CN103053812A - Feed additive basic zinc chloride and method for preparing feed additive basic zinc chloride by using zinc suboxide - Google Patents
Feed additive basic zinc chloride and method for preparing feed additive basic zinc chloride by using zinc suboxide Download PDFInfo
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- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 title claims abstract description 146
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 239000011701 zinc Substances 0.000 title claims abstract description 75
- 235000005074 zinc chloride Nutrition 0.000 title claims abstract description 74
- 239000011592 zinc chloride Substances 0.000 title claims abstract description 72
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000003674 animal food additive Substances 0.000 title abstract 6
- 239000012535 impurity Substances 0.000 claims abstract description 28
- 238000005406 washing Methods 0.000 claims abstract description 20
- 238000002386 leaching Methods 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 72
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 56
- 239000007787 solid Substances 0.000 claims description 49
- 238000006243 chemical reaction Methods 0.000 claims description 47
- 239000000243 solution Substances 0.000 claims description 46
- 238000000967 suction filtration Methods 0.000 claims description 46
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 40
- 239000011787 zinc oxide Substances 0.000 claims description 36
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 28
- 239000000706 filtrate Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 235000019270 ammonium chloride Nutrition 0.000 claims description 20
- GLHGFMYBJKLJFS-UHFFFAOYSA-N zinc azanide dichloroazanide Chemical compound ClN([Zn]N)Cl GLHGFMYBJKLJFS-UHFFFAOYSA-N 0.000 claims description 20
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 9
- 125000004122 cyclic group Chemical group 0.000 claims description 8
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910001385 heavy metal Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 10
- 238000002360 preparation method Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 abstract description 3
- 230000036039 immunity Effects 0.000 abstract description 3
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 25
- 238000002156 mixing Methods 0.000 description 16
- 239000010949 copper Substances 0.000 description 9
- 229910052793 cadmium Inorganic materials 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052785 arsenic Inorganic materials 0.000 description 6
- 229910052745 lead Inorganic materials 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000012010 growth Effects 0.000 description 5
- 239000012452 mother liquor Substances 0.000 description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 5
- 229960001763 zinc sulfate Drugs 0.000 description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 230000003115 biocidal effect Effects 0.000 description 3
- 235000016709 nutrition Nutrition 0.000 description 3
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 3
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 3
- 229940007718 zinc hydroxide Drugs 0.000 description 3
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000004060 metabolic process Effects 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000035764 nutrition Effects 0.000 description 2
- 235000019629 palatability Nutrition 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 206010012735 Diarrhoea Diseases 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- WHMDKBIGKVEYHS-IYEMJOQQSA-L Zinc gluconate Chemical compound [Zn+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O WHMDKBIGKVEYHS-IYEMJOQQSA-L 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002180 anti-stress Effects 0.000 description 1
- 235000019789 appetite Nutrition 0.000 description 1
- 230000036528 appetite Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229940038879 chelated zinc Drugs 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000019621 digestibility Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 229940070818 glycyrrhizate Drugs 0.000 description 1
- LPLVUJXQOOQHMX-QWBHMCJMSA-N glycyrrhizinic acid Chemical compound O([C@@H]1[C@@H](O)[C@H](O)[C@H](O[C@@H]1O[C@@H]1C([C@H]2[C@]([C@@H]3[C@@]([C@@]4(CC[C@@]5(C)CC[C@@](C)(C[C@H]5C4=CC3=O)C(O)=O)C)(C)CC2)(C)CC1)(C)C)C(O)=O)[C@@H]1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@H]1O LPLVUJXQOOQHMX-QWBHMCJMSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003054 hormonal effect Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000957 no side effect Toxicity 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000033458 reproduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- WGIWBXUNRXCYRA-UHFFFAOYSA-H trizinc;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WGIWBXUNRXCYRA-UHFFFAOYSA-H 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 235000016804 zinc Nutrition 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011746 zinc citrate Substances 0.000 description 1
- 235000006076 zinc citrate Nutrition 0.000 description 1
- 229940068475 zinc citrate Drugs 0.000 description 1
- 239000011670 zinc gluconate Substances 0.000 description 1
- 235000011478 zinc gluconate Nutrition 0.000 description 1
- 229960000306 zinc gluconate Drugs 0.000 description 1
- 229940110280 zinc methionine Drugs 0.000 description 1
- CNMFGFBWPBBGKX-SCGRZTRASA-L zinc;(2s)-2-amino-4-methylsulfanylbutanoate Chemical compound [Zn+2].CSCC[C@H](N)C([O-])=O.CSCC[C@H](N)C([O-])=O CNMFGFBWPBBGKX-SCGRZTRASA-L 0.000 description 1
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a feed additive basic zinc chloride which is characterized in that the feed additive comprises 58.20-59.88% of zinc by mass, 12.63-12.97% of chlorine by mass, 10.40-30.02ppm of Fe, and 3.50-11.55ppm of Cu. The invention also provides a method for preparing the feed additive basic zinc chloride by using zinc suboxide. The method comprises leaching, iron removing, impurity removing, synthesizing, and washing. According to the basic zinc chloride preparation method, a raw material source is wide, process flow is simple, and production operation is easy. When the synthesized basic zinc chloride is used as a feed additive, feed utilization rate can be improved, and animal immunity and stress resistance can be improved.
