CN113713777B - Preparation method of eggshell powder vomitoxin adsorbent - Google Patents
Preparation method of eggshell powder vomitoxin adsorbent Download PDFInfo
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- CN113713777B CN113713777B CN202111068757.0A CN202111068757A CN113713777B CN 113713777 B CN113713777 B CN 113713777B CN 202111068757 A CN202111068757 A CN 202111068757A CN 113713777 B CN113713777 B CN 113713777B
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- eggshell powder
- vomitoxin
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- 210000003278 egg shell Anatomy 0.000 title claims abstract description 150
- 108010000912 Egg Proteins Proteins 0.000 title claims abstract description 111
- 102000002322 Egg Proteins Human genes 0.000 title claims abstract description 111
- 239000000843 powder Substances 0.000 title claims abstract description 86
- LINOMUASTDIRTM-QGRHZQQGSA-N deoxynivalenol Chemical compound C([C@@]12[C@@]3(C[C@@H](O)[C@H]1O[C@@H]1C=C(C([C@@H](O)[C@@]13CO)=O)C)C)O2 LINOMUASTDIRTM-QGRHZQQGSA-N 0.000 title claims abstract description 48
- LINOMUASTDIRTM-UHFFFAOYSA-N vomitoxin hydrate Natural products OCC12C(O)C(=O)C(C)=CC1OC1C(O)CC2(C)C11CO1 LINOMUASTDIRTM-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000003463 adsorbent Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
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- 239000006228 supernatant Substances 0.000 claims description 16
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- 238000000034 method Methods 0.000 claims description 9
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
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- 229910021641 deionized water Inorganic materials 0.000 claims description 4
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- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
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- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 241000288049 Perdix perdix Species 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
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- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 2
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 claims description 2
- DRRZZMBHJXLZRS-UHFFFAOYSA-N n-[3-[dimethoxy(methyl)silyl]propyl]cyclohexanamine Chemical compound CO[Si](C)(OC)CCCNC1CCCCC1 DRRZZMBHJXLZRS-UHFFFAOYSA-N 0.000 claims description 2
- 150000002891 organic anions Chemical group 0.000 claims description 2
- 229950009215 phenylbutanoic acid Drugs 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 229940005605 valeric acid Drugs 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims 1
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- 239000004094 surface-active agent Substances 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000001179 sorption measurement Methods 0.000 description 13
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- 239000012224 working solution Substances 0.000 description 6
- 244000144977 poultry Species 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 244000144972 livestock Species 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 231100000678 Mycotoxin Toxicity 0.000 description 3
- 239000003674 animal food additive Substances 0.000 description 3
- 229930002954 deoxynivalenol Natural products 0.000 description 3
- 230000000968 intestinal effect Effects 0.000 description 3
- 239000002636 mycotoxin Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 210000001035 gastrointestinal tract Anatomy 0.000 description 2
- 238000000338 in vitro Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 150000004666 short chain fatty acids Chemical class 0.000 description 2
- 239000003053 toxin Substances 0.000 description 2
- 231100000765 toxin Toxicity 0.000 description 2
- 230000008673 vomiting Effects 0.000 description 2
- 241000283690 Bos taurus Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
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- 206010061218 Inflammation Diseases 0.000 description 1
- 108010076876 Keratins Proteins 0.000 description 1
- 102000011782 Keratins Human genes 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- OAUKXDWHXFHBAE-UHFFFAOYSA-L [O--].[Ca++].[Ca++].[O-]C([O-])=O Chemical compound [O--].[Ca++].[Ca++].[O-]C([O-])=O OAUKXDWHXFHBAE-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
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- 229910052791 calcium Inorganic materials 0.000 description 1
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- 229930013292 trichothecene Natural products 0.000 description 1
- LZAJKCZTKKKZNT-PMNGPLLRSA-N trichothecene Chemical compound C12([C@@]3(CC[C@H]2OC2C=C(CCC23C)C)C)CO1 LZAJKCZTKKKZNT-PMNGPLLRSA-N 0.000 description 1
- 210000004916 vomit Anatomy 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K35/00—Medicinal preparations containing materials or reaction products thereof with undetermined constitution
- A61K35/56—Materials from animals other than mammals
- A61K35/57—Birds; Materials from birds, e.g. eggs, feathers, egg white, egg yolk or endothelium corneum gigeriae galli
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P1/00—Drugs for disorders of the alimentary tract or the digestive system
-
- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Animal Behavior & Ethology (AREA)
- Veterinary Medicine (AREA)
- Medicinal Chemistry (AREA)
- Pharmacology & Pharmacy (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Epidemiology (AREA)
- Engineering & Computer Science (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Chemical & Material Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a preparation method of an eggshell powder vomitoxin adsorbent with detoxication and intestinal health care functions, which comprises the steps of cleaning, crushing and burning waste eggshells, adding a mineralization coupling agent for mineralization modification, adding an organic acid surfactant for full reaction after purifying impurities, and obtaining a novel vomitoxin adsorbent with detoxication and intestinal health care functions after precipitation, washing, drying and sieving of products.
