CN104799017A - Preparation method of modified montmorillonite powder for feeds - Google Patents
Preparation method of modified montmorillonite powder for feeds Download PDFInfo
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- CN104799017A CN104799017A CN201410032876.4A CN201410032876A CN104799017A CN 104799017 A CN104799017 A CN 104799017A CN 201410032876 A CN201410032876 A CN 201410032876A CN 104799017 A CN104799017 A CN 104799017A
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Abstract
The present invention provides a preparation method of modified montmorillonite powder for feeds. The preparation method comprises: heating crushed montmorillonite powder to a temperature of 80-90 DEG C, adding a measured quaternary ammonium salt solid, carrying out thermal insulation and high speed stirring modification, drying, and beating to obtain the large interlayer distance montmorillonite powder for feeds, wherein the d001value of the montmorillonite powder is 2.90-4.55 nm through the X-ray diffraction detection. According to the present invention, the modified montmorillonite powder prepared by using the method of the present invention has characteristics of high quaternary ammonium salt cation compounding proportion and large interlayer distance; and with the application of the modified montmorillonite powder as the feed mildew inhibitor, the good effects of adsorption, fixation and removal can be provided for weakly polar molecule mould in the feed production, storage and transportation processes, and the good application effect can be provided for prevention of feed mildewing deterioration.
Description
Technical field
The invention belongs to Modification of Montmorillonite powder preparation field, particularly a kind of preparation method of feed smectite powder, be suitable for calcium base or na-montmorillonite modification.
Background technology
Montmorillonite powder is the important Natural anti-mildew in modern feed formula, de-mould auxiliary agent, and consumption increases year by year to some extent.Common calcium base after processing or na-montmorillonite powder have been widely used in removing the strong aflatoxin of polarity etc., but it is poor to the toxin absorption such as the low pole produced in Feed Manufacturing, storage, transportation, large volume zearalenone, removal effect.
Quaternary ammonium salt is band long chain alkane, can dissociates the cationic efficient germicide of large volume, and its heat chemical property is more stable, and energy is water-soluble and be insoluble in non-polar solven.Quaternary ammonium salt bactericide have easy dispersion, inhibition, efficient, low toxicity, without accumulation, by pH affect little, easy to use, have the effects such as comparatively strong stripping to rete malpighii, its sterilization and sterilization are widely used in the fields such as food, food and drink, pharmacy, environment.The quaternary ammonium salt bactericide mechanism of action mainly discharges cationic electrostatic force, hydrogen bond force by it, and the effect such as hydrophobic binding between quaternary ammonium salt and protein molecule, the electronegative mould of effective absorption (bacterium) body is also gathered on cell membrane, cause bacteriolysis and generating chamber's inhibition effect, cause mould (bacterium) to grow suppressed and dead; Simultaneously its hydrophobic alkyl can also with the hydrophilic group effect of bacterium, change the permeability of film, then lysis occur, destroy eucaryotic cell structure, cause dissolving and the death of mould (bacterium) cell.
Be made into the aqueous solution with quaternary ammonium salt to add montmorillonite slurry and carry out modification to montmorillonite wet method and do feed formulation to take off mould bactericide be existing published technology, existing patent report.As Authorization Notice No. be the Chinese invention of CN101669574B, CN101366450B special used modified montmorillonite used be that montmorillonite powder is added in the quaternary ammonium salt aqueous solution of 1mol/L for twice respectively, 60 DEG C of constant temperature, concussion add up to reaction 2h continuously, then be separated, dry, pulverize and obtain smectite powder.
Application number be 201210164730.6 Chinese invention patent be the na-montmorillonite 10g that purification, acidifying, sodium pre-treatment step obtain is added in softex kw (CTAB) aqueous solution of 100ml concentration 0.5%-3.5%, pH value 4-6, control 30-90 DEG C, 100-400r/min, 0.5h-5h conditioned response, modified slip obtains smectite powder etc. through separation, 80 DEG C of dryings, 110 DEG C of activation, pulverizing.
It is steady that above-mentioned existing technique has course of reaction, the advantages such as goods stable components, but the quaternary ammonium salt solution concentration that there is use is low, dissolve during quaternary ammonium salt solution preparation difficult (especially containing Long carbon chain more than 18 carbon), montmorillonite reaction paste concentration is low, quaternary ammonium salt compound montmorillonite ratio is low, modifier need dewater separation, energy consumption for drying is high, the defects such as technological process is long, Product processing cost is higher, technique is also mainly suitable for single long chain quaternary, but, the modified gas producing formation spacing of the more single carbon chain quaternary ammonium salt of two Long carbon chain is larger, be more suitable for low pole, the mildew-resistant of large volume mould, de-mould.