Description
Technical field
The present invention relates to a kind of feed addictive, particularly a kind of feed addictive basic zinc chloride and utilize secondary zinc oxide to prepare the method for feed addictive basic zinc chloride.
Background technology
Zinc is a kind of important trace element in the animal life activity, almost animal can both find that the zinc element participates in the trace of vital movement in a organized way with in the organ.The simple metabolism of the growth of animal, skeleton development, coat health, appetite and human body etc. all be unable to do without zinc, zinc is also being played the part of important catalyst role in protein, lipid, carbohydrate and nucleic acid metabolism, contain the every aspect of the life systems such as growth, reproduction, circulation, immunity and hormone activity.Have now found that relying on the zinc element carries out the enzyme of vital movement above 200 kinds.Zinc is so important in vital movement, and animal only leans against and obtains in the picked-up of nature food to replenish is inadequate, considers from improving the feeding efficiency aspect, also needs constantly to replenish.
The zinc that adds at present in the animal feed mainly contains three kinds of forms: the 1. inorganic zinc such as zinc sulfate, zinc oxide source; 2. organic zinc sources such as zinc gluconate, zinc citrate, zinc glycyrrhizate; 3. the chelated zinc such as lysine-zn, zinc methionine.
In current feed, generally add zinc sulfate or zinc oxide.Because animal is very low to the digestibility of this two classes zinc, has so just aggravated the pollution of production of fodder to environment.Find after deliberation, animal is to the good absorbing effect of amino-acid zinc, but the amino-acid zinc price is high, is several times of inorganic zinc, can not be accepted by production of fodder producer.A.B, Batal (2002) has reported basic zinc chloride [Zn
5(OH)
8C1
2H
2O, Tetrabasic Zinc Cloride, TBZC] as feed addictive, prove that through animal experiment it has higher bioavailability, can effectively solve the production relevant with zinc nutrition and ecological problem, and the price of TBZC and zinc sulfate, zinc oxide are suitable, can not increase feed producer production cost, are a kind of very promising feed addictives.
At present, domestic study on the synthesis report about TBZC mainly contains:
Wang Gang etc. are with the synthetic basic zinc chloride of condition of zinc chloride and zinc oxide mol ratio 1:4,90 ℃ of reaction temperatures, reaction time 2.5h, reacting liquid pH value 5.5,80 ℃ of product baking temperatures, drying time 2h, productive rate can reach 88%, and product contains the Zn mass percent up to 60%.
Liao Weifeng etc. adopt the coordination catalysis sluggish precipitation, at pH value 6.0 ~ 6.5,65 ~ 75 ℃ of temperature, zinc oxide concentration 110 ~ 210gL
-1, catalyst amount 0.2% ~ 0.3%, charging rate 2.0 ~ 4.0mLmin
-1And under the condition of suitable mixing speed, synthetic basic zinc chloride purity contains the zinc mass percent greater than 60% greater than 98%.
Huang Yiqiang adopts zinc oxide and zinc chloride take mol ratio as 4:1, under 75 ~ 95 ℃ of temperature, and control pH value 6 ~ 8, react 1.5 ~ 3h under the condition of normal pressure, generate basic zinc chloride, then centrifugation, washing, oven dry, pulverize, be packaged into finished product, wherein containing the zinc mass percent is 60%.
The zinc fragmentation of will giving up places saturated liquor zinci chloridi, continues to pass into air under 70 ~ 90 ℃ reaction temperature, and reaction time visual response degree and deciding reaches reaction end when the pH value is 6 ~ 8, and reaction equation is ZnCl
2+ 4Zn+2O
2+ 5H
2O=Zn
5Cl
2(OH)
8H
2O, pulverizes, is packaged into finished product at centrifugation, washing, oven dry.It contains the zinc mass percent is 60%.
