CN106179194A - A kind of modified clay and its preparation method and application - Google Patents
A kind of modified clay and its preparation method and application Download PDFInfo
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- CN106179194A CN106179194A CN201610526879.2A CN201610526879A CN106179194A CN 106179194 A CN106179194 A CN 106179194A CN 201610526879 A CN201610526879 A CN 201610526879A CN 106179194 A CN106179194 A CN 106179194A
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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
- B01J20/16—Alumino-silicates
- B01J20/165—Natural alumino-silicates, e.g. zeolites
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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
- B01J20/02—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
- B01J20/14—Diatomaceous earth
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Abstract
The present invention relates to the modified field of clay, particularly relate to a kind of phospholipid modified clay and its preparation method and application.A kind of modified clay, the modifying agent of this modification clay includes phospholipid.Above-mentioned modified clay is for the application as mold toxin sorbent.The present invention innovates employing phospholipid and clay compounds and prepares mold toxin sorbent, and phospholipid belongs to feed additive composition, it is allowed to adds using in feedstuff, overcomes conventional quaternary ammonium salts and compound the issuable safety issue of clay.Compound fungus endotoxin adsorbent toxin multiple to aflatoxin, 6-(10-hydroxy-6-oxo-trans-1-undecenyl)-.beta.-resorcylic acid lactone etc. all has preferable adsorption effect.
Description
Technical field
The present invention relates to the modified field of clay, particularly relate to a kind of phospholipid modified clay and its preparation method and application.
Background technology
Mycotoxin is mycete product of metabolism in growth course, and the toxin that mycete and mycete produce easily is enriched in
In feedstuff and feedstuff, livestock-raising is caused huge economic loss.The whole world there are about the corn of 20-30% every year and is subject to
The pollution of known mycotoxin.The most common mycotoxin has: aflatoxin, 6-(10-hydroxy-6-oxo-trans-1-undecenyl)-.beta.-resorcylic acid lactone, vomitoxin, volt horse
Toxin, ochratoxin etc..The mycotoxin that in feed industry, raw material and feed mold produce can reduce the growth performance of animal
With immunity of organisms, increase death rate, cause huge economic loss.Different mycotoxins are different to the harm of animal health,
As aflatoxin mainly produces damage to liver, cellular immunization and humoral immunization can be had a direct impact simultaneously；Semen Maydis is red
Mould ketenes toxin then causes immunosuppressant, and macrophage activity reduces, and causes breeding stock fertility to decline；Vomitoxin is to animal
Digestive tract produces damage, makes poultry feed intake decline even and vomiting phenomenon occurs.
In reduction mycotoxin entrance animal body, dosage is the effective way reducing mycotoxin harm.The most conventional side
Method has physisorphtion, chemical detoxication, enzyme process biodegradation.Physical absorption comprises: adsorption by clay (zeolite, meerschaum, attapulgite
Stone, kieselguhr etc.), activated carbon adsorption, yeast cell wall immunostimulant absorption.Mycotoxin is mainly fixed on by physical absorption
In adsorbing medium, toxin is transferred out in animal body, thus reduces the toxin injury to animal body.Chemical detoxication processes such as ammonia
Toxin effectively can be degraded or destroy by the chemical substance such as water, oxidant, thus loses toxicity, but can affect the peace of feedstuff
Full property and palatability.Enzyme process biodegradation is maximally effective Mycotoxin detoxification agent from principle, and it can be by mycotoxin
It is decomposed into hypotoxicity or other material avirulent, is inherently eliminated mycotoxin contamination.But enzyme product plays to be made
With needing suitable temperature, body fluid system agent acid or alkali environment, and in animal body, complex environment causes single enzyme or compound enzyme
Toxin Degradation efficiency is low, and toxin is most of when not being able to do in time through enzymolysis processing enters (CN in animal body
101720848A), so the effect of enzymatic isolation method is limited.
