high, generally on the high alkali side, and exhibits high swellability with respect to water. Furthermore, it exhibits the property of gelling and solidifying.
- the amount of hydrogen ions existing between the laminated layers of the unit layer is large, and therefore the pH of the dispersion suspended in water is low, generally on the acidic side, and also swellable to water.
- the swelling property is generally low and gelation does not occur.
- Various mineral acids can be used for the acid treatment of the above-mentioned dioctahedral smectite clay, but it is easy to obtain, and the acid treatment can be performed quickly without applying a load to the equipment such as acid corrosion. Sulfuric acid is preferred from the standpoint that it can be carried out.
- the obtained acid-treated product is filtered, washed with water, dried if necessary, and then used as a starting material for the activated clay of the present invention.
- the activated clay of the present invention is obtained by alkali treatment and acid cleaning of an acid-treated product of smectite clay as described above (that is, equivalent to a conventionally known activated clay).
- the pore volume in the pore diameter (pore diameter) at 1.7 to 100 nm is 0.40 to 0.60 cm 3 / g, and the solid of Ho ⁇ ⁇ 3.0 What is acid-treated so that the acid amount is in the range of 0.15 to 0.40 mmol / g is used. That is, the alkali treatment and the acid cleaning described above are treatments for increasing the pores having a large diameter without reducing the solid acid amount, and basically increase the pore volume and increase the solid acid amount. It is not a thing.
- the acid-treated product having the pore volume and the solid acid amount as described above has an effect of increasing the pore volume and decreasing the solid acid amount by the acid treatment, and depending on the composition of the raw clay, It can be obtained by adjusting acid treatment conditions (for example, acid concentration, acid treatment time, etc.).
- the acid treatment as described above causes an increase in the BET specific surface area.
- the BET specific surface area of the acid-treated product as described above is generally in the range of 250 m 2 / g or more.
- the pore volume and the pore volume with a pore diameter of 1.7 to 11.5 nm are generated by the acid treatment for obtaining the pore volume and the solid acid amount as described above.
- the pore volume ratio (B / A) between (A) and the pore volume (B) at a pore diameter greater than 11.5 nm and less than 100 nm is in the range of 0.70 or less, and there are many small pores Is generated.
- the alkali treatment of the acid-treated product is a treatment for increasing pores having a large diameter. That is, the alkali treatment hardly changes the pore volume at 1.7 to 100 nm of the acid-treated product described above, but the amorphous silica contained in the acid-treated product (clay particles by acid-treating the raw clay) Among the silica generated on the surface), the silica constituting the smaller pores dissolves to increase the amount of large-diameter pores and simultaneously close the small pores. As a result, the pore volume ratio ( The value of B / A) increases. Further, due to dissolution and desorption of silica existing on the surface, the irregularities on the particle surface are flattened, and the specific surface area is reduced.
- the solid acid contained in the acid-treated product is neutralized by the alkali treatment. Therefore, by performing acid washing after the alkali treatment and removing the alkali neutralizing the solid acid, the solid acid amount is restored to the same level as the raw smectite-treated product.
- the alkali treatment is performed by using an aqueous alkali solution such as sodium hydroxide, potassium hydroxide, or calcium hydroxide and mixing and stirring the aqueous alkali solution and the smectite-treated product. If the treatment is excessively performed, amorphous silica is eluted more than necessary, and if all of the amorphous silica is detached, it returns to the smectite clay used for the acid treatment, and the pores disappear. End up. Therefore, this alkali treatment needs to be performed moderately, and is performed to such an extent that the above pore volume ratio (B / A) is achieved while maintaining the pore volume of the acid-treated product within the above-mentioned range. .
- an aqueous alkali solution such as sodium hydroxide, potassium hydroxide, or calcium hydroxide
- the specific conditions vary depending on the composition of the acid-treated product to be used (for example, the degree of acid treatment) and cannot be generally specified, but generally the suspension concentration is about 10 to 25% by weight.
- An aqueous alkali solution may be added to and mixed with an aqueous suspension of the acid-treated product, followed by heat treatment, and an alkali treatment may be performed so that the pH is about 7 to 11.
- the acid cleaning performed after the alkali treatment is such that the alkali neutralizing the solid acid can be removed, for example, by showering with about 0.1 to 1.0% by weight of dilute sulfuric acid. This is performed by washing the alkali-treated product.