Or zinc oxide and hydrochloric acid are take mol ratio as 5:2, first a certain amount of hydrochloric acid is diluted in 5 ~ 10 times reaction water, again zinc oxide is dropped into, under 55 ~ 95 ℃ of temperature, control pH value is 6 ~ 8, react 1 ~ 3h under the condition of normal pressure, generate basic zinc chloride (it is 57.5% ~ 60.5% that zinc contains mass percent), the reactant liquor after the centrifugation can be used as again mother liquor and recycles in lower secondary response; Its reaction is as follows: 2HCl+5ZnO+4H
2O=Zn
5Cl
2(OH)
8H
2O; Centrifugation, washing, oven dry, pulverize, be packaged into finished product.
Basic zinc carbonate is rendered in the hydrochloric acid, and the mol ratio of hydrogen chloride content is 2:4 in the consumption of basic zinc carbonate and the hydrochloric acid, is that 60 ~ 95 ℃, pH value are under 5 ~ 8 the condition in temperature, obtains product behind reaction 0.5 ~ 2h; After product washing, centrifugation, drying, make basic zinc chloride.Wherein containing the zinc mass percent is 59.6%.
NaOH or ammoniacal liquor are added in the liquor zinci chloridi, and the mol ratio of NaOH or ammoniacal liquor and zinc chloride is (7.5 ~ 8.5): 5, and be that 60 ~ 105 ℃, pH value are to react under 5 ~ 9 the condition in temperature, after finishing, reaction obtains product; To make basic zinc chloride after product washing, centrifugal, the drying.Wherein containing the zinc mass percent is 59%.
The zinc hydroxide slurry is added in the liquor zinci chloridi, and the mol ratio of zinc hydroxide and zinc chloride is 3 ~ 4.5:1, is that 70 ~ 105 ℃, pH value are to react under 5 ~ 9 the condition in temperature, obtains product after reaction is finished; To make basic zinc chloride after product washing, centrifugal, the drying.Wherein containing the zinc mass percent is 58.9%.
Above report about the basic zinc chloride Study on Preparation, only limit to use in the laboratory pure chemistry reagent to synthesize, raw material mainly uses slightly high product or the intermediates of price such as zinc oxide, zinc hydroxide, basic zinc carbonate, relative cost is higher, and about the suitability for industrialized production of basic zinc chloride rarely seen report especially.
Summary of the invention
The invention provides that a kind of operating procedure is simple, safety and environmental protection and lower-cost feed addictive basic zinc chloride and utilize secondary zinc oxide to prepare the method for feed addictive basic zinc chloride.
The invention provides a kind of feed addictive basic zinc chloride, it is characterized in that, wherein containing the zinc mass percent is 58.20～59.88%, and chloride mass percent is 12.63～12.97%, containing the Fe amount is 10.40～30.02ppm, and containing the Cu amount is 3.50～11.55ppm.
The present invention also provides the method for utilizing secondary zinc oxide to prepare the feed addictive basic zinc chloride, may further comprise the steps:
Step 1: leaching
Take secondary zinc oxide as raw material, leach as leaching agent with ammonium chloride solution;
Step 2: deironing
In upper step leaching process, add hydrogen peroxide and carry out the rear suction filtration of deironing reaction;
Step 3: removal of impurities
With suction filtration behind gained filtrate employing of the upper step zinc dust precipitation removal heavy metal, obtaining filtrate is that the zinc ammino closes solution;
Step 4: synthetic
Synthesis mode one: liquor zinci chloridi or hydrochloric acid solution are slowly added upper step gained zinc ammino close and separate out solid, suction filtration in the solution behind the stirring reaction;
Or synthesis mode two: gained zinc ammino of upper step is closed solution cooling, separate out dichloro diamino zinc solid, suction filtration, air-dry, then the dichloro diamino zinc solid after air-dry is joined and carry out synthetic reaction in liquor zinci chloridi or the hydrochloric acid solution and separate out solid, suction filtration;
Step 5: washing
Behind the suction filtration gained solid is washed with pure water, the suction filtration oven dry namely obtains basic zinc chloride.
Secondary zinc oxide in the step 1 contains the zinc mass percent and is preferably 55%～65%; Ammonium chloride solution preferably adopts chloride solid to add pure water or to add the aqueous solution of containing ammonium chloride formulated, and wherein the mass percent of containing ammonium chloride is preferably 20%～30%; In the described ammonium chloride solution in ammonium chloride and the secondary zinc oxide mol ratio of zinc oxide be preferably 2 ~ 6:1.
Step 1 leaching reaction condition is preferably: speed of agitator is 225 ~ 675 rev/mins, and reaction temperature is 60 ~ 90 ℃, and pH value is 5.0 ~ 8.0, and the reaction time is 30 ~ 90 minutes.