Description
Technical Field
The invention relates to a preparation method of an eggshell powder vomitoxin adsorbent, and belongs to the field of research and development of functional feed additives.
Background
China is a large country for producing and consuming eggs, and more than 400 ten thousand tons of waste eggshells are produced in each year. The waste eggshells and eggshell membranes contain rich nutritional value components such as calcium, bioactive peptides, keratin and the like, the utilization rate of the eggshells in China is only 1% -2% of the total yield, and a great amount of eggshell resources are wasted. Therefore, by developing a deep processing method of the waste eggshells, the economic added value of the waste eggshells can be improved, and the efficient utilization of agricultural product resources can be promoted.
The pollution of mycotoxin to feed and raw materials is a global problem, and vomit toxin (also known as Deoxynivalenol (DON)) is the most representative type B trichothecene type, and is easy to generate in the growth and storage processes of feed raw materials such as corn, wheat and the like; the vomitoxin has very stable chemical properties, and the countermeasures adopted for solving the existing problem of feed raw material vomitoxin pollution mainly comprise: adding non-nutritive adsorbent, microbial degradation, chemical isomerism modification, biological enzyme deactivation and raw material dilution. Various biodegradation and chemical modification methods have the problems of harsh reaction conditions, unstable effect, change of nutrient components of the feed and the like in the using process; the adsorption rate of the common adsorbent to vomit toxin in the artificial simulated pig alimentary canal is only 15-19%.
Vomitoxin in feeds and raw materials can cause damage to animal intestinal barriers, cause pathogenic bacteria and endotoxin in intestinal tracts to enter blood circulation, cause inflammatory reactions of animals, and damage animal self-immunity and growth performance. Therefore, the research and development of the feed additive with vomitoxin adsorption and intestinal health care performance is a safe and effective way for reducing the harm of vomitoxin in the feed and realizing healthy cultivation of livestock and poultry.
The adsorption method is one of the effective methods for treating the excessive vomitoxin in the feed and the raw materials, and the eggshells have larger surface area and rich pore structures, so that the method has good vomitoxin adsorption potential theoretically. Chinese patent CN106955677a (an eggshell/activated carbon adsorbent based on ionic liquid modification and a preparation method thereof) discloses a preparation method of ion modified eggshell and activated carbon, which realizes efficient adsorption of heavy metal ions in wastewater. To date, there has been no relevant case of modifying an eggshell powder into a vomitoxin adsorbent.
Organic acids, particularly short chain fatty acids, have been shown to be effective in improving intestinal health in animals. The specific mechanism mainly comprises: regulating animal intestinal flora, promoting nutrient absorption and metabolism of intestinal tissue, and regulating gene expression by regulating transcription factor and epigenetic mechanism. At present, a large number of animal experiments show that the addition of short chain fatty acid/organic acid with a certain level can improve the yield of pigs, poultry and cattle, improve meat quality and feed return, and improve animal immunity and survival rate. Therefore, the modification and activation of the waste eggshell powder by the organic acid are key links for further improving the functional value of the waste eggshells.