Quaternary ammonium salt-modified montmorillonite product has good effect to the toxin such as zearalenone removing low pole in feed, but existing technique exists more defect needs to improve and optimize, the product that, cost more excellent with processability is lower.Although long carbon chain quaternary ammonium salt is more difficult be dissolved in water, but itself heating is had certain fluidity of molten by when more than 70 DEG C, especially stir the effect in the field of force at high speed machine under, can flow, be inserted into montmorillonite lamellar structure in carry out exchange reaction with the calcium of interlayer, sodium plasma, select suitable temperature, mixing speed and aftertreatment technology, the quaternary ammonium salts at high proportion of nonaqueous solvents, exchange can be realized, obtain the large interlamellar spacing modification feed montmorillonite powder of different quaternary ammonium salt compositely proportional.
Summary of the invention
The object of the invention is to the deficiency overcoming existing product and production technology, prepare and take off the composite modified montmorillonite powder of large interlamellar spacing, the at high proportion quaternary ammonium salt cationic of mould application for feed, for achieving the above object, the present invention includes following steps:
(1), the montmorillonite powder of pulverizing is heated to 80-90 DEG C;
(2), add solid quaternary ammonium salt, insulation, high speed whip modified;
(3), by modified montmorillonite dry, break up, obtain X-ray diffraction and detect d
001the large interlamellar spacing feed montmorillonite powder that value is 2.90nm-4.55nm.
More specifically, (1) described step uses its smectite content >=80% of montmorillonite powder, cation exchange total amount (CEC) 0.7 mmol-1.1mmol/g that pulverize, montmorillonite available ca base or na-montmorillonite, grinding particle size d97≤75 μm;
(2) described step uses quaternary ammonium salt content >=70% of solid quaternary ammonium salt, and quaternary ammonium salt consumption counts 0.1-1.0mmol/g by montmorillonite powder, high-speed stirred speed 1000r/min-2000r/min, time 20min-60min during modification;
Described step (3) modified montmorillonite oven dry extent control is 105 DEG C of fugitive constituent≤5%.
beneficial effect of the present invention
Adopt the present invention of foregoing invention content technologies scheme, make full use of quaternary ammonium salt heat and melt flowable characteristic, select rational temperature, mixing speed, modification time and aftertreatment technology, anhydrous solvent is adopted can directly to prepare montmorillonite layer spacing large, the smectite powder that quaternary ammonium salt cationic compositely proportional is high, goods are used for feed and produce it, store, low pole large molecule mould (as zearalenone etc.) easily produced in transportation has good absorption, fixing, remove effect, to preventing, feed mouldization is rotten has good anti-mildew change effect, whole set process has material properties and selects rationally, flow process is short, energy consumption for drying is low, the excellent distinguishing feature of end properties, there is good actual application value.
accompanying drawing illustrates:
Fig. 1 is the former powder X-ray diffractogram of unmodified ca-montmorillonite;
Fig. 2 is dioctadecyl dimethyl ammonium chloride smectite powder X-ray diffractogram;
Fig. 3 is OTAC smectite powder X-ray diffractogram;
Fig. 4 is hexadecyltrimethylammonium chloride smectite powder X-ray diffractogram;
Fig. 5 is dioctadecyl dimethyl ammonium chloride smectite powder X-ray diffractogram.
Detailed description of the invention
Embodiment 1
A kind of preparation method of feed smectite powder, first by smectite content >=80%, cation exchange total amount (CEC) is 1.0mmol/g montmorillonite powder, d001 value is that the 100g ca-montmorillonite powder of 1.42nm joins in electrical heating oil bath mixed at high speed mixer, be heated with stirring to 85 DEG C, add the solid dioctadecyl dimethyl ammonium chloride by every g montmorillonite 0.7mmol again, with 1000r/min mixed at high speed whip modified 30 minutes under insulation, the dispersant that unnecessary moisture and quaternary ammonium salt bring into is removed 105 DEG C of dryings, drying time to expect that detection 105 DEG C of fugitive constituent≤5% control after dry, modified montmorillonite usedly dispersion is broken up further by dried, obtaining by X-ray diffraction method detection layers spacing d001 value is 4.16nm, 850 DEG C of burn tinctuer are the 325 order smectite powder of 35.3%, finished product X ray diffracting spectrum is shown in accompanying drawing 2, accompanying drawing 1 is the former powder X-ray diffractogram of unmodified ca-montmorillonite.
