技术领域technical field
本发明属于工业废弃物资源化处理技术领域，具体涉及一种增强增韧的磷石膏及其制备方法。The invention belongs to the technical field of industrial waste resource treatment, and in particular relates to a reinforced and toughened phosphogypsum and a preparation method thereof.
背景技术Background technique
磷石膏是指在磷酸生产中用硫酸处理磷矿时产生的固体废渣，其主要成分为硫酸钙，磷石膏中还含砷、铜、锌、铁、锰、铅、镉、汞均极其微量，且大多数为不溶性固体，而且磷石膏中所含氟化物、游离磷酸、P2O5、磷酸盐等杂质是导致磷石膏在堆存过程中造成环境污染的主要因素。磷石膏的大量堆存，不仅侵占了土地资源，而且由于风蚀、雨蚀造成了大气、水系及土壤的污染。长时间接触磷石膏，可能导致人的死亡或病变。磷石膏为灰白色或灰黑色，附着水10-30%，PH=1.9-5.3，F<0.5%，颗粒直径一般为5～50μm，化学成分复杂，含有残留有机磷和无机磷、氟化物及氟、钾、钠等成分及其它无机物。制取1吨磷酸（以100%P2O5计）一般会产生4.8～5.0吨磷石膏；同时磷石膏还是生产高浓度磷复肥时产生的一种工业副产石膏。现如今，随着磷酸与磷肥的生产，磷石膏的产生量也快速增加，累计堆存量已远远超过1亿吨。Phosphogypsum refers to the solid waste residue produced when sulfuric acid is used to treat phosphate rock in the production of phosphoric acid. Its main component is calcium sulfate. Phosphogypsum also contains arsenic, copper, zinc, iron, manganese, lead, cadmium, and mercury in extremely small amounts. Most of them are insoluble solids, and impurities such as fluoride, free phosphoric acid, P2 O5 , and phosphate in phosphogypsum are the main factors that cause environmental pollution during the storage of phosphogypsum. The large stockpiling of phosphogypsum not only encroached on land resources, but also polluted the atmosphere, water system and soil due to wind erosion and rain erosion. Prolonged exposure to phosphogypsum may cause death or disease in humans. Phosphogypsum is gray-white or gray-black, with 10-30% attached water, PH=1.9-5.3, F<0.5%, particle diameter is generally 5-50μm, complex chemical composition, containing residual organic phosphorus and inorganic phosphorus, fluoride and fluorine , potassium, sodium and other components and other inorganic substances. The production of 1 ton of phosphoric acid (calculated as 100% P2 O5 ) will generally produce 4.8 to 5.0 tons of phosphogypsum; at the same time, phosphogypsum is also an industrial by-product gypsum produced in the production of high-concentration phosphorus compound fertilizers. Nowadays, with the production of phosphoric acid and phosphate fertilizer, the production of phosphogypsum has also increased rapidly, and the cumulative stockpiles have far exceeded 100 million tons.
长期以来，由于磷石膏的性能不稳定，强度、韧度不够致使这种来源广阔的资源无法得以有效利用，目前综合利用率仅10%左右，年利用量仅在400～500万吨，而绝大部分的磷石膏堆存给环境造成了巨大的压力和破坏。For a long time, due to the unstable performance of phosphogypsum, insufficient strength and toughness, this resource with a wide source cannot be effectively utilized. At present, the comprehensive utilization rate is only about 10%, and the annual utilization is only 4 to 5 million tons. Most of the phosphogypsum stockpiles cause enormous stress and damage to the environment.
目前虽然已有针对磷石膏处理的研究，但是还存在诸多问题，例如现有技术中有先将磷石膏陈化，然后利用石灰等改性处理、烘干、煅烧的处理方法；还有的现有技术将磷石膏、通用硅酸盐水泥和水混合湿磨后陈化的处理方法。这些处理方法虽然给出了一些磷石膏的改性处理的方向，但是都存在添加剂成分复杂，陈化时间过长的问题，有些还存在温度处理高且处理复杂的问题，因此改性处理的成本高，工艺也不易推广。Although there have been researches on the treatment of phosphogypsum at present, there are still many problems. For example, in the prior art, there is a treatment method in which the phosphogypsum is first aged, and then modified with lime, dried, and calcined; There is a treatment method of mixing phosphogypsum, general-purpose Portland cement and water for wet grinding and aging. Although these treatment methods have given some directions for the modification of phosphogypsum, they all have the problems of complex additive components and long aging time, and some of them also have the problem of high temperature treatment and complicated treatment, so the cost of modification treatment High, and the technology is not easy to promote.