The eggshell mainly contains calcium carbonate, has a porous structure and good liquid phase adsorptivity, can keep the porous performance after being calcined at a high temperature under certain conditions, and is converted into a calcium oxide-calcium carbonate multi-stage pore structure. The silane coupling agent can form a silicon ore body structure on the basis of the multistage hole structure, improves the hydrophobicity and the adsorption performance of the eggshell powder, and has the effects of mycotoxin adsorption, intestinal health care and the like on the basis of the organic acid modified eggshell powder. Therefore, the waste eggshells are modified and developed into the feed vomitoxin adsorbent, and the feed vomitoxin adsorbent has good feasibility and market application prospect.
Disclosure of Invention
Aiming at the problem of damage to livestock and poultry cultivation caused by mycotoxin pollution in feeds and raw materials, the invention provides a preparation method of an eggshell powder vomitoxin adsorbent. The preparation method realizes the recycling of the waste eggshells, successfully improves the vomitoxin adsorption performance of eggshell powder by using methods such as high-temperature burning, mineralization modification, organic acid activation and the like, and simultaneously effectively plays the antibacterial and intestinal health-care characteristics of the organic acid. The product prepared by the invention generally has the functions of vomitoxin adsorption, intestinal health care and the like, and can be safely applied to livestock and poultry feed addition to improve the intestinal health of livestock and poultry.
The preparation principle of the invention is as follows: cleaning eggshells, crushing, burning, adding a mineralization coupling agent for mineralization modification, adding an organic acid surfactant for modification after purifying impurities, and obtaining a vomitoxin adsorbent with detoxification and intestinal health care functions after precipitation, roasting, washing, drying and sieving of a pre-product.
The technical scheme related by the invention (preparation method of the eggshell powder vomitoxin adsorbent) comprises the following steps:
step one: collecting a certain amount of fresh eggshells, cleaning, crushing into a homogeneous state by using a grinder, sieving by using a 100-600 mesh sieve, burning at a high temperature of 200-700 ℃ to remove organic matters attached to the surfaces of the eggshells, then adding a sufficient amount of mineralization modifier according to a proportion (volume mass ratio is 5:1 or higher), fully reacting for 4-12h, centrifuging at a high speed of 1000rpm-20000rpm, discarding the supernatant, washing for 3 times by using a sufficient amount of deionized water, removing unbound mineralization modifier, removing impurities by using a 100-600 mesh sieve, and drying the purified eggshell powder to obtain the' burned-mineralized modified eggshell powder with good hydrophobicity and larger specific surface area (BET).
Step two (organic acid modification of eggshell powder): weighing a certain amount of the 'burning-mineralizing modified eggshell powder' prepared in the first step, adding an organic acid modifier according to a certain proportion, fully reacting for 4-12h at 30-90 ℃, centrifuging at 1000-20000 rpm at a high speed, and removing the supernatant to obtain a pre-product.
Step three (washing, drying and homogenizing): adding deionized water into the pre-product prepared in the second step for washing, removing the organic acid modifier which is not coupled with eggshell powder, drying for 4-8 hours at 30-90 ℃, crushing into homogeneity by a grinder, and sieving by a 100-600 mesh sieve to obtain the vomitoxin adsorbent with the functions of detoxification and intestinal health care.
Wherein the eggshell raw material in the first step is one or a combination of eggshell, duck eggshell, goose eggshell, quail eggshell, pheasant eggshell, partridge eggshell and pigeon eggshell; the mineralization modifier is one or a combination of silane coupling agent (gamma-aminopropyl trimethoxy silane, 3-aminopropyl triethoxy silane, gamma-diethylenetriamine propyl methyl dimethoxy silane, N-2-aminoethyl-3-aminopropyl trimethoxy silane, N-2-aminoethyl-3-aminopropyl methyl dimethoxy silane, gamma-aminopropyl methyl diethoxy silane) and tetraethoxysilane, and the ratio of the volume (L) of the mineralization modifier to the mass (kg) of eggshell powder is 5:1 or higher.
