高纯硼酸及其钠盐和锌盐的制备和表征
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摘要
硼酸、硼砂是硼化工的基础性原料,在传统行业和高技术领域都有广泛的应用。目前国内对工业硼酸、硼砂的纯化技术距离制备核工业级硼酸和高硼硅酸盐玻璃用硼砂还有一定差距,杂质含量达不到要求。同时,随着高温工程塑料的发展,一些特种塑料的加工温度已经接近目前商业化的低水合硼酸锌的分解温度。本文以对硼酸、硼砂进行深加工,提高附加值为目的,以工业级的硼酸和硼砂作为原料,分别通过酯化-间歇精馏工艺和络合-结晶工艺得到核工业级硼酸和高硼硅酸盐玻璃用硼砂,并考察了主要的工艺参数。在此基础上制备了一种新型的高热稳定性的低水合硼酸锌,表征了产物形貌并分析了影响反应的因素。主要研究内容如下：
(1)核工业级硼酸的制备工艺研究。在固体酸催化下以酯化-间歇精馏工艺制备了核工业级硼酸。研究了硼酸与甲醇的物料比、收集共沸物馏分的温度、回收过量甲醇的温度、水解用水量等条件对反应转化率、产率的影响。使用电感耦合等离子体原子发射光谱和离子色谱对产物纯度进行了表征。实验中硼酸转化率不低于85%,产率70～75%,纯度达到核工业级标准。
(2)络合-结晶法制备高纯十水、五水硼砂的工艺研究。基于络合平衡理论和络离子的稳定常数,利用硼砂的溶解度梯度,制备出高纯度的十水硼砂。使用电感耦合等离子体原子发射光谱对产物主要阳离子杂质进行了表征。考察了络合剂种类和用量、络合时间、络合温度以及溶液浓度对络合效果的影响。同时与五水硼砂高温结晶工艺衔接,一步得到满足高硼硅酸盐玻璃工业需求的高纯度的五水硼砂。
(3)新型硼酸锌Zn6O(OH)(BO3)3的制备研究。以十水硼砂和硫酸锌为原料,在表面活性剂作用下制备了颗粒状硼酸锌Zn60(OH)(B03)3。使用X射线粉末衍射(XRD)、扫描电子显微镜(SEM)、傅里叶变换红外光谱(FT-IR)等进行了表征。研究了硼砂和硫酸锌的摩尔比、反应温度、反应时间对产物产率的影响,产物平均粒径1.21μm,分解温度高于500℃；反应体系中引入聚乙二醇时可以降低平均粒径至0.73μm,同时出现片层状的表面结构。
Boric acid and borax are the basis of boron industry as raw materials. They have a wide range of applications in both traditional industries and high-tech fields. At present, the domestic purification technologies of industrial boric acid and borax have a certain gap for preparation of nuclear grade boric acid and borax for high-borosilicate glass. Impurity content is obviously higher than standard or required. With the development of high-temperature engineering plastics, the processing temperature of some specialty plastics is close to the decomposition temperature of the commercial low hydrated zinc borate flame retardants. This paper has deeply processed boric acid and borax in the aim of increasing added values, using industrial grade boric acid and borax as raw materials to produce nuclear grade boric acid and borax meeting the requirement of high borosilicate glass industry by esterification-batch distillation process and complexation-crystallization process, respectively. And the main process parameters have been examined. On this basis, a new high thermal stability low hydrated zinc borate which raises highest decomposition temperature from currently415℃to500℃and higher has been prepared. The morphologies of this zinc borate were characterized and influencing factors on preparation process were studied. The main contents are as follows:
(1) Preparation process of nuclear grade boric acid has been studied. Using solid acid as catalyst, nuclear grade boric acid was prepared by esterification-batch distillation process and process conditions have been determined. Effect of molar ratio of boric acid and methanol, temperature of collecting azeotrope of trimethyl borate ester and methanol, temperature of excessive methanol recovery and water amount used in hydrolysis to conversion ratio and yield were studied. Use inductively coupled plasma atomic emission spectrometry and ion chromatography to characterize the purity of the product. Experiments show boric acid conversion rate of no less than85%and a70～75%yield. The purity of the product meets nuclear industry requirement..
(2) Preparation processes of high purity borax decahydrate and borax pentahydrate by complex-crystalization method have been studied. Based on complexing balanced theory and stability constants of complex ions, borax solubility gradient has been used on borax purification. Main cationic impurities of the product were characterized using inductively coupled plasma atomic emission spectrometry. The influences of type and amount of complexing agent, time of complexation, complex temperature and concentration on the complexation have been studied and high purity borax decahydrate has been prepared. Then the process was combined with borax pentahydrate borax high temperature crystallization process and high purity borax pentahydrate meeting the requirement of high-borosilicate glass industry was prepared by one step.