The mass percent that hydrogen peroxide contains hydrogen peroxide in the described step 2 is preferably 27.5%, and the quality optimization of hydrogen peroxide accounts for 2%～6% of secondary zinc oxide quality, and the deironing reaction time is preferably 20 ~ 60 minutes.
The zinc powder consumption is preferably every liter of filtrate and adds 3～10g in the described step 3, and conditions of replacement reaction is preferably: speed of agitator is 225 ~ 675 rev/mins, and reaction temperature is 60 ~ 90 ℃, and the reaction time is 30 ~ 90 minutes.
Zinc powder preferably is divided into twice adding in the described step 3: add first 55% ~ 72% of total zinc powder quality, stirring reaction filtered after 15 ~ 60 minutes, and then added remaining zinc powder in filtrate, and stirring reaction is suction filtration after 15 ~ 40 minutes.
Synthesis mode one is preferably in the described step 4: to close the mol ratio of dichloro diamino zinc in the solution be 0.5 ~ 1.5:4 for zinc chloride and zinc ammino in the liquor zinci chloridi, to close the mol ratio of dichloro diamino zinc in the solution be 1.5 ~ 2.5:5 for hydrogen chloride and zinc ammino in the hydrochloric acid solution, to close the liquor capacity ratio with the zinc ammino be 1.5 ~ 2.5:1 for liquor zinci chloridi or hydrochloric acid solution in the reaction system, adding liquor zinci chloridi or hydrochloric acid solution speed is 8 ~ 12ml/min, synthetic reaction condition is: speed of agitator is 225 ~ 675 rev/mins, reaction temperature is 70 ~ 90 ℃, the pH value is 5.0 ~ 8.0, and total time is 60 ~ 120 minutes.
Synthesis mode two is preferably in the described step 4: zinc chloride is that hydrogen chloride is 1.5 ~ 2.5:5 with the mol ratio of separating out solid dichloro diamino zinc in 0.5 ~ 1.5:4, the hydrochloric acid solution with the mol ratio of separating out solid dichloro diamino zinc in the liquor zinci chloridi, liquor zinci chloridi or hydrochloric acid solution and dichloro diamino zinc solid liquid-solid ratio are 7 ~ 12:1 in the reaction system, synthetic reaction condition is: speed of agitator is 225 ~ 675 rev/mins, reaction temperature is 70 ~ 90 ℃, the pH value is 5.0 ~ 8.0, and total time is 60 ~ 120 minutes.
After the gained solid preferably is amount cyclic washing, the suction filtration 2 ~ 5 times of 5 ~ 9:1 with pure water by liquid-solid ratio in the described step 5,65 ~ 85 ℃ of lower 6 ~ 10 hours oven dry, i.e. gained basic zinc chlorides.
The relevant physicochemical property of basic zinc chloride is: chemical name is basic zinc chloride, and its commodity are called good happy zinc (TBZC), and molecular formula is Zn
5Cl
2(OH)
8H
20, molecular weight is 551.89, is white in color Powdered, and the utmost point is insoluble in water, is difficult for deliquescence, stable chemical nature, safety non-toxic.
As a kind of newfound little nutrition zinc additive, basic zinc chloride has advantages of very outstanding:
(1) basic zinc chloride has relatively high bioavailability.Evidence is arranged, the growth basic zinc chloride of pig is made moderate progress than zinc oxide, zinc sulfate, more zinc is entered participate in the synthetic of plurality of enzymes in the body and activate, strengthened the physique of pig.
(2) basic zinc chloride has better stability.The zinc activity is low in the product, can not impact other nutritional labelings in the feed.
(3) basic zinc chloride is neutral, water insoluble, thereby has splendid palatability (being better than zinc carbonate and basic zinc sulfate).
(4) basic zinc chloride has higher antibiotic property and Antidiarrheic effect.Result of the test shows, it can replace antibiotic as growth accelerator, and the prevention and control diarrhea of weaned piglets significantly promotes the weanling pig growth, improves efficiency of feed utilization, thereby eliminates in animal body residual of antibiotic, the nuisanceless animal flesh of production high-quality.
(5) basic zinc chloride is than zinc oxide, and basic zinc chloride not only bioavailable efficiency is high, and additive amount is few, and discharge rate is low, can not cause the zinc source too much to waste good palatability, stable, nontoxic, have no side effect, less to the animal product quality influence, reduced environmental pollution.
Technique effect of the present invention is: its raw materials wide material sources of basic zinc chloride of the present invention, and technological process is simple, and production operation is easy; Synthetic basic zinc chloride is used for immunity and the anti-stress ability that feed addictive can improve efficiency of feed utilization and improve animal.
