CN104525101A - Preparation method of attapulgite-based adsorption decolorizing agent used for soybean oil refining - Google Patents
Preparation method of attapulgite-based adsorption decolorizing agent used for soybean oil refining Download PDFInfo
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- CN104525101A CN104525101A CN201410678549.6A CN201410678549A CN104525101A CN 104525101 A CN104525101 A CN 104525101A CN 201410678549 A CN201410678549 A CN 201410678549A CN 104525101 A CN104525101 A CN 104525101A
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- attapulgite
- convex rod
- concave convex
- soybean oil
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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
- B01J20/30—Processes for preparing, regenerating, or reactivating
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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
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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Abstract
The invention discloses a preparation method of an attapulgite-based adsorption decolorizing agent used for soybean oil refining. According to the preparation method, attapulgite raw ore is subjected to acid activation, roasting activation, and crushing; Lewis acid and a small amount of lime are added for uniform mixing; and the attapulgite-based adsorption decolorizing agent with excellent adsorptive property is obtained via sieving. Separation of the attapulgite-based adsorption decolorizing agent from products is convenient to realize; decolorizing efficiency is high; dosage is less; no pollution is caused; equipment corrosion is not caused; and product post-treatment is simple and convenient.
Description
Technical field
The present invention relates to a kind of preparation method of the concave convex rod soil matrix adsorption decolouriser for soybean oil refining, what belong to attapulgite utilizes technical field.
Background technology
Soybean oil is a kind of vegetable fat produced by soya seeds milling process or lixiviation process, is the grease that output is maximum in the world.Grease after coming unstuck and neutralizing, still containing some not the material that accepts by people, such as phosphatide, soap class, trace meter, carotenoid, lutein, chlorophyll etc.The existence of these impurity affects soybean cast of oil and quality, needs to carry out refining to remove these impurity to it.
The method of grease-decolor is a lot, but industrial what be most widely used is adsorption decoloring method.Conventional adsorbent has active carbon and atlapulgite etc.The price of active carbon is higher, and the decolouring being applied to grease is subject to certain restrictions.At present, the decolorizer of grease, mainly based on atlapulgite, has the ore deposit soil of clay property, as bentonite, attapulgite clay (attapulgite), kaolinite clay, sepiolite clay etc., all can be used as the raw material of atlapulgite, generally use bentonite as the raw material of atlapulgite at present.But compared with other clay particularly attapulgite clay, bentonitic price is relatively high.
Attapulgite is a kind of natural nano inorganic matter with special layers chain structure, and have larger specific area, adsorptivity is strong.Attapulgite has higher heat endurance and stronger anti-salt property, and decoloring ability is strong, and adsorption capacity is good, have percent of decolourization high, not containing plurality of advantages such as residual acids, there is the good reputation of " kings of thousand soil ".Attapulgite itself has certain L acid site and B acid site, by modified, the acidity of attapulgite can be strengthened, improve the binding ability of the impurity such as itself and free fatty, wax, pigment, thus effectively can adsorb the impurity such as the pigment in grease, be a kind of adsorbent and decolorizer of excellent performance.As Chinese invention patent CN 101497026 B discloses a kind of concave convex rod soil matrix decolorizer for the production of injection soybean oil.Chinese invention patent CN 103055802A discloses a kind of preparation method with antioxygenic property attapulgite clay palm oil decolorizer.
Summary of the invention
The object of the invention is: the preparation method providing a kind of concave convex rod soil matrix adsorption decolouriser for soybean oil refining, the concave convex rod soil matrix adsorption decolouriser prepared by the present invention is used for features such as having reaction condition gentleness when soybean oil is refined, corrosivity is little, pollution-free, decolorizing efficiency is high, consumption is easily separated with product less, product postprocessing is easy.
Technical solution of the present invention is: first attapulgite raw ore is carried out acid activation, calcination activation, pulverizing, then adds lewis acid and a small amount of lime mixes, and sieves, obtains concave convex rod soil matrix adsorption decolouriser.
