CN1826943A - Sustained-releasing sulfur supplementing agent, its preparation method and uses - Google Patents
Sustained-releasing sulfur supplementing agent, its preparation method and uses Download PDFInfo
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- CN1826943A CN1826943A CNA2006100501091A CN200610050109A CN1826943A CN 1826943 A CN1826943 A CN 1826943A CN A2006100501091 A CNA2006100501091 A CN A2006100501091A CN 200610050109 A CN200610050109 A CN 200610050109A CN 1826943 A CN1826943 A CN 1826943A
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- CN
- China
- Prior art keywords
- hydrotalcite
- sulfur
- controlled release
- release type
- supplementary agent
- Prior art date
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Links
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000011593 sulfur Substances 0.000 title claims abstract description 41
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 41
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims description 13
- 230000001502 supplementing effect Effects 0.000 title 1
- 230000002459 sustained effect Effects 0.000 title 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 claims abstract description 45
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 44
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 13
- 150000001450 anions Chemical class 0.000 claims abstract description 12
- 241001494479 Pecora Species 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 244000144977 poultry Species 0.000 claims abstract description 7
- 239000005864 Sulphur Substances 0.000 claims description 43
- 238000013270 controlled release Methods 0.000 claims description 27
- 239000002002 slurry Substances 0.000 claims description 22
- 239000000725 suspension Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 14
- 244000144972 livestock Species 0.000 claims description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 8
- 230000018044 dehydration Effects 0.000 claims description 8
- 238000006297 dehydration reaction Methods 0.000 claims description 8
- 239000012065 filter cake Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 230000008901 benefit Effects 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 11
- 210000002268 wool Anatomy 0.000 abstract description 11
- 241000283973 Oryctolagus cuniculus Species 0.000 abstract description 9
- 210000004209 hair Anatomy 0.000 abstract description 5
- 239000011229 interlayer Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 210000001035 gastrointestinal tract Anatomy 0.000 abstract description 2
- 241000283690 Bos taurus Species 0.000 abstract 1
- 210000004877 mucosa Anatomy 0.000 abstract 1
- 230000002687 intercalation Effects 0.000 description 7
- 238000009830 intercalation Methods 0.000 description 7
- 239000003814 drug Substances 0.000 description 6
- 235000001014 amino acid Nutrition 0.000 description 5
- 150000001413 amino acids Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229930182817 methionine Natural products 0.000 description 5
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 4
- 241001465754 Metazoa Species 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 235000018102 proteins Nutrition 0.000 description 4
- 108090000623 proteins and genes Proteins 0.000 description 4
- 102000004169 proteins and genes Human genes 0.000 description 4
- -1 sulfuric acid ester Chemical class 0.000 description 4
- 108020004414 DNA Proteins 0.000 description 3
- 241000282849 Ruminantia Species 0.000 description 3
- 230000010412 perfusion Effects 0.000 description 3
- YBJHBAHKTGYVGT-ZKWXMUAHSA-N (+)-Biotin Chemical compound N1C(=O)N[C@@H]2[C@H](CCCCC(=O)O)SC[C@@H]21 YBJHBAHKTGYVGT-ZKWXMUAHSA-N 0.000 description 2
- LEVWYRKDKASIDU-QWWZWVQMSA-N D-cystine Chemical compound OC(=O)[C@H](N)CSSC[C@@H](N)C(O)=O LEVWYRKDKASIDU-QWWZWVQMSA-N 0.000 description 2
- HTTJABKRGRZYRN-UHFFFAOYSA-N Heparin Chemical compound OC1C(NC(=O)C)C(O)OC(COS(O)(=O)=O)C1OC1C(OS(O)(=O)=O)C(O)C(OC2C(C(OS(O)(=O)=O)C(OC3C(C(O)C(O)C(O3)C(O)=O)OS(O)(=O)=O)C(CO)O2)NS(O)(=O)=O)C(C(O)=O)O1 HTTJABKRGRZYRN-UHFFFAOYSA-N 0.000 description 2
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 description 2
- 102000011782 Keratins Human genes 0.000 description 2
- 108010076876 Keratins Proteins 0.000 description 2
