磷石膏基胶凝材料的制备理论及应用技术研究
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摘要
磷石膏是湿法生产磷酸过程中排出的硫酸钙固体废弃物,通常以二水硫酸钙的形式存在,生产1吨P2O5约排放4.5-5.5吨磷石膏。与天然石膏相比,磷石膏中通常含有磷、氟、有机物等成分影响其使用性能,并增加其利用成本,目前主要采用堆存处理。随着我国磷化工行业的迅速发展,2011年,我国磷石膏的新增年产量接近7千万吨,利用率不到20%,累计堆积量已经超过3亿吨,不仅占用大量的土地、浪费资源,而且其中的有害组分还对周围土壤、植被、水系和空气造成严重的污染。2006年国家环保总局将磷石膏列为危险固体废弃物,磷石膏问题已经成为严重制约磷化工行业可持续发展和环境保护的世界难题。
国内外利用磷石膏代替天然石膏制备胶凝材料方面存在的主要问题有：(1)磷石膏基胶凝材料的生产成本较高,尽管磷石膏中的Ca2SO4·2H2O含量很高,但其中的有害杂质对其应用性能影响很大,一般都需要预处理后才能使用,经预处理后的磷石膏与天然石膏相比不但价格方面没有任何优势,而且产品性能也存在一定的差异；(2)使用性能优异、附加值高的高强α半水石膏类胶凝材料要在高温高压的蒸压气氛中制备,存在工艺复杂、能耗高、操作控制不便、性能不稳定、生产成本高的问题,从而限制了其广泛应用；(3)常压水热电解质溶液中制备α半水石膏具有反应条件温和、便于操作的特点,但目前的研究主要还集中在实验室和理论研究阶段,且限于天然石膏、脱硫石膏等杂质含量较少的原料。
本研究依托“十二五”国家科技支撑计划项目“低成本、低能耗建筑节能技术集成研究与示范”(2011BAJ03B03)、湖北省重大科技专项计划项目“磷化工副产物高效资源化利用与产业化”(DZS0005)以及湖北省研究与开发计划项目“磷石膏的综合利用”(2009BCB030),针对磷石膏制备高强度石膏胶凝材料的理论及工艺技术难题,探讨了磷石膏基石膏胶凝材料(Phosphogypsum Based Gypsum Plaster,简称PBGP)的制备体系设计与选择、原料预处理对PBGP形成及晶体形态调控的影响、杂质对PBGP水化硬化性能的影响以及PBGP制备工艺优化及应用技术,揭示了PBGP组成一结构一性能之间的相关规律,并形成了PBGP的制备工艺、晶形调控、性能优化及工业化应用的关键理论与技术。主要工作及成果如下：
1、PBGP的体系设计与选择
在85～100℃水热环境中,分别以NaCU CaCl2及其混合物为活度剂,研究了活度剂种类和浓度、固液比以及反应温度和时间对产品性质的影响,结果表明：磷石膏在NaCl溶液中水热反应一定时间可以发生相变反应,但固相产物α半水石膏中含有其同质异构的杂质相omangwaite(Na2Ca5(SO4)6·3H2O),因而NaCl不适合作为磷石膏相变制备PBGP的活度剂；而磷石膏在CaCl2溶液中水热反应一定时间后的固相产物为α半水石膏；在24%Ca-Na-Cl溶液中,随着NaCl含量从0增加到4%,磷石膏的相变为半水石膏的时间从240min缩短为50min,且固相产物均为a-半水石膏,但随着水热反应介质中NaCl含量的增加,产物中Na2O含量也呈增加的趋势,从半水石膏晶体各晶面发育的完整和规则性降低；NaCl增大磷石膏的溶解度并促进α半水石膏晶体的成核生长,CaCl2则是由于同离子效应降低了磷石膏的溶解度,但Ca2+的活度仍比较高,表面扩散和吸附能够极大地促进α-半水石膏晶体长大。
2、原料预处理对PBGP的形成及晶形调控的影响
研究了酸性杂质、可溶盐、不溶性杂质对磷石膏相变过程、产物形态和强度的影响,并选用常用媒晶剂对PBGP的晶体形态进行调控,结果表明：原料磷石膏中可溶磷、氟为磷石膏的相变反应提供了必需的酸性环境,同时使PBGP晶体的长径比变大、晶体直径减小；自制媒晶剂NS和EN对PBGP晶习有明显的调控作用,可以得到长径比接近1的短柱状晶体,产物抗压强度在35MPa以上,其合适掺量分别为0.15%和0.4%；可溶性酸性杂质使媒晶剂的合适掺量增加,产品强度降低；可溶性钠盐使高强石膏晶体中出现细小的颗粒,强度降低；可溶性盐类杂质和有机物使PBGP晶体变得细碎,产品强度降低；不溶性杂质则使产物α半水石膏晶体向短棒状发展,晶体发育不均齐,强度增大；原状磷石膏不适合直接作为PBGP的原料使用,经水洗处理后可以大幅降低媒晶剂的使用量,优化晶体形态,提高产品强度；当PBGP晶体直径大于8μm、长径比1-3且发育相对均齐时,产品的绝干抗压强度与晶体体积呈线性相关关系.。