The polarity of mycotoxin molecule, molecular weight, space structure and CHARGE DISTRIBUTION have obvious diversity, various
Property.Polarity as little in aflatoxin molecular weight is high, and water solublity is low；Semen Maydis red enzyme ketenes molecular weight is relatively big, and hydrophilic is poor；Vomiting poison
Element is containing relatively polyhydroxy, good hydrophilic property.Therefore by the screening of contratoxin adsorbent material, the material of various different efficacies is merged
Efficient, the mold toxin sorbent of wide spectrum, more using value can be obtained.
Chinese invention patent (CN201410080032.7) " a kind of food mycotoxin detoxification agent and preparation method thereof with
Application ", montmorillonite, inactivation lactic acid bacteria and Fermented Condensed thing thereof, yeast cell wall polysaccharide are carried out compound compounding, prepares mould bacterium
Element detoxifying agent, for removing the mycotoxin in food.
Chinese invention patent (CN201410094045.X) " preparation method of Yi Meng mixing clay mold toxin sorbent ",
The quaternary ammonium salt of different length carbochain is dissolved in aqueous, is subsequently adding Yi Meng clay and carries out intercalation, obtain her and deceive people
Close clay mold toxin sorbent.
Chinese invention patent (CN 201410094915.3) " boar detoxicating mycotoxin feed additive ", this adds
Add the groups such as agent complex polysaccharide, refined Carapax Eriocheir sinensis powder, marigold residue, refined bagasse, Herba Medicaginis superfine powder minces, Radix Rubiae superfine powder minces
Become, it is possible to mycotoxin in effective adsorbent feedstuff, mycostatic growth can also be pressed down simultaneously, prevent the product of mycotoxin
Raw, eliminate the mycotoxin impact on animal physiological, improve the animal resistance to disease.
Chinese invention patent (the CN201410420489.8) " manufacturer of the de-mould feed additive with clay as adsorbent
Method ", clay and activated carbon are proportionally mixed；Radix Scutellariae, the ethanol extraction of the Rhizoma Atractylodis Macrocephalae add appropriate contracting methylcellulose steaming and decocting,
It is dried, pulverizes, be subsequently adding egg albumen powder, seaweed meal, antifungus agent, antioxidant, and obtain in clay-activity charcoal mixing granulation
De-mould feed additive.
Chinese invention patent (CN201410564991.6) " a kind of pig's feed degrading mold toxin adsorbent and should
With ", by bacillus subtilis, Lactobacillus plantarum, Lactobacillus acidophilus, leuconostoc lactis, moral formula lactobacillus, Lactobacillus fermenti,
Lactobacillus salivarius, vitamin C, vitamin E, Huang Shi, zinc methionine, potassium chloride, Cortex cinnamomi japonici (Ramulus Cinnamomi), Flos Caryophylli, Herba Artemisiae Scopariae, Folium Artemisiae Argyi, Herba Artemisiae Annuae, Herba Dendranthematis indici
Flower, Semen Plantaginis, yeast cell wall and phytase mixing composition, common mycotoxin multiple in feedstuff is respectively provided with suppression produce,
Degraded and absorption multiple action, also can improve Swinery immunity power, promote that poisonous substance moral is drained, had comprehensive premium properties.
Chinese invention patent (CN 201510285208.7) " inhale by the attapulgite 6-(10-hydroxy-6-oxo-trans-1-undecenyl)-.beta.-resorcylic acid lactone with antibacterial functions
The preparation method of attached dose ", attapulgite clay acidulant is processed, sieves after removing quartz and carbonate impurities, add
Ion liquid type surfactant, then 40-90 degree Celsius of reaction 4-12h, separate, wash, be dried, pulverize and obtain having antibacterial merit
The attapulgite 6-(10-hydroxy-6-oxo-trans-1-undecenyl)-.beta.-resorcylic acid lactone adsorbent of energy.
Chinese invention patent (CN 201510439640.7) " a kind of trophism absorption alleviating piglet mycotoxicosis
Agent ", raw for dimension E, sodium butyrate, Huang Shi polysaccharide, glucomannan, hydrous calcium aluminate silicon are mixed and prepare adsorbent by literary composition.
