脲硫酸复肥工艺优化及工业化的基础研究
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摘要
清洁型脲硫酸复肥生产工艺能够直接利用中低品位的磷矿生产NPK复合肥,因其生产工艺简单、产品性能优良且在生产过程中无“三废”排放,具有较好经济效益、社会效益和环境效益。本文针对清洁型脲硫酸复肥生产工艺技术进行了深入系统的研究,主要对脲硫酸溶液的物性数据如密度、粘度进行了测定与关联,对脲硫酸溶液分解磷矿的工艺条件进行了优化,制备了脲硫酸复肥并对其氮素缓释性能进行了研究。
1脲硫酸溶液密度、粘度的测定与关联。采用比重瓶法测定了组成为(尿素：硫酸：水(摩尔比)=X：1：Y；X=0.5、1、1.5、2、2.5、3、3.5,Y=1、2)的脲硫酸溶液在283.15K-363.15K范围内的密度；采用旋转粘度计测定了组成为(尿素：硫酸：水=X：1：Y；X=1、1.5、2、2.5、3、3.5,Y=1、2)的脲硫酸溶液在288.15K-363.15K范围内的粘度。实验结果表明：
脲硫酸溶液组成一定时,溶液的密度随温度的增加而减小；温度一定时,脲硫酸溶液的密度随尿素的摩尔分率的增加而减小,随水的摩尔分率增加而减小。脲硫酸溶液的密度(p/g·cm3)与溶液中尿素摩尔分率m和溶液体系的温度(T/K)之间的关系满足如下方程：
脲硫酸溶液组成一定时,溶液的粘度随温度的升高而减小。溶液粘度减小的过程可以分为三个阶段：粘度急剧减小阶段、粘度缓慢减小阶段、粘度基本不变阶段。温度一定时,溶液的粘度随尿素的摩尔分率增加呈现先增大后减小趋势,随水的摩尔分率的增加而减小。脲硫酸溶液的粘度(η/mPa·s)与温度(T/K)之间的关系可以由如下方程拟合：
2脲硫酸溶液分解磷矿工艺条件的优化。考察了脲硫酸溶液分解中、低品位的磷矿过程中：反应时间、反应温度、搅拌速度、矿粉粒度、酸解剂用量、酸解剂配比、活化剂的使用等对磷矿转化率的影响,获得了脲硫酸溶液分解磷矿较优的工艺条件。在优化的工艺条件下,脲硫酸溶液分解磷矿的转化率能够达到94%左右,工艺条件的优化为脲硫酸复合肥的工业化实施提供了依据。
3脲硫酸复肥的制备及氮素缓释性能的研究。采用圆盘造粒法制备了两种养分规格的脲硫酸复肥,以考察脲硫酸复肥的缓释性能。本文采用水溶出率法对普通复合肥料和脲硫酸复肥的养分释放特性进行评价,实验结果表明与普通的复合肥料相比脲硫酸复肥具有一定的缓释效果。脲硫酸复肥中的氮素有两种形态即：络合态和非络合态,其中络合态氮是以络合物CaSO4·XCO(NH2)2的形式存在,脲硫酸复肥中有缓释性的就是这部分络合态的氮。
Clean process of urea-sulfuric acid compound fertilizer technology can produce NPK fertilizers directly with low grade phosphate rock has great economic, social and environmental benefits due to its simple process, excellent performance and no "three wastes" discharge.In this paper, clean process of urea sulfuric acid compound fertilizer technology was systematically studied. Physical properties of urea-sulfuric acid, such as density and viscosity, were measured and related; The technology conditions of decomposing phosphate rock with urea sulfuric-acid were optimized; Urea-sulfuric acid compound fertilizer were prepared and the slow release properties of nitrogen were also studied.