- 210000003165 abomasum Anatomy 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229960003067 cystine Drugs 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920000669 heparin Polymers 0.000 description 2
- 229960002897 heparin Drugs 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 125000001741 organic sulfur group Chemical group 0.000 description 2
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 2
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 2
- 108090000765 processed proteins & peptides Proteins 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 210000004767 rumen Anatomy 0.000 description 2
- ONFOSYPQQXJWGS-UHFFFAOYSA-N 2-hydroxy-4-(methylthio)butanoic acid Chemical compound CSCCC(O)C(O)=O ONFOSYPQQXJWGS-UHFFFAOYSA-N 0.000 description 1
- SQDAZGGFXASXDW-UHFFFAOYSA-N 5-bromo-2-(trifluoromethoxy)pyridine Chemical compound FC(F)(F)OC1=CC=C(Br)C=N1 SQDAZGGFXASXDW-UHFFFAOYSA-N 0.000 description 1
- 229920002567 Chondroitin Polymers 0.000 description 1
- 229920001287 Chondroitin sulfate Polymers 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 102000053602 DNA Human genes 0.000 description 1
- 101710088194 Dehydrogenase Proteins 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000371 Esterases Proteins 0.000 description 1
- 102000008946 Fibrinogen Human genes 0.000 description 1
- 108010049003 Fibrinogen Proteins 0.000 description 1
- 229920002683 Glycosaminoglycan Polymers 0.000 description 1
- 229910001051 Magnalium Inorganic materials 0.000 description 1
- CMWTZPSULFXXJA-UHFFFAOYSA-N Naproxen Natural products C1=C(C(C)C(O)=O)C=CC2=CC(OC)=CC=C21 CMWTZPSULFXXJA-UHFFFAOYSA-N 0.000 description 1
- WBWWGRHZICKQGZ-UHFFFAOYSA-N Taurocholic acid Natural products OC1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(=O)NCCS(O)(=O)=O)C)C1(C)C(O)C2 WBWWGRHZICKQGZ-UHFFFAOYSA-N 0.000 description 1
- JZRWCGZRTZMZEH-UHFFFAOYSA-N Thiamine Natural products CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N JZRWCGZRTZMZEH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 235000019728 animal nutrition Nutrition 0.000 description 1
- 229940121363 anti-inflammatory agent Drugs 0.000 description 1
- 239000002260 anti-inflammatory agent Substances 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229960000074 biopharmaceutical Drugs 0.000 description 1
- 235000020958 biotin Nutrition 0.000 description 1
- 229960002685 biotin Drugs 0.000 description 1
- 239000011616 biotin Substances 0.000 description 1
- 230000023852 carbohydrate metabolic process Effects 0.000 description 1
- 235000021256 carbohydrate metabolism Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- DLGJWSVWTWEWBJ-HGGSSLSASA-N chondroitin Chemical compound CC(O)=N[C@@H]1[C@H](O)O[C@H](CO)[C@H](O)[C@@H]1OC1[C@H](O)[C@H](O)C=C(C(O)=O)O1 DLGJWSVWTWEWBJ-HGGSSLSASA-N 0.000 description 1
- 229940059329 chondroitin sulfate Drugs 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 210000002808 connective tissue Anatomy 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229960001259 diclofenac Drugs 0.000 description 1
- DCOPUUMXTXDBNB-UHFFFAOYSA-N diclofenac Chemical compound OC(=O)CC1=CC=CC=C1NC1=C(Cl)C=CC=C1Cl DCOPUUMXTXDBNB-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003797 essential amino acid Substances 0.000 description 1
- 235000020776 essential amino acid Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229940012952 fibrinogen Drugs 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 210000000003 hoof Anatomy 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 229910052945 inorganic sulfide Inorganic materials 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229960002009 naproxen Drugs 0.000 description 1
- CMWTZPSULFXXJA-VIFPVBQESA-N naproxen Chemical compound C1=C([C@H](C)C(O)=O)C=CC2=CC(OC)=CC=C21 CMWTZPSULFXXJA-VIFPVBQESA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002777 nucleoside Substances 0.000 description 1
- 239000002773 nucleotide Substances 0.000 description 1
- 125000003729 nucleotide group Chemical group 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- WBWWGRHZICKQGZ-HZAMXZRMSA-N taurocholic acid Chemical compound C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(=O)NCCS(O)(=O)=O)C)[C@@]2(C)[C@@H](O)C1 WBWWGRHZICKQGZ-HZAMXZRMSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 235000019157 thiamine Nutrition 0.000 description 1