- the target activated clay of the present invention can be obtained by acid washing, water washing and drying, and if necessary, firing and particle size adjustment.
- the activated clay obtained as described above is obtained from an acid-treated product of smectite clay, it generally has the following composition in terms of oxide. SiO 2 ; 65 to 85% by weight Al 2 O 3 ; 6 to 12% by weight Fe 2 O 3 ; 1 to 8% by weight MgO: 1 to 3% by weight CaO; 0.1 to 2% by weight Na 2 O; 0.1 to 1% by weight K 2 O; 0.1 to 1% by weight Other oxides (such as TiO 2); 1 wt% or less Ig-loss (1050 °C); 4 to 8 wt%
- the pore volume in the pore diameter (pore diameter) at 1.7 to 100 nm is in the range of 0.40 to 0.60 cm 3 / g as measured by the nitrogen adsorption method.
- the same as the acid-treated product of smectite clay, and the solid acid amount of Ho ⁇ ⁇ 3.0 is 0.15 to 0.40 mmol / g, preferably 0.18 to 0.35 mmol / g. This is also in the same range as the acid-treated product of smectite clay used as a raw material.
- the pore volume ratio (B / A) to the pore volume (B) in the pore diameter is in the range of 0.75 to 1.5, preferably 0.8 to 1.4.
- the BET specific surface area is reduced by alkali treatment as compared with the acid-treated product of the raw smectite clay.
- the BET specific surface area is 150 to 300 m 2 / g, preferably 150 to 250 m 2 / g. Is in range.
- the alkali treatment described above is performed at least so that the BET specific surface area is maintained in the above range. This is because if the BET specific surface area is lower than the above range, the field required for adsorption is reduced, so that the adsorption performance with respect to the dye molecules is lowered and the decolorization performance may be lowered.
- the activated clay obtained as described above has a pH (25 ° C.) of 2% by weight aqueous suspension since the alkali content neutralizing the solid acid is removed by acid washing. It is in the range of 5 to 5.0.
- the activated clay of the present invention has a remarkably improved adsorptivity with respect to giant pigment molecules as compared with conventionally known activated clay, and is therefore suitably used as a decolorizer for animal and plant oils and mineral oils. .
- oils and fats of animals and plants to be decolorized include at least one of vegetable oils, animal fats and mineral oils.
- Oils and fats of raw materials are widely present in the natural animal and plant kingdoms, and are mainly composed of esters of fatty acids and glycerin, such as safflower oil, soybean oil, rapeseed oil, palm oil, palm kernel oil, beni flower oil, Vegetable oil such as cottonseed oil, coconut oil, rice bran oil, sesame oil, castor oil, linseed oil, olive oil, tung oil, coconut oil, peanut oil, kapok oil, cacao oil, wood wax, sunflower oil, corn oil and sardine oil, herring oil, Examples thereof include fish oils such as squid oil and saury oil, liver oil, whale oil, beef tallow, beef tallow, horse oil, pork tallow, sheep fat and other animal oils alone or in combination.
- 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, Gear oil, cutting oil, insulating oil, automatic transmission oil, compressor oil, hydraulic fluid, rolling oil and the like can be mentioned.
- the activity of the present invention is adjusted to a suitable particle size (generally a median diameter of about 18 to 30 ⁇ m on a volume basis measured by a laser diffraction method) to the fat or mineral oil to be decolorized.
- a suitable particle size generally a median diameter of about 18 to 30 ⁇ m on a volume basis measured by a laser diffraction method
- Decolorization is carried out by adding a white clay powder and stirring them uniformly to adsorb colored components and impurity components contained in the oil or mineral oil into the white clay particles.
- the decolorization treatment of animal and plant fats and oils or mineral oils is a per se known condition.
- a decoloring agent of 5% or less is added on a weight basis per fat or oil or mineral oil, and a temperature of 90 to 150 ° C. is 5 to 30.
- the decolorization process can be completed by stirring both compositions for a minute.
- the mixture after the decolorization treatment is supplied to an arbitrary filter such as a filter press, a belt filter, an olive filter, an American filter, a centrifugal filter, or a reduced pressure or pressure filter to remove the decolored oil or fat or It is separated into mineral oil and so-called waste clay that is a used decoloring agent.