Embodiment 2
A kind of preparation method of feed smectite powder, first by smectite content >=80%, cation exchange total amount (CEC) is 1.0mmol/g montmorillonite powder, d001 value is that the 100g ca-montmorillonite powder of 1.42nm joins in electrical heating oil bath mixed at high speed mixer and is heated with stirring to 85 DEG C, add the solid OTAC by every g montmorillonite 0.7mmol again, with 1000r/min mixed at high speed whip modified 30 minutes under insulation, the dispersant that unnecessary moisture and quaternary ammonium salt bring into is removed 105 DEG C of dryings, drying time to expect that detection 105 DEG C of fugitive constituent≤5% control after dry, driedly modified montmorillonite usedly break up dispersion further, obtaining by X-ray diffraction method detection layers spacing d001 value is 3.59nm, 850 DEG C of burn tinctuer are the 325 order smectite powder of 24.2%, finished product X ray diffracting spectrum is shown in accompanying drawing 3.
Embodiment 3
A kind of preparation method of feed smectite powder, first by smectite content >=80%, cation exchange total amount (CEC) is 1.0mmol/g montmorillonite powder, d001 value is that the 100g ca-montmorillonite powder of 1.42nm joins in electrical heating oil bath mixed at high speed mixer and is heated with stirring to 85 DEG C, add the solid hexadecyltrimethylammonium chloride by every g montmorillonite 0.7mmol again, with 1000r/min mixed at high speed whip modified 30 minutes under insulation, the dispersant that unnecessary moisture and quaternary ammonium salt bring into is removed 105 DEG C of dryings, drying time to expect that detection 105 DEG C of fugitive constituent≤5% control after dry, driedly modified montmorillonite usedly break up dispersion further, obtaining by X-ray diffraction method detection layers spacing d001 value is 3.27nm, 850 DEG C of burn tinctuer are the 325 order smectite powder of 20.5%, finished product X ray diffracting spectrum is shown in accompanying drawing 4.
Embodiment 4
A kind of preparation method of feed smectite powder, first by smectite content >=80%, cation exchange total amount (CEC) is 0.7mmol/g montmorillonite powder, d001 value is that the 100g na-montmorillonite powder of 1.2nm joins in electrical heating oil bath mixed at high speed mixer and is heated with stirring to 80 DEG C, add the solid dioctadecyl dimethyl ammonium chloride by every g montmorillonite 0.1mmol again, with 1000r/min mixed at high speed whip modified 20 minutes under insulation, the dispersant that unnecessary moisture and quaternary ammonium salt bring into is removed 105 DEG C of dryings, drying time to expect that detection 105 DEG C of fugitive constituent≤5% control after dry, driedly modified montmorillonite usedly break up dispersion further, obtain measuring interlamellar spacing d001 value for 4.05nm by X-ray diffraction method, 850 DEG C of burn tinctuer are the 325 order smectite powder of 5.4%.
Embodiment 5
A kind of preparation method of feed smectite powder, first by smectite content >=80%, cation exchange total amount (CEC) is 1.1mmol/g montmorillonite powder, d001 value is that the 100g ca-montmorillonite powder of 1.5nm joins in electrical heating oil bath mixed at high speed mixer and is heated with stirring to 90 DEG C, add the solid dioctadecyl dimethyl ammonium chloride by every g montmorillonite 1.0mmol again, insulation, with 2000r/min mixed at high speed whip modified 60 minutes, the dispersant that unnecessary moisture and quaternary ammonium salt bring into is removed 105 DEG C of dryings, drying time to expect that detection 105 DEG C of fugitive constituent≤5% control after dry, driedly modified montmorillonite usedly break up dispersion further, obtain measuring interlamellar spacing d001 value for 4.55nm by X-ray diffraction method, 850 DEG C of burn tinctuer are the 325 order smectite powder of 42.1%, finished product X ray diffracting spectrum is shown in accompanying drawing 5.
Embodiment 6
A kind of preparation method of feed smectite powder, first by smectite content >=80%, cation exchange total amount (CEC) is 1.1mmol/g montmorillonite powder, d001 value is that the 100g na-montmorillonite powder of 1.2nm joins in electrical heating oil bath mixed at high speed mixer and is heated with stirring to 80 DEG C, add the solid OTAC by every g montmorillonite 1.0mmol again, insulation, with 1500r/min mixed at high speed whip modified 45 minutes, the dispersant that unnecessary moisture and quaternary ammonium salt bring into is removed 105 DEG C of dryings, drying time to expect that detection 105 DEG C of fugitive constituent≤5% control after dry, driedly modified montmorillonite usedly break up dispersion further, obtain measuring interlamellar spacing d001 value for 3.65nm by X-ray diffraction method, 850 DEG C of burn tinctuer are the 325 order smectite powder of 31.3%.