- KYMBYSLLVAOCFI-UHFFFAOYSA-N thiamine Chemical compound CC1=C(CCO)SCN1CC1=CN=C(C)N=C1N KYMBYSLLVAOCFI-UHFFFAOYSA-N 0.000 description 1
- 229960003495 thiamine Drugs 0.000 description 1
- 239000011721 thiamine Substances 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 239000013598 vector Substances 0.000 description 1
Landscapes
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Fodder In General (AREA)
Abstract
The invention discloses a sulfur compensating agent which release sulfur slowly and the method for preparing the same and the usage. The product takes hydrotalcite as carrier, with the sulfate radical proportion in total anion in hydrotalcite interlayer being 80-100%. The process comprises: inserting the sulfate radical into hydrotalcite interlayer by making use of the interlayer assembling property of hydrotalcite, or calcining the hydrotalcite to 450-550 Deg C to get bimetallic oxide, then carrying sulfate radical by using the property of bimetallic oxide adsorbing anion. The hydrotalcite can release sulfur slowly because of the features it possesses: bio-availability, compatibility to gastrointestinal tract mucosa, commutativity between layers, high surface activity and large specific surface area. The product can be used for sulfur compensation for cow, sheep, poultry and aquatic creature and can also improve the quantity and quality of wool and rabbit hair.
Description
Technical field
The present invention relates to a kind of sulfur supplementary agent and preparation method and purposes of controlled release type sulphur.
Background technology
Sulphur is the essential nonmetalloid of organism, and in distribution each cell in animal body, mainly the form with organic sulfur is present in methionine, cystine, the cysteine.In addition, also be present in chondroitin sulfate and mucoitinsulfuric acid in biotin, thiamine, the mucopolysaccharide, and in heparin, coacetylase, fibrinogen and the sweet phthalein of paddy Guang.Also contained element sulphur in the keratin such as the quilt hair of animal, hoof tips, angle.Sulphur in the various in vivo tissues all exists with the form of sulfate or sulfuric acid ester, comprising chondroitin, cholyltaurine, heparin and sulfate.
Sulphur participates in synthetic rumen microorganism mycoprotein; Participate in the biosynthesis of keratin protein; Sulphur compound is the activator of some enzyme (as dehydrogenase and esterase), participate in the synthetic of body protein and lactoprotein, and fat metabolism and carbohydrate metabolism, be present in polypeptide chain, connect collagen and connective tissue with the disulfide bond form, can also participate in acid-base balance and detoxification processes.Sulphur occupies critical role in ruminant animal nutrition, the productivity that promotes ruminant to grow and to improve ruminant is had crucial meaning.In rabbit, wool fiber, constitute between the peptide chain of hair (suede) protein and be coupled to netted big molecule by disulfide bond, sat linkage and hydrogen bond, wherein the disulfide bond connection effect that is provided by cystine is the strongest.Sulphur plays an important role to the chemical stability and the steric configuration of rabbit, wool (suede) protein molecule, and the high sulfur content and the disulfide bond structure of rabbit, wool (suede) are the material bases of physicochemical properties such as rabbit, wool.Therefore, sulphur has material impact to textile performances such as the elasticity of rabbit, wool (suede) output and hair (suede), intensity.
Under the current raising condition of China, the protein of livestock and poultry and the main source of energy or plant feed, but the amino acid contained and inorganic sulfide compound of plant feed can not satisfy the needs of body far away, the contents of essential amino acids that can supply with in the plant feed lacks 30%～40% than requirement, and wherein sulfur-containing amino acid especially needs to replenish.Therefore the sulfur additives of seeking to suit has important and practical meanings to the production performance that improves livestock and poultry.