The specific embodiment
The principle of each step of the present invention is as follows:
Leaching: chemical equation is as follows:
ZnO+2NH
4Cl＝Zn(NH
3)
2Cl
2+H
2O
Deironing: the Fe in the leaching process Raw
2+Can enter in the solution, affect the leaching rate of zinc, this patent adopts the hydrogen peroxide oxidation deironing.Chemical equation is as follows:
2Fe
2++H
2O
2+2H
+=2Fe
3++2H
2O
Fe
3++3OH
-=Fe(OH)
3
Removal of impurities: owing to containing the impurity such as lead, cadmium, copper, iron in the secondary zinc oxide, can leach a small amount of impurity in leaching process, this patent adopts the zinc powder segmented replacement except delead, cadmium, copper.Chemical equation is as follows:
M
2++ Zn=M+Zn
2+(this M represents other impurity element)
Synthetic: when adopting zinc chloride to be raw material, chemical equation is as follows:
4Zn(NH
3)
2Cl
2+ZnCl
2+9H
2O＝ZnCl
2·4Zn(OH)
2·H
2O+8NH
4Cl
When adopting hydrochloric acid to be raw material, chemical equation is as follows:
5Zn(NH
3)
2Cl
2+2HCl+9H
2O＝ZnCl
2·4Zn(OH)
2·H
2O+10NH
4Cl
Primary raw material used among the embodiment has: from the secondary zinc oxide that Foshan City China source foundation foreign trade Co., Ltd buys, its main minute content and major impurity content see Table 1; Ammonium chloride, zinc powder, zinc chloride and hydrochloric acid are technical grade, wherein the ammonium chloride mass percent is 94%, containing zinc mass percent (purity) in the zinc powder is 99.99%, zinc chloride mass percent (purity) is 99%, the containing hydrogen chloride mass percent is 35% in the hydrochloric acid, it is 27.5% that hydrogen peroxide contains the hydrogen peroxide mass percent, and water is running water.
Table 1 secondary zinc oxide master's content and impurity analysis
| Element term | Zn | Fe | Cu | Pb | Cd | As |
| Measurement unit | % | μg/kg | μg/kg | % | μg/kg | μg/kg |
| Mass percent | 56.35 | 6523 | 1079 | 6.43 | 2268 | 45 |
Below by specific embodiment the present invention is further detailed:
Embodiment 1
Utilize secondary zinc oxide to prepare the method for feed addictive basic zinc chloride in the present embodiment, comprise the steps:
(1) leaching
In the 5000ml beaker, add the 774g chloride solid, add the running water dissolving, be made into the 3400ml ammonium chloride solution, be heated to 80 ℃, for subsequent use; Other gets 394.5g secondary zinc oxide solid and slowly adds in the above-mentioned ammonium chloride solution, and mixing speed is 675 rev/mins, and adding and recording the pH value when complete is 6.5, reacts 30 minutes;
(2) deironing:
In above-mentioned reactant liquor, add the 20ml hydrogen peroxide and carry out deironing reaction, 30 minutes reaction time, while hot suction filtration;
(3) removal of impurities
Suction filtration gained 3100ml filtrate is heated to 80 ℃, slowly adds the 16g zinc powder, mixing speed is 675 rev/mins, reacts after 30 minutes, while hot suction filtration; Add the 12g zinc powder in the gained filtrate, mixing speed is 560 rev/mins again, reacts after 30 minutes, and suction filtration obtains filtrate and keeps 80 ℃ while hot, and it is 70g/l that filtrate contains the zinc mass concentration; Gained filtrate is highly purified zinc ammino and closes solution, and main component in solution is dichloro diamino zinc;
(4) synthetic
Get the above-mentioned zinc ammino of 150ml and close solution in the 500ml beaker, for subsequent use; Other gets 5.5g zinc chloride solid and is dissolved in the 300ml pure water, is made into liquor zinci chloridi; Liquor zinci chloridi is slowly added the zinc ammino close in the solution, mixing speed is 337 rev/mins, and reaction temperature is 80 ℃, and liquor zinci chloridi adding speed is 10ml/min, adds that to record the pH value when complete be 5.5, reacts after 30 minutes again and separates out solid, suction filtration;
(5) washing
Behind the suction filtration with the gained solid with behind from the beginning three each water 55ml cyclic washings of moisture, the suction filtration, baking is 8 hours in 65 ℃ of baking ovens, gets the 10.2g product, is basic zinc chloride.
The zinc mass percent of the basic zinc chloride of the present embodiment preparation is 58.8% after testing, and the chlorine mass percent is 12.90%; Do not detect impurity Pb, Cd, As existence in the product, impurity F e content is 15.70ppm, and impurity Cu content is 6.50ppm.
