KR101117074B1 - Porous Adsorbent Specifically Adsorbing Fat-soluble Pigments and Manufacturing Method Thereof - Google Patents

Abstract

The present invention relates to a porous adsorbent for selectively adsorbing fat-soluble pigments in cooking oils whose color has changed to be used for frying and the like. More specifically, the finely crushed porous chaff is dried and first carbonized, and then immersed in an activator to secondary carbonization under nitrogen gas to prepare chaff activated carbon, and mixed with a mineral and a binder to the chaff activated carbon in a mold. Inserting, pressing and extruding to produce granules, carbonizing granules consisting of chaff activated carbon, minerals and binders again to form granular chaff / mineral activated carbon, and treating chaff / mineral activated carbon with dilute acid and washing with hot water. And then drying.

Description

Porous Adsorbent Specifically Adsorbing Fat-soluble Pigments and Manufacturing Method Thereof}

The present invention relates to a porous adsorbent for selectively adsorbing fat-soluble pigments in cooking oils whose color has changed to a deep color used for frying and the like, and a method of manufacturing the same. More specifically, the present invention relates to a porous adsorbent prepared by four steps and a porous adsorbent prepared by the same method.

1) Grind the porous rice husk into 1.0 ~ 2.0mm size, dry it at 110 ℃, put it in an electric furnace, and primary carbonization at 700 ℃ for 2 hours while injecting nitrogen gas at 100ml / min. (KOH = 1: 2, ZnCl ₂ = 1: 3, K ₂ CO ₃ = 1: 2) and then immersed in an aqueous solution to dry, and then carbonized for 2 hours at 850 ℃ under nitrogen atmosphere to prepare chaff activated carbon. .

2) 0.1 to 1.0 parts by weight of acid clay or bentonite as a mineral and 0.1 to 0.5 parts by weight of binder (molasses). It is put in the mold of granulator and pressurized and extruded at 5-20kg / cm ² to make granules.

3) Charcoal granules consisting of chaff activated carbon, minerals and binders are carbonized again at 700∼900 ℃ for 1 ~ 2 hours to burn the binder and make solid granular chaff / mineral activated carbon.

4) Wash granular rice hull / mineral activated charcoal with purified water to remove residual components and dry it as a product, or put it in dilute acid (0.1N HCl, HNO ₃ , H ₂ SO ₃ or H ₃ PO ₃ ) solution for 1 hour. After stirring for a while, washed with hot purified water until the pH is neutral, and dried overnight in an oven at 110 ℃ to make a product.

The hulls and other agricultural by-products and grains contain iron, calcium, magnesium, sodium, potassium, and manganese in the form of oxides, which can be reduced by appropriate incubation and post-treatment to form porous surfaces of various sizes. It is believed that the adsorption power of the adsorbents prepared from the by-products of the agricultural and by-products including grains will be improved.

As a representative example of agricultural by-products, the US, which used chaff for industrial use, produces whiskers, which are fine silicon crystals, and exports them at high prices.In Korea, research results using chaff as compost, ceramic raw material, and methane gas adsorbent Although some have been introduced, there is no example used in the refining process.

Adsorbents to remove substances that accelerate the transformation of conventional frying oils include α-cellulose, silica gel, alumina, magnesium silicate, calcium silicate, aluminum oxide, magnesium oxide, activated carbon, or a mixture of water, citric acid and porous volcanic ash. There are powder (Frypowder) and it is used alone or in combination. Activated carbon removes impurities by adsorption and absorption based on chemical properties, while silica removes impurities by interactions between protruding silanol groups and degradation products.

The reason why the adsorbents are not widely used in the purification of fried oil is that the adsorbents such as metal silicates used in the process are expensive products that must mainly depend on imports. Therefore, an economical food adsorbent containing a large amount of silica, but cheap and environmentally friendly materials can be competitive. A typical example of this material is rice hull, an agricultural by-product, which contains 35-46% crude fiber, 22-35% soluble sugars, 13-21% ash, and 2-3% crude protein. % Or more is silica, and potassium, calcium, magnesium, etc. are contained in addition. Carbohydrates and proteins other than silicon in rice husks can be carbonized and ingested to remove naturally occurring amorphous silicon powder as an adsorbent.

The fat-soluble pigments present in fats and oils are mainly yellow to red, brown carotene, xanthophyll, gossypol and green chlorophyll. The color of is dark because these pigments are severely oxidized.

