CN1826946A - Superfine chromium-supported chromium-replenishing feedstuff addictive, its preparation and application method - Google Patents
Superfine chromium-supported chromium-replenishing feedstuff addictive, its preparation and application method Download PDFInfo
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- CN1826946A CN1826946A CNA2006100503190A CN200610050319A CN1826946A CN 1826946 A CN1826946 A CN 1826946A CN A2006100503190 A CNA2006100503190 A CN A2006100503190A CN 200610050319 A CN200610050319 A CN 200610050319A CN 1826946 A CN1826946 A CN 1826946A
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- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims description 23
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 113
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 82
- 239000011651 chromium Substances 0.000 claims abstract description 82
- 239000000463 material Substances 0.000 claims abstract description 52
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 48
- 239000011707 mineral Substances 0.000 claims abstract description 48
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 6
- 241001494479 Pecora Species 0.000 claims abstract description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 31
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 31
- 239000002002 slurry Substances 0.000 claims description 31
- 239000000725 suspension Substances 0.000 claims description 30
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- 229910021536 Zeolite Inorganic materials 0.000 claims description 27
- 239000010457 zeolite Substances 0.000 claims description 27
- 230000001502 supplementing effect Effects 0.000 claims description 25
- 239000003674 animal food additive Substances 0.000 claims description 24
- 239000004113 Sepiolite Substances 0.000 claims description 23
- 229910052624 sepiolite Inorganic materials 0.000 claims description 23
- 235000019355 sepiolite Nutrition 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 19
- 230000004913 activation Effects 0.000 claims description 15
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 15
- 229910052625 palygorskite Inorganic materials 0.000 claims description 12
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 11
- 230000018044 dehydration Effects 0.000 claims description 11
- 238000006297 dehydration reaction Methods 0.000 claims description 11
- 239000012065 filter cake Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 8
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 230000002194 synthesizing effect Effects 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- -1 boron triethyl sodium hydride Chemical compound 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 5
- 239000012312 sodium hydride Substances 0.000 claims description 5
- 241001465754 Metazoa Species 0.000 claims description 4
- 244000144972 livestock Species 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 150000001844 chromium Chemical class 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 11
- 238000009826 distribution Methods 0.000 abstract description 4
- 239000000843 powder Substances 0.000 abstract description 4
- 231100000053 low toxicity Toxicity 0.000 abstract description 3
- 244000144977 poultry Species 0.000 abstract description 2
- 241000283690 Bos taurus Species 0.000 abstract 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 abstract 1
- 235000010755 mineral Nutrition 0.000 description 30
- NOESYZHRGYRDHS-UHFFFAOYSA-N insulin Chemical compound N1C(=O)C(NC(=O)C(CCC(N)=O)NC(=O)C(CCC(O)=O)NC(=O)C(C(C)C)NC(=O)C(NC(=O)CN)C(C)CC)CSSCC(C(NC(CO)C(=O)NC(CC(C)C)C(=O)NC(CC=2C=CC(O)=CC=2)C(=O)NC(CCC(N)=O)C(=O)NC(CC(C)C)C(=O)NC(CCC(O)=O)C(=O)NC(CC(N)=O)C(=O)NC(CC=2C=CC(O)=CC=2)C(=O)NC(CSSCC(NC(=O)C(C(C)C)NC(=O)C(CC(C)C)NC(=O)C(CC=2C=CC(O)=CC=2)NC(=O)C(CC(C)C)NC(=O)C(C)NC(=O)C(CCC(O)=O)NC(=O)C(C(C)C)NC(=O)C(CC(C)C)NC(=O)C(CC=2NC=NC=2)NC(=O)C(CO)NC(=O)CNC2=O)C(=O)NCC(=O)NC(CCC(O)=O)C(=O)NC(CCCNC(N)=N)C(=O)NCC(=O)NC(CC=3C=CC=CC=3)C(=O)NC(CC=3C=CC=CC=3)C(=O)NC(CC=3C=CC(O)=CC=3)C(=O)NC(C(C)O)C(=O)N3C(CCC3)C(=O)NC(CCCCN)C(=O)NC(C)C(O)=O)C(=O)NC(CC(N)=O)C(O)=O)=O)NC(=O)C(C(C)CC)NC(=O)C(CO)NC(=O)C(C(C)O)NC(=O)C1CSSCC2NC(=O)C(CC(C)C)NC(=O)C(NC(=O)C(CCC(N)=O)NC(=O)C(CC(N)=O)NC(=O)C(NC(=O)C(N)CC=1C=CC=CC=1)C(C)C)CC1=CN=CN1 NOESYZHRGYRDHS-UHFFFAOYSA-N 0.000 description 14
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 239000002105 nanoparticle Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 8
- 102000004877 Insulin Human genes 0.000 description 7
- 108090001061 Insulin Proteins 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 229940125396 insulin Drugs 0.000 description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 7
- 239000002808 molecular sieve Substances 0.000 description 6
- 239000002734 clay mineral Substances 0.000 description 5