针对以上问题，有必要发明一种成本低、操作简单的增强增韧的磷石膏及其制备方法。In view of the above problems, it is necessary to invent a low-cost, easy-to-operate reinforced and toughened phosphogypsum and a preparation method thereof.
发明内容Contents of the invention
本发明的第一目的在于提供了一种增强增韧的磷石膏，第二目的在于提供一种增强增韧的磷石膏的制备方法。The first object of the present invention is to provide a reinforced and toughened phosphogypsum, and the second object is to provide a method for preparing the reinforced and toughened phosphogypsum.
本发明的第一目的是这样实现的，所述的增强增韧的磷石膏是将磷酸和/或磷肥的生产过程中产生的废弃磷石膏经过筛选、添加增强增韧材料、陈化、烘干、脱硫的步骤得到的，所述的增强增韧的磷石膏的2h抗折强度≥10MPa，2h抗压强度≥25MPa。The first object of the present invention is achieved in that the described reinforced and toughened phosphogypsum is obtained by screening waste phosphogypsum produced in the production process of phosphoric acid and/or phosphate fertilizer, adding reinforced and toughened materials, aging and drying and desulfurization steps, the 2h flexural strength of the reinforced and toughened phosphogypsum is more than or equal to 10MPa, and the 2h compressive strength is more than or equal to 25MPa.
本发明的第二目的是这样实现的，包括以下步骤：Second object of the present invention is achieved like this, comprises the following steps:
1）筛选：收集磷酸和/或磷肥生产过程中从排渣口排出的磷石膏，用4~6倍量的水在常温下进行冲洗，然后使用8~12目的筛网进行初步过滤，得到粗石膏，将粗石膏使用20～80目的筛网进行1~2次分选，得到精石膏；1) Screening: Collect the phosphogypsum discharged from the slag discharge outlet during the production of phosphoric acid and/or phosphate fertilizer, wash it with 4-6 times the amount of water at room temperature, and then use 8-12 mesh screens for preliminary filtration to obtain crude For gypsum, the coarse gypsum is sorted 1-2 times with a 20-80 mesh screen to obtain refined gypsum;
2）添加增强增韧材料：在精石膏中加入增强增韧材料，将其搅拌均匀，所述的增强增韧材料与磷石膏的质量比为0.2~5：100；2) Adding reinforcing and toughening materials: adding reinforcing and toughening materials to refined gypsum and stirring them evenly, the mass ratio of the said reinforcing and toughening materials to phosphogypsum is 0.2~5:100;
3）陈化：将经过步骤（2）处理的精石膏在室温下陈化；3) Aging: Aging the refined gypsum treated in step (2) at room temperature;
4）烘干：将陈化后的精石膏烘干；4) Drying: drying the aged refined gypsum;
5）脱硫：将烘干后的精石膏加热5～20分钟脱硫，即可。5) Desulfurization: heat the dried fine gypsum for 5 to 20 minutes to desulfurize.
与现有技术相比，本发明的有益效果是：Compared with prior art, the beneficial effect of the present invention is:
1、本发明通过以制造磷酸、磷肥企业产生的废弃物磷石膏为原料，通过筛选、添加增强增韧材料、陈化、烘干、脱硫等工艺，生产出强度、韧性极佳的磷建筑石膏，可实现大量堆存磷石膏的资源化利用，消除其对环境的危害，同时工艺简单，成本低廉，便于推广应用。1. The present invention uses the waste phosphogypsum produced by enterprises producing phosphoric acid and phosphate fertilizer as raw material, and produces phosphogypsum with excellent strength and toughness through processes such as screening, adding reinforcing and toughening materials, aging, drying, and desulfurization , can realize the resource utilization of a large amount of stockpiled phosphogypsum, eliminate its harm to the environment, and at the same time, the process is simple, the cost is low, and it is convenient for popularization and application.