Filtrate after filtering in above-mentioned steps (4) and (5) can be used as the mother liquor of ammonium chloride solution in the preparation steps (1).
Embodiment 2
The present embodiment utilizes secondary zinc oxide to prepare the method for feed addictive basic zinc chloride, in accordance with the following steps:
(1) leaching
In the 50L reactor, add the 11.6kg chloride solid, add the running water dissolving, be mixed with the 42kg ammonium chloride solution, be heated to 85 ℃, for subsequent use; Other gets 5.9kg secondary zinc oxide solid and slowly adds in the ammonium chloride solution, and mixing speed is 675 rev/mins, adds that the pH value is 6.5 when complete, reacts 30 minutes;
(2) deironing:
In above-mentioned reactant liquor, add the 306ml hydrogen peroxide, continue reaction after 60 minutes, while hot suction filtration;
(3) removal of impurities
Suction filtration gained filtrate is heated to 85 ℃, slowly adds the 255g zinc powder, mixing speed is 560 rev/mins, reacts after 40 minutes, while hot suction filtration; To add the 153g zinc powder in the gained filtrate, mixing speed is 450 rev/mins again, react after 40 minutes, and suction filtration while hot, gained filtrate is highly purified zinc ammino and closes solution, and main component in solution is dichloro diamino zinc, and it is 70g/l that filtrate contains the zinc mass concentration;
(4) synthetic
Get the above-mentioned zinc ammino of 16kg and close solution in the 50L reactor, for subsequent use; Other gets 524.8g zinc chloride solid and is dissolved in the 32kg running water, is made into liquor zinci chloridi; Liquor zinci chloridi is added above-mentioned being equipped with in the reactor that the zinc ammino closes solution with the speed of 300ml/min, and mixing speed is 225 rev/mins, and reaction temperature is 85 ℃, adds that pH is about 6.5 when complete, reacts 10 minutes again, separates out solid in the reactant liquor, suction filtration;
(5) washing
Above-mentioned solid from the beginning three each water 5.5L cyclic washings of moisture, suction filtration, baking is 10 hours in 75 ℃ of baking ovens, gets the 1.1kg product, is basic zinc chloride.
The zinc mass percent of the basic zinc chloride of the present embodiment preparation is 58.98% after testing, and the chlorine mass percent is 12.85%.Do not detect impurity Pb, Cd, As existence in the product, impurity F e content is 30.02ppm, and impurity Cu content is 11.55ppm.
Embodiment 3
The component content of mother liquor behind the basic zinc chloride synthetic reaction suction filtration in embodiment 1 step (4): containing the zinc mass concentration is 10～15g/l, and the containing ammonium chloride mass concentration is 7%～10%.Utilize secondary zinc oxide to prepare the method for feed addictive basic zinc chloride in the present embodiment, comprise the steps:
(1) leaching
Mother liquor in employing embodiment 1 step (4) behind the basic zinc chloride synthetic reaction suction filtration is got the 800ml mother liquor in the 1000ml beaker as extracting solvent, adds the 118.4g chloride solid, and heating is stirred to 90 ℃ of dissolvings, and for subsequent use, mixing speed is 675 rev/mins; Other gets 78.6g secondary zinc oxide solid and adds in the beaker, and adding and recording the pH value when complete is 6.5, leaches 30 minutes;
(2) deironing:
In above-mentioned reactant liquor, add the 4ml hydrogen peroxide, react after 30 minutes, while hot suction filtration;
(3) removal of impurities
Gained 800ml filtrate is heated to 90 ℃, slowly adds the 5g zinc powder, mixing speed is 450 rev/mins, reacts after 30 minutes, while hot suction filtration; Add the 2g zinc powder in gained filtrate, mixing speed is 450 rev/mins again, react after 30 minutes, and suction filtration while hot, filtrate keeps 90 ℃, and it is 70g/l that filtrate contains the zinc mass concentration;
(4) synthetic
Get the above-mentioned filtrate of 150ml in the 500ml beaker, for subsequent use; Other gets 5.5g zinc chloride solid and is dissolved in the 300ml pure water, is made into liquor zinci chloridi; The speed of liquor zinci chloridi with 10ml/min is slowly added in the filtrate beaker, and mixing speed is 225 rev/mins, and reaction temperature is 90 ℃, adds that to record pH when complete be about 6.0, react again 30 minutes after, suction filtration;
(5) washing
Solid from the beginning three each water 60ml cyclic washings of moisture, suction filtration, baking is 6 hours in 85 ℃ of baking ovens, gets the 10g product, is basic zinc chloride,
The zinc mass percent that contains of the basic zinc chloride of the present embodiment preparation is 58.20% after testing, and chloride mass percent is 12.80%, does not detect impurity Pb, Cd, As existence, and impurity F e content is 13.60ppm, and impurity Cu content is 6.40ppm.