- 239000011229 interlayer Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
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- 238000004519 manufacturing process Methods 0.000 description 4
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- 239000000243 solution Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 102000002322 Egg Proteins Human genes 0.000 description 3
- 108010000912 Egg Proteins Proteins 0.000 description 3
- XRSBTDBLFNPGOE-UHFFFAOYSA-M O[Cr] Chemical compound O[Cr] XRSBTDBLFNPGOE-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000004071 biological effect Effects 0.000 description 3
- 210000004369 blood Anatomy 0.000 description 3
- 239000008280 blood Substances 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- VTNXYFSWTADICO-UHFFFAOYSA-N chromium 2-methylpyridine Chemical compound [Cr].CC1=NC=CC=C1 VTNXYFSWTADICO-UHFFFAOYSA-N 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 210000002969 egg yolk Anatomy 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000012000 cholesterol Nutrition 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 235000013345 egg yolk Nutrition 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 230000036039 immunity Effects 0.000 description 2
- 235000020997 lean meat Nutrition 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 150000001457 metallic cations Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 210000002966 serum Anatomy 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000206761 Bacillariophyta Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000287828 Gallus gallus Species 0.000 description 1
- 108010001483 Glycogen Synthase Proteins 0.000 description 1
- 229910003849 O-Si Inorganic materials 0.000 description 1
- 229910003872 O—Si Inorganic materials 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 210000000577 adipose tissue Anatomy 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 1
- 239000010868 animal carcass Substances 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 229940090012 bentyl Drugs 0.000 description 1
- 230000008827 biological function Effects 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- HPCCGRCEBFBZQP-UHFFFAOYSA-N chromium;pyridine-3-carboxylic acid Chemical compound [Cr].OC(=O)C1=CC=CN=C1 HPCCGRCEBFBZQP-UHFFFAOYSA-N 0.000 description 1
- 229910001603 clinoptilolite Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 230000037213 diet Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 235000013601 eggs Nutrition 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 210000001035 gastrointestinal tract Anatomy 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000008799 immune stress Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
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- 239000011147 inorganic material Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 210000004698 lymphocyte Anatomy 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
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- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 229910052665 sodalite Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 210000000952 spleen Anatomy 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses feed addictive carrying super fine chromium and the preparing and usage method. The super fine chromium is carried by porous mineral material, the average grain size of chromium is smaller than100 nanometer, and the chromium content in the porous mineral material is 0.05-0.5% by weight percent. The invention employs porous mineral material as microreactor, and adds reducer to reduce chromate salt to chromium. The bore diameter of porous material is uniform, and so the distribution of grain size of chromium is narrow. The chromium powder is characterized by low toxicity and high effective, and can be used for cow, sheep, poultry and aquatic creature, and the powder is easy to mix with feed stuff.
Description
Technical field
The present invention relates to a kind of chromium supplementing feed additive having and preparation and using method of carried type, super-fine chromium, is chromium supplementing feed additive having and the preparation and the using method of the ultra-fine chromium powder of a kind of porous mineral material load specifically.
Background technology
Trace element chromium is a kind of transition metal of being found first by french chemist (Louis Vanquelin) in 1797.Nineteen fifty-seven Mertz and Schwarz propose glucose tolerance factor first, and (nineteen fifty-nine confirms that chromium is rat growth and the indispensable element of keeping GTF for glucose tolerance factor, GTF) hypothesis.The biological function of chromium:
(1) immunocompetence of raising animal: can stimulate lymphocyte after in feed, adding chromium, thereby produce the immunological stress product, improve the immunity of animal.