Wherein the organic acid in the second step is one or a combination of lactic acid, citric acid, malic acid, benzoic acid, tartaric acid, formic acid, acetic acid, propionic acid, isobutyric acid, butyric acid, valeric acid, isovaleric acid, caproic acid and 4-phenylbutyric acid, and the addition ratio of the mole number of the acidulant (mol based on the mole equivalent of H+ as a conversion standard) to the mass ratio (kg) of the burning-mineralizing modified eggshell powder is 5:1 or higher.
Wherein, the chemical formula of the prepared eggshell powder vomitoxin adsorbent is generally characterized in that: ca 5 Si 8O 20 (OH) 2X4.4H2O, wherein X is the organic anion of an acid modifier. Taking a silane coupling agent and acetic acid as mineralization modifier and an organic acid modifier as examples in the first step and the second step respectively, the molecular formula of the obtained eggshell powder vomitoxin adsorbent is Ca 5 Si 8O 20 (OH) 2Ac 4.4H2O.
Compared with the existing vomitoxin adsorbent, the invention has the following advantages:
1. the raw materials required by the preparation mainly adopt waste eggshells, belong to the recycling of waste agricultural product resources, and are green and environment-friendly and low in cost.
2. The preparation method has simple process and easy control and optimization of production conditions, and the modification method provided by the invention can obviously improve the adsorption efficiency of the eggshell powder on vomitoxin under neutral and acidic conditions.
3. The product obtained by the preparation method has stable physicochemical properties and is easy to store.
4. The product is safe and nontoxic, is not easy to react with other products, and can be compatible with the compound use of other feed additive products.
5. Under the same test conditions, the attenuation efficacy of vomitoxin is better than that of the current commercial most widely used vomitoxin adsorbent products.
Drawings
FIG. 1 IR spectrum of unmodified eggshell powder and modified eggshell vomitoxin adsorbent.
FIG. 2 is an electron microscopy topography of unmodified eggshell powder and modified eggshell vomitoxin adsorbent.
Figure 3 comparison of specific surface area of unmodified eggshell powder versus modified eggshell vomitoxin adsorbent and efficiency of adsorption of DON in vitro.
Figure 4 in vitro evaluation of attenuation ability of unmodified eggshell powder and modified eggshell vomitoxin adsorbent.
Detailed Description
The following describes the technical solution of the present invention with reference to examples, but the technical solution of the present invention is not limited to the following specific embodiments.
Embodiment case 1: weighing 100g of waste eggshells, washing with tap water, removing inner membranes on the surfaces of the eggshells, drying, putting the eggshells into a grinder, grinding the eggshells into a homogeneous state, putting the pretreated eggshell powder into a crucible, putting the crucible into a muffle furnace for burning at 300 ℃ for 1h, cooling, grinding and grinding again, and sieving the cooled eggshell powder with a 300-mesh sieve to obtain 'burnt modified eggshell powder'; then preparing 1L of mineralizing modifier working solution (the preparation ratio of 3-aminopropyl triethoxysilane and tetraethyl silicate is 1:2), adding the burnt modified eggshell powder, magnetically stirring in a 65 ℃ water bath, reacting for 3h, centrifuging at a high speed of 12000rpm, removing the supernatant, and drying at 80 ℃ by a dryer to obtain the burnt-mineralized modified eggshell powder with good physicochemical stability and multiple layers of pores; preparing 1mmol/L acetic acid solution 1L, adding into 'burning-mineralizing modified eggshell powder', standing at 65deg.C for 4h in a constant-temperature water bath, slowly dripping 1mmol/L sodium hydroxide solution to adjust pH to 6, centrifuging at 12000rpm at high speed, discarding supernatant, washing the product with double distilled water for 3 times, drying at 80deg.C, homogenizing with a grinder, and sieving with 200 mesh sieve to obtain vomitoxin adsorbent (300-acetic acid modified eggshell powder) with detoxication and intestinal tract health promotion functions.