Embodiment 4
Identical with (1)～(3) step of embodiment 1, difference is that the present embodiment (4) synthesis step is: after part filtrate is cooled off naturally, separate out dichloro diamino zinc solid, and suction filtration, solid is air-dry; Get 5.5g zinc chloride solid and in the 500ml beaker, add water and be made into the 300ml liquor zinci chloridi, be heated to 65 ℃, for subsequent use; Other gets 28.5g dichloro diamino zinc solid and slowly adds in the liquor zinci chloridi, and mixing speed is 450 rev/mins, and adding and recording pH when complete is about 5.5, reacts after 90 minutes suction filtration; Step (5) is: solid from the beginning three each water 70ml cyclic washings of moisture, suction filtration, baking is 8 hours in 65 ℃ of baking ovens, gets the 10.5g product, is basic zinc chloride.
The zinc mass percent that contains of the basic zinc chloride of the present embodiment preparation is 59.88% after testing, and chloride mass percent is 12.77%.Do not detect impurity Pb, Cd, As existence in the product, impurity F e content is 12.20ppm, and impurity Cu content is 3.50ppm.
Embodiment 5
Identical with (1)～(3) step of embodiment 1, difference is that the present embodiment (4) synthesis step is: get 230ml filtrate in the 500ml beaker, and for subsequent use; Other gets 10.8ml hydrochloric acid thin up to 300ml; The speed of hydrochloric acid solution with 10ml/min is slowly added in the filtrate beaker, and mixing speed is 225 rev/mins, and reaction temperature is 80 ℃, adds that to record pH when complete be about 5.0, react again 60 minutes after, reactant liquor is separated out solid, suction filtration; Step (5) is: solid from the beginning three each water 150ml cyclic washings of moisture, suction filtration, baking is 8 hours in 65 ℃ of baking ovens, gets the 20g product, is basic zinc chloride.
The zinc mass percent that contains of the basic zinc chloride of the present embodiment preparation is 59.21% after testing, and chloride mass percent is 12.63%, does not detect impurity Pb, Cd, As existence in the product, and impure Fe is that 13.70ppm, Cu are 8.50ppm.
Embodiment 6
Identical with (1)～(3) step of embodiment 1, difference is that the present embodiment (4) synthesis step is: after part filtrate is cooled off naturally, separate out dichloro diamino zinc solid, and suction filtration, solid is air-dry; Get 10.8ml hydrochloric acid thin up in the 500ml beaker and be heated to 75 ℃ to 300ml, for subsequent use; Other gets 42.6g dichloro diamino zinc solid and slowly adds in the hydrochloric acid solution, and mixing speed is 337 rev/mins, and adding and recording pH when complete is about 5.2, reacts after 60 minutes suction filtration; Step (5) is: solid from the beginning three each water 130ml cyclic washings of moisture, suction filtration, baking is 6 hours in 85 ℃ of baking ovens, gets the 16.2g product, is basic zinc chloride.
The zinc mass percent that contains of the basic zinc chloride of the present embodiment preparation is 58.94% after testing, and chloride mass percent is 12.97%.Do not detect impurity Pb, Cd, As existence in the product, impurity F e content is 10.40ppm, and impurity Cu content is 5.90ppm.
Claims (10)
1. a feed addictive basic zinc chloride is characterized in that, wherein containing the zinc mass percent is 58.20～59.88%, and chloride mass percent is 12.63～12.97%, and containing the Fe amount is 10.40～30.02ppm, and containing the Cu amount is 3.50～11.55ppm.
2. a method of utilizing secondary zinc oxide to prepare feed addictive basic zinc chloride claimed in claim 1 is characterized in that, may further comprise the steps:
Step 1: leaching
Take secondary zinc oxide as raw material, leach as leaching agent with ammonium chloride solution;
Step 2: deironing
In upper step leaching process, add hydrogen peroxide and carry out the rear suction filtration of deironing reaction;
Step 3: removal of impurities
With suction filtration behind gained filtrate employing of the upper step zinc dust precipitation removal heavy metal, obtaining filtrate is that the zinc ammino closes solution;
Step 4: synthetic
Synthesis mode one: liquor zinci chloridi or hydrochloric acid solution are slowly added upper step gained zinc ammino close and separate out solid, suction filtration in the solution behind the stirring reaction;
Or synthesis mode two: gained zinc ammino of upper step is closed solution cooling, separate out dichloro diamino zinc solid, suction filtration, air-dry, then the dichloro diamino zinc solid after air-dry is joined and carry out synthetic reaction in liquor zinci chloridi or the hydrochloric acid solution and separate out solid, suction filtration;
Step 5: washing
Behind the suction filtration gained solid is washed with pure water, the suction filtration oven dry namely obtains basic zinc chloride.