(2) improve the animal carcass quality: studies show that in a large number, mend chromium and can improve lean meat percentage, reduce fat, improve carcass quality.Lindemann etc. (1993) report: to store pig additional 0.1 or 0.2mg/kg chromium (methylpyridine chromium), eye muscle area and lean meat percentage improve 18% and 7% respectively, and protein content increases, and fat content reduces, and the tenth rib place thickness of backfat descends 21%.Chromium is that the important component part as insulin GTF (GTF) increases the sensitiveness to insulin, thereby reaches the effect that reduces serum insulin.The effect of insulin also has the fat of promotion synthetic except that reducing blood sugar, suppresses fat-splitting effect.
(3) cholesterol in the reduction egg: according to research reports, mend chromium and can improve the living fat speed of laying hen (comprising that aliphatic acid and glycerine are synthetic); Strengthen production performance, improve the egg protein amount, reduce the laying hen blood cholesterol levels.Lien etc. (1996) report, 0.22,0.4,0.8mg/kg in coming carrier's product layer diets in vain, adds the Organic Chromium (methylpyridine chromium) of varying level:, can make the cholesterol level in the yolk reduce by 14%, 29% and 34% respectively, and little to the laying rate influence.Chi Xinliang (2000) research thinks that trivalent chromium can stimulate glycogen synthetase and insulin active, and with GTF performance biological effect, because chromium is the reinforcing agent of insulin, insulin can promote body fat to store, suppress the hydrolysis of depot lipid, make free aliphatic acid minimizing in the blood, cholesterol level also reduces thereupon, and the cholesterol level in the egg yolk is from chicken serum, so the cholesterol in the egg yolk also reduces thereupon.
Chromium supplementing agent commonly used has chromium chloride, methylpyridine chromium, nicotinic acid chromium, yeast chromium etc.Yet, all the biological effect of chromium powder is not studied both at home and abroad.Existing research report, copper powder, metal iron powder have biological effect; And their biological value is relevant with the granularity of powder.Zhao Qiuyan (2001) has summarized the influence of iron particle size to the relative biology utilization rate of iron powder in the food, the relative biology utilization rate of 10～20 μ m, 43 μ m, 147 μ m reduced iron powders is respectively 54%, 34% and 18%, shows that the granularity that reduces iron powder can significantly improve its biology utilization rate.Chinese patent (application number 03133894.1, Granted publication CN1194668C) discloses the application of a kind of copper nanoparticle as the preparation medicament for immunity enhancement.Studies show that in a large number that in recent years the simple substance selenium of particle diameter below 200 nanometers is compared with general simple substance selenium, and the variation of essence has taken place: take place " red shift " or " blue shift ", color shows as red or orange; Become from inertia and can directly efficiently remove free radical; From the inanimate object activity become efficiently, low toxicity.But along with copper powder, metal iron powder is equigranular reduces, its non-oxidizability also decreases, and the contradiction that therefore how to solve granularity and stability is a great problem in the superfine powder practical application.
Hard template method synthesis of nano structural system, be grow up the mid-90 in 20th century a kind of new technology of constructing nanostructured by self assembly, promptly utilize and have nanometer level microporous template (being commonly called as nano die), select suitable deposition technique, directly synthesis of nano structure in the micropore of template; Because nib pore size unanimity, the material of preparation has the mono-dispersed nano structure, and synthetic method is comparatively simple, and the material of preparation is applied to many aspects such as medicine release, photocatalysis, molecular separation and bioengineering and has extremely wide application prospect.
The porous mineral material is meant that those have the mineral of abundant structures duct or pore structure, comprises natural porous mineral material and artificial synthesizing porous mineral material.The porous mineral material comprises that mainly zeolite and correlation molecule sieve material, sepiolite group clay mineral, layer column type porous material (adobe material and porous laminated dihydroxylated thing (hydrotalcite) material) etc., can show the dimensional effect and the skin effect of portalling.The porous mineral material possesses even or approximate uniform duct, aperture and opening structure, and its nanochannel structure can be used as " miniature nano-reactor ", as carrier and the media of making the nanostructured assembled material.Utilize the porous mineral material as " microreactor of confinement " nano materials, the nano material of preparation has narrow grain size and distributes, and is expected to solve preferably nano particle and reunites and stability problem suitability for industrialized production.
Summary of the invention
The chromium supplementing feed additive having and preparation and the using method that the purpose of this invention is to provide a kind of carried type, super-fine chromium.