3、杂质对PBGP水化硬化性能的影响
研究了不同pH值的H2SO4、HCl、H3PO4以及中性环境下不同CaCl2含量对高强石膏的凝结时间、强度变化的影响与相应机理,并对影响PBGP'性能的主要因素进行了归纳,结果表明：三种酸均对高强石膏的初凝、终凝均起促进作用,且对初凝时间、终凝时间的影响规律大致相同,在不同pH值的同种酸和相同pH值的不同酸对高强石膏的凝结性能影响不同；当pH小于3.0时,H2SO4、 HCl和H3P04均会显著降低2h强度和绝干强度,当pH值为3到7之间时,抗压强度性能因酸根离子的种类与含量不同而出现不同的变化；活度剂CaCl2也会使高强石膏早凝,其对高强石膏强度尤其是绝干强度的损失随含量的增加而增强；这几类杂质均延长了加速期的反应时间,增大结晶相变热；水化产物中二水石膏相的含量只是影响产物强度的一个因素,而杂质离子H2PO4、H+、Cl-改变了结晶接触点的性质对产物绝干强度起重要的影响；CaCl2抑制了高强石膏的水化,CaCl2含量越高,高强石膏未水化的比例越高,绝干强度下降越明显。
4、PBGP的制备工艺优化及应用
在实验室范围内扩大了试验规模,测试了PBGP粉的凝结时间、强度性能,并对PBGP制备工艺进行优化,结果表明：原料水洗预处理时产生的部分废水经处理后可以循环利用；PBGP浆体经洗涤、干燥后,产物的晶体边界清晰程度有所下降,但抗压强度仍能超过40MPa; PBGP浆体滤液经沉淀剂处理后循环利用4次制备出PBGP的抗压强度在35Mpa以上,循环利用5次制备出PBGP的抗压强度在25Mpa以上；水热反应过程中,磷石膏中部分硅、铝、铁等不溶性杂质从原料中析出,从而提高了PBGP的纯度；PBGP制备工艺经优化后可以分为原料的预处理工艺、常压水热反应工艺、浆体制备工艺、PBGP粉及石膏制品的生产工艺四个过程。
Phosphogypsum (PG) is solid waste of calcium sulfate discharged from wet process phosphoric acid production.Generally,4.5-5.5tons PG are generated when per ton of P2O5are produced and most of the calcium sulfate is in the form of dihydrate (DH, CaSO4·2H2O). Currently the mainly way of disposal PG is stockpilling for the phosphorus, fluorine, organic compounds and other ingredients containing in PG affect its performance and increae its using cost compared to natural gypsum. In2011, with the growing demand of phosphoric fertilizer the production of PG was up to70million tons in China and less than20.0%is used at present.It is estimated that the accumulative total of PG is over300million tons throughout China, which not only occupies plenty of lands, waste of resources, and harmful constituents also cause serious pollution to the surrounding soil, vegetation, water and air. In2006, PG was classified as "hazardous solid waste"by SEPA (state environmental protection administration),the problem of PG disposal has been a worldwide problem that seriously hampered the sustainable development of the phosphorus chemical industry and environmental protection.