Wherein, described activation step is by 5 ~ 10 weight portion attapulgite raw ores, 1 ~ 5 weight portion acid and the mixing of 15 ~ 50 weight parts waters, stirs 0.5 ~ 12 h in 30 ~ 90 DEG C of constant temperature.
Wherein, described acid is the one in sulfuric acid, hydrochloric acid, phosphoric acid, formic acid and acetic acid.
Wherein, described sintering temperature is 80 ~ 400 DEG C, and roasting time is 1 h ~ 24 h.
Wherein, after roasting the hybrid mode of attapulgite and lewis acid, lime for grinding or through bipyramid, V-Mixer mixing.
Wherein, described Lewis acid is MgCl
2, AlCl
3, FeCl
3in one or both, described Lewis acid mass fraction is 1% ~ 20.0% of attapulgite raw ore.
Wherein, described lime is quick lime or white lime, and the mass fraction of described lime is 0.1% ~ 5.0% of attapulgite raw ore.
Wherein, after sieving, concave convex rod soil matrix adsorption decolouriser order number is 150 ~ 200 orders.
Compared with prior art, tool has the following advantages in the present invention:
(1) the structural hydroxyl group in attapulgite Rotating fields forms Bronst acid site, and the Al exposed
3+ion then forms Lewis acid site, strengthening B acid or the L acid site of attapulgite further, improve the binding ability of the impurity such as adsorbent and free fatty, wax, pigment, thus improve the decoloration performance of decolorizer by adding Lewis acid.
(2) be filled with carbonate cement between crystal He in natural duct in natural attapulgite, adsorption capacity is more weak, after acid activation process, and carbonate cement stripping in attapulgite duct, duct is dredged; Simultaneously, the hydrogen ion that radius is less displaces the metal ion in attapulgite interlayer portion, thus enlarged hole volume, thus improve its specific area, there is facilitation to absorption property and ion-exchange capacity, be conducive to impurity component in soybean oil to the brilliant diffusion inside of rod, to prevent between impurity bonding mutually to form fine and close jelly plastid, reduce filtration resistance, be conducive to follow-up filtration treatment; Moreover, after calcination process, further increase specific area and the pore volume of attapulgite.
(3) by adding the acidic materials produced in a certain amount of limestone vegetation decolorization, thus while soybean oil is decoloured, the acid in oil is removed, cost-saving.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but protection scope of the present invention is not limited in this.
embodiment 1:5 kg attapulgite raw ores, 1 kg sulfuric acid and 20 L water mix, and after at 80 DEG C, constant temperature stirs 120 min, solid-liquid centrifugation is separated, and it is interior in 400 DEG C of calcination activation 1 h that rotary kiln sent into by filter cake, obtains roasting attapulgite; Attapulgite after roasting is proceeded in ball mill, adds MgCl
250 g and quick lime 5 g, stir, mixture are crossed 200 mesh sieves, obtain concave convex rod soil matrix adsorption decolouriser.
Take dry in 105 DEG C ± 3 DEG C concave convex rod soil matrix adsorption decolouriser 0.4g, add fresh soyabean oil 40 g, filter stir decolouring 25min at 115 DEG C after, obtain refined soybean oil.The percent of decolourization of this concave convex rod soil matrix adsorption decolouriser is 98.9%.
embodiment 2:10 kg attapulgite raw ores, 3 kg hydrochloric acid and 40 L water are mixed, after at 60 DEG C, constant temperature stirs 60 min, solid-liquid centrifugation is separated, and it is interior in 80 DEG C of calcination activation 10 h that rotary kiln sent into by filter cake, obtains roasting attapulgite; Attapulgite after roasting is proceeded in V-Mixer, adds AlCl
32 kg and white lime 500 g, stir, mixture are crossed 150 mesh sieves, obtain concave convex rod soil matrix adsorption decolouriser.