The chromium supplementing feed additive having of carried type, super-fine chromium is the ultra-fine chromium powder of a kind of porous mineral material load, and the average grain diameter of ultra-fine chromium powder is less than 100 nanometers, and by weight percentage, the content of chromium in the porous mineral material is 0.05～0.5%.
The preparation method of the chromium supplementing feed additive having of carried type, super-fine chromium may further comprise the steps:
1) the porous mineral material is ground to greater than 300 orders, adds water and stir, make concentration and be 1%～10% suspension slurry;
2) with chrome content be the chromic salts of porous mineral material weight 0.05～0.5%, be pre-configured to the aqueous solution of chromium salt of 0.1～1mol/L, in stirring the suspension slurry that slowly adds step 1) down, adding molar ratio again is the reducing agent of 3～6 times of chromic salts, and 40～80 ℃ were reacted 5～15 hours;
3) the centrifugal or filtering means dehydration of suspension slurry step 2);
4) filter cake of step 3) gained is dried, is crushed to greater than 300 orders, obtain the chromium supplementing feed additive having of carried type, super-fine chromium.
The said porous mineral material of the present invention is natural porous mineral material or artificial synthesizing porous mineral material, natural porous mineral material can be natural zeolite, montmorillonite, diatomite, sepiolite or palygorskite, and artificial synthesizing porous mineral material can be synthetic zeolite, pillared montmorillonite, acid activation sepiolite, acid activation palygorskite, mesoporous silicon oxide.Said chromic salts can be chromium chloride, chromic nitrate or chromium sulfate.Said reducing agent can be boron triethyl sodium hydride, sodium borohydride or potassium borohydride.
Preparation method's slurries dewatering process can be suited measures to local conditions, and selects for use centrifugal or method such as filtration is dewatered.The filter cake of dehydration back gained can use conventional drying plant drying.The chromium supplementing feed additive having of the carried type, super-fine chromium after the oven dry is block, can select for use conventional disintegrating apparatus to be crushed to granularity greater than 300 orders.
The using method of the chromium supplementing feed additive having of carried type, super-fine chromium is: the dosage by the 0.1～1.0mg/kg that accounts for the feed gross weight (in chromium) is added in aquatic livestock, ox, sheep, the animal and fowl fodder.
The present invention has the following advantages:
(1) the present invention utilizes the porous mineral material as " microreactor of confinement " synthetic carried type, super-fine chromium powder, the pore size unanimity of porous mineral material, therefore the carried type, super-fine chromium powder of preparation has narrow grain size distribution, and solved preferably that nano particle is reunited and stability problem, suitability for industrialized production.
(2) the porous mineral material has good biocompatibility and gastrointestinal tract mucous compatibility, and characteristics such as high surface and huge specific area make it that the ultra-fine chromium powder of institute's load is had the control slow releasing function, thereby improved the absorption rate of chromium greatly.
(3) the prepared carried type, super-fine chromium powder of the present invention has low toxicity, characteristics of high efficiency, can be applicable to the benefit chromium of livestock and poultry, aquatic livestock etc., and the carried type, super-fine chromium powder is easy to mix with feed, forms even disperse system, and is easy to use.The specific embodiment
Because the nano particle specific surface energy is very high, if do not handled in preparation process, the nano particle that obtains has often been lost the due many character of nano particle because of reunion, makes its research and use all to be restricted.In order to overcome the reunion of nano particle, generally all in course of reaction by adding stabilizing agent, be coated on the surface of nano particle as polymer, surfactant etc., reduce its surperficial energy.In recent years, utilizing the confinement effect of nano-reactor, is reaction medium as the nanometer watercore at capsule and microemulsion droplets center, the nano particle of can evenly be disperseed, particle diameter is less.Equally, the porous mineral material that has nano pore on some structure is also to have the confinement effect, can be used as carrier and the media of making the nanostructured assembled material.The present invention utilizes the nano pore structure of porous mineral material as " microreactor of confinement ", chromic salts is added the reducing agent reduction generate ultra-fine chromium powder, the pore size unanimity of porous mineral material, therefore the carried type, super-fine chromium powder of preparation has narrow grain size distribution, and has solved nano particle reunion and stability problem preferably.