Embodiment case 2: weighing 50g of waste eggshells, washing with tap water, removing inner membranes on the surfaces of the eggshells, drying, putting the eggshells into a grinder, grinding the eggshells into a homogeneous state, putting the pretreated eggshell powder into a crucible, putting the crucible into a muffle furnace for burning at 500 ℃ for 2 hours, cooling, grinding and grinding again, and sieving the cooled eggshell powder with a 300-mesh sieve to obtain 'burnt modified eggshell powder'; then preparing 0.5L of mineralizing modifier working solution (the preparation ratio of 3-aminopropyl triethoxysilane and tetraethyl silicate is 1:2), adding the burnt and modified eggshell powder, magnetically stirring in a 65 ℃ water bath, reacting for 3h, centrifuging at a high speed of 12000rpm, removing the supernatant, and drying at 80 ℃ by a dryer to obtain the burnt-mineralizing modified eggshell powder with good physicochemical stability and multiple layers of pores; preparing 0.5L of acetic acid solution with the concentration of 1mmol/L, adding the mixture into the 'burnt-mineralized modified eggshell powder', carrying out constant-temperature water bath for 4 hours at the temperature of 65 ℃, slowly dripping 1mmol/L sodium hydroxide solution to adjust the pH to 6, centrifuging at a high speed of 12000rpm, discarding the supernatant, washing the product for 3 times by using double distilled water, drying the product at the temperature of 80 ℃ by a dryer, homogenizing the product by using a grinder, and sieving the product by using a 200-mesh sieve to obtain the vomitoxin adsorbent (500-acetic acid modified eggshell powder) with the functions of detoxification and intestinal health care.
Embodiment 3: weighing 50g of waste eggshells, washing with tap water, removing inner membranes on the surfaces of the eggshells, drying, putting the eggshells into a grinder, grinding the eggshells into a homogeneous state, putting the pretreated eggshell powder into a crucible, putting the crucible into a muffle furnace for burning at 700 ℃ for 3 hours, cooling, grinding and grinding again, and sieving the cooled eggshell powder with a 300-mesh sieve to obtain 'burnt modified eggshell powder'; then preparing 0.5L of mineralization modifier working solution (the preparation ratio of 3-aminopropyl triethoxysilane and tetraethyl silicate is 1:2), adding the burnt modified eggshell powder, magnetically stirring in a 65 ℃ water bath, reacting for 3h, centrifuging at a high speed of 12000rpm, removing the supernatant, and drying at 80 ℃ by a dryer to obtain the burnt-mineralization modified eggshell powder with good physicochemical stability and multiple layers of pores; preparing 0.5L of acetic acid solution with the concentration of 1mmol/L, adding the mixture into the eggshell powder subjected to calcination-mineralization modification, carrying out constant-temperature water bath at 65 ℃ for 4 hours, slowly dripping 1mmol/L sodium hydroxide solution to adjust the pH to 6, centrifuging at 12000rpm at a high speed, discarding the supernatant, washing the product for 3 times by using double distilled water, drying the product at the temperature of 80 ℃ by a dryer, homogenizing the product by using a grinder, and sieving the product by using a 200-mesh sieve to obtain the vomitoxin adsorbent (700-acetic acid modified eggshell powder) with the functions of detoxification and intestinal health care.
Embodiment 4: weighing 50g of waste eggshells, washing with tap water, removing inner membranes on the surfaces of the eggshells, drying, putting the eggshells into a grinder, grinding the eggshells into a homogeneous state, putting the pretreated eggshell powder into a crucible, putting the crucible into a muffle furnace for burning at 300 ℃ for 1h, cooling, grinding and grinding again, and sieving the cooled eggshell powder with a 300-mesh sieve to obtain 'burnt modified eggshell powder'; then preparing 0.5L of mineralizing modifier working solution (the preparation ratio of 3-aminopropyl triethoxysilane and tetraethyl silicate is 1:2), adding the burnt and modified eggshell powder, magnetically stirring in a 65 ℃ water bath, reacting for 3h, centrifuging at a high speed of 12000rpm, removing the supernatant, and drying at 80 ℃ by a dryer to obtain the burnt-mineralizing modified eggshell powder with good physicochemical stability and multiple layers of pores; preparing 0.5L of 1mmol/L propionic acid solution, adding into 'burnt-mineralized modified eggshell powder', carrying out constant-temperature water bath at 65 ℃ for 4 hours, slowly dripping 1mmol/L sodium hydroxide solution to adjust the pH to 6, centrifuging at 12000rpm at high speed, discarding the supernatant, washing the product for 3 times by using double distilled water, drying at 80 ℃ by a dryer, homogenizing the product by using a grinder, and sieving by using a 200-mesh sieve to obtain the vomitoxin adsorbent (300-propionic acid modified eggshell powder) with detoxification and intestinal health care functions.