The main problems of cementitious materials preparation from PG instead of natural gypsum at home and abroad are:(1) PG based cementitious materials have higher preparation costs for the harmful impurities influencing the performace despite the high Ca2SO4·2H2O content, while PG pretreament has no superiority compared to natural gypsum not only in the price but in products performance;(2)widely useage of a-hemihydrate sulphsate calcium (a-HH) with high performance and high value-added prepared under autoclave atmosphere is restricted by the complex process, high energy consumption, inconvenience to the control, unstable performance and high price;(3) preparation of a-HH in hydrothermal electrolytic solutions with characteristic of mild reaction conditions and easy to conrol under atmospheric pressure is still at the laboratory or theoretical stage, meanwhile the raw materls are limited to natural gypsum, desulfurized gypsum or gypsum with little impurities.
Funded by Chinese National Technology Support Project "Low-cost and Energy-saving Technology Research and Demonstration of Energy-efficient Building" (Project No.2011BAJ03B03), Major Science and Technology Plan of Hubei Province" Utilization Efficiently and Industrialization of Phosphorus Chemical Byproducts"(Project No. DZS0005), and Research and Plan Project of Hubei Province"Comprehensive Utilization of Phosphogypsum"(Project No.2009BCB030), based on theoretical and technical problems of high-strength gypsum cementitious materials preparation, design and selection of Phosphogypsum Based Gypsum Plaster (PBGP) preparation system are presented in the paper. Influences of raw material pretreatment to the formation and crystal morphology control of PBGP is studied, then effects of impurities on the performance of PBGP hydration and hardening are discussed, next optimization of PBGP preparation process and industrialization technology are considered, meanwhile the relation of PBGP composition-structure-performance is diccovered, and the critical theory and technology of PBGP preparation process, crystal morphology control, performance optimization and industrialization are established. The main research work and compliments are listed are as follows:
1. Design and selection of PBGP preparation system.
At hydrothermal temperature of85℃～100℃, NaCl, CaCl2and its mixtures are selected as activity agent, respectively.Influences of activity agent type and concentration, solid-liquid ratio and the reaction temperature and time to the products are researched. The experiment results show that phase transition of PG from DH to HH can conduct in strong NaCl solution, but NaCl is not favourable for preparation of a-HH from PG phase transition, for the phase transition product of PG is a mixture of a-HH and omongwaite (Na2Ca5(SO4)6·3H2O)-a structural isomer of HH; α-HH can be obtained as the product of PG phase transiton in strong CaCl2solution; the reaction time of PG transiton to a-HH shortens from240min to50min with increasing NaCl content from0to4%in24%Ca-Na-Cl solution, but it is accompanied with increasing of Na2O content and irregular uncompleted crystal shapes in the reaction product; NaCl increases the solubility of PG and promote the nucleation and growth of HH crystal, while CaCl2reduces the solubility of PG for the common ion effect, a-HH crystal growth can be greatly accerlated by surface diffusion and adsorption of relatively high activity of Ca2+
2. Influences of raw material pretreatment to the formation and crystal morphology of PBGP
Influences of the acidic impurities, soluble salts, insoluble impurities contained in PG to phase transiton process, product shapes and compressive strength are studied, crystal modifier commonly used are choosed to modify PGGP crystal morphology. It turns out that soluble phosphate and fluoride impurities elongate a-HH crystal aspect ration, decrease a-HH crystal diameter while provide the necessary acidic conditions for PG phase transition; homemade crystal modifier NS and EN have obvious effects on a-HH cryatal habit, short columnar PBGP crystal of aspect ratio nearly1with compressive strength beyond35MPa can be obtained when the dosages of NS and EN are0.15%and0.4%respectively;solube acidic impurities increase appropriate dosage of crystal modifier and decrease the product compressive strength;soluble salts and organic matters fine a-HH crystal partles, and reduce the product strength as well; insoluble impurities shorten a-HH crystal to rode-like shape, uneven length and distribution,improve product strength;unpretreated PG is not appropriate for PBGP preparation,water-washing of raw material is beneficial for subsequent crystal modifier usage, crystal morphology control and strength of the product; linear correlation of the product dry compressive strength and crystal volume is showed when PBGP has a uniform crystal shapes of diameter≥8μm and1-3aspect ratio.