Take dry in 105 DEG C ± 3 DEG C concave convex rod soil matrix adsorption decolouriser 0.2g, add fresh soyabean oil 40 g, filter stir decolouring 25min at 115 DEG C after, obtain refined soybean oil.The percent of decolourization of this concave convex rod soil matrix adsorption decolouriser is 91.2%.
embodiment 3:10 kg attapulgite raw ores, 2 kg phosphoric acid and 50 L water are mixed, at 90 DEG C, constant temperature stirs solid-liquid centrifugation separation after after 180 min, and it is interior in 180 DEG C of calcination activation 4 h that rotary kiln sent into by filter cake, obtains roasting attapulgite; Attapulgite after roasting is proceeded in double-cone mixer, adds MgCl
20.3g, AlCl
30.2g kg and quick lime 50 g, stirs, mixture is crossed 180 mesh sieves, obtains concave convex rod soil matrix adsorption decolouriser.
Take dry in 105 DEG C ± 3 DEG C concave convex rod soil matrix adsorption decolouriser 0.2g, add fresh soyabean oil 40 g, filter stir decolouring 25min at 115 DEG C after, obtain refined soybean oil.The percent of decolourization of this concave convex rod soil matrix adsorption decolouriser is 90.5%.
embodiment 4:10 kg attapulgite raw ores, 4 kg formic acid and 30 L water are mixed, after at 80 DEG C, constant temperature stirs 120 min, solid-liquid centrifugation is separated, and it is interior in 200 DEG C of calcination activation 6 h that rotary kiln sent into by filter cake, obtains roasting attapulgite; Attapulgite after roasting is proceeded in ball mill, adds AlCl
3, 0.1 kg and quick lime 100 g, stir, mixture crossed 200 mesh sieves, obtain concave convex rod soil matrix adsorption decolouriser.
Take dry in 105 DEG C ± 3 DEG C concave convex rod soil matrix adsorption decolouriser 0.2g, add fresh soyabean oil 40 g, filter stir decolouring 25min at 115 DEG C after, obtain refined soybean oil.The percent of decolourization of this concave convex rod soil matrix adsorption decolouriser is 94.7%.
embodiment 5:6 kg attapulgite raw ores, 1.5 kg acetic acid and 30 L water are mixed, after at 70 DEG C, constant temperature stirs 90 min, solid-liquid centrifugation is separated, and it is interior in 250 DEG C of calcination activation 16 h that rotary kiln sent into by filter cake, obtains roasting attapulgite; Attapulgite after roasting is proceeded in ball mill, adds FeCl
30.8 kg and quick lime 200 g, stirs, mixture is crossed 200 mesh sieves, obtains concave convex rod soil matrix adsorption decolouriser.
Take dry in 105 DEG C ± 3 DEG C concave convex rod soil matrix adsorption decolouriser 0.2g, add fresh soyabean oil 40 g, filter stir decolouring 25min at 115 DEG C after, obtain refined soybean oil.The percent of decolourization of this concave convex rod soil matrix adsorption decolouriser is 90.1%.
embodiment 6:8 kg attapulgite raw ores, 3.5 kg sulfuric acid and 45 L water are mixed, after at 80 DEG C, constant temperature stirs 60 min, solid-liquid centrifugation is separated, and it is interior in 300 DEG C of calcination activation 12 h that rotary kiln sent into by filter cake, obtains roasting attapulgite; Attapulgite after roasting is proceeded in ball mill, adds AlCl
3600g, FeCl
3400g and white lime 400 g, stirs, mixture is crossed 200 mesh sieves, obtains concave convex rod soil matrix adsorption decolouriser.
Take dry in 105 DEG C ± 3 DEG C concave convex rod soil matrix adsorption decolouriser 0.2g, add fresh soyabean oil 40 g, filter stir decolouring 25min at 115 DEG C after, obtain refined soybean oil.The percent of decolourization of this concave convex rod soil matrix adsorption decolouriser is 93.8%.
Claims (8)
1. for the preparation method of the concave convex rod soil matrix adsorption decolouriser of soybean oil refining, it is characterized in that: first attapulgite raw ore is carried out acid activation, calcination activation, pulverizing, then add lewis acid and a small amount of lime mixes, sieve, obtain concave convex rod soil matrix adsorption decolouriser.