Embodiment case 5: weighing 50g of waste eggshells, washing with tap water, removing inner membranes on the surfaces of the eggshells, drying, putting the eggshells into a grinder, grinding the eggshells into a homogeneous state, putting the pretreated eggshell powder into a crucible, putting the crucible into a muffle furnace for burning at 500 ℃ for 2 hours, cooling, grinding and grinding again, and sieving the cooled eggshell powder with a 300-mesh sieve to obtain 'burnt modified eggshell powder'; then preparing 0.5L of mineralizing modifier working solution (the preparation ratio of 3-aminopropyl triethoxysilane and tetraethyl silicate is 1:2), adding the burnt modified eggshell powder, magnetically stirring in a 65 ℃ water bath, reacting for 3h, centrifuging at a high speed of 12000rpm, removing the supernatant, and drying at 80 ℃ by a dryer to obtain the burnt-mineralizing modified eggshell powder with good physicochemical stability and multiple layers of pores; preparing 0.5L of 1mmol/L propionic acid solution, adding the mixture into the eggshell powder modified by burning-mineralizing, carrying out constant-temperature water bath at 65 ℃ for 4 hours, slowly dripping 1mmol/L sodium hydroxide solution to adjust the pH to 6, centrifuging at 12000rpm at high speed, discarding the supernatant, washing the product for 3 times by using double distilled water, drying the product at 80 ℃ by a dryer, homogenizing the product by using a grinder, and sieving the product with a 200-mesh sieve to obtain the vomitoxin adsorbent (500-propionic acid modified eggshell powder) with the functions of detoxification and intestinal health care.
Embodiment 6: weighing 50g of waste eggshells, washing with tap water, removing inner membranes on the surfaces of the eggshells, drying, putting the eggshells into a grinder, grinding the eggshells into a homogeneous state, putting the pretreated eggshell powder into a crucible, putting the crucible into a muffle furnace for burning at 700 ℃ for 3 hours, cooling, grinding and grinding again, and sieving the cooled eggshell powder with a 300-mesh sieve to obtain 'burnt modified eggshell powder'; then preparing 0.5L of mineralizing modifier working solution (the preparation ratio of 3-aminopropyl triethoxysilane and tetraethyl silicate is 1:2), adding the burnt and modified eggshell powder, magnetically stirring in a 65 ℃ water bath, reacting for 3h, centrifuging at a high speed of 12000rpm, removing the supernatant, and drying at 80 ℃ by a dryer to obtain the burnt-mineralizing modified eggshell powder with good physicochemical stability and multiple layers of pores; preparing 0.5L of 1mmol/L propionic acid solution, adding the mixture into the eggshell powder modified by burning-mineralizing, carrying out constant-temperature water bath at 65 ℃ for 4 hours, slowly dripping 1mmol/L sodium hydroxide solution to adjust the pH to 6, centrifuging at 12000rpm at high speed, discarding the supernatant, washing the product for 3 times by using double distilled water, drying the product at 80 ℃ by a dryer, homogenizing the product by using a grinder, and sieving the product with a 200-mesh sieve to obtain the vomitoxin adsorbent (700-propionic acid modified eggshell powder) with the functions of detoxification and intestinal health care.
The infrared spectrograms of the egg shell powder vomitoxin adsorbent obtained in examples 1-6 are shown in figure 1.