At present, adopt artificial sulfur-containing amino acid that synthesizes and sulfate supplementary source usually as sulphur.The absorption of sulphur is different with the difference of sulfur-containing compound kind.In general, tiring of organic sulfur source is higher than the inorganic sulfur source, and when with methionine during as evaluation criterion, other sulphur sources especially inorganic sulfur source relative potency are very low.Pour into methionine (2g/d) at cud and abomasum respectively to sheep by stages, find that the cud perfusion makes production of wool improve 28%, the wool sulfur content has improved 4.5%; And the abomasum perfusion, production of wool has improved 68%, and the wool sulfur content has improved 19.7%.As seen the degradation of rumen microorganism has reduced the utilization ratio of perfusion methionine, and in order to improve the biological value of sulfur-containing amino acid, people have transferred to research emphasis on the rumen-bypass amino acid.Methionine hydroxy analog (MnA), methionine metal complex and hydroxy analogs thereof can pass through cud safely, but its cost is higher.
The control slow-released system has selectivity and controllability to release position, speed and the mode of medicine, agricultural chemicals, fertilizer, spices, can realize the target transmission and the control slowly-releasing of object, improve its utilization rate and action effect, the research and the application of control slow-releasing system will bring new technological revolution to relevant industries.The control slow release method is also representing great application prospect and theory significance aspect the research and development of feed addictive, it can promote the high performance and the environmental friendlinessization of product, will provide material and technical guarantee for sustainable development of animal husbandry on new level.
The key of control slow release method is the selection of controlled release carrier.Hydrotalcite (Hydrotalcites, or Layered DoubleHydroxides, LDHs) be the anionic inorganic functional material, possess the Modulatory character of laminate chemical composition, leafing subcategory and quantity, crystallite dimension and distribution thereof on the structure, have purposes widely at aspects such as catalysis, ion-exchange, absorption, chemical industry.In recent years, hydrotalcite has had new application at aspects such as biological medicines, and hydrotalcite is realized commercialization rapidly as the specific drug of treatment stomach trouble in Europe.Performance that the intercalation that utilizes hydrotalcite to have is assembled and good biocompatibility, its transport vehicle as the bio-pharmaceutical molecule had very high using value, hydrotalcite is considered to the spacetabs type carrier of a class formation and mechanism of action novelty, more and more is subjected to researcher's extensive concern.
Document 1:Choy, J.K., Kwak, S.Y., Jeong, Y.J., Park, J.S.2000.Inorganic layerd doublehydroxides as nonviral vectors.Angew.Chem.39, people such as 4041～4045.Choy are successfully with biomolecule nucleotides (Nucleoside Monophosphates) and DNA (Deoxyribonucleic Acid, DNA) method with ion-exchange is inserted into the LDHs interlayer, forms bio-LDH layer molecule composite.Hydrotalcite is used as the transport vehicle of biomolecule.
Document 2:Khan AI, Lei L, Norquist AJ, O ' Hare D.Intercalation and controlled release ofpharmaceutically active compounds from a layered double hydroxide.Chem Commun (Camb), 2001,21:2342-2343. has prepared anti-inflammatory agent intercalated houghites such as Diclofenac, brufen and naproxen.
Document 3:Ambrogi V, Fardella G, Grandolini G, Perioli L.Intercalation compounds ofhydrotalcite-like anionic clays with antiinflammatory agents--I.Intercalation and in vitro release ofibuprofen.Int J Pharm., 2001,220:23-32. hydrotalcite is used as the transport vehicle of medicament slow release, carried out the intercalation of brufen in hydrotalcite, release performance to the intercalation product studies show that, under the condition of pH neutral, the rate of release of medicine becomes slowly, has reached to delay the purpose that medicine discharges.
Hydrotalcite will destroy its layer structure 450 ℃～550 ℃ following calcinings, obtain bimetallic oxide.Bimetallic oxide can come the restoration and reconstruction hydrotalcite structure by anion and the hydrone in the absorption environment, and because of having bigger specific area and pore volume, acceptant object.Bimetallic oxide after the roasting has bigger specific area than its predecessor, and has structure " memory " effect, promptly reuptakes anion and make it recover original layer structure in water environment.