Applicant has applied for a kind of composite mold toxin sorbent of Chinese invention patent (CN201310469425.2), should
Composite mold toxin sorbent is coated with montmorillonite by 20-80% high-purity montmorillonite, 0-40% surface modification montmorillonite and 0-40% charcoal
Composition；Described surface modification montmorillonite is prepared into as surface modifying agent by cationic or nonionic compound
Arrive；Described charcoal is coated with after montmorillonite is mixed homogeneously with acidifying montmorillonite underflow by the acidifying underflow of carbon source material through high-temperature calcination
Activation obtains.Should patent be adsorption of aflatoxin at the Main Function of high-purity montmorillonite；Surface modification montmorillonite main
Effect is absorption 6-(10-hydroxy-6-oxo-trans-1-undecenyl)-.beta.-resorcylic acid lactone and ochratoxin；The Main Function of charcoal cladding montmorillonite is absorption vomitoxin, passes through
Synergism after several components are compound makes product that multiple mycotoxin is respectively provided with good absorbability.
Clay minerals, especially montmorillonite, meerschaum, zeolite etc., owing to self having preferable mycotoxin adsorption
Ability, often with the mycotoxin inhibitor such as antioxidant, antifungus agent, plant (medicine) extract with the use of, play and preferably prevent
Mould antibacterial action；Also often and the nutrition 5 such as vitamin, aminoacid, yeast cell wall polysaccharide hereby with the use of, at antibacterial and mouldproof
Have additional nutrients simultaneously, improve animal feeding comprehensive nutrient level, reach animal health protective effect.But clay minerals adsorbent
Absorption to mycotoxin has obvious selectivity.As a example by montmorillonite, it is very strong to the absorbability of aflatoxin, but
The absorbability of enzyme ketenes red to Semen Maydis and vomiting is the most weak.By montmorillonite is carried out surface modification treatment, can significantly carry
The absorbability of its enzyme ketenes red to Semen Maydis high, but conventional montmorillonite surface modifier is long aliphatic chain alkyl quaternary ammonium salts, tool
Having certain toxicity, use is restricted.Therefore, research one is safely, effectively, make without absorption medicine and other nutrient substance
Mold toxin sorbent, be that one meaningful and the research topic of application prospect.
Summary of the invention
In order to overcome the problem that existing mold toxin sorbent product absorbing mycotoxin kind is single, the of the present invention
One purpose is to provide a kind of modified clay, and second object of the present invention is to provide the preparation method of above-mentioned modified clay,
Third object of the present invention is to provide the application of above-mentioned modified clay.The modified clay of the present invention is possible not only to effectively inhale
Multiple mycotoxin in attached feedstuff, but also it is improved the effect of animal body immunity.
In order to realize the first above-mentioned purpose, present invention employs following technical scheme:
A kind of modified clay, the modifying agent of this modification clay includes phospholipid.
As preferably, the usage amount of described phospholipid is the 5 ~ 70% of modified clay gross mass, is further preferably 20 ~ 40%.
As preferably, described clay includes the one or many in montmorillonite, meerschaum, attapulgite, illite/smectite mixed layer clay
Kind.
As preferably, described phospholipid is plant source phospholipid.
As preferably, described phospholipid includes phosphatidylcholine, PHOSPHATIDYL ETHANOLAMINE, Phosphatidylserine, phosphatidyl-4
One or more in alcohol, phosphatidyl glycerol and phosphoglyceride acid.
As preferably, described modifying agent also includes in stearic acid, organosilicon, titante coupling agent and organic quaternary ammonium salt
One or more.
In order to realize the second above-mentioned purpose, present invention employs following technical scheme:
A kind of method preparing above-mentioned modified clay, the method comprises the following steps: to weigh clay and modifying agent in mixing
In equipment, add suitable quantity of water, 40 ~ 80 DEG C of mix and blend 1 ~ 5h, take out, dry, pulverizing.
In order to realize the 3rd above-mentioned purpose, present invention employs following technical scheme:
Above-mentioned modified clay is as the application of mold toxin sorbent.
As preferably, described mycotoxin includes aflatoxin, 6-(10-hydroxy-6-oxo-trans-1-undecenyl)-.beta.-resorcylic acid lactone, vomitoxin, fumonisin
With one or more in ochratoxin.
