XXXX郭吉原微量元素添加剂的品质与微量元素预混料变色

微量元素添加剂的品质与微量元素预混料变色,(Guo Jiyuan),2023-04-18,The Quality and Discoloration,of Trace Mineral Additive Premix,2,一、交流的内容,Content,微量元素预混料变成黄褐,-,褐色是生产中的难题之一。,Tawny-brown of trace mineral premix is one of the production problems.,变色的预混料对饲料的质量产生严峻的影响。,Discoloration of the premix has a serious impact on feeds quality.,变色的原因有多种原因，但根本原因是氧化造成的。,Many reasons for discoloration of premix,oxidation is primary reason.,微量元素添加剂的质量对变色的影响及改善方法。,Effects of discoloration on premix quality and improvement measures.,3,2004-2006,年变色的预混料给全价料的质量造成严峻的影响,生产打包时,数小时至,3,天后,Discoloration of the premix causing serious impact on mixed batch,A few hours to 3 days,when the production of packaging,4,二、微量元素预混料变色的原因,变色的原因有多种,Fe,2+,Fe,3+,、,IO,-,3,I,2,、,Mn,2+,MnO,2,硫酸亚铁被氧化,(Fe,2+,Fe,3+,),是主要因素。,Fe,2,(SO,4,),3,Fe(OH)SO,4,The reasons of discoloration for trace mineral premix,5,初始,30,天,A1,0.03,12.6,A2,0.03,43.2,B1,0.03,7.1,B2,0.03,31.7,C1,0.03,0.5,C2,0.03,10.9,D,0.03,56.1,E,0.03,25.0,Fe,3+,/Fe,%,Fe,3+,/Fe,%,预混料,6,1.,变色主要原因：硫酸锌的质量,1.1,硫酸锌生产中大量使用氧化剂除铁,Fe,2+,+H,2,O,2,+H,+,Fe,3+,+H,2,O,Fe,3+,+OH,-,Fe(OH),3,PH=1.6-1.8,加热条件,Fe,3+,水解生成黄色的黄铁矾沉淀,M,2,Fe,6,(SO),4,(OH),12,氧化剂有：,H,2,O,2,、,KMnO,4,、,NaClO,3,The primary reason for discoloration:the quality of Zinc Sulfate,7,1.2,生产中可能生成某些有氧化性的物质,(,如过氧化物,ZnO,2,),，这类物质的存在使得硫酸锌具有了“氧化性”；并有吸湿性久放易结块。,1.3,局部硫酸锌内含氯化物，使硫酸锌易结块和吸湿性，加速亚铁的被氧化。,8,硫酸锌生产中正在使用,H,2,O,2,除铁,Used of hydrogen peroxide disposed of iron,in Zinc Sulfate production,9,1.4,不同工艺生产的硫酸锌,(,用双氧水除铁和不除铁,),与同一硫酸亚铁混合,(1:1),的图片,过氧化物在酸性,碱性均有氧化性,E,0,HO2-,/,OH-,=0.88V,E,0,H2O2,/,H2O,=1.78V,10,不同的硫酸锌生产的预混料中,Fe,3+,的变化情况,石粉为载体的预混料三价铁含量的变化,沸石粉为载体的预混料三价铁含量的变化,Fe3+Changing of premix with different zinc sulfate production,Fe 3+changing of premix used,mountain meal as carrier,Fe 3+changing of premix used,zeolite as carrier,11,2.,变色原因之二：载体的,pH,值,2.1,硫酸亚铁在不同的,PH,值环境下稳定性有很大的差异,Variety stability of Ferrous Sulfate in different pH environment.,在酸性介质下,Fe,3+,+e=Fe,2+,E,0,=0.77 V,在碱性介质下,Fe(OH),3,+e=Fe(OH),2,+OH,-,E,0,=-0.56 V,可见,Fe,2+,在酸性介质下稳定性好,而在碱性介质下极易被氧化为,Fe,3+,。,Fe2+is stability in acidic medium,but easily to oxidized into Fe3+in alkaline medium.,Discoloration reason:the pH value of carrier,12,2.2,常见载体的,pH,值,pH value of the common carrier,石粉,Limestone meal,9,CaCO,3,的理论,PH=7.4,差异的原因,?,石粉粉碎时,CaCO,3,分解成,CaO,，,CaO+H,2,O=Ca(OH),2,沸石粉,zeolite,7-8,稻壳粉,p,owdered rice hulls,5-6,脱脂米糠,rice bran solvent extracted,6-7,麦麸,wheat bran,6.5,玉米芯粉,maize cob meal,5,磷酸氢钙,Calcium Hydrogen Phosphate,5-6,13,不同载体的预混料变 况,The discoloration of premix in different carrier,14,3.,变色原因之三：硫酸亚铁的质量,3.1,硫酸亚铁,(FeSO,4,H,2,O),有不同的质量差异，主要表现是稳定性差异大。