3. Effect of impurities on PBGP hydration and hardening performance
Seting time, strength variation and corresponding mechanism of high-strength gypsum in dilute solution of H2SO4、H3PO4and HC1of different pH values and in different contents of CaCl2are studied, the factors influencing PBGP performance are analyzed.The results reveal that acid solutions accelerate initial and final setting of high-strength gypsum at roughly the same rule, high-strength gypsum show different setting performance in the same acidic solutions of the different pH values or in the different acidic solutions of the same pH values;2h and dry strength values of gypsum plaster are lowered markly by H2S04,H3PO4and HC1solutions of pH values less than3.0, and the strength values vary with the kind and content of acid radical ions when the pH value is between3to7; high-strength gypsum setting may also be accerlerated by activity agent CaCl2, its strength especially dry strength loss increasing with the addition of CaCl2content; acceleration periods are all prolonged and phase change heats are all enhanced by these impurities; product strength is effected by DH phase content, while impurities ions, such as E2PO4,H+,Cl" play important impacts through changing the nature of contact points; hydration reaction of high-strength gypsum is inhibited by CaCl2addition, the higher the CaCl2content, the higher the proportion of high-strength gypsum unhydration, more obviously the dry strength decreased.
4. Optimization of PBGP preparation process and application
PBGP preparation-scal is expanded in the laboratory, setting and strength properties of PBGP are tested, and the PBGP preparation process is optimized, the results indicate that waste water from raw material pretreatment can be recycled after disposal; the product compressive strength is still more than40MPa, though crystal boundary become unsharp after PBGP slurry was washed and dried; filtrate from PBGP slurry treated by precipitator can be recycled, the compressive strength of the product is greater than35MPa and25MPa when the diltrate cycle times are4and5respectively; silicon, aluminum, iron and other insoluble impurities containing in PG can leach out during hydrothermal reaction process, thereby the purity of PBGP is improved; the optimized preparation process of PBGP can be devied into four stages,that is, raw material pretreatment, hydrothermal reaction under atmospheric pressure,slurry preparation, PBGP power and gypsum products preparation.
国内外利用磷石膏代替天然石膏制备胶凝材料方面存在的主要问题有：(1)磷石膏基胶凝材料的生产成本较高,尽管磷石膏中的Ca2SO4·2H2O含量很高,但其中的有害杂质对其应用性能影响很大,一般都需要预处理后才能使用,经预处理后的磷石膏与天然石膏相比不但价格方面没有任何优势,而且产品性能也存在一定的差异；(2)使用性能优异、附加值高的高强α半水石膏类胶凝材料要在高温高压的蒸压气氛中制备,存在工艺复杂、能耗高、操作控制不便、性能不稳定、生产成本高的问题,从而限制了其广泛应用；(3)常压水热电解质溶液中制备α半水石膏具有反应条件温和、便于操作的特点,但目前的研究主要还集中在实验室和理论研究阶段,且限于天然石膏、脱硫石膏等杂质含量较少的原料。