2、本发明所使用的磷石膏为工业废料，然后加入棉花（或旧棉花）、锆棉、硅酸铝棉、玻璃丝等丝状棉，原料具有储量大、价格低的优点，得到的增强增韧的磷石膏性能稳定、质量可靠，在实现工业废料资源化处理的基础上减轻其对环境的影响，而且与改良前的石膏相比，磷石膏的抗折强度、抗压强度明显提高。2. The phosphogypsum used in the present invention is industrial waste, and then cotton (or old cotton), zirconium wool, aluminum silicate wool, glass wool and other filamentary cotton are added. The raw material has the advantages of large reserves and low price, and the obtained enhanced Tough phosphogypsum has stable performance and reliable quality, and reduces its impact on the environment on the basis of realizing the recycling of industrial waste. Compared with gypsum before improvement, the flexural strength and compressive strength of phosphogypsum are significantly improved.
3、本发明的制备方法成本低、操作简单，能将固体废弃物磷石膏转变成性能稳定的磷建筑石膏，而且与现有技术相比，陈化时间短，可显著缩短生产周期。3. The preparation method of the present invention has low cost and simple operation, and can convert solid waste phosphogypsum into phosphogypsum with stable performance. Compared with the prior art, the aging time is short, and the production cycle can be significantly shortened.
4、本发明的制备方法处理温度低、设备投资小、原料价格低廉，具有投资小、能耗低、过程易实现的优势。4. The preparation method of the present invention has the advantages of low processing temperature, small investment in equipment, and low price of raw materials, and has the advantages of small investment, low energy consumption, and easy realization of the process.
具体实施方式detailed description
下面结合实施例对本发明作进一步的说明，但不以任何方式对本发明加以限制，基于本发明教导所作的任何变换或替换，均属于本发明的保护范围。The present invention will be further described below in conjunction with the examples, but the present invention is not limited in any way, and any transformation or substitution made based on the teaching of the present invention belongs to the protection scope of the present invention.
本发明所述的增强增韧的磷石膏是将磷酸和/或磷肥的生产过程中产生的废弃磷石膏经过筛选、添加增强增韧材料、陈化、烘干、脱硫的步骤得到的，所述的增强增韧的磷石膏的2h抗折强度≥10MPa，2h抗压强度≥25MPa。The reinforced and toughened phosphogypsum of the present invention is obtained through the steps of screening waste phosphogypsum produced in the production process of phosphoric acid and/or phosphate fertilizer, adding reinforcing and toughening materials, aging, drying, and desulfurization. The 2h flexural strength of the reinforced and toughened phosphogypsum is ≥10MPa, and the 2h compressive strength is ≥25MPa.
所述的废弃磷石膏的2h抗折强度为不超过10MPa，2h抗压强度为1~10MPa。The 2h flexural strength of the waste phosphogypsum is not more than 10MPa, and the 2h compressive strength is 1~10MPa.
所述的废弃磷石膏的成分为：固体杂质：3%～20%、SO3：8%～35%、CaSO4·2H2O：30%～75%。The composition of the waste phosphogypsum is: solid impurities: 3%-20%, SO3 : 8%-35%, CaSO4 ·2H2 O: 30%-75%.