(3) A novel zinc borate Zn6O(OH)(BO3)3has been prepared. With borax decahydrate and zinc sulphate as raw materials, granular zinc borate Zn6O(OH)(BO3)3was prepared in the present of surfactant. Molar ratio of borax decahydrate and zinc sulphate, reaction temperature and reaction time on the yield has been studied. The product was characterized using X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FT-IR). The average particle size of product is1.21μm. The decomposition temperature is higher than500℃. The average particle size of the product can reduce to0.73μm while polyethylene glycol was introduced in reaction system. In the mean time particles show a kind of lamellar surface structure.
(1)核工业级硼酸的制备工艺研究。在固体酸催化下以酯化-间歇精馏工艺制备了核工业级硼酸。研究了硼酸与甲醇的物料比、收集共沸物馏分的温度、回收过量甲醇的温度、水解用水量等条件对反应转化率、产率的影响。使用电感耦合等离子体原子发射光谱和离子色谱对产物纯度进行了表征。实验中硼酸转化率不低于85%,产率70～75%,纯度达到核工业级标准。
(2)络合-结晶法制备高纯十水、五水硼砂的工艺研究。基于络合平衡理论和络离子的稳定常数,利用硼砂的溶解度梯度,制备出高纯度的十水硼砂。使用电感耦合等离子体原子发射光谱对产物主要阳离子杂质进行了表征。考察了络合剂种类和用量、络合时间、络合温度以及溶液浓度对络合效果的影响。同时与五水硼砂高温结晶工艺衔接,一步得到满足高硼硅酸盐玻璃工业需求的高纯度的五水硼砂。
(3)新型硼酸锌Zn6O(OH)(BO3)3的制备研究。以十水硼砂和硫酸锌为原料,在表面活性剂作用下制备了颗粒状硼酸锌Zn60(OH)(B03)3。使用X射线粉末衍射(XRD)、扫描电子显微镜(SEM)、傅里叶变换红外光谱(FT-IR)等进行了表征。研究了硼砂和硫酸锌的摩尔比、反应温度、反应时间对产物产率的影响,产物平均粒径1.21μm,分解温度高于500℃；反应体系中引入聚乙二醇时可以降低平均粒径至0.73μm,同时出现片层状的表面结构。
Boric acid and borax are the basis of boron industry as raw materials. They have a wide range of applications in both traditional industries and high-tech fields. At present, the domestic purification technologies of industrial boric acid and borax have a certain gap for preparation of nuclear grade boric acid and borax for high-borosilicate glass. Impurity content is obviously higher than standard or required. With the development of high-temperature engineering plastics, the processing temperature of some specialty plastics is close to the decomposition temperature of the commercial low hydrated zinc borate flame retardants. This paper has deeply processed boric acid and borax in the aim of increasing added values, using industrial grade boric acid and borax as raw materials to produce nuclear grade boric acid and borax meeting the requirement of high borosilicate glass industry by esterification-batch distillation process and complexation-crystallization process, respectively. And the main process parameters have been examined. On this basis, a new high thermal stability low hydrated zinc borate which raises highest decomposition temperature from currently415℃to500℃and higher has been prepared. The morphologies of this zinc borate were characterized and influencing factors on preparation process were studied. The main contents are as follows:
(1) Preparation process of nuclear grade boric acid has been studied. Using solid acid as catalyst, nuclear grade boric acid was prepared by esterification-batch distillation process and process conditions have been determined. Effect of molar ratio of boric acid and methanol, temperature of collecting azeotrope of trimethyl borate ester and methanol, temperature of excessive methanol recovery and water amount used in hydrolysis to conversion ratio and yield were studied. Use inductively coupled plasma atomic emission spectrometry and ion chromatography to characterize the purity of the product. Experiments show boric acid conversion rate of no less than85%and a70～75%yield. The purity of the product meets nuclear industry requirement..
(2) Preparation processes of high purity borax decahydrate and borax pentahydrate by complex-crystalization method have been studied. Based on complexing balanced theory and stability constants of complex ions, borax solubility gradient has been used on borax purification. Main cationic impurities of the product were characterized using inductively coupled plasma atomic emission spectrometry. The influences of type and amount of complexing agent, time of complexation, complex temperature and concentration on the complexation have been studied and high purity borax decahydrate has been prepared. Then the process was combined with borax pentahydrate borax high temperature crystallization process and high purity borax pentahydrate meeting the requirement of high-borosilicate glass industry was prepared by one step.
(3) A novel zinc borate Zn6O(OH)(BO3)3has been prepared. With borax decahydrate and zinc sulphate as raw materials, granular zinc borate Zn6O(OH)(BO3)3was prepared in the present of surfactant. Molar ratio of borax decahydrate and zinc sulphate, reaction temperature and reaction time on the yield has been studied. The product was characterized using X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FT-IR). The average particle size of product is1.21μm. The decomposition temperature is higher than500℃. The average particle size of the product can reduce to0.73μm while polyethylene glycol was introduced in reaction system. In the mean time particles show a kind of lamellar surface structure.
引文
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