- a filter press such as a filter press, a belt filter, an olive filter, an American filter, a centrifugal filter, or a reduced pressure or pressure filter to remove the decolored oil or fat or It is separated into mineral oil and so-called waste clay that is a used decoloring agent.
- the activated clay of the present invention can be used not only for defatting agents for animal and plant oils or mineral oils, but also for purification of aromatic hydrocarbons such as BTX (benzene, toluene, xylene).
- aromatic hydrocarbons such as BTX (benzene, toluene, xylene).
- aluminum sulfate, aluminum chloride or the like can be added to the activated clay of the present invention.
- Solid acid amount (A) The solid acid amount of Ho ⁇ ⁇ 3.0 was measured by n-butylamine titration method. The sample was measured in advance for one dried at 150 ° C. for 3 hours. [Reference: "Catalyst” Vol.11, No6, P210-216 (1969)]
- Pore volume and pore volume ratio Measured by nitrogen adsorption method using Tri Star 3000 manufactured by Micromeritics, and obtained pore volume of pore diameter from 1.7 to 100 nm by BJH method from adsorption data. It was. Further, the ratio (B / A) of the pore volume (A) at a pore diameter of 1.7 to 11.5 nm and the pore volume (B) at a pore diameter larger than 11.5 nm and not larger than 100 nm is smaller than (B / A). The pore volume ratio was determined.
- Pore distribution Measurement was performed by a nitrogen adsorption method using Tri Star 3000 manufactured by Micromeritics, and the pore distribution was determined by BJH method from the adsorption data.
- Decoloring test method For the test of the performance of the decoloring agent, a decoloring tester shown in the figure of the clay handbook 2nd edition, Japan Clay Society (Gihodo Publishing) p917 was used. In this decoloring tester, eight large glass test tubes (capacity 200 ml) can be set in an oil bath. Each test tube has a corrugated stir bar with a rounded lower end, and the lower end is adjusted with a rubber tube so that it always contacts the bottom of the test tube. Since the eight stirring rods are rotated by the child gear separated from the central parent gear, the rotation speeds are kept exactly the same. A stirring blade for stirring the oil bath is attached under the central master gear, and the temperature in the oil bath is kept uniform.
- a maximum of 8 decolorization tests can be performed. Collect 50 g of deoxidized rapeseed oil in each test tube, add 0.75 g of each decolorizing agent sample (1.5% to the oil) and mix well with a stir bar for decolorization test. Each test tube is set in the above-mentioned decoloring test machine maintained at 110 ° C., stirred for 20 minutes, then taken out from the decoloring test machine, and filtered to remove the mixed suspension of oil and decoloring agent. obtain. The white light transmittance (relative value when the transmittance of distilled water is 100%) of each decolorizing oil was measured with a photoelectric colorimeter 2C type manufactured by Hirama Rika Laboratory Co., Ltd. Decolorization performance. The higher the numerical value of the transmittance, the higher the decoloring performance of the used decoloring agent.
- Example 1 The acid-treated product (water-containing product before drying) after completion of water washing in Comparative Example 1 was used as a raw material. Water was added to the acid-treated product and pulverized with a household mixer to obtain an aqueous suspension having a solid content of 20% by weight. To 1250 g of this suspension, 66 g of a 7.5 wt% NaOH aqueous solution was added, and the mixture was stirred at 90 ° C. for 5 hours for alkali treatment. This suspension was filtered, the filter cake was dispersed in 1% by weight dilute sulfuric acid, acid washed by a decantation method, and then washed with water.
- the suspension after washing with water was filtered, and the filter cake was dried, pulverized and classified at 110 ° C. to obtain an activated clay powder.
- the obtained activated clay powder was measured for various physical properties, and the results are shown in Table 1.
- the pore distribution of the sample is shown in FIG. 1 in comparison with the sample of Comparative Example 1.
- FIG. 1 shows that pores having a pore diameter of about 5 nm are changed to pores having a large diameter of 10 nm or more by alkali treatment.
- Example 2 An activated clay powder was obtained in the same manner as in Example 1 except that 50 g of 7.5 wt% NaOH aqueous solution was used instead of 66 g of 7.5 wt% NaOH aqueous solution in Example 1. The obtained activated clay powder was measured for various physical properties, and the results are shown in Table 1.