本发明所述的增强增韧的磷石膏的制备方法，包括以下步骤：The preparation method of the reinforced and toughened phosphogypsum of the present invention comprises the following steps:
1）筛选：收集磷酸和/或磷肥生产过程中从排渣口排出的磷石膏，用4~6倍量的水在常温下进行冲洗，然后使用8~12目的筛网进行初步过滤，得到粗石膏，然后将粗石膏使用20～80目的筛网进行1~2次分选，得到精石膏；1) Screening: Collect the phosphogypsum discharged from the slag discharge outlet during the production of phosphoric acid and/or phosphate fertilizer, wash it with 4-6 times the amount of water at room temperature, and then use 8-12 mesh screens for preliminary filtration to obtain crude Gypsum, and then use a 20-80 mesh screen to sort the coarse gypsum for 1-2 times to obtain refined gypsum;
2）添加增强增韧材料：在精石膏中加入增强增韧材料，将其搅拌均匀，所述的增强增韧材料与磷石膏的质量比为0.2~5：100；2) Adding reinforcing and toughening materials: adding reinforcing and toughening materials to refined gypsum and stirring them evenly, the mass ratio of the said reinforcing and toughening materials to phosphogypsum is 0.2~5:100;
3）陈化：将经过步骤（2）处理的精石膏在室温下陈化；3) Aging: Aging the refined gypsum treated in step (2) at room temperature;
4）烘干：将陈化后的精石膏烘干；4) Drying: drying the aged refined gypsum;
5）脱硫：将烘干后的精石膏加热5～20分钟脱硫，即可。5) Desulfurization: heat the dried fine gypsum for 5 to 20 minutes to desulfurize.
步骤（2）中所述的增强增韧材料为丝状棉。The reinforcing and toughening material described in step (2) is silky cotton.
所述的丝状棉为棉花、锆棉、硅酸铝棉、玻璃丝中的一种或多种。The filamentous cotton is one or more of cotton, zirconium wool, aluminum silicate wool and glass wool.
步骤（3）中所述的陈化的时间为1-7天。The aging time described in step (3) is 1-7 days.
步骤（3）中所述的陈化为陈化至附着水含量7%～10%。The aging described in step (3) is aging until the attached water content is 7%-10%.
步骤（4）中所述的烘干的温度保持在50～150℃，烘干至含水量1%～3%。The drying temperature in step (4) is kept at 50-150° C., and dried to a moisture content of 1%-3%.
步骤（5）中所述的脱硫的温度保持在150～200℃，脱硫后磷石膏含硫1%～5%。The desulfurization temperature in step (5) is kept at 150-200° C., and the sulfur content of phosphogypsum after desulfurization is 1%-5%.
实施例1Example 1
原料成分：磷石膏渣中含10%固体杂质、25%的SO3、65%的CaSO4·2H2O。Raw material composition: Phosphogypsum slag contains 10% solid impurities, 25% SO3 , and 65% CaSO4 ·2H2 O.
工艺流程：Process flow:
（1）首先从制造磷酸、磷肥企业的排渣口取磷石膏液，5倍的水量在常温下进行冲洗以除去大量杂质，使用10目的筛网进行初步过滤，得到粗石膏；(1) First, take phosphogypsum liquid from the slag outlet of the phosphoric acid and phosphate fertilizer manufacturing enterprises, rinse with 5 times the amount of water at room temperature to remove a large amount of impurities, and use a 10-mesh screen for preliminary filtration to obtain coarse gypsum;
（2） 将粗石膏排入80目的筛子一次分选，得到精石膏；(2) Put the coarse gypsum into an 80-mesh sieve for one-time sorting to obtain refined gypsum;
（3）在精石膏陈化之前放入增强增韧材料，将其搅拌均匀，增强增韧材料与磷石膏的质量比为5︰100，增强增韧材料为锆棉；(3) Before the refined gypsum is aged, the reinforcing and toughening material is put in and stirred evenly. The mass ratio of the reinforcing and toughening material to phosphogypsum is 5:100, and the reinforcing and toughening material is zirconium wool;
（4）将精石膏放入陈化槽在室温下陈化七天，陈化至附着水含量7%；(4) Put the refined gypsum into the aging tank and age it at room temperature for seven days until the attached water content is 7%;
（5）将陈化后的精石膏放入烘干设备烘干，烘干温度为150℃，烘干至含水量3%；(5) Put the aged fine gypsum into the drying equipment for drying, the drying temperature is 150°C, and dry to a moisture content of 3%;
（6）将烘干后的精石膏在加热炉中加热脱硫，加热20分钟。加热温度为200℃，脱硫后磷石膏含硫5%。(6) Desulfurize the dried fine gypsum in a heating furnace for 20 minutes. The heating temperature is 200°C, and the sulfur content of phosphogypsum after desulfurization is 5%.