The nano-pore mineral material comprises that mainly zeolite and correlation molecule sieve material, sepiolite group clay mineral, layer column type porous material etc.The natural porous mineral material that the present invention uses, as natural zeolite, montmorillonite, diatomite, sepiolite or palygorskite, its place of production and content do not have specific (special) requirements.The artificial synthesizing porous mineral material that uses among the present invention, as synthetic zeolite, pillared montmorillonite, acid activation sepiolite, acid activation palygorskite, mesoporous silicon oxide, can be the commercial goods, also can be according to prior art for preparing, its technology of preparing is well-known.
Zeolite is natural existence of a class or the artificial synthetic alumino-silicate with regular pore canal structure, and its chemical composition is: M
2/nAl
2O
3XxSiO
2YH
2O, wherein M represents metal cation, and n is the valence state of metal cation, and x is a silica alumina ratio, and y is the saturation moisture subnumber.Natural zeolite is because of minerogentic condition difference complex structure, and artificial synthetic zeolite molecular sieve is simple in structure, controlled.In the structure of zeolite, SiO
4Become the polyhedron of various forms with the Al04 tetrahedron by the crystal chemistry principle combinations, just constituted the porous basket structure of zeolite in spatial arrangement and combination.Modal in the basket structure of zeolite is that α cage (main body of A type zeolite), β cage (constitute the unique cage of sodalite, the main body of y-type zeolite), the size of these cages is from several dusts to tens dust, have a duct to link to each other between cage and the cage, these ducts and cage are evenly distributed in the crystal by certain orientation.For a kind of zeolite molecular sieve, its aperture is certain, and the spatial distribution mode is also certain.Therefore people claim that zeolite is a kind of miniature nano-reactor, and they have same size and form all as the nanometer test tube, provide template for forming size nano material single, that be evenly distributed.
Montmorillonite is the silicate mineral with nanometer laminated structure and since have big inner surface as reactor and in the aqueous solution good swellability, be particularly useful for making load nano particle thereon with narrow particle diameter and polymolecularity.The interlamination region of montmorillonite also has the pillared characteristic of interlayer except character such as interlayer exchange with general clay mineral interlamination region, interlayer absorption, interlayer catalysis, interlayer polymerization.Pillared montmorillonite is exactly by pillaring agent or claims crosslinking agent (the macrocation group of organic or inorganic) by ion-exchange method or directly enter between montmorillonite layer, make the novel lamellar aluminium silicate mineral that " post " shape supports that is that montmorillonite mineral interlamination region microenvironment changes, have big specific area, big aperture and high surface-active.Pillaring agent (or crosslinking agent) can be quaternary ammonium alkyl ion and bentyl cation, also can be metallo-chelate or multinuclear hydroxy metal cation.The present invention is the pillared montmorillonite of single element polymer/metallic cation preferably, as Al-pillared montmorillonite, Cr-pillared montmorillonite, Ti-pillared montmorillonite, Fe-pillared montmorillonite, and the pillared montmorillonite of multielement polymer/metallic cation, as Fe-Al-pillared montmorillonite, Cu-Al-pillared montmorillonite.
Diatomite is that the remains of the Diatomeae that grows in ocean or the lake are at subaqueous deposit, through the natural environment effect and a kind of nonmetallic mineral that forms gradually.The diatomite specific surface is big, and the porosity height has unique nanometer micropore structure.
Sepiolite is the moisture magnesium silicate clay mineral of a kind of natural fiber shape, has the transiens feature of stratiform and chain structure, and is not only cheap, the specific area height, and have the characteristic of molecular sieve analog.The acid treatment of adopting at present is generally strong acid, as HNO
3, H
2SO
4And HCl etc.Different strong acid are basic identical to the processing mechanism of sepiolite, are H
+Replace the Mg in the skeleton
2+, sepiolite has become two Si-OH keys through its Si-O-Mg-O-Si key of acid treatment, the structure of " we opens " state promptly occurred, and this moment, the inner passage was connected, and surface area increases.
Attapulgite (palygorskite) is to have chain layered crystal structure zeopan clay mineral, present the about 30～40nm of diameter, length can reach several microns rhabdolith form, be the abundant natural nano-mineral material of output, show nano effect, adsorption activity and chemism.Palygorskite acid activation effect mainly shows as two aspects: the one, and the depolymerization between fibre bundle is mainly the decomposition of intergranular impurity cement, and the 2nd, to cationic extraction, i.e. H
+To octahedra middle-jiao yang, function of the spleen and stomach ION Mg
2+, Fe
3+, Al
3+Displacement successively by edge to center (is mainly Mg
2+).Because H
+To cationic displacement in the crystal, long radius is cationic to be separated out and causes that microvoid increases, specific area increases.And the displacement of the different valency isomorphism of acid activation palygorskite grows, and the crystal growth defective is extremely grown, by crystal growth theories as can be known these defective bit be that plane of crystal can accumulation regions, thereby make it have higher absorption property.