There is no example of making granular activated carbon using rice hulls for adsorption of fat-soluble pigments of fried oil, but the present inventors' research report on the adsorption function and use of agricultural fiber (E051003, 2005.12) and fried oil for extending the life of fried oil We have announced the development of a biodegradable adsorbent for purification (LWT-Food Science and Technology Vol. 41. Issue 4, May 2008, P 701-706).

Adsorption power increases with increasing concentration of adsorbent, while loss of oil also increases proportionally with concentration of treated adsorbent. Therefore, it is important to determine the application concentration of the adsorbent where the oil loss is small and the quality improvement of the frying oil is maximized.

The present invention is to develop the agricultural by-products chaff as an adsorbent to develop a porous adsorbent to selectively adsorb fat-soluble pigments in the cooking oil to realize the processing of agricultural by-products and edible oil at the same time.

According to the present invention, carbonized chaff is carbonized to prepare chaff activated carbon, mixed with minerals and a binder, and then put into a mold to make granules and carbonized again to neutralize the granular chaff / mineral activated carbon to wash and dry to provide a porous adsorbent. Can be.

The porous adsorbent of the present invention not only selectively adsorbs fat-soluble pigments, but also provides the advantage of not having to use a filtration aid due to the large particles in granular granules.

1 is a process chart for preparing a porous adsorbent of the present invention.

The present invention shows a method for producing a porous adsorbent.

The present invention shows a method for producing a porous adsorbent for selectively adsorbing fat-soluble pigments.

The present invention comprises the steps of drying the chaff and the first carbonization and then immersed in the activator to secondary carbonization under nitrogen gas to prepare the chaff activated carbon, by mixing the mineral and the binder in the chaff activated carbon, put into a mold and pressurized, extruded Making granules, carbonizing the granules composed of chaff activated carbon, minerals and binders again to form granular chaff / mineral activated carbon, treating the chaff / mineral activated carbon with weak acid, washing with hot water and drying It shows a method for producing a porous adsorbent to selectively adsorb fat-soluble pigments comprising the step of.

In the above-mentioned primary carbonization, the porous chaff is pulverized to 1.0∼2.0mm size, dried at 100∼120 ℃, put into an electric furnace, and injected with nitrogen gas at 80∼120ml / min for 1 ~ 3 hours at 650∼750 ℃. Can be carried out.

In the above, the first carbonization may be carried out at 700 ° C. for 2 hours while the porous chaff is ground to a size of 1.0˜2.0 mm and dried at 110 ° C., and then injected into an electric furnace at 100 ml / min.

The carbonized sample and the activator are mixed and immersed in an aqueous solution and dried, followed by secondary carbonization at 800 to 900 ° C. under nitrogen atmosphere for 2 to 4 hours to obtain chaff activated carbon.

The carbonized sample and the activator are mixed and immersed in an aqueous solution and dried, followed by secondary carbonization at 850 ° C. for 3 hours under a nitrogen atmosphere to obtain chaff activated carbon.

In the above activator KOH, ZnCl ₂ or K ₂ CO ₃ It can be used.

When the carbonized sample and the activator are mixed, the mixing ratio of the carbonized sample and the activator is carbonized sample: KOH = 1: 2, carbonized sample: ZnCl ₂ = 1: 3 or carbonized sample: K ₂ CO ₃ = 1: 2 Mix as much as possible.

Minerals mixed with the quenched activated carbon may be acidic clay or bentonite.

The binder mixed in the quenched activated carbon may be a molasses fermentation waste solution or waste starch.

1 to 2 parts by weight of charcoal activated carbon, minerals are mixed with 0.1 to 1.0 parts by weight of acidic clay or bentonite, and 0.1 to 0.5 parts by weight of molasses fermentation waste or waste starch is added to the mold of granulator and 5 to 20 kg / cm. Pressurized and extruded to ² to form granules.

The mineral is 0.1 ~ 1.0 parts by weight of acidic clay or bentonite, and the binder is 0.1 to 0.5 parts by weight of molasses fermentation waste or waste starch, and put into the mold of granulator 5 to 20 kg / cm ² Pressurized and extruded to produce granules.

The granules composed of chaff activated carbon, minerals and binders may be carbonized again at 700 to 900 ° C. for 1 to 2 hours to burn the binder component to obtain a granular chaff / mineral activated carbon.

The granular rice hull / mineral activated carbon may be washed with purified water to remove residual components and then dried to prepare a porous adsorbent product.