表1：实施例1得到的增强增韧的磷石膏与原有磷石膏的抗折强度和抗压强度对比Table 1: Comparison of flexural strength and compressive strength between the reinforced and toughened phosphogypsum obtained in Example 1 and the original phosphogypsum
结论：原磷石膏经过本申请所述的方法处理后，其抗压强度、抗折强度大幅提高。Conclusion: After the original phosphogypsum is treated by the method described in this application, its compressive strength and flexural strength are greatly improved.
实施例2Example 2
原料成分：磷石膏渣中含20%固体杂质、35%的SO3、45%的CaSO4·2H2O。Raw material composition: Phosphogypsum slag contains 20% solid impurities, 35% SO3 , and 45% CaSO4 ·2H2 O.
工艺流程：Process flow:
（1）首先从制造磷酸、磷肥企业的排渣口取磷石膏液，4倍的水量在常温下进行冲洗以除去大量杂质，使用10目的筛网进行初步过滤，得到粗石膏；(1) First, take phosphogypsum liquid from the slag outlet of the phosphoric acid and phosphate fertilizer manufacturing enterprises, wash it with 4 times the amount of water at room temperature to remove a large amount of impurities, and use a 10-mesh screen for preliminary filtration to obtain coarse gypsum;
（2） 将粗石膏排入20目的筛子一次分选，得到精石膏；(2) Put the coarse gypsum into a 20-mesh sieve for one-time sorting to obtain refined gypsum;
（3）在精石膏陈化之前放入增强增韧材料，将其搅拌均匀，增强增韧材料与磷石膏的质量比为0.2︰100，增强增韧材料为棉花中的旧棉花；(3) Before the refined gypsum is aged, the reinforcing and toughening material is put in and stirred evenly. The mass ratio of the reinforcing and toughening material to phosphogypsum is 0.2:100, and the reinforcing and toughening material is old cotton in cotton;
（4）将精石膏放入陈化槽在室温下陈化一天，陈化至附着水含量10%；(4) Put the refined gypsum into the aging tank and age at room temperature for one day until the attached water content is 10%;
（5）将陈化后的精石膏放入烘干设备烘干，烘干温度为50℃，烘干至含水量1%；(5) Put the aged fine gypsum into the drying equipment for drying, the drying temperature is 50°C, and dry to 1% water content;
（6）将烘干后的精石膏在加热炉中加热脱硫，加热5分钟。加热温度为150℃，脱硫后磷石膏含硫1%。(6) Desulfurize the dried fine gypsum in a heating furnace for 5 minutes. The heating temperature is 150°C, and the sulfur content of phosphogypsum after desulfurization is 1%.
表2：实施例2得到的增强增韧的磷石膏与原有磷石膏的抗折强度和抗压强度对比Table 2: Comparison of flexural strength and compressive strength between the reinforced and toughened phosphogypsum obtained in Example 2 and the original phosphogypsum
结论：原磷石膏经过本申请所述的方法处理后，其抗压强度、抗折强度大幅提高。Conclusion: After the original phosphogypsum is treated by the method described in this application, its compressive strength and flexural strength are greatly improved.
实施例3Example 3
原料成分：磷石膏渣中含20%固体杂质、15%的SO3、65%的CaSO4·2H2O。Raw material composition: Phosphogypsum slag contains 20% solid impurities, 15% SO3 , and 65% CaSO4 ·2H2 O.