The present invention is further described in conjunction with following example.
Embodiment 1
1) montmorillonite that will originate from the Inner Mongol is ground to 300 orders, adds water and stirs, and makes concentration and be 10% suspension slurry;
2) with chrome content be the chromium chloride of montmorillonite weight 0.05%, be pre-configured to the chromium chloride solution of 0.1mol/L, in stirring the suspension slurry that slowly adds step 1) down, slowly adding molar ratio again is the sodium borohydride of 3 times of chromium chlorides, and 40 ℃ were reacted 15 hours;
3) suspension slurry centrifugal dehydration step 2);
4) filter cake of step 3) gained is dried, is crushed to 300 orders, obtain the chromium supplementing feed additive having of carried type, super-fine chromium.
Transmission electron microscope observing shows the average grain diameter 10nm of montmorillonite-loaded ultra-fine chromium powder, and particle diameter is distributed between 5～25nm.By weight percentage, the content of chromium in montmorillonite is 0.05%.
Embodiment 2
1) clinoptilolite that will originate from Jinyun county, Zhejiang province is ground to 400 orders, adds water and stirs, and makes concentration and be 1% suspension slurry;
2) be the chromic nitrate of zeolite weight 0.1% with chrome content, be pre-configured to the chromium nitrate aqueous solution of 1mol/L, in stirring the suspension slurry that slowly adds step 1) down, slowly adding molar ratio again is the potassium borohydride of 6 times of chromic nitrates, and 80 ℃ were reacted 10 hours;
3) suspension slurry filtering means dehydration step 2);
4) filter cake of step 3) gained is dried, is crushed to 500 orders, obtain the chromium supplementing feed additive having of carried type, super-fine chromium.
Transmission electron microscope observing shows the average grain diameter 18nm of zeolite-loaded ultra-fine chromium powder, and particle diameter is distributed between 12～28nm.By weight percentage, the content of chromium in zeolite is 0.1%.
Embodiment 3
1) commercially available ZSM-5 type zeolite molecular sieve is ground to 500 orders, adds water and stir, make concentration and be 5% suspension slurry;
2) with chromium content be the chromium sulfate of zeolite weight 0.2%, be pre-configured to the chromium sulfate aqueous solution of 0.5mol/L, in stirring the suspension slurry that slowly adds step 1) down, slowly adding molar ratio again is the boron triethyl sodium hydride of 3 times of chromium sulfates, and 80 ℃ were reacted 5 hours;
3) suspension slurry filtering means dehydration step 2);
4) filter cake of step 3) gained is dried, is crushed to 500 orders, obtain the chromium supplementing feed additive having of carried type, super-fine chromium.
Transmission electron microscope observing shows the average grain diameter 35nm of zeolite-loaded chromium powder, and particle diameter is distributed between 27～65nm.By weight percentage, the content of chromium in zeolite is 0.2%.
Embodiment 4
1) sepiolite that will originate from Jiangxi is ground to 600 orders, adds water and stirs, and makes concentration and be 3% suspension slurry;
2) with chrome content be the chromium chloride of sepiolite weight 0.25%, be pre-configured to the chromium chloride solution of 0.8mol/L, in stirring the suspension slurry that slowly adds step 1) down, slowly adding molar ratio again is the boron triethyl sodium hydride of 5 times of chromium chlorides, and 80 ℃ were reacted 5 hours;
3) suspension slurry centrifugal dehydration step 2);
4) filter cake of step 3) gained is dried, is crushed to 500 orders, obtain the chromium supplementing feed additive having of carried type, super-fine chromium.
Transmission electron microscope observing shows the average grain diameter 35nm of sepiolite supported ultra-fine chromium powder, and particle diameter is distributed between 20～50nm.By weight percentage, the content of chromium in sepiolite is 0.25%.
Embodiment 5
The preparation: according to " hydroxyl chromium aluminium pillared montmorillonite Keggin stability of structure " (Wu Pingxiao, Zhang Huifen, Guo Jiugao, Wang Fuya. the mineral journal, 1999, method 19:132-138) prepares hydroxyl chromium aluminium pillared montmorillonite.