The granular rice hull / mineral activated carbon was added to the weak acid solution, stirred for 0.5 to 1.5 hours, washed with hot purified water until the pH became neutral, and dried at 105 to 115 ° C for 24 to 48 hours to prepare a porous adsorbent product. can do.

The granular rice hull / mineral activated carbon is added to the weak acid solution, stirred for 1 hour, washed with hot purified water until the pH becomes neutral, and dried at 110 ° C. for 24 hours to prepare a porous adsorbent product.

The method for preparing the porous adsorbent for selectively adsorbing the fat-soluble pigment of the present invention was carried out under various conditions. In order to achieve the object of the present invention, the method for producing the porous adsorbent for selectively adsorbing the fat-soluble pigment under the above-mentioned conditions. It is desirable to provide.

The present invention includes a porous adsorbent for selectively adsorbing fat-soluble pigments prepared by the above-mentioned method.

Hereinafter, the present invention will be described in detail with reference to Examples and Test Examples. However, these are for the purpose of illustrating the present invention in more detail, and the scope of the present invention is not limited thereto.

<Examples 1 to 4>

The rice husk was crushed to 1.0∼2.0mm size and dried in 110 ℃ oven, then put into a graphite boat, flowing nitrogen gas at 100ml / min into a tube-type electric furnace, and heated to 10 ℃ / min from room temperature to 700 ℃ and then heated at 700 ℃. Primary carbonization for 2 hours. Primary carbonization of rice husk was 1: 2 (ZnCl ₂ 1: 3, K ₂ CO ₃ 1: 2) After immersing 50g of carbonized sample in the activator aqueous solution, dried overnight in 110 ℃ oven, and put it in a graphite boat, flowing nitrogen gas at 100ml / min, raising the temperature to 10 ℃ / min to 850 ℃. Second carbonization was maintained at temperature for 3 hours to obtain chaff activated carbon.

With respect to the chaff activated carbon 1 part by weight, mixed with the mineral acid clay or bentonite, 0.1 to 1.0 parts by weight of the binder is molasses fermentation waste liquid (waste sugar solution) or lung metastases minutes from 0.1 to 0.5 parts by weight, placed in a mold of a granulator 15kg / cm ² Pressurized and extruded to make granules.

Granulated charcoal consisting of chaff activated carbon, minerals and binder was carbonized again at 800 ° C. for 1.5 hours to burn the binder component to form a solid granular chaff mineral activated carbon.

The granular rice hull / mineral activated carbon was washed with purified water to remove residual components, then placed in 0.1N HCl solution, stirred for 1 hour, washed with 45 ℃ purified water until the pH became neutral, and dried overnight at 110 ℃ oven. To prepare a porous adsorbent (see Table 1).

Mixing ratio of chaff mineral activated carbon division Example 1 Example 2 Example 3 Example 4 Chaff activated carbon One One One One Mineral Acid clay 0.1 - - 1.0 Bentonite - 0.5 0.7 - chemistry
matter KOH One 2 - - ZnCl ₂ - - 3 - K ₂ CO ₃ - - - 2 Binder Waste sugar 0.1 0.3 - - Waste starch - - 0.4 0.5

<Test Example>

1) Absorption degree of fat-soluble pigment (unit: ppm)

Chlorophyll, carotene, and xanthophyll were optionally added to determine the adsorption degree of fat-soluble pigments present in or optionally added to soybean oil.

Adsorption degree of fat-soluble pigment division Concentration before treatment
(ppm) Concentration after treatment Example 1 Example 2 Example 3 Example 4 Control group Chlororoll 0.2 N.D. N.D. N.D. N.D. N.D. Carotene 500 N.D. N.D. N.D. N.D. N.D. Xanthophyll 100 N.D. N.D. N.D. N.D. N.D.

* In Table 2, N.D (Not detected) indicates that it is not detected.

* In Table 2, the control means activated carbon that is commercially available.

As shown in Table 2, it can be seen that the activated carbons of Examples 1 to 4 prepared by the present invention exhibit very good fat-soluble pigment adsorption.

2) Lutein Content

The lutein content in the pigment contained in the crude oil was measured by modifying the method of Proctor (1987). 0.7 ± 0.005 g of the fat treated with the adsorbent was accurately taken and mixed well with 5 mL of a solvent mixed with chloroform and methanol at 3: 1 (v / v), and the absorbance was measured at 445 nm with a UV-visible spectrophotometer. The exact concentration was calculated using the standard curve.