工艺流程：Process flow:
（1）首先从制造磷酸、磷肥企业的排渣口取磷石膏液，6倍的水量在常温下进行冲洗以除去大量杂质，使用10目的筛网进行初步过滤，得到粗石膏；(1) Firstly, take phosphogypsum liquid from the slag outlet of the phosphoric acid and phosphate fertilizer manufacturing enterprises, rinse with 6 times the amount of water at room temperature to remove a large amount of impurities, and use a 10-mesh screen for preliminary filtration to obtain coarse gypsum;
（2） 将粗石膏排入50目的筛子一次分选，得到精石膏；(2) Put the coarse gypsum into a 50-mesh sieve for one-time sorting to obtain refined gypsum;
（3）在精石膏陈化之前放入增强增韧材料，将其搅拌均匀，增强增韧材料与磷石膏的质量比为0.6︰100，增强增韧材料为玻璃丝；(3) Before the refined gypsum is aged, the reinforcing and toughening material is put in and stirred evenly. The mass ratio of the reinforcing and toughening material to phosphogypsum is 0.6:100, and the reinforcing and toughening material is glass wool;
（4）将精石膏放入陈化槽在室温下陈化三天，陈化至附着水含量8.5%；(4) Put the refined gypsum into the aging tank and age it at room temperature for three days until the attached water content is 8.5%;
（5）将陈化后的精石膏放入烘干设备烘干，烘干温度为130℃，烘干至含水量2%；(5) Put the aged refined gypsum into the drying equipment for drying, the drying temperature is 130°C, and dry to a moisture content of 2%;
（6）将烘干后的精石膏在加热炉中加热脱硫，加热10分钟。加热温度为175℃，脱硫后磷石膏含硫3%。(6) Desulfurize the dried fine gypsum in a heating furnace for 10 minutes. The heating temperature is 175°C, and the sulfur content of phosphogypsum after desulfurization is 3%.
表3：实施例3得到的增强增韧的磷石膏与原有磷石膏的抗折强度和抗压强度对比Table 3: Comparison of flexural strength and compressive strength between the reinforced and toughened phosphogypsum obtained in Example 3 and the original phosphogypsum
结论：原磷石膏经过本申请所述的方法处理后，其抗压强度、抗折强度大幅提高。Conclusion: After the original phosphogypsum is treated by the method described in this application, its compressive strength and flexural strength are greatly improved.
实施例4Example 4
原料成分：磷石膏渣中含15%固体杂质、30%的SO3、55%的CaSO4·2H2O。Raw material composition: Phosphogypsum slag contains 15% solid impurities, 30% SO3 , and 55% CaSO4 ·2H2 O.
工艺流程：Process flow:
（1）首先从制造磷酸、磷肥企业的排渣口取磷石膏液，4.5倍的水量在常温下进行冲洗以除去大量杂质，使用10目的筛网进行初步过滤，得到粗石膏；(1) First, take phosphogypsum liquid from the slag outlet of the phosphoric acid and phosphate fertilizer manufacturing enterprises, rinse with 4.5 times the amount of water at room temperature to remove a large amount of impurities, and use a 10-mesh screen for preliminary filtration to obtain coarse gypsum;
（2） 将粗石膏排入40目的筛子一次分选，得到精石膏；(2) Put the coarse gypsum into a 40-mesh sieve for one-time sorting to obtain refined gypsum;
（3）在精石膏陈化之前放入增强增韧材料，将其搅拌均匀，增强增韧材料与磷石膏的质量比为1.6︰100，增强增韧材料为玻璃丝；(3) Before the refined gypsum is aged, put the reinforcing and toughening material, stir it evenly, the mass ratio of the reinforcing and toughening material to phosphogypsum is 1.6:100, and the reinforcing and toughening material is glass wool;
（4）将精石膏放入陈化槽在室温下陈化五天，陈化至附着水含量8%；(4) Put the refined gypsum into the aging tank and age it at room temperature for five days until the attached water content is 8%;
（5）将陈化后的精石膏放入烘干设备烘干，烘干温度为110℃，烘干至含水量2%；(5) Put the aged fine gypsum into the drying equipment for drying, the drying temperature is 110°C, and dry to a moisture content of 2%;
（6）将烘干后的精石膏在加热炉中加热脱硫，加热15分钟。加热温度为160℃，脱硫后磷石膏含硫2%。(6) Desulfurize the dried refined gypsum in a heating furnace for 15 minutes. The heating temperature is 160°C, and the sulfur content of phosphogypsum after desulfurization is 2%.
表4：实施例4得到的增强增韧的磷石膏与原有磷石膏的抗折强度和抗压强度对比Table 4: Comparison of flexural strength and compressive strength between the reinforced and toughened phosphogypsum obtained in Example 4 and the original phosphogypsum
结论：原磷石膏经过本申请所述的方法处理后，其抗压强度、抗折强度大幅提高。Conclusion: After the original phosphogypsum is treated by the method described in this application, its compressive strength and flexural strength are greatly improved.