- Example 4 An active clay powder was prepared in the same manner as in Example 1 except that 66 g of 7.0 wt% Ca (OH) 2 suspension was used instead of 66 g of 7.5 wt% NaOH aqueous solution in Example 1. Obtained. The obtained activated clay powder was measured for various physical properties, and the results are shown in Table 1.
- Example 5 The activated clay powder obtained in Comparative Example 1 was used as a raw material. 250 g of this powder was dispersed in 1000 g of a 0.5 wt% NaOH aqueous solution and stirred at 90 ° C. for 5 hours for alkali treatment. Thereafter, acid washing, water washing and filtration were carried out in the same manner as in Example 1, and the filter cake was dried at 110 ° C. to obtain an activated clay powder. The obtained activated clay powder was measured for various physical properties, and the results are shown in Table 1.
- Comparative Example 2 An activated clay powder was obtained in the same manner as in Comparative Example 1 except that the acid treatment was performed at 90 ° C. for 5 hours in place of the 35 wt% sulfuric acid aqueous solution in place of the 35 wt% sulfuric acid aqueous solution. The obtained activated clay powder was measured for various physical properties, and the results are shown in Table 2.
- Example 6 An activated clay powder was obtained in the same manner as in Example 1 except that the acid-treated product (hydrated product before drying) after completion of washing in Comparative Example 2 was used as a raw material. The obtained activated clay powder was measured for various physical properties, and the results are shown in Table 1.
- Comparative Example 4 The same smectite clay as in Comparative Example 1 was dispersed in water, coarse particles were removed with a water tank, filtered, and dried at 110 ° C. Into a beaker, 920 g of a 15 wt% sulfuric acid aqueous solution was taken, 360 g of this dry clay was added, and acid treatment was performed at 70 ° C. for 12 hours while stirring on a heater. After completion of the acid treatment, water was added to the acid-treated product, washed by a decantation method, and filtered. The filter cake was dried, pulverized and classified at 110 ° C. to obtain an activated clay powder. The obtained activated clay powder was measured for various physical properties, and the results are shown in Table 2.