1) the hydroxyl chromium aluminium pillared montmorillonite that obtains in the preliminary step is ground to 400 orders, adds water and stir, make concentration and be 1% suspension slurry;
2) with chrome content be the chromium chloride of pillared montmorillonite weight 0.5%, be pre-configured to the chromium chloride solution of 1mol/L, in stirring the suspension slurry that slowly adds step 1) down, slowly adding molar ratio again is the sodium borohydride of 5 times of chromium chlorides, and 60 ℃ were reacted 5 hours;
3) suspension slurry centrifugal dehydration step 2);
4) filter cake of step 3) gained is dried, is crushed to 400 orders, obtain the chromium supplementing feed additive having of carried type, super-fine chromium.
Transmission electron microscope observing shows the average grain diameter 30nm of the ultra-fine chromium powder of pillared montmorillonite load, and particle diameter is distributed between 25～50nm.By weight percentage, the content of chromium in pillared montmorillonite is 0.5%.
Embodiment 6
The preparation: according to " acidity of sepiolite and performance study I: the structure of modification course and modified product " (Jiang Wenbin, Liu Deyi, Tu Shiying. petroleum journal (PETROLEUM PROCESSING), 1994,10:29～35) method prepare the acid activation sepiolite.
1) the acid activation sepiolite that obtains in the preliminary step is ground to 400 orders, adds water and stir, make concentration and be 2% suspension slurry;
2) with chromium content be the chromium chloride of acid activation sepiolite weight 0.05%, be pre-configured to the chromium chloride solution of 0.1mol/L, in stirring the suspension slurry that slowly adds step 1) down, slowly adding molar ratio again is the boron triethyl sodium hydride of 3 times of chromium chlorides, and 80 ℃ were reacted 10 hours;
3) suspension slurry filtering means dehydration step 2);
4) filter cake of step 3) gained is dried, is crushed to 500 orders, obtain the chromium supplementing feed additive having of carried type, super-fine chromium.
Transmission electron microscope observing shows the average grain diameter 28nm of the ultra-fine chromium powder that acid activation is sepiolite supported, and particle diameter is distributed between 15～45nm.By weight percentage, the content of chromium in the acid activation sepiolite is 0.05%.
Embodiment 7
The preparation: according to " Preparation of monodisperse nanosized mesoporous silica " (Liang Yan, Jinsong ZHANG, Zhang Junqi. the investigation of materials journal, 2004, method 18:149-154) prepares mesoporous nano silicon dioxide.
1) mesoporous nano silicon dioxide that obtains in the preliminary step is ground to 300 orders, adds water and stir, make concentration and be 5% suspension slurry;
2) with chrome content be the chromium sulfate of mesoporous silicon oxide weight 0.4%, be pre-configured to the chromium sulfate aqueous solution of 0.5mol/L, in stirring the suspension slurry that slowly adds step 1) down, slowly adding molar ratio again is the potassium borohydride of 5 times of chromium sulfates, and 60 ℃ were reacted 5 hours;
3) suspension slurry filtering means dehydration step 2);
4) filter cake of step 3) gained is dried, is crushed to 400 orders, obtain the chromium supplementing feed additive having of carried type, super-fine chromium.
Transmission electron microscope observing shows the average grain diameter 58nm of the ultra-fine chromium powder of mesoporous silicon oxide load, and particle diameter is distributed between 35～78nm.By weight percentage, the content of chromium in mesoporous silicon oxide is 0.4%.
Embodiment 8
The preparation: according to " modification of mesopore molecular sieve MCM-41 and sign under the temperate condition " (Zheng Shan, high Lian, Guo Jingkun. Journal of Inorganic Materials, 2000,15 (5): method 844-848) prepares mesopore molecular sieve MCM-41.
1) the mesopore molecular sieve MCM-41 that obtains in the preliminary step is ground to 300 orders, adds water and stir, make concentration and be 4% suspension slurry;
2) with chrome content be the chromic nitrate of MCM-41 weight 0.5%, be pre-configured to the chromium nitrate aqueous solution of 0.5mol/L, in stirring the suspension slurry that slowly adds step 1) down, slowly adding molar ratio again is the potassium borohydride of 6 times of chromic nitrates, and 60 ℃ were reacted 15 hours;
3) suspension slurry filtering means dehydration step 2);
4) filter cake of step 3) gained is dried, is crushed to 500 orders, obtain the chromium supplementing feed additive having of carried type, super-fine chromium.