Summary of the invention
The sulfur supplementary agent and preparation method and the purposes that the purpose of this invention is to provide a kind of controlled release type sulphur.
The sulfur supplementary agent of controlled release type sulphur be a kind of be the sulfur supplementary agent of carrier with the hydrotalcite, sulfate radical accounts for 80～100% of hydrotalcite layers anion total amount.
The preparation method of the sulfur supplementary agent of controlled release type sulphur may further comprise the steps:
1) hydrotalcite or bimetallic oxide are ground to greater than 400 orders, add water and stir, make concentration and be 1%～10% suspension slurry;
2) with molal quantity be the sulfate of 1～2 times of hydrotalcite or bimetallic oxide, slowly add in the suspension slurry of step 1) room temperature reaction 5～15 hours down in stirring;
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 sulfur supplementary agent of controlled release type sulphur.
The hydrotalcite that uses in the invention can be the commercial goods, also can be according to prior art for preparing, and its technology of preparing is well-known.The hydrotalcite chemical structure of general formula is: [M
2+ 1-xM
3+ x(OH)
2]
X+[A
N- X/nMH
2O], wherein, bivalent metal ion M
2+Be Mg
2+, Zn
2+, Fe
2+, Mn
2+, Co
2+, Ni
2+, Cu
2+, Ca
2+In any, trivalent metal ion M
3+Be Al
3+, Fe
3+, Cr
3+, Co
3+, Ti
3+In any; A
N-Be CO
3 2-Perhaps Cl
-X=0.5～0.17; M
2+/ M
3+=1～5.The bimetallic oxide that uses in the invention is for forming above-mentioned hydrotalcite at 450～550 ℃ of temperature lower calcinations.
Among the preparation method of the present invention, said sulfate can be sodium sulphate, potassium sulfate, niter cake, potassium acid sulfate.
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 sulfur supplementary agent of the controlled release type sulphur after the oven dry is block, can select for use conventional disintegrating apparatus to be crushed to granularity greater than 300 orders.
The sulfur supplementary agent of controlled release type sulphur is as the benefit sulphur feed addictive of ox, sheep, livestock and poultry, aquatic livestock.
Advantage of the present invention is:
(1) intercalation assembling performance and the bimetallic oxide that utilizes hydrotalcite to have carries sulfate radical by the character of layer structure reconstruction adsorpting anion, and implementation method is easy, suitability for industrialized production, and cost is lower.
(2) because hydrotalcite has good biocompatibility and characteristics such as gastrointestinal tract mucous compatibility, interlayer interchangeability, high surface and bigger serface, make it that the sulphur of institute's load is had the control slow releasing function, thereby improved the absorption rate of sulphur greatly.
(3) sulfur supplementary agent of the prepared controlled release type sulphur of the present invention is easy to mix with feed, forms even disperse system, and is easy to use.
(4) sulfur supplementary agent of controlled release type sulphur of the present invention can be used as the benefit sulphur of ox, sheep, livestock and poultry, aquatic livestock, and can improve the output and the quality of wool, the rabbit hair.
The specific embodiment
The present invention is further described in conjunction with following example.
Embodiment 1
1) with commercially available hydrotalcite at 450 ℃ of temperature lower calcinations, make bimetallic oxide, be ground to 500 orders again, add water and stir, make concentration and be 10% suspension slurry;
2) with molal quantity be the sodium sulphate of 2 times of bimetallic oxides, slowly add in the suspension slurry of step 1) room temperature reaction 15 hours down in stirring;
3) suspension slurry centrifugal dehydration step 2);
4) filter cake of step 3) gained is dried, is crushed to 300 orders, obtain the sulfur supplementary agent of controlled release type sulphur.Sulfate radical accounts for 100% of hydrotalcite layers anion total amount.
Embodiment 2
1) commercially available hydrotalcite is ground to 400 orders, adds water and stir, make concentration and be 4% suspension slurry;
2) with molal quantity be the potassium sulfate of 2 times of hydrotalcites, slowly add in the suspension slurry of step 1) room temperature reaction 10 hours down in stirring;
3) suspension slurry filtering means dehydration step 2);
4) filter cake of step 3) gained is dried, is crushed to 500 orders, obtain the sulfur supplementary agent of controlled release type sulphur.Sulfate radical accounts for 85% of hydrotalcite layers anion total amount.