A kind of animal feed mold toxin sorbent, the modified clay that this mold toxin sorbent is above-mentioned.
The know-why of the present invention: clay material such as montmorillonite, meerschaum, attapulgite, illite/smectite mixed layer clay, kieselguhr are equal
There is the hole or lamellar structure more grown, there is bigger specific surface area, possess good adsorption capacity.By with phospholipid
Compounding, in phospholipid cladding or intercalation to the hole or lamella of clay material so that the surface portion oleophylic of clay material, have
Certain lipophile, shows preferable absorbability to lipophile mycotoxins such as 6-(10-hydroxy-6-oxo-trans-1-undecenyl)-.beta.-resorcylic acid lactones.
Compared with the conventional method, the invention have the advantages that
The present invention innovates employing phospholipid and clay compounds and prepares mold toxin sorbent, and phospholipid belongs to feed additive composition, permits
Permitted to add in feedstuff to use, overcome conventional quaternary ammonium salts and compound the issuable safety issue of clay.Compound fungus toxin
Adsorbent toxin multiple to aflatoxin, 6-(10-hydroxy-6-oxo-trans-1-undecenyl)-.beta.-resorcylic acid lactone etc. all has preferable adsorption effect.
Specific implementation method:
Being described further the technical solution of the present invention below in conjunction with embodiment, these embodiments are it is not intended that to skill
The restriction of art scheme.
Embodiment 1:
Weigh montmorillonite powder (smectite content >=85%) 800g, soybean phospholipid powder: 200g, in mixing apparatus, add appropriate
Water, 50 degrees Celsius of constant temperature mix and blend 2h, take out, dry, pulverizing, obtain mold toxin sorbent outturn sample (1#).
Embodiment 2:
Weigh montmorillonite powder (smectite content >=85%) 700g, soybean phospholipid powder: 300g, in mixing apparatus, add appropriate
Water, 50 degrees Celsius of constant temperature mix and blend 2h, take out, dry, pulverizing, obtain mold toxin sorbent outturn sample (2#).
Embodiment 3:
Weigh montmorillonite powder (smectite content >=85%) 600g, soybean phospholipid powder: 400g, in mixing apparatus, add appropriate
Water, 50 degrees Celsius of constant temperature mix and blend 2h, take out, dry, pulverizing, obtain mold toxin sorbent outturn sample (3#).
Embodiment 4:
Weigh sepiolite powder (meerschaum content >=85%) 700g, soybean phospholipid powder: 300g, in mixing apparatus, add appropriate
Water, 50 degrees Celsius of constant temperature mix and blend 2h, take out, dry, pulverizing, obtain mold toxin sorbent outturn sample (4#).
Embodiment 5:
Weigh sepiolite powder (meerschaum content >=85%) 600g, soybean phospholipid powder: 400g, in mixing apparatus, add appropriate
Water, 50-80 degree Celsius of constant temperature mix and blend 2h, takes out, dries, pulverizing, obtain mold toxin sorbent outturn sample (5#).
Embodiment 6:
Weigh her mask clay 800g, soybean phospholipid powder: 200g, in mixing apparatus, add suitable quantity of water, 50-80 degree Celsius of perseverance
Temperature mix and blend 2h, takes out, dries, pulverizing, obtains mold toxin sorbent outturn sample (6#).
Embodiment 7:
Weigh her mask clay 700g, soybean phospholipid powder: 300g, in mixing apparatus, add suitable quantity of water, 50-80 degree Celsius of perseverance
Temperature mix and blend 2h, takes out, dries, pulverizing, obtains mold toxin sorbent outturn sample (7#).
Embodiment 8:
Weigh attapulgite (attapulgite content >=90%) 800g, soybean phospholipid powder: 200g, in mixing apparatus, add appropriate
Water, 50-80 degree Celsius of constant temperature mix and blend 2h, takes out, dries, pulverizing, obtain mold toxin sorbent outturn sample (8#).
Embodiment 9:
Weigh attapulgite (attapulgite content >=90%) 700g, soybean phospholipid powder: 300g, in mixing apparatus, add appropriate
Water, 50-80 degree Celsius of constant temperature mix and blend 2h, takes out, dries, pulverizing, obtain mold toxin sorbent outturn sample (9#).