- Example 5 Alkali treatment was performed in the same manner as in Example 1. The suspension after alkali treatment was filtered, and the filter cake was dispersed in water and washed with water by a decantation method (acid washing with 1% sulfuric acid in Example 1 was omitted). Thereafter, an activated clay powder was obtained in the same manner as in Example 1. The obtained activated clay powder was measured for various physical properties, and the results are shown in Table 2.
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Abstract
Description
本発明によれば、さらに、活性白土からなる動植物の油脂類もしくは鉱物油の脱色剤が提供される。
(1)5重量%水性懸濁液でのpH(25℃)が2.5乃至5.0の範囲にあること、
(2)150乃至300m2/gのBET比表面積を有していること、
が好適である。
本発明の活性白土は、ジオクタヘドラル型スメクタイトを主成分とする粘土の酸処理物(従来公知の活性白土に相当)を出発原料とし、これを、アルカリ処理し、次いで酸洗浄により付着しているアルカリを除去することにより得られる。
上記のようにして得られる活性白土は、スメクタイト粘土の酸処理物から得られることから、一般的には、酸化物換算で以下のような組成を有している。
SiO2;65乃至85重量%
Al2O3;6乃至12重量%
Fe2O3;1乃至8重量%
MgO;1乃至3重量%
CaO;0.1乃至2重量%
Na2O;0.1乃至1重量%
K2O;0.1乃至1重量%
その他の酸化物(TiO2など);1重量%以下
Ig-loss(1050℃);4乃至8重量%
n-ブチルアミン滴定法にてHo≦-3.0の固体酸量を測定した。試料は、予め、150℃で3時間乾燥したものについて測定を行った。
[参考文献:「触媒」Vol.11,No6,P210-216(1969)]
Micromeritics社製Tri Star 3000を用いて窒素吸着法により測定を行い、吸着データから、BJH法により細孔直径1.7~100nmまでの細孔容積を求めた。
また、1.7~11.5nmの細孔直径における細孔容積(A)と11.5nmより大で100nm以下の細孔直径における細孔容積(B)の比(B/A)より、細孔容積比を求めた。
Micromeritics社製Tri Star 3000を用いて窒素吸着法により測定を行い、吸着データから、BJH法により細孔分布を求めた。
Micromeritics社製Tri Star 3000を用いて窒素吸着法により測定を行い、BET法により解析した。
Malvern社製Mastersizer2000を使用し、溶媒に水を用いてレーザ回折散乱法で体積基準での中位径(D50)を測定した。
JIS K 5101-17-1:2004に準拠して調製した5重量%水性懸濁液のpH値を測定した。
脱色剤の性能を試験には、粘土ハンドブック第二版 日本粘土学会編(技報堂出版)p917の図に示す脱色試験機を用いた。
この脱色試験機には8本の硬質ガラス製大型試験管(容量200ml)が油浴にセットできる。各試験管には、下端が丸くなった波形の撹拌棒を入れ、その下端は試験管の底部に常に接触するようにゴム管で調節する。8本の撹拌棒は中央の親歯車から分かれた子歯車によって回転するので、その回転速度は全く等しく保たれる。中央の親歯車の下には油浴を撹拌する撹拌羽根がついていて、油浴内の温度を均一に保っている。脱色試験は最大8個まで、任意の数で試験できる。各試験管に脱酸処理済みの菜種油を50gずつ採取し、各脱色剤サンプルを0.75gずつ(油に対して1.5%)加えて脱色試験用の撹拌棒でよく混ぜる。各試験管を110℃に保たれた前記の脱色試験機にセットし、20分間撹拌を行った後脱色試験機から取り出し、油と脱色剤の混合懸濁液をろ過することにより各脱色油を得る。
各脱色油の白色光線透過率(蒸留水の透過率を100%としたときの相対値)を(株)平間理化研究所製光電比色計2C型で測定し、その数値をもって各脱色剤の脱色性能とする。透過率の数値が高いほど用いた脱色剤の脱色性能も高いことを表している。
新潟県胎内市産のスメクタイト系粘土を原料として用い、この原料を粗砕、混練し5mm径に造粒した。得られた造粒物の水分は37%であった。
この造粒物1500gを処理槽に充填し、そこに35重量%硫酸水溶液2000mlを循環させ酸処理を行った。その時の処理温度は90℃、処理時間は7時間であった。酸処理終了後、酸処理物に洗浄水を循環して水洗を行った後110℃で乾燥、粉砕、分級して活性白土粉末を得た。
得られた活性白土粉末について、各種物性測定を行い、その結果を表2に示した。
比較例1における水洗終了後の酸処理物(乾燥前の含水物)を原料として用いた。この酸処理物に水を加え、家庭用ミキサーで解砕することにより、固形分濃度20重量%の水性懸濁液を得た。
この懸濁液1250gに7.5重量%のNaOH水溶液66gを加え、90℃で5時間攪拌することによりアルカリ処理を行った。この懸濁液をろ過し、ろ過ケーキを1重量%の希硫酸に分散させ、デカンテーション法により酸洗浄を行った後、水洗した。