本研究依托“十二五”国家科技支撑计划项目“低成本、低能耗建筑节能技术集成研究与示范”(2011BAJ03B03)、湖北省重大科技专项计划项目“磷化工副产物高效资源化利用与产业化”(DZS0005)以及湖北省研究与开发计划项目“磷石膏的综合利用”(2009BCB030),针对磷石膏制备高强度石膏胶凝材料的理论及工艺技术难题,探讨了磷石膏基石膏胶凝材料(Phosphogypsum Based Gypsum Plaster,简称PBGP)的制备体系设计与选择、原料预处理对PBGP形成及晶体形态调控的影响、杂质对PBGP水化硬化性能的影响以及PBGP制备工艺优化及应用技术,揭示了PBGP组成一结构一性能之间的相关规律,并形成了PBGP的制备工艺、晶形调控、性能优化及工业化应用的关键理论与技术。主要工作及成果如下：
1、PBGP的体系设计与选择
在85～100℃水热环境中,分别以NaCU CaCl2及其混合物为活度剂,研究了活度剂种类和浓度、固液比以及反应温度和时间对产品性质的影响,结果表明：磷石膏在NaCl溶液中水热反应一定时间可以发生相变反应,但固相产物α半水石膏中含有其同质异构的杂质相omangwaite(Na2Ca5(SO4)6·3H2O),因而NaCl不适合作为磷石膏相变制备PBGP的活度剂；而磷石膏在CaCl2溶液中水热反应一定时间后的固相产物为α半水石膏；在24%Ca-Na-Cl溶液中,随着NaCl含量从0增加到4%,磷石膏的相变为半水石膏的时间从240min缩短为50min,且固相产物均为a-半水石膏,但随着水热反应介质中NaCl含量的增加,产物中Na2O含量也呈增加的趋势,从半水石膏晶体各晶面发育的完整和规则性降低；NaCl增大磷石膏的溶解度并促进α半水石膏晶体的成核生长,CaCl2则是由于同离子效应降低了磷石膏的溶解度,但Ca2+的活度仍比较高,表面扩散和吸附能够极大地促进α-半水石膏晶体长大。
2、原料预处理对PBGP的形成及晶形调控的影响
研究了酸性杂质、可溶盐、不溶性杂质对磷石膏相变过程、产物形态和强度的影响,并选用常用媒晶剂对PBGP的晶体形态进行调控,结果表明：原料磷石膏中可溶磷、氟为磷石膏的相变反应提供了必需的酸性环境,同时使PBGP晶体的长径比变大、晶体直径减小；自制媒晶剂NS和EN对PBGP晶习有明显的调控作用,可以得到长径比接近1的短柱状晶体,产物抗压强度在35MPa以上,其合适掺量分别为0.15%和0.4%；可溶性酸性杂质使媒晶剂的合适掺量增加,产品强度降低；可溶性钠盐使高强石膏晶体中出现细小的颗粒,强度降低；可溶性盐类杂质和有机物使PBGP晶体变得细碎,产品强度降低；不溶性杂质则使产物α半水石膏晶体向短棒状发展,晶体发育不均齐,强度增大；原状磷石膏不适合直接作为PBGP的原料使用,经水洗处理后可以大幅降低媒晶剂的使用量,优化晶体形态,提高产品强度；当PBGP晶体直径大于8μm、长径比1-3且发育相对均齐时,产品的绝干抗压强度与晶体体积呈线性相关关系.。
3、杂质对PBGP水化硬化性能的影响
研究了不同pH值的H2SO4、HCl、H3PO4以及中性环境下不同CaCl2含量对高强石膏的凝结时间、强度变化的影响与相应机理,并对影响PBGP'性能的主要因素进行了归纳,结果表明：三种酸均对高强石膏的初凝、终凝均起促进作用,且对初凝时间、终凝时间的影响规律大致相同,在不同pH值的同种酸和相同pH值的不同酸对高强石膏的凝结性能影响不同；当pH小于3.0时,H2SO4、 HCl和H3P04均会显著降低2h强度和绝干强度,当pH值为3到7之间时,抗压强度性能因酸根离子的种类与含量不同而出现不同的变化；活度剂CaCl2也会使高强石膏早凝,其对高强石膏强度尤其是绝干强度的损失随含量的增加而增强；这几类杂质均延长了加速期的反应时间,增大结晶相变热；水化产物中二水石膏相的含量只是影响产物强度的一个因素,而杂质离子H2PO4、H+、Cl-改变了结晶接触点的性质对产物绝干强度起重要的影响；CaCl2抑制了高强石膏的水化,CaCl2含量越高,高强石膏未水化的比例越高,绝干强度下降越明显。
4、PBGP的制备工艺优化及应用
在实验室范围内扩大了试验规模,测试了PBGP粉的凝结时间、强度性能,并对PBGP制备工艺进行优化,结果表明：原料水洗预处理时产生的部分废水经处理后可以循环利用；PBGP浆体经洗涤、干燥后,产物的晶体边界清晰程度有所下降,但抗压强度仍能超过40MPa; PBGP浆体滤液经沉淀剂处理后循环利用4次制备出PBGP的抗压强度在35Mpa以上,循环利用5次制备出PBGP的抗压强度在25Mpa以上；水热反应过程中,磷石膏中部分硅、铝、铁等不溶性杂质从原料中析出,从而提高了PBGP的纯度；PBGP制备工艺经优化后可以分为原料的预处理工艺、常压水热反应工艺、浆体制备工艺、PBGP粉及石膏制品的生产工艺四个过程。
Phosphogypsum (PG) is solid waste of calcium sulfate discharged from wet process phosphoric acid production.Generally,4.5-5.5tons PG are generated when per ton of P2O5are produced and most of the calcium sulfate is in the form of dihydrate (DH, CaSO4·2H2O). Currently the mainly way of disposal PG is stockpilling for the phosphorus, fluorine, organic compounds and other ingredients containing in PG affect its performance and increae its using cost compared to natural gypsum. In2011, with the growing demand of phosphoric fertilizer the production of PG was up to70million tons in China and less than20.0%is used at present.It is estimated that