Embodiment 10:
Weigh montmorillonite powder (smectite content >=90%): 500g, attapulgite (attapulgite content >=90%): 200g, Semen sojae atricolor phosphorus
Cosmetics: 300g, in mixing apparatus, adds suitable quantity of water, 50-80 degree Celsius of constant temperature mix and blend 2h, takes out, dries, pulverizing,
To mold toxin sorbent outturn sample (10#).
Embodiment 11:
Weigh montmorillonite powder (smectite content >=90%): 300g, diatomite in powder (dioxide-containing silica >=95%): 400g, Semen sojae atricolor
Phosphatide powder: 300g, in mixing apparatus, adds suitable quantity of water, 50-80 degree Celsius of constant temperature mix and blend 2h, takes out, dries, pulverizing,
Obtain mold toxin sorbent outturn sample (11#).
Embodiment 12:
Weighing montmorillonite powder (smectite content >=85%) 700g, soybean phospholipid powder: 200g, stearic acid 100 g, in mixing apparatus
In, add suitable quantity of water, 50-80 degree Celsius of constant temperature mix and blend 2h, take out, dry, pulverizing, obtain mold toxin sorbent product
Sample (12#).
Embodiment 13:
Weigh montmorillonite powder (smectite content >=85%) 600g, soybean phospholipid powder: 200g, stearic acid 100 g, organic quaternary ammonium salt
100 g, in mixing apparatus, add suitable quantity of water, 50-80 degree Celsius of constant temperature mix and blend 2h, take out, dry, pulverizing, obtain mould
Verticillium toxin adsorbent product sample (13#).
Use the assay method of vitro Adsorption, 11 samples are carried out mycotoxin adsorption rate test.Method of testing is: mould
Verticillium toxin standard solution, aflatoxin standard solution (3ppm), Semen Maydis red enzyme ketenes standard solution (3ppm)；Every 10ml toxin
Standard solution adds 30mg sample of sorbent, 37 degrees Celsius of isothermal vibrations 3 hours, centrifugation, takes supernatant, use liquid phase color
Spectrometer measures toxin residue in supernatant, calculates the adsorption rate of sample contratoxin.
In table, embodiment, sample is to mycotoxin adsorption rate test result
。
Claims (10)
1. a modified clay, it is characterised in that the modifying agent of this modification clay includes phospholipid.
A kind of modified clay the most according to claim 1, it is characterised in that: the usage amount of phospholipid is modified clay gross mass
5 ~ 70%, preferably 20 ~ 40%.
A kind of modified clay the most according to claim 1, it is characterised in that: clay includes montmorillonite, meerschaum, concavo-convex
One or more in rod, illite/smectite mixed layer clay.
A kind of modified clay the most according to claim 1, it is characterised in that: phospholipid is plant source phospholipid.
A kind of modified clay the most according to claim 1, it is characterised in that: phospholipid includes phosphatidylcholine, phosphatidyl second
One or more in hydramine, Phosphatidylserine, phosphatidylinositols, phosphatidyl glycerol and phosphoglyceride acid.
A kind of modified clay the most according to claim 1, it is characterised in that: modifying agent also includes stearic acid, organosilicon, titanium
One or more in esters of gallic acid coupling agent and organic quaternary ammonium salt.
7. the method for the modified clay prepared described in claim 1 ~ 6, it is characterised in that the method comprises the following steps:
Weigh clay and modifying agent in mixing apparatus, add suitable quantity of water, 40 ~ 80 DEG C of mix and blend 1 ~ 5h, take out, dry, pulverizing.
8. the modified clay described in claim 1 ~ 6 is as the application of mold toxin sorbent.
Application the most according to claim 8, it is characterised in that mycotoxin include aflatoxin, 6-(10-hydroxy-6-oxo-trans-1-undecenyl)-.beta.-resorcylic acid lactone,
One or more in vomitoxin, fumonisin and ochratoxin.
10. an animal feed mold toxin sorbent, it is characterised in that this mold toxin sorbent includes claim 1 ~ 6
Described modified clay.
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