你不知道的磷酸一二钙

        磷矿石多产于沉积岩,也有产于变质岩和火成岩,除个别情况外,矿物中的磷总是以正磷酸盐形态存在,磷的主要矿物为磷灰石。磷是重要的化工原料,也是农作物生长的必要元素,工业用磷必须大量从磷矿中提取,用于制造黄磷、赤磷、磷酸、磷肥、磷酸盐。英文名为PHOSPHATE ROCK 。分子式:3Ca3(PO4)2·CaR2。

        磷的物理性质: 游离态磷有白磷、红磷和黑磷三种同素异型体.

        白磷: 分子是由四个磷原子构成的正四面体.键角60°. 白色蜡状, 因常带有黄色, 有叫黄磷. 难溶于水,易溶于非极性溶剂如CS2,有剧毒(0.01g―0.06g致命),着火点40℃ 所以少量的白磷保存在冷水;

        红磷: 复杂的大分子, 结构尚未完全清楚, 但已知其结构中有磷原子构成的环和链,棕红色粉末,基本无毒,常压下加热则升华为磷蒸汽, 遇冷凝结为白磷,难溶于水和二硫化碳等;

       黑磷: 黑色有金属光泽的晶体, 它是用白磷在很高压强和较高温度下转化而成的磷, 使用价值不大。

        我国磷矿资源比较丰富,已探明的资源储量仅次于摩洛哥和美国,居世界第3位。云南、贵州、四川、湖北和湖南5省是我国主要磷矿资源储藏地区,储量达98.6亿t,占全国总储量的74.5%。

        磷化工包括磷肥工业、黄磷及磷化物工业、磷酸及磷酸盐工业、有机磷化物工业、含磷农药及医药工业等等。世界上磷矿石的消费结构中约80%左右生产磷肥后用于农业,其余的用于提取黄磷、磷酸及制造其它磷酸盐系列产品。磷化工产品在工业、国防、尖端科学和人民生活中已被普遍应用。除了在农业中用作磷肥、含磷农药、家禽和牲畜的饲料以外,在洗涤剂、冶金、机械、选矿、钻井、电镀、颜料、涂料、纺织、印染、制革、医药、食品、玻璃、陶瓷、搪瓷、水处理、耐火材料、建筑材料、日用化工、造纸、弹药、阻燃及灭火等方面广泛使用。随着科技的发展,高纯度及特种功能磷化工产品在尖端科学、国防工业等方面被进一步的推广应用,出现了大量新产品,如:电子电气材料、传感元件材料、离子交换剂、催化剂、人工生物材料、太阳能电池材料、光学材料等等。由于磷化工产品不断向更多的产业部门渗透,特别是在尖端科学和新兴产业部门中的应用,使磷化工成为国民经济中的一个重要的产业。磷化工产品在人们的衣、食、住、行各个领域,发挥着越来越重要的作用

        采矿方法:我国磷矿的开采方式分为地下开采和露天开采两大类;地下开采约占开采总产量的60%,其采矿方法主要为房柱法。露天开采有代表性的大中型矿山是云南磷化学工业(集团)公司、昆阳、晋宁磷矿、湖北黄麦岭磷化工集团公司、贵州瓮福、湖北荆襄大峪口磷矿,约占磷矿总产量的40%。