,钛白粉的副产品,FeSO,4,7H,2,O,是饲料级,硫酸亚铁的主要原料，杂质主要为,TiO,2,、,TiOSO,4,好的产品初始,Fe,3+,=200 ppm,，差的产品初始,Fe,3+,500 ppm,，在水中被氧化迅速。,硫酸清洗钢铁外表,(,除锈,),所得废液和由废铁生产的,FeSO,4,7H,2,O,，,杂质复杂稳定性差。,Discoloration reason:the quality of Ferrous Sulfate,15,4.,变色原因之四：硫酸铜的游离水,4.1,在铜、铁、锌、锰这几个微量元素中,硫酸铜带,5,个结晶水,CuSO,4,5H,2,O,，,其余均是一水盐。,FeSO,4,H,2,O,、,ZnSO,4,H,2,O,、,MnSO,4,H,2,O,CuSO,4,5H,2,O=,CuSO,4,H,2,O,+,4H,2,O (114,0,C),CuSO,4,H,2,O,和,CuSO,4,吸水性強,不稳定；,4.2,在,CuSO,4,5H,2,O,中除结晶水外还有游离水。,游离水：好的产品,0.5%,H,2,O,是,H,+,和,OH,-,的传递剂,使一些氧化,-,复原反响更易进行。,Discoloration reason:free moisture in Copper Sulfate,16,5.,变色原因之五：其它原因,5.1,碘酸钙未预稀释,直接投料与硫酸亚铁反响,-,发生的情况很少。,Calcinol is not pre-diluted,then directly action with Ferrous Sulfate,rarely happened.,IO,3,-,+Fe,2+,+H,+,=Fe,3+,+I,2,+H,2,O,5.2,载体的,pH,值更高,-,发生的情况更少。,The pH value of carrier is highest.Such case is less happened.,强碱性,Mn,2+,被氧化成,MnO,2,H,2,O,引起变色,5.3,温度和光照,Temperature and light,Other reasons for discoloration,17,小结：微量元素预混料变色解析,A,1.,硫酸锌中氧化性物质的残留和载体的,pH,值，在预混料变色中起主导作用，其它的为次要因素。,The residual of oxidation substances and pH value of carriers in Zinc Sulfate play a leading role for discoloration of trace minerals premix.,2.,在上述,2,个主要因素中硫酸锌中氧化性物质的残留更重要,(,决定性的,),，饲料级硫酸锌应把氧化性物质残留作为质控工程。,Above-mentioned two major factors,the residual of oxidation substances in Zinc Sulfate is more important(crucial).So feed-grade Zinc Sulfate should put residual of oxidation substances as quality control item.,Summary:Analysis of discoloration in trace minerals premix,18,3.,改变载体的,pH,值可减缓硫酸亚铁被氧化的速度，使变色时间延迟，微量元素预混料的载体应采用弱酸性,-,中性物质，石粉不能做预混料的载体（碱性太强,pH,10,），沸石粉也应慎用。,Change of the pH value of carrier can decrease oxidation rate in Ferrous Sulfate,then delay the time of discoloration.Weak acid-neutral materials of carrier was used in trace minerals premix,limestone meal should not be used(too alkaline PH 10),and zeolite should be used with caution.,4.,关注硫酸亚铁的稳定性。,Concern about the stability of Ferrous Sulfate.,19,三、铜铁锌锰微量元素添加剂质控要点,1.,硫酸锌,ZnSO,4,H,2,O,质控要点,Quality control of Zinc Sulfate,饲料级硫酸锌含量,the content of feed grade Zinc Sulfate,高含量高质量,high content high quality,锌含量的测定方法,determination methods,氧化性物质残留,-,零容忍,the residual of oxidation substances,重金属,heavy metals-,-,镉,Cd,、铅,Pb,、铬,Cr,氯化物的残留,the residual of chloride,Quality control of trace minerals additive,20,硫酸锌含量的测定方法,A,称取,0.15g,一水硫酸锌或,0.2g,七水硫酸锌（准确至,0.0002g,）于,250ml,三角瓶中，加,10ml,水，,1ml,硝酸溶液，摇匀，盖上外表皿，电炉上小火煮沸,1min,，加水,50ml,、氟化铵溶液,10ml,、硫脲溶液,5 ml,、抗坏血酸,0.2g,，摇匀溶