实施例5Example 5
原料成分：磷石膏渣中12.5%固体杂质、27.5%的SO3、60%的CaSO4·2H2O。Raw material composition: 12.5% solid impurities, 27.5% SO3 , 60% CaSO4 ·2H2 O in phosphogypsum slag.
工艺流程：Process flow:
（1）首先从制造磷酸、磷肥企业的排渣口取磷石膏液，5.5倍的水量在常温下进行冲洗以除去大量杂质，使用10目的筛网进行初步过滤，得到粗石膏；(1) First, take phosphogypsum liquid from the slag outlet of the phosphoric acid and phosphate fertilizer manufacturing enterprises, rinse with 5.5 times the amount of water at room temperature to remove a large amount of impurities, and use a 10-mesh screen for preliminary filtration to obtain coarse gypsum;
（2） 将粗石膏排入40目的筛子一次分选，得到精石膏；(2) Put the coarse gypsum into a 40-mesh sieve for one-time sorting to obtain fine gypsum;
（3）在精石膏陈化之前放入增强增韧材料，将其搅拌均匀，增强增韧材料与磷石膏的质量比为2.5︰100，增强增韧材料为硅铝酸棉；(3) Before the refined gypsum is aged, put the reinforcing and toughening material, and stir it evenly. The mass ratio of the reinforcing and toughening material to phosphogypsum is 2.5:100, and the reinforcing and toughening material is aluminosilicate cotton;
（4）将精石膏放入陈化槽在室温下陈化两天，陈化至附着水含量8%；(4) Put the refined gypsum into the aging tank and age it at room temperature for two days until the attached water content is 8%;
（5）将陈化后的精石膏放入烘干设备烘干，烘干温度为105℃，烘干至含水量2%；(5) Put the aged fine gypsum into the drying equipment for drying, the drying temperature is 105°C, and dry to a moisture content of 2%;
（6）将烘干后的精石膏在加热炉中加热脱硫，加热18分钟。加热温度为180℃，脱硫后磷石膏含硫2%。(6) Desulfurize the dried fine gypsum in a heating furnace for 18 minutes. The heating temperature is 180°C, and the sulfur content of phosphogypsum after desulfurization is 2%.
表5：实施例5得到的增强增韧的磷石膏与原有磷石膏的抗折强度和抗压强度对比Table 5: Comparison of flexural strength and compressive strength between the reinforced and toughened phosphogypsum obtained in Example 5 and the original phosphogypsum
结论：原磷石膏经过本申请所述的方法处理后，其抗压强度、抗折强度大幅提高。Conclusion: After the original phosphogypsum is treated by the method described in this application, its compressive strength and flexural strength are greatly improved.
实施例6Example 6
原料成分：磷石膏渣中含16.5%固体杂质、23.5%的SO3、60%的CaSO4·2H2O。Raw material composition: Phosphogypsum slag contains 16.5% solid impurities, 23.5% SO3 , and 60% CaSO4 ·2H2 O.
工艺流程：Process flow:
（1）首先从制造磷酸、磷肥企业的排渣口取磷石膏液，5倍的水量在常温下进行冲洗以除去大量杂质，使用10目的筛网进行初步过滤，得到粗石膏；(1) First, take phosphogypsum liquid from the slag outlet of the phosphoric acid and phosphate fertilizer manufacturing enterprises, rinse with 5 times the amount of water at room temperature to remove a large amount of impurities, and use a 10-mesh screen for preliminary filtration to obtain coarse gypsum;
（2） 将粗石膏排入60目的筛子一次分选，得到精石膏；(2) Discharge the coarse gypsum into a 60-mesh sieve for one-time sorting to obtain refined gypsum;
（3）在精石膏陈化之前放入增强增韧材料，将其搅拌均匀，增强增韧材料与磷石膏的质量比为3.8︰100，增强增韧材料为锆棉；(3) Before the refined gypsum is aged, put the reinforcing and toughening material, and stir it evenly. The mass ratio of the reinforcing and toughening material to phosphogypsum is 3.8:100, and the reinforcing and toughening material is zirconium wool;
（4）将精石膏放入陈化槽在室温下陈化三天，陈化至附着水含量9%；(4) Put the refined gypsum into the aging tank and age it at room temperature for three days until the attached water content is 9%;
（5）将陈化后的精石膏放入烘干设备烘干，烘干温度为95℃，烘干至含水量3%；(5) Put the aged fine gypsum into the drying equipment for drying, the drying temperature is 95°C, and dry to a moisture content of 3%;
（6）将烘干后的精石膏在加热炉中加热脱硫，加热12分钟。加热温度为190℃，脱硫后磷石膏含硫4%。(6) Desulfurize the dried fine gypsum in a heating furnace for 12 minutes. The heating temperature is 190°C, and the sulfur content of phosphogypsum after desulfurization is 4%.