Embodiment 3
Preparation: according to " magnalium type hydrotalcite hydro-thermal synthetic " (Xie Hui rectifys the celebrating pool, section snow. applied chemistry, 2001, method 18:70-72) prepares hydrotalcite.
1) with the hydrotalcite that obtains in the preliminary step at 550 ℃ of temperature lower calcinations, make bimetallic oxide, be ground to 600 orders again, add water and stir, make concentration and be 5% suspension slurry;
2) with molal quantity be the niter cake of 1.5 times of bimetallic oxides, slowly add in the suspension slurry of step 1) room temperature reaction 15 hours down in stirring;
3) suspension slurry centrifugal dehydration step 2);
4) filter cake of step 3) gained is dried, is crushed to 400 orders, obtain the sulfur supplementary agent of controlled release type sulphur.Sulfate radical accounts for 90% of hydrotalcite layers anion total amount.
Embodiment 4
Preparation: according to " binary metal houghite synthetic and as the Study on adsorption properties of presoma " (Guo Zhiqiang, Ni Zheming, Yu Weihua to NOx, Wang Ligeng, Ge Zhonghua. the Materials Science and Engineering journal, 2004,22 (6): method 878-880) prepares hydrotalcite.
1) hydrotalcite that obtains in the preliminary step is ground to 600 orders, adds water and stir, make concentration and be 1% suspension slurry;
2) with molal quantity be the potassium acid sulfate of 1.5 times of hydrotalcites, slowly add in the suspension slurry of step 1) room temperature reaction 5 hours down in stirring;
3) suspension slurry centrifugal dehydration step 2);
4) filter cake of step 3) gained is dried, is crushed to 500 orders, obtain the sulfur supplementary agent of controlled release type sulphur.Sulfate radical accounts for 80% of hydrotalcite layers anion total amount.
Embodiment 5
1) with commercially available hydrotalcite at 500 ℃ of temperature lower calcinations, make bimetallic oxide, be ground to 500 orders again, add water and stir, make concentration and be 6% suspension slurry;
2) will with the sodium sulphate of molal quantity such as bimetallic oxide, in stirring the suspension slurry that slowly adds step 1) down, room temperature reaction 5 hours;
3) suspension slurry filtering means dehydration step 2);
4) filter cake of step 3) gained is dried, is crushed to greater than 300 orders, obtain the sulfur supplementary agent of controlled release type sulphur.Sulfate radical accounts for 90% of hydrotalcite layers anion total amount.
Controlled release type sulphur of the present invention is as the benefit sulphur feed addictive of ox, sheep, livestock and poultry, aquatic livestock.Using method is: with the sulfur supplementary agent of pulverous controlled release type sulphur, admix (in sulphur) in ox, sheep, rabbit, the animal and fowl fodder by following additive capacity: ox 0.1～0.2%, sheep 0.15～0.3%, rabbit 0.15～0.3%, pig 0.05～0.15%, fowl 0.05～0.2%.
Claims (7)
1. the sulfur supplementary agent of a controlled release type sulphur is characterized in that, it be a kind of be the sulfur supplementary agent of carrier with the hydrotalcite, sulfate radical accounts for 80～100% of hydrotalcite layers anion total amount.
2. the sulfur supplementary agent of a kind of controlled release type sulphur according to claim 1 is characterized in that said hydrotalcite chemical structure of general formula is: [M
2+ 1-xM
3+ x(OH)
2]
X+[A
N- X/nMH
2O], wherein, bivalent metal ion M
2+Be Mg
2+, Zn
2+, Fe
2+, Mn
2+, Co
2+, Ni
2+, Cu
2+, Ca
2+In any, trivalent metal ion M
3+Be Al
3+, Fe
3+, Cr
3+, Co
3+, Ti
3+In any; A
N-Be CO
3 2-Perhaps Cl
-X=0.5～0.17; M
2+/ M
3+=1～5.