the accumulative total of PG is over300million tons throughout China, which not only occupies plenty of lands, waste of resources, and harmful constituents also cause serious pollution to the surrounding soil, vegetation, water and air. In2006, PG was classified as "hazardous solid waste"by SEPA (state environmental protection administration),the problem of PG disposal has been a worldwide problem that seriously hampered the sustainable development of the phosphorus chemical industry and environmental protection.
The main problems of cementitious materials preparation from PG instead of natural gypsum at home and abroad are:(1) PG based cementitious materials have higher preparation costs for the harmful impurities influencing the performace despite the high Ca2SO4·2H2O content, while PG pretreament has no superiority compared to natural gypsum not only in the price but in products performance;(2)widely useage of a-hemihydrate sulphsate calcium (a-HH) with high performance and high value-added prepared under autoclave atmosphere is restricted by the complex process, high energy consumption, inconvenience to the control, unstable performance and high price;(3) preparation of a-HH in hydrothermal electrolytic solutions with characteristic of mild reaction conditions and easy to conrol under atmospheric pressure is still at the laboratory or theoretical stage, meanwhile the raw materls are limited to natural gypsum, desulfurized gypsum or gypsum with little impurities.
Funded by Chinese National Technology Support Project "Low-cost and Energy-saving Technology Research and Demonstration of Energy-efficient Building" (Project No.2011BAJ03B03), Major Science and Technology Plan of Hubei Province" Utilization Efficiently and Industrialization of Phosphorus Chemical Byproducts"(Project No. DZS0005), and Research and Plan Project of Hubei Province"Comprehensive Utilization of Phosphogypsum"(Project No.2009BCB030), based on theoretical and technical problems of high-strength gypsum cementitious materials preparation, design and selection of Phosphogypsum Based Gypsum Plaster (PBGP) preparation system are presented in the paper. Influences of raw material pretreatment to the formation and crystal morphology control of PBGP is studied, then effects of impurities on the performance of PBGP hydration and hardening are discussed, next optimization of PBGP preparation process and industrialization technology are considered, meanwhile the relation of PBGP composition-structure-performance is diccovered, and the critical theory and technology of PBGP preparation process, crystal morphology control, performance optimization and industrialization are established. The main research work and compliments are listed are as follows:
1. Design and selection of PBGP preparation system.
At hydrothermal temperature of85℃～100℃, NaCl, CaCl2and its mixtures are selected as activity agent, respectively.Influences of activity agent type and concentration, solid-liquid ratio and the reaction temperature and time to the products are researched. The experiment results show that phase transition of PG from DH to HH can conduct in strong NaCl solution, but NaCl is not favourable for preparation of a-HH from PG phase transition, for the phase transition product of PG is a mixture of a-HH and omongwaite (Na2Ca5(SO4)6·3H2O)-a structural isomer of HH; α-HH can be obtained as the product of PG phase transiton in strong CaCl2solution; the reaction time of PG transiton to a-HH shortens from240min to50min with increasing NaCl content from0to4%in24%Ca-Na-Cl solution, but it is accompanied with increasing of Na2O content and irregular uncompleted crystal shapes in the reaction product; NaCl increases the solubility of PG and promote the nucleation and growth of HH crystal, while CaCl2reduces the solubility of PG for the common ion effect, a-HH crystal growth can be greatly accerlated by surface diffusion and adsorption of relatively high activity of Ca2+
2. Influences of raw material pretreatment to the formation and crystal morphology of PBGP
Influences of the acidic impurities, soluble salts, insoluble impurities contained in PG to phase transiton process, product shapes and compressive strength are studied, crystal modifier commonly used are choosed to modify PGGP crystal morphology. It turns out that soluble phosphate and fluoride impurities elongate a-HH crystal aspect ration, decrease a-HH crystal diameter while provide the necessary acidic conditions for PG phase transition; homemade crystal modifier NS and EN have obvious effects on a-HH cryatal habit, short columnar PBGP crystal of aspect ratio nearly1with compressive strength beyond35MPa can be obtained when the dosages of NS and EN are0.15%and0.4%respectively;solube acidic impurities increase appropriate dosage of crystal modifier and decrease the product compressive strength;soluble salts and organic matters fine a-HH crystal partles, and reduce the product strength as well; insoluble impurities shorten a-HH crystal to rode-like shape, uneven length and distribution,improve product strength;unpretreated PG is not appropriate for PBGP preparation,water-washing of raw material is beneficial for subsequent crystal modifier usage, crystal morphology control and strength of the product; linear correlation of the product dry compressive strength and crystal volume is showed when PBGP has a uniform crystal shapes of diameter≥8μm and1-3aspect ratio.
3. Effect of impurities on PBGP hydration and hardening performance
Seting time, strength variation and corresponding mechanism of high-strength gypsum in dilute solution of H2SO4、H3PO4and HC1of different pH values and in different contents of CaCl2are studied, the factors influencing PBGP performance are analyzed.The results reveal that acid solutions accelerate initial and final setting of high-strength gypsum at roughly the same rule, high-strength gypsum show different setting performance in the same acidic solutions of the different pH values or in the different acidic solutions of the same pH values;2h and dry strength values of gypsum plaster are lowered markly by H2S04,H3PO4and HC1solutions of pH values less than3.0, and the strength values vary with the kind and content of acid radical ions when the pH value is between3to7; high-strength gypsum setting may also be accerlerated by activity agent CaCl2, its strength especially dry strength loss increasing with the addition of CaCl2content; acceleration periods are all prolonged and phase change heats are all enhanced by these impurities; product strength is effected by DH phase content, while impurities ions, such as E2PO4,H+,Cl" play important impacts through changing the nature of contact points; hydration reaction of high-strength gypsum is inhibited by CaCl2addition, the higher the CaCl2content, the higher the proportion of high-strength gypsum unhydration, more obviously the dry strength decreased.
4. Optimization of PBGP preparation process and application
PBGP preparation-scal is expanded in the laboratory, setting and strength properties of PBGP are tested, and the PBGP preparation process is optimized, the results indicate that waste water from raw material pretreatment can be recycled after disposal; the product compressive strength is still more than40MPa, though crystal boundary become unsharp after PBGP slurry was washed and dried; filtrate from PBGP slurry treated by precipitator can be recycled, the compressive strength of the product is greater than35MPa and25MPa when the diltrate cycle times are4and5respectively; silicon, aluminum, iron and other insoluble impurities containing in PG can leach out during hydrothermal reaction process, thereby the purity of PBGP is improved; the optimized preparation process of PBGP can be devied into four stages,that is, raw material pretreatment, hydrothermal reaction under atmospheric pressure,slurry preparation, PBGP power and gypsum products preparation.
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