1 Determination and correlation of densities and viscosities of solutions with urea-sulfuric acid. Densities data of the solution (urea:sulfuric acid:water=X:1:Y; X=0.5,1,1.5,2,2.5,3,3.5,Y=1,2) were measured by Gay-Lussac type pycnometers at the temperature range of (283.15 to 363.15) K. Viscosities data of the solution (urea:sulfuric acid:water=X:1:Y; X=1,1.5,2,2.5,3,3.5,Y=1,2) were measured by rotational viscometer at the temperature range of (288.15 to 363.15) K.The results show that:
When the composition of the solutions with urea-sulfuric acid is constant, the density decreases with increasing temperature. When the temperature is constant, the density of the solutions decreases with increasing mole fraction of urea and the mole fraction of water.It is found that the density (ρ/g·cm-3) of urea-sulfuric acid has the correlation with mole fraction of urea and temperature(T/K):
When the composition of the solutions with urea-sulfuric acid is constant, the viscosity decreases with increasing temperature. The processs of viscosity can be divided into three phases:sharply decreasing phase, slowly decreasing phase, stable phase. When the temperature is constant, as the mole fraction of urea increases, the viscosity increases at first, but then decreases;The viscosity decreases with the increasing mole fraction of water. It is found that the viscosity (η/mPa·s) of urea-sulfuric acid has the correlation with temperature(T/K):
2 The technology optimization of decomposition of low grade phosphate rock using urea-sulfuric acid. The influencing factors, such as reation time, reation temperature, stirring speed, consumption of urea-sulfuric acid, particle size of phosphorus rock, composition of acidolysis agent and consumption of active addition agent have been investigated in the acidification by urea sulfuric acid for low grade phosphate rock and the better process conditions have been obtained. Under the optimized process conditions, conversion rate can be up to 94% or so. Optimized process conditions provide a basis for the industrialization of producing compound fertilizer with urea-sulfuric acid.
3 Preparation of urea-sulfuric acid compound fertilizer and determination on nitrogen slow release properties. Two standard urea-sulfuric acid compound fertilizers of different nutrient specifications, were prepared by disc granulation. In order to evaluate the nitrogen slow release effects of commercialized compound fertilizer and prepared urea-sulfuric acid compound fertilizer, water-immersion rate method was adopted. Results show that urea-sulfuric acid compound fertilizer has better slow release capability than commercialized compound fertilizer. Nitrogen in urea-sulfuric acid compound fertilizer is of two types:one is complex state and the other is non-complex state. Furthermore, the complex nitrogen, which has the ability of slow releasing, exists as CaSO4·XCO(NH2)2 in urea-sulfuric acid compound fertilizer.
1脲硫酸溶液密度、粘度的测定与关联。采用比重瓶法测定了组成为(尿素：硫酸：水(摩尔比)=X：1：Y；X=0.5、1、1.5、2、2.5、3、3.5,Y=1、2)的脲硫酸溶液在283.15K-363.15K范围内的密度；采用旋转粘度计测定了组成为(尿素：硫酸：水=X：1：Y；X=1、1.5、2、2.5、3、3.5,Y=1、2)的脲硫酸溶液在288.15K-363.15K范围内的粘度。实验结果表明：
脲硫酸溶液组成一定时,溶液的密度随温度的增加而减小；温度一定时,脲硫酸溶液的密度随尿素的摩尔分率的增加而减小,随水的摩尔分率增加而减小。脲硫酸溶液的密度(p/g·cm3)与溶液中尿素摩尔分率m和溶液体系的温度(T/K)之间的关系满足如下方程：
脲硫酸溶液组成一定时,溶液的粘度随温度的升高而减小。溶液粘度减小的过程可以分为三个阶段：粘度急剧减小阶段、粘度缓慢减小阶段、粘度基本不变阶段。温度一定时,溶液的粘度随尿素的摩尔分率增加呈现先增大后减小趋势,随水的摩尔分率的增加而减小。脲硫酸溶液的粘度(η/mPa·s)与温度(T/K)之间的关系可以由如下方程拟合：
2脲硫酸溶液分解磷矿工艺条件的优化。考察了脲硫酸溶液分解中、低品位的磷矿过程中：反应时间、反应温度、搅拌速度、矿粉粒度、酸解剂用量、酸解剂配比、活化剂的使用等对磷矿转化率的影响,获得了脲硫酸溶液分解磷矿较优的工艺条件。在优化的工艺条件下,脲硫酸溶液分解磷矿的转化率能够达到94%左右,工艺条件的优化为脲硫酸复合肥的工业化实施提供了依据。
3脲硫酸复肥的制备及氮素缓释性能的研究。采用圆盘造粒法制备了两种养分规格的脲硫酸复肥,以考察脲硫酸复肥的缓释性能。本文采用水溶出率法对普通复合肥料和脲硫酸复肥的养分释放特性进行评价,实验结果表明与普通的复合肥料相比脲硫酸复肥具有一定的缓释效果。脲硫酸复肥中的氮素有两种形态即：络合态和非络合态,其中络合态氮是以络合物CaSO4·XCO(NH2)2的形式存在,脲硫酸复肥中有缓释性的就是这部分络合态的氮。