3. the preparation method of the sulfur supplementary agent of a kind of controlled release type sulphur as claimed in claim 1 is characterized in that the step of method is as follows:
1) hydrotalcite or bimetallic oxide are ground to greater than 400 orders, add water and stir, make concentration and be 1%～10% suspension slurry;
2) with molal quantity be the sulfate of 1～2 times of hydrotalcite or bimetallic oxide, slowly add in the suspension slurry of step 1) room temperature reaction 5～15 hours down in stirring;
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 sulfur supplementary agent of controlled release type sulphur.
4. the preparation method of the sulfur supplementary agent of controlled release type sulphur according to claim 3 is characterized in that, said bimetallic oxide is for to form hydrotalcite at 450～550 ℃ of temperature lower calcinations.
5. the preparation method of the sulfur supplementary agent of controlled release type sulphur according to claim 3 is characterized in that said hydrotalcite chemical structure of general formula is: [M
2+ 1-xM
3+ x(OH)
2]
X+[A
N- X/nMH
2O], wherein, bivalent metal ion M
2+Be Mg
2+, Zn
2+, Fe
2+, Mn
2+, Co
2+, Ni
2+, Cu
2+, Ca
2+In any, trivalent metal ion M
3+Be Al
3+, Fe
3+, Cr
3+, Co
3+, Ti
3+In any; A
N-Be CO
3 2-Perhaps Cl
-X=0.5～0.17; M
2+/ M
3+=1～5.
6. the preparation method of the sulfur supplementary agent of controlled release type sulphur according to claim 3 is characterized in that said sulfate is sodium sulphate, potassium sulfate, niter cake or sulfuric acid hydrogen clock.
7. the purposes of the sulfur supplementary agent of a controlled release type sulphur as claimed in claim 1 is characterized in that, it is as the benefit sulphur feed addictive of ox, sheep, livestock and poultry, aquatic livestock.
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| CNB2006100501091A CN100506068C (en) | 2006-03-31 | 2006-03-31 | Sustained-releasing sulfur supplementing agent, its preparation method and uses |
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| WO2020012994A1 (en) * | 2018-07-12 | 2020-01-16 | 国立研究開発法人物質・材料研究機構 | Packaged body containing hydrogen sulfide slow-release agent and method for producing same, and hydrogen sulfide slow-release agent, hydrogen sulfide slow-release body and hydrogen sulfide generation method using same |
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2006
- 2006-03-31 CN CNB2006100501091A patent/CN100506068C/en not_active Expired - Fee Related
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| WO2020012994A1 (en) * | 2018-07-12 | 2020-01-16 | 国立研究開発法人物質・材料研究機構 | Packaged body containing hydrogen sulfide slow-release agent and method for producing same, and hydrogen sulfide slow-release agent, hydrogen sulfide slow-release body and hydrogen sulfide generation method using same |
| CN112368238A (en) * | 2018-07-12 | 2021-02-12 | 国立研究开发法人物质·材料研究机构 | Package containing hydrogen sulfide slow-release agent, method for producing same, hydrogen sulfide slow-release agent, hydrogen sulfide slow-release body, and method for producing hydrogen sulfide using same |
| JPWO2020012994A1 (en) * | 2018-07-12 | 2021-08-12 | 国立研究開発法人物質・材料研究機構 | A package containing a sustained-release agent for hydrogen sulfide and a method for producing the same, and a sustained-release agent for hydrogen sulfide, a sustained-release substance for hydrogen sulfide, and a method for generating hydrogen sulfide using them. |
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| US11932479B2 (en) | 2018-07-12 | 2024-03-19 | National Institute For Materials Science | Method for producing package including hydrogen sulfide sustained release agent, hydrogen sulfide sustained release agent, hydrogen sulfide sustained release composite, and method for generating hydrogen sulfide using same |
| CN114230240A (en) * | 2021-11-15 | 2022-03-25 | 中化环境修复(上海)有限公司 | Slow release material for stabilizing treatment of barium slag and stabilizing treatment method of barium slag |
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| CN100506068C (en) | 2009-07-01 |
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