3. method according to claim 2 is characterized in that, it is 55%～65% that the secondary zinc oxide in the step 1 contains the zinc mass percent; Ammonium chloride solution is to adopt chloride solid to add pure water or to add the aqueous solution of containing ammonium chloride formulated, and wherein the mass percent of containing ammonium chloride is 20%～30%; In the described ammonium chloride solution in ammonium chloride and the secondary zinc oxide mol ratio of zinc oxide be 2 ~ 6:1.
4. method according to claim 3 is characterized in that, step 1 leaching reaction condition: speed of agitator is 225 ~ 675 rev/mins, and reaction temperature is 60 ~ 90 ℃, and pH value is 5.0 ~ 8.0, and the reaction time is 30 ~ 90 minutes.
5. method according to claim 2 is characterized in that, to contain the mass percent of hydrogen peroxide be 27.5% to hydrogen peroxide in the described step 2, and the quality of hydrogen peroxide accounts for 2%～6% of secondary zinc oxide quality, and the deironing reaction time is 20 ~ 60 minutes.
6. method according to claim 2 is characterized in that, the zinc powder consumption is that every liter of filtrate adds 3～10g, conditions of replacement reaction in the described step 3: speed of agitator is 225 ~ 675 rev/mins, and reaction temperature is 60 ~ 90 ℃, and the reaction time is 30 ~ 90 minutes.
7. method according to claim 6, it is characterized in that, zinc powder is divided into twice adding in the described step 3: add first 55% ~ 72% of total zinc powder quality, stirring reaction filtered after 15 ~ 60 minutes, and then in filtrate, adding remaining zinc powder, stirring reaction is suction filtration after 15 ~ 40 minutes.
8. method according to claim 2, it is characterized in that, synthesis mode one in the described step 4: to close the mol ratio of dichloro diamino zinc in the solution be 0.5 ~ 1.5:4 for zinc chloride and zinc ammino in the liquor zinci chloridi, to close the mol ratio of dichloro diamino zinc in the solution be 1.5 ~ 2.5:5 for hydrogen chloride and zinc ammino in the hydrochloric acid solution, to close the liquor capacity ratio with the zinc ammino be 1.5 ~ 2.5:1 for liquor zinci chloridi or hydrochloric acid solution in the reaction system, adding liquor zinci chloridi or hydrochloric acid solution speed is 8 ~ 12ml/min, synthetic reaction condition is: speed of agitator is 225 ~ 675 rev/mins, reaction temperature is 70 ~ 90 ℃, the pH value is 5.0 ~ 8.0, and total time is 60 ~ 120 minutes.
9. method according to claim 2, it is characterized in that, synthesis mode two in the described step 4: zinc chloride is that hydrogen chloride is 1.5 ~ 2.5:5 with the mol ratio of separating out solid dichloro diamino zinc in 0.5 ~ 1.5:4, the hydrochloric acid solution with the mol ratio of separating out solid dichloro diamino zinc in the liquor zinci chloridi, liquor zinci chloridi or hydrochloric acid solution and dichloro diamino zinc solid liquid-solid ratio are 7 ~ 12:1 in the reaction system, synthetic reaction condition is: speed of agitator is 225 ~ 675 rev/mins, reaction temperature is 70 ~ 90 ℃, the pH value is 5.0 ~ 8.0, and total time is 60 ~ 120 minutes.
10. method according to claim 2 is characterized in that, after the gained solid is amount cyclic washing, the suction filtration 2 ~ 5 times of 5 ~ 9:1 with pure water by liquid-solid ratio in the described step 5, and 65 ~ 85 ℃ of lower 6 ~ 10 hours oven dry, i.e. gained basic zinc chlorides.
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| RU2621999C1 (en) * | 2016-01-11 | 2017-06-08 | Федеральное государственное бюджетное научное учреждение "Курский научно-исследовательский институт агропромышленного производства" | Composition for stimulation of nonspecific resistance and metabolism of broiler chicks |
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| CN114304395A (en) * | 2022-01-17 | 2022-04-12 | 株洲冶炼集团股份有限公司 | Method for preparing feed additive basic zinc chloride by using zinc hypoxide as raw material |
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