2. according to the preparation method of the concave convex rod soil matrix adsorption decolouriser for soybean oil refining described in claim 1, it is characterized in that: described activation step, for 5 ~ 10 weight portion attapulgite raw ores, 1 ~ 5 weight portion acid and 15 ~ 50 weight parts waters being mixed, stirs 0.5 ~ 12 h in 30 ~ 90 DEG C of constant temperature.
3. the preparation method of the concave convex rod soil matrix adsorption decolouriser for soybean oil refining according to claim 2, is characterized in that: described acid is the one in sulfuric acid, hydrochloric acid, phosphoric acid, formic acid and acetic acid.
4. according to the preparation method of the concave convex rod soil matrix adsorption decolouriser for soybean oil refining described in claim 1, it is characterized in that: described sintering temperature is 80 ~ 400 DEG C, roasting time is 1 h ~ 24 h.
5. according to the preparation method of the concave convex rod soil matrix adsorption decolouriser for soybean oil refining described in claim 1, it is characterized in that: after roasting, the hybrid mode of attapulgite and lewis acid, lime is for grinding or through bipyramid, V-Mixer mixing.
6. the preparation method of the concave convex rod soil matrix adsorption decolouriser for soybean oil refining according to claim 5, is characterized in that: described Lewis acid is MgCl
2, AlCl
3, FeCl
3in one or both, the mass fraction of described Lewis acid is 1% ~ 20.0% of attapulgite raw ore.
7. the preparation method of the concave convex rod soil matrix adsorption decolouriser for soybean oil refining according to claim 5, it is characterized in that: described lime is quick lime or white lime, the mass fraction of described lime is 0.1% ~ 5.0% of attapulgite raw ore.
8., according to the preparation method of the concave convex rod soil matrix adsorption decolouriser for soybean oil refining described in claim 1, it is characterized in that: after sieving, the order number of concave convex rod soil matrix adsorption decolouriser is 150 ~ 200 orders.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106166475A (en) * | 2016-07-27 | 2016-11-30 | 南京大学昆山创新研究院 | A kind of biodiesel solid decolorizer and preparation method |
| CN109954477A (en) * | 2017-12-26 | 2019-07-02 | 金昌红泉膨润土有限责任公司 | A kind of atlapulgite acid lowering agent |
| CN111111608A (en) * | 2019-12-27 | 2020-05-08 | 泰州医药城国科化物生物医药科技有限公司 | Method for selectively removing traditional Chinese medicine notoginseng pigment by adopting silicate minerals |
| CN112076730A (en) * | 2020-09-16 | 2020-12-15 | 盐城工学院 | Dye wastewater decolorizer and preparation method and application thereof |
| CN112275262A (en) * | 2020-11-16 | 2021-01-29 | 中国石油化工股份有限公司 | Refinery anhydrous liquid ammonia decolorant and preparation method thereof |
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| CN1903990A (en) * | 2006-07-27 | 2007-01-31 | 宁守俭 | Deacidification adsorber of oil product and its preparation method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106166475A (en) * | 2016-07-27 | 2016-11-30 | 南京大学昆山创新研究院 | A kind of biodiesel solid decolorizer and preparation method |
| CN109954477A (en) * | 2017-12-26 | 2019-07-02 | 金昌红泉膨润土有限责任公司 | A kind of atlapulgite acid lowering agent |
| CN111111608A (en) * | 2019-12-27 | 2020-05-08 | 泰州医药城国科化物生物医药科技有限公司 | Method for selectively removing traditional Chinese medicine notoginseng pigment by adopting silicate minerals |
| CN112076730A (en) * | 2020-09-16 | 2020-12-15 | 盐城工学院 | Dye wastewater decolorizer and preparation method and application thereof |
| CN112275262A (en) * | 2020-11-16 | 2021-01-29 | 中国石油化工股份有限公司 | Refinery anhydrous liquid ammonia decolorant and preparation method thereof |
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