Embodiment 7
A kind of preparation method of feed smectite powder, first by smectite content >=80%, cation exchange total amount (CEC) is 1.0mmol/g montmorillonite powder, d001 value is that the 100g ca-montmorillonite powder of 1.42nm joins in electrical heating oil bath mixed at high speed mixer and is heated with stirring to 80 DEG C, add the solid OTAC by every g montmorillonite 0.1mmol again, with 1000r/min mixed at high speed whip modified 20 minutes under insulation, the dispersant that unnecessary moisture and quaternary ammonium salt bring into is removed 105 DEG C of dryings, drying time to expect that detection 105 DEG C of fugitive constituent≤5% control after dry, driedly modified montmorillonite usedly break up dispersion further, obtain measuring interlamellar spacing d001 value for 3.15nm by X-ray diffraction method, 850 DEG C of burn tinctuer are the 325 order smectite powder of 6.5%.
Embodiment 8
A kind of preparation method of feed smectite powder, first by smectite content >=80%, cation exchange total amount (CEC) is 1.0mmol/g montmorillonite powder, d001 value is that the 100g ca-montmorillonite powder of 1.42nm joins in electrical heating oil bath mixed at high speed mixer and is heated with stirring to 80 DEG C, add the solid hexadecyltrimethylammonium chloride by every g montmorillonite 0.2mmol again, with 1000r/min mixed at high speed whip modified 25 minutes under insulation, the dispersant that unnecessary moisture and quaternary ammonium salt bring into is removed 105 DEG C of dryings, drying time to expect that detection 105 DEG C of fugitive constituent≤5% control after dry, driedly modified montmorillonite usedly break up dispersion further, obtain measuring interlamellar spacing d001 value for 2.90nm by X-ray diffraction method, 850 DEG C of burn tinctuer are the 325 order smectite powder of 8.1%.
Claims (2)
1. a preparation method for feed smectite powder, is characterized in that it comprises following steps:
(1), the montmorillonite powder of pulverizing is heated to 80-90 DEG C;
(2), add solid quaternary ammonium salt, insulation, high speed whip modified;
(3), by modified montmorillonite dry, break up, obtain X-ray diffraction and detect d
001the large interlamellar spacing feed montmorillonite powder that value is 2.90nm-4.55nm.
2. the preparation method of a kind of smectite powder as claimed in claim 1, it is characterized in that: described step is (1) with its smectite content >=80% of montmorillonite powder, cation exchange total amount (CEC) 0.7 mmol-1.1mmol/g that pulverize, montmorillonite available ca base or na-montmorillonite, grinding particle size d97≤75 μm;
A kind of preparation method of smectite powder as claimed in claim 1, it is characterized in that: (2) described step uses quaternary ammonium salt content >=70% of solid quaternary ammonium salt, quaternary ammonium salt consumption counts 0.1-1.0mmol/g by montmorillonite powder, controls high-speed stirred speed 1000r/min-2000r/min, time 20min-60min during modification;
A modified montmorillonite used powder, preparation method thereof as claimed in claim 1, is characterized in that: described step (3) modified montmorillonite oven dry extent control is 105 DEG C of fugitive constituent≤5%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108142703A (en) * | 2018-02-05 | 2018-06-12 | 湖北喜乐佳生物科技有限公司 | A kind of small swine feed and preparation method thereof |
| CN109287935A (en) * | 2018-09-26 | 2019-02-01 | 深圳市裕农科技股份有限公司 | A kind of mycotoxins in feed adsorbent and its application, feed |
| CN110124617A (en) * | 2019-05-27 | 2019-08-16 | 中国矿业大学(北京) | A kind of vitamin B1Modified montmorillonite used compound fungus endotoxin adsorbent and its preparation method and application |
| CN115137035A (en) * | 2022-07-14 | 2022-10-04 | 浙江维精科技有限公司 | Preparation method of montmorillonite mildew preventive |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108142703A (en) * | 2018-02-05 | 2018-06-12 | 湖北喜乐佳生物科技有限公司 | A kind of small swine feed and preparation method thereof |
| CN109287935A (en) * | 2018-09-26 | 2019-02-01 | 深圳市裕农科技股份有限公司 | A kind of mycotoxins in feed adsorbent and its application, feed |
| CN110124617A (en) * | 2019-05-27 | 2019-08-16 | 中国矿业大学(北京) | A kind of vitamin B1Modified montmorillonite used compound fungus endotoxin adsorbent and its preparation method and application |
| CN110124617B (en) * | 2019-05-27 | 2020-01-17 | 中国矿业大学(北京) | Vitamin B1Modified montmorillonite composite mycotoxin adsorbent and preparation method and application thereof |
| CN115137035A (en) * | 2022-07-14 | 2022-10-04 | 浙江维精科技有限公司 | Preparation method of montmorillonite mildew preventive |
| CN115137035B (en) * | 2022-07-14 | 2024-04-16 | 浙江维精科技有限公司 | Preparation method of montmorillonite mildew inhibitor |
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Application publication date: 20150729 |