In order to measure the decolorizing effect of activated carbon, the lutein content was measured after adding 1% of activated carbon sold in Examples 1, 2, 3, and 4 of the present invention to deoxidized oil from which free fatty acid was removed. One result is shown in Table 3. The activated carbons of Examples 1, 2, 3 and 4 adsorbed at least 70% of lutein at 1% concentration, but only about 48% of commercial activated carbon was adsorbed.

Lutein Content (ppm) by Treatment of Activated Carbon of Cooking Oil division  Before treatment  Example 1  Example 2  Example 3  Example 4  Commercially available activated carbon lutein 58 17 21 18 15 36

3) Adsorption degree of pigment substance in frying oil

3 wt% of the porous adsorbent of the experimental group and the activated carbon of the control group were used as the control group with the porous adsorbents prepared in Examples 1 to 4 as the experimental group for the waste cooking oil collected at the franchise specialty franchise store. Were each put into a Erlenmeyer flask and stirred for 1 hour at 200 rpm in an incubator at 32 ° C., and then passed through a filter paper (whatman No. 41) to remove an adsorbent. 0.7 ± 0.005 g of fats and fats treated with adsorbent were accurately taken, mixed with 5 mL of solvent mixed with chloroform and methanol at 3: 1 (v / v), and then absorbed at 200-800 nm with UV-visible spectrophotometer. The chromaticity of is expressed by Hunter L, a, b values (see Table 4).

Pigment material adsorption degree division fresh
Soybean oil After frying Absorbent treatment after frying Example 1 Example 2 Example 3 Example 4 Control group L 98.5 91.9 97.2 96.5 96.7 97.0 94.3 a -4.3 -8.1 -6.2 -7.1 -6.9 -6.3 -7.8 b 4.2 22.3 7.1 7.6 7.4 7.9 9.1

From the above results, it was found that the fats and oils after frying were markedly browned. It can be seen that the activated carbon of Examples 1 to 4 of the present invention exhibits superior adsorption power than commercial products.

Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims. It will be understood that the present invention can be changed.

The present invention has industrial applicability since the development of agricultural by-products chaff as an adsorbent to develop a porous adsorbent to selectively adsorb fat-soluble pigments in cooking oil.

Claims (8)

Drying and chaffing the rice husks and immersing them in an activator to secondary carbonization under nitrogen gas to prepare chaff activated carbon;
Mixing the mineral and the binder with the chaff activated carbon into a mold to pressurize and extrude to form granules;
Carbonizing the granules composed of the chaff activated carbon and minerals and binders again to form granular chaff / mineral activated carbon,
Method of producing a porous adsorbent to selectively adsorb fat-soluble pigment, characterized in that the step of treating the chaff / mineral activated carbon with a weak acid and washed with hot water and dried. The method of claim 1, wherein the primary carbonization is a porous chaff pulverized to 1.0 ~ 2.0mm size and dried at 110 ℃, put into an electric furnace and primary carbonization at 700 ℃ for 2 hours while injecting nitrogen gas at 100ml / min Method for producing a porous adsorbent to selectively adsorb fat-soluble pigments, characterized in that The method of claim 1, wherein the carbonized sample and the chemical activator are mixed and immersed in an aqueous solution and dried, followed by secondary carbonization at 850 ° C. for 3 hours under nitrogen atmosphere to prepare chaff activated carbon. The method of claim 1, wherein the mixing ratio of the carbonized sample and the chemical activator is KOH = 1: 2, ZnCl ₂ = 1: 3 or K ₂ CO ₃ = 1: 2. According to claim 1, 1 to 2 parts by weight of chaff activated carbon minerals are mixed with 0.1 to 1.0 parts by weight of acidic clay or bentonite, 0.1 to 0.5 parts by weight of molasses fermentation waste or waste starch, and put into a mold of granulator 5 Method for producing a porous adsorbent, characterized in that the granules are made by pressing and extruding at ˜20kg / cm ² The porous adsorbent according to claim 1, wherein the granules composed of chaff activated carbon, minerals and binder are carbonized again at 700-900 ° C for 1-2 hours to burn the binder component to form a granular chaff / mineral activated carbon. Manufacturing method The granular rice hull / mineral activated carbon is washed with purified water to remove residual components and then dried to produce a product or stirred in a weak acid solution for 1 hour and washed with hot purified water until the pH is neutral. After drying at 110 ℃ for 24 hours to produce a porous adsorbent, characterized in that to make a product delete

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