Transmission electron microscope observing shows the average grain diameter 40nm of the chromium powder of MCM-41 load, and particle diameter is distributed between 25～60nm.By weight percentage, the content of chromium in MCM-41 is 0.5%.
Claims (7)
1. the chromium supplementing feed additive having of a carried type, super-fine chromium, it is characterized in that it is the ultra-fine chromium powder of a kind of porous mineral material load, the average grain diameter of ultra-fine chromium powder is less than 100 nanometers, by weight percentage, the content of chromium in the porous mineral material is 0.05～0.5%.
2. the chromium supplementing feed additive having of a kind of carried type, super-fine chromium according to claim 1, it is characterized in that, said porous mineral material is natural porous mineral material or artificial synthesizing porous mineral material, natural porous mineral material is natural zeolite, montmorillonite, diatomite, sepiolite or palygorskite, and artificial synthesizing porous mineral material is synthetic zeolite, pillared montmorillonite, acid activation sepiolite, acid activation palygorskite or mesoporous silicon oxide.
3. the preparation method of the chromium supplementing feed additive having of a carried type, super-fine chromium as claimed in claim 1 is characterized in that its step is as follows:
1) the porous mineral material is ground to greater than 300 orders, adds water and stir, make concentration and be 1%～10% suspension slurry;
2) with chrome content be the chromic salts of porous mineral material weight 0.05～0.5%, be pre-configured to the aqueous solution of chromium salt of 0.1～1mol/L, in stirring the suspension slurry that slowly adds step 1) down, adding molar ratio again is the reducing agent of 3～6 times of chromic salts, and 40～80 ℃ were reacted 5～15 hours;
3) the centrifugal or filtering means dehydration of suspension slurry step 2);
4) filter cake of step 3) gained is dried, is crushed to greater than 300 orders, obtain the chromium supplementing feed additive having of carried type, super-fine chromium.
4. the preparation method of a kind of carried type, super-fine chromium powder according to claim 3, it is characterized in that, said porous mineral material is natural porous mineral material or artificial synthesizing porous mineral material, natural porous mineral material is natural zeolite, montmorillonite, diatomite, sepiolite or palygorskite, and artificial synthesizing porous mineral material is synthetic zeolite, pillared montmorillonite, acid activation sepiolite, acid activation palygorskite or mesoporous silicon oxide.
5. the preparation method of the chromium supplementing feed additive having of a kind of carried type, super-fine chromium according to claim 3 is characterized in that, said chromic salts is chromium chloride, chromic nitrate or chromium sulfate.
6. the preparation method of the chromium supplementing feed additive having of a kind of carried type, super-fine chromium according to claim 3 is characterized in that, said reducing agent is boron triethyl sodium hydride, sodium borohydride or potassium borohydride.
7, a kind of using method of chromium supplementing feed additive having of carried type, super-fine chromium as claimed in claim 1 is characterized in that being added in aquatic livestock, ox, sheep, the animal and fowl fodder in the dosage of chromium by the 0.1～1.0mg/kg that accounts for the feed gross weight.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101507470B (en) * | 2009-03-16 | 2012-05-30 | 浙江大学 | Preparation method of nano chrome additive |
| CN106173197A (en) * | 2015-04-30 | 2016-12-07 | 扬州中微生物技术有限公司 | A kind of iron phosphate feed additive and its production and use |
| CN115053937A (en) * | 2022-06-20 | 2022-09-16 | 浙江惠嘉生物科技股份有限公司 | Preparation method of chromium nicotinate nano dispersion preparation |
-
2006
- 2006-04-12 CN CNA2006100503190A patent/CN1826946A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101507470B (en) * | 2009-03-16 | 2012-05-30 | 浙江大学 | Preparation method of nano chrome additive |
| CN106173197A (en) * | 2015-04-30 | 2016-12-07 | 扬州中微生物技术有限公司 | A kind of iron phosphate feed additive and its production and use |
| CN115053937A (en) * | 2022-06-20 | 2022-09-16 | 浙江惠嘉生物科技股份有限公司 | Preparation method of chromium nicotinate nano dispersion preparation |
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