水洗後の懸濁液をろ過し、ろ過ケーキを110℃で乾燥、粉砕、分級して活性白土粉末を得た。
得られた活性白土粉末について、各種物性測定を行い、その結果を表1に示した。
なお、サンプルの細孔分布を比較例1のサンプルと対比して図1に示した。図1より、細孔直径5nm前後の細孔がアルカリ処理により10nm以上の大きな径の細孔に変化しているのがわかる。
実施例1において7.5重量%のNaOH水溶液66gに変えて、7.5重量%のNaOH水溶液50gを使用した他は、実施例1と同様にして行い活性白土粉末を得た。得られた活性白土粉末について各種物性測定を行い、その結果を表1に示した。
実施例1において7.5重量%のNaOH水溶液66gに変えて、7.5重量%のNaOH水溶液98gを使用した他は、実施例1と同様にして行い活性白土粉末を得た。得られた活性白土粉末について各種物性測定を行い、その結果を表1に示した。
実施例1において7.5重量%のNaOH水溶液66gに変えて、7.0重量%のCa(OH)2懸濁液66gを使用した他は、実施例1と同様にして行い活性白土粉末を得た。得られた活性白土粉末について各種物性測定を行い、その結果を表1に示した。
比較例1で得られた活性白土粉末を原料として用いた。この粉末250gを0.5重量%のNaOH水溶液1000g中に分散させ、90℃で5時間攪拌することによりアルカリ処理を行った。以下、実施例1と同様にして酸洗浄、水洗、ろ過を行い、ろ過ケーキを110℃で乾燥して活性白土粉末を得た。
得られた活性白土粉末について各種物性測定を行い、その結果を表1に示した。
比較例1において35重量%硫酸水溶液に変えて、30重量%硫酸水溶液を用い、90℃で5時間酸処理した他は、比較例1と同様にして行い活性白土粉末を得た。
得られた活性白土粉末について各種物性測定を行い、その結果を表2に示した。
比較例2における水洗終了後の酸処理物(乾燥前の含水物)を原料として用いた他は、実施例1と同様にして行い活性白土粉末を得た。
得られた活性白土粉末について各種物性測定を行い、その結果を表1に示した。
比較例1において35重量%硫酸水溶液に変えて、45重量%硫酸水溶液を用い、90℃で12時間酸処理した他は、比較例1と同様にして行い活性白土粉末を得た。
得られた活性白土粉末について各種物性測定を行い、その結果を表2に示した。
比較例1と同様のスメクタイト系粘土を水に分散させ、水簸により粗粒分を除去した後ろ過し、110℃で乾燥した。ビーカーに15重量%硫酸水溶液920gを採り、この乾燥粘土360gを加え、ヒーター上で攪拌しながら70℃で12時間酸処理を行った。
酸処理終了後、酸処理物に水を加えてデカンテーション法により洗浄した後ろ過し、ろ過ケーキを110℃で乾燥、粉砕、分級して活性白土粉末を得た。
得られた活性白土粉末について各種物性測定を行い、その結果を表2に示した。
実施例1と同様にしてアルカリ処理を行った。アルカリ処理後の懸濁液をろ過し、ろ過ケーキを水に分散させてデカンテーション法により水洗を行った(実施例1における1%硫酸による酸洗浄を省いた)。以下、実施例1と同様にして活性白土粉末を得た。
得られた活性白土粉末について各種物性測定を行い、その結果を表2に示した。
Claims (4)
- 窒素吸着法で測定して、1.7乃至100nmでの細孔径における細孔容積が0.40乃至0.60cm3/gの範囲にあり、且つ1.7乃至11.5nmの細孔径での細孔容積(A)と11.5nmより大で100nm以下の細孔径における細孔容積(B)との細孔容積比(B/A)が0.75乃至1.5の範囲にあるとともに、Ho≦-3.0の固体酸量が0.15乃至0.40mmol/gの範囲にあることを特徴とする活性白土。
- 5重量%水性懸濁液でのpH(25℃)が2.5乃至5.0の範囲にある請求項1に記載の活性白土。
- 150乃至300m2/gのBET比表面積を有している請求項1に記載の活性白土。
- 請求項1に記載の活性白土からなる動植物の油脂類もしくは鉱物油の脱色剤。
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JP5837467B2 (ja) * | 2012-08-23 | 2015-12-24 | 水澤化学工業株式会社 | 芳香族炭化水素処理用活性白土 |
CN103521171B (zh) * | 2013-10-10 | 2015-11-18 | 湖南省地质科学研究院 | 一种镉污染复合岩矿修复剂及其制备方法 |
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 |
JP6664191B2 (ja) * | 2015-11-02 | 2020-03-13 | 水澤化学工業株式会社 | 脱色剤及び脱色剤の製造方法 |
JP7076276B2 (ja) * | 2017-07-31 | 2022-05-27 | 水澤化学工業株式会社 | テアニン吸着剤 |
JP7273529B2 (ja) * | 2018-04-25 | 2023-05-15 | 水澤化学工業株式会社 | テアニン捕集剤 |
JP2022051551A (ja) * | 2020-09-18 | 2022-03-31 | 日本ポリプロ株式会社 | イオン交換性層状珪酸塩粒子、オレフィン重合用触媒成分、オレフィン重合用触媒、オレフィン重合用触媒の製造方法およびそれを用いたオレフィン重合体の製造方法 |
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