        本发明涉及一种制造磷酸一二钙的方法,具体涉及一种利用稀磷酸与含钙化合物(碳酸钙、氧化钙、氢氧化钙及脱氟磷酸三钙)进行两步液相中和反应生产磷酸一二钙的方法

        饲料级磷酸一二钙是在性能上介于饲料级磷酸二氢钙与饲料级磷酸氢钙之间,其基本组成为磷酸氢钙与磷酸二氢钙的矿物质饲料添加剂,由于在磷的组成上既含有水溶磷又含有枸溶磷,因而在适用范围上既适用畜禽饲料,也作为水产饲料的矿物质饲料添加剂,尤其是用在畜禽饲料中与磷酸氢钙相比磷的消化利用率高出7%-14%。该品种在国内已逐步得到推广,在国外已得到广泛的应用。
        目前磷酸一二钙的生产方法有两种一种是采用稀磷酸与沉淀法磷酸氢钙半成品或成品反应,让一部分沉淀法磷酸氢钙与磷酸作用生成磷酸二氢钙,生成的含有磷酸氢钙与磷酸二氢钙的料浆经喷雾干燥,制得微粒状的磷酸一二钙产品,例如ZL01107221.0。
        另一种方法是国外普遍采用的浓磷酸“固相反应”法,用五氧化二磷为51-54%的浓磷酸与一定量配比的碳酸钙进行固相反应,反应结束后物料经熟化、粉碎、筛分得到磷酸一二钙的产品。例如英国KUAERNER工艺,意大利BASLINI PROFILE工艺等均采用碳酸钙、氧化钙粉与五氧化二磷50%左右的浓磷酸固相转化反应,直接得到饲料级磷酸一二钙产品。
        现行的两种工艺方法都存在不同的缺陷第一种方法采用磷酸与磷酸氢钙半成品反应,第一步要制得沉淀法磷酸氢钙半成品使生产工艺过程变长,在制得沉淀法磷酸氢钙的同时产生了白磷肥与母液沉淀和废水,应用该工艺路线生产成本高、磷的利用率低、环境影响大。
        另一种方法采用浓缩净化磷酸与碳酸钙直接反应,虽不再产生白磷肥与母液沉淀,磷的利用率提高,但由于采用磷酸浓缩脱氟技术,磷酸浓缩装置投入大、设备维护费用高;同时因采用浓磷酸与碳酸钙固相转化反应,熟化时间长,物料反应不完全,产品纯度不高。最重要的是由于反应体系的游离水不足,使得生成的磷酸氢钙与磷酸二氢钙结晶水不完全。据四川农大曹惠(2003)和RUCKER(1968)的研究发现含结晶水的磷酸盐在酸性环境下的溶解速度要大于不含结晶水磷酸盐的溶解速度,含结晶水的磷酸盐在小肠胃酸的作用下能迅速溶解被动物吸收,因此动物对含结晶水的磷酸盐的吸收利用率要高于不含结晶水的磷酸盐,所以浓磷酸固相反应生产的磷酸一二钙产品的实际生物学效价低于含结晶水完全的磷酸一二钙产品。
        本发明所采用的磷酸一二钙生产方法克服了上述两种生产方法的不足。本发明直接采用稀磷酸与含钙化合物(碳酸钙、氧化钙、氢氧化钙及脱氟磷酸三钙)进行第一步液相中和反应,生成磷酸二氢钙的料浆,再向该料浆中加入含钙化合物(碳酸钙、氧化钙、氢氧化钙)进行第二步液相中和反应,使一部分磷酸二氢钙转化为磷酸氢钙生成含磷酸氢钙和磷酸二氢钙的混合料浆,再将该料浆进行喷雾干燥,获得磷酸一二钙产品。
        本发明直接采用稀磷酸与含钙化合物反应,原料便宜易得,无白肥、废水排放,生产成本低;并且在料浆反应的全过程始终是液相反应,干燥过程采用闪干,湿球温度低,因而产品结晶水保持完全,产品质量优异。

        产品名称 磷酸一二钙

        产品英文简称 MDCP

        产品别名 磷酸氢钙

        分子式 Ca(H2PO4)2•H2O+CaHPO4•2H20

        产品用途 用作饲料添加剂,多用于补充幼小畜禽动物对磷和钙的需求。

        物化性质 磷酸一二钙,干燥后呈松散的白色粉状结晶体或颗粒。产品呈中性,熔于稀酸,40%溶于水,加热至90℃左右开始逐渐失去结晶水。

        磷酸一二的优势

        颗粒状一二钙与粉状氢钙相比,减少粉尘,改善饲料厂车间加工环境,尤其是预混料粉尘较大,物料浪费严重,而且存在火灾安全隐患,使用一二钙可以有效的减少物料的浪费和成本流失

        磷酸一二钙总磷21%,水溶磷含量高。磷酸氢钙总磷16.5%,不含水溶磷,它只能通过溶于酸来消化吸收,吸收率只有60%~70%左右,剩下的就随粪便排出体外,造成资源浪费和环境污染,而磷酸一二钙即溶于酸又溶于水,比氢钙吸收率高20%左右,生物学效价更高,即减少环境污染更节约成本。

        磷酸氢钙PH值=7~8,磷酸一二钙PH值=3.5~4.5呈酸性,提高饲料适口性,减少酸化剂用量,改善肠胃道环境,缓解预混料氧化、变色。

        磷酸一二钙遵循欧洲重金属标准,远低于国内标准,减轻肝肾负担,提高动物健康指标,例如像帝斯曼这样的很少外企,还有集团公司要求氢钙中砷在15ppm一下,国内标准是30ppm一下,欧洲标准是10ppm一下,一二钙砷含量低于企业要求。

        磷酸一二钙价格随磷酸氢钙价格上下浮动。磷酸一二钙的生物学效价比磷酸氢钙高,与农科院合作的最新实验数据结果高出20%。为了稳妥起见,我们推荐磷酸一二钙的生物学效价比磷酸氢钙的高出10%,氢钙添加量:一二钙添加量=1:0.7,就可以达到您现在的磷的水平。

       千里之行始于足下

       今年是潍坊利民饲料成立15 周年,风雨兼程公司一直致力于国内磷酸盐的发展和推广

        磷酸一二钙从无到有,时间证明了这条路并不平坦,也验证了一个公司的发展壮大历程。感恩一路陪伴着的你们。

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