The electron microscope morphology of the egg shell powder vomitoxin adsorbent obtained in examples 1-6 is shown in FIG. 2.
Specific surface area and vomitoxin adsorption efficiency of the egg shell powder vomitoxin adsorbent obtained in examples 1 to 6 are shown in FIG. 3.
Examples 1-6 the three eggshell powder vomitoxin adsorbents (500-acetic acid modified eggshell powder, 500-propionic acid modified eggshell powder, 700-acetic acid modified eggshell powder) with optimal adsorption performance were prepared, and the measured cell attenuation capacities are shown in figure 4.
Claims (3)
1. The preparation method of the eggshell powder vomitoxin adsorbent is characterized by comprising the following four steps:
step one, burning, mineralizing and modifying eggshell powder: collecting a certain amount of fresh eggshells, cleaning with clear water, and grinding with a grinder
Pulverizing into homogeneous powder, sieving with 100-600 mesh sieve, high temperature burning at 200-700 deg.C to remove organic matters adhered to eggshell surface, adding sufficient mineralization modifier at a certain proportion, fully reacting for 4-12h, centrifuging at 1000-20000 rpm, discarding supernatant, washing with sufficient deionized water for 3 times, removing unbound mineralization modifier, sieving with 100-600 mesh sieve to remove impurities, and drying purified eggshell powder to obtain "burnt-mineralized modified eggshell powder" with good hydrophobicity and larger specific surface area;
step two, modifying the eggshell powder by using organic acid: weighing a certain amount of the 'burning-mineralizing modified eggshell powder' prepared in the first step, adding an organic acid modifier according to a certain proportion, fully reacting for 4-12h at 30-90 ℃, centrifuging at 1000-20000 rpm at a high speed, and removing the supernatant to obtain a pre-product;
step three, washing, drying and homogenizing: sequentially adding deionized water into the pre-product prepared in the step two for washing, removing the organic acid modifier which is not coupled with eggshell powder, drying for 4-8 hours at 30-90 ℃, crushing into homogeneity by a grinder, and sieving by a 100-600 mesh sieve to obtain the vomitoxin adsorbent with detoxification and intestinal health care functions;
the mineralization modifier is compounded by silane coupling agent and tetraethoxysilane, the ratio of the volume L of the mineralization modifier to the mass kg of eggshell powder is 5:1 or higher, and the silane coupling agent is one or the compounding of gamma-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, gamma-diethylenetriamine propyl methyl dimethoxy silane, N-2-aminoethyl-3-aminopropyl trimethoxysilane, N-2-aminoethyl-3-aminopropyl methyl dimethoxy silane and gamma-aminopropyl methyl diethoxy silane;
the organic acid in the second step is one or more of lactic acid, citric acid, malic acid, benzoic acid, tartaric acid, formic acid, acetic acid, propionic acid, isobutyric acid, butyric acid, valeric acid, isovaleric acid, caproic acid and 4-phenylbutyric acid, and H is used as the organic acid + The molar equivalent of (2) is a conversion standard, and the addition ratio of the mol of the added acidulant to the mass kg of the 'burnt-mineralized modified eggshell powder' is 5:1 or higher.
2. The method of manufacturing according to claim 1, characterized in that: the eggshell raw material is one or more of eggshell, duck eggshell, goose eggshell, quail eggshell, pheasant eggshell, partridge eggshell and pigeon eggshell.
3. The method of manufacturing according to claim 1, characterized in that: the chemical formula of the prepared eggshell powder vomitoxin adsorbent is generally characterized in that: ca (Ca) 5 Si 8 O 20 (OH) 2 X 4 ·4H 2 O, wherein X is an organic anion of an acid modifierThe method comprises the steps of carrying out a first treatment on the surface of the The first and second steps of claim 1, wherein the silane coupling agent, acetic acid are used as mineralization modifier and organic acid modifier respectively, and the molecular formula of the obtained organic acid modified eggshell powder is Ca 5 Si 8 O 20 (OH) 2 Ac 4 ·4H 2 O。
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