Clean process of urea-sulfuric acid compound fertilizer technology can produce NPK fertilizers directly with low grade phosphate rock has great economic, social and environmental benefits due to its simple process, excellent performance and no "three wastes" discharge.In this paper, clean process of urea sulfuric acid compound fertilizer technology was systematically studied. Physical properties of urea-sulfuric acid, such as density and viscosity, were measured and related; The technology conditions of decomposing phosphate rock with urea sulfuric-acid were optimized; Urea-sulfuric acid compound fertilizer were prepared and the slow release properties of nitrogen were also studied.
1 Determination and correlation of densities and viscosities of solutions with urea-sulfuric acid. Densities data of the solution (urea:sulfuric acid:water=X:1:Y; X=0.5,1,1.5,2,2.5,3,3.5,Y=1,2) were measured by Gay-Lussac type pycnometers at the temperature range of (283.15 to 363.15) K. Viscosities data of the solution (urea:sulfuric acid:water=X:1:Y; X=1,1.5,2,2.5,3,3.5,Y=1,2) were measured by rotational viscometer at the temperature range of (288.15 to 363.15) K.The results show that:
When the composition of the solutions with urea-sulfuric acid is constant, the density decreases with increasing temperature. When the temperature is constant, the density of the solutions decreases with increasing mole fraction of urea and the mole fraction of water.It is found that the density (ρ/g·cm-3) of urea-sulfuric acid has the correlation with mole fraction of urea and temperature(T/K):
When the composition of the solutions with urea-sulfuric acid is constant, the viscosity decreases with increasing temperature. The processs of viscosity can be divided into three phases:sharply decreasing phase, slowly decreasing phase, stable phase. When the temperature is constant, as the mole fraction of urea increases, the viscosity increases at first, but then decreases;The viscosity decreases with the increasing mole fraction of water. It is found that the viscosity (η/mPa·s) of urea-sulfuric acid has the correlation with temperature(T/K):
2 The technology optimization of decomposition of low grade phosphate rock using urea-sulfuric acid. The influencing factors, such as reation time, reation temperature, stirring speed, consumption of urea-sulfuric acid, particle size of phosphorus rock, composition of acidolysis agent and consumption of active addition agent have been investigated in the acidification by urea sulfuric acid for low grade phosphate rock and the better process conditions have been obtained. Under the optimized process conditions, conversion rate can be up to 94% or so. Optimized process conditions provide a basis for the industrialization of producing compound fertilizer with urea-sulfuric acid.
3 Preparation of urea-sulfuric acid compound fertilizer and determination on nitrogen slow release properties. Two standard urea-sulfuric acid compound fertilizers of different nutrient specifications, were prepared by disc granulation. In order to evaluate the nitrogen slow release effects of commercialized compound fertilizer and prepared urea-sulfuric acid compound fertilizer, water-immersion rate method was adopted. Results show that urea-sulfuric acid compound fertilizer has better slow release capability than commercialized compound fertilizer. Nitrogen in urea-sulfuric acid compound fertilizer is of two types:one is complex state and the other is non-complex state. Furthermore, the complex nitrogen, which has the ability of slow releasing, exists as CaSO4·XCO(NH2)2 in urea-sulfuric acid compound fertilizer.
引文
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