表6：实施例6得到的增强增韧的磷石膏与原有磷石膏的抗折强度和抗压强度对比Table 6: Comparison of flexural strength and compressive strength between the reinforced and toughened phosphogypsum obtained in Example 6 and the original phosphogypsum
结论：原磷石膏经过本申请所述的方法处理后，其抗压强度、抗折强度大幅提高。Conclusion: After the original phosphogypsum is treated by the method described in this application, its compressive strength and flexural strength are greatly improved.
实施例7Example 7
原料成分：磷石膏渣中含3%固体杂质、22%的SO3、75%的CaSO4·2H2O。Raw material composition: Phosphogypsum slag contains 3% solid impurities, 22% SO3 , and 75% CaSO4 ·2H2 O.
工艺流程：Process flow:
1）筛选：收集磷酸和/或磷肥生产过程中从排渣口排出的磷石膏，用5倍量的水在常温下进行冲洗，然后使用8目的筛网进行初步过滤，得到粗石膏，然后将粗石膏使用20目的筛网进行1次分选，得到精石膏；1) Screening: Collect the phosphogypsum discharged from the slag outlet during the production of phosphoric acid and/or phosphate fertilizer, wash it with 5 times the amount of water at room temperature, and then use an 8-mesh screen for preliminary filtration to obtain coarse gypsum, and then Coarse gypsum is sorted once with a 20-mesh screen to obtain refined gypsum;
2）添加增强增韧材料：在精石膏中加入增强增韧材料，将其搅拌均匀，所述的增强增韧材料与磷石膏的质量比为4：100；所述的增强增韧材料为丝状棉，所述的丝状棉为棉花、锆棉、硅酸铝棉、玻璃丝的多种混合，混合比例为1:1:1:1；2) Add reinforcement and toughening material: add reinforcement and toughening material to fine gypsum, stir it evenly, the mass ratio of the reinforcement and toughening material to phosphogypsum is 4:100; the reinforcement and toughening material is silk Shaped cotton, described filamentous cotton is the multiple mixing of cotton, zirconium cotton, aluminum silicate wool, glass fiber, and mixing ratio is 1:1:1:1;
3）陈化：将经过步骤（2）处理的精石膏在室温下陈化，陈化的时间为6天，陈化至附着水含量10%；3) Aging: Aging the refined gypsum treated in step (2) at room temperature for 6 days until the attached water content is 10%;
4）烘干：将陈化后的精石膏烘干，所述的烘干的温度保持在140℃，烘干至含水量2.5%；4) Drying: Dry the aged refined gypsum at a temperature of 140°C until the water content is 2.5%;
5）脱硫：将烘干后的精石膏加热8分钟脱硫，脱硫的温度保持在160℃，脱硫后磷石膏含硫5%，即可。5) Desulfurization: Heat the dried fine gypsum for 8 minutes to desulfurize. The desulfurization temperature is kept at 160°C. After desulfurization, the sulfur content of phosphogypsum is 5%.
表7：实施例7得到的增强增韧的磷石膏与原有磷石膏的抗折强度和抗压强度对比Table 7: Comparison of flexural strength and compressive strength between the reinforced and toughened phosphogypsum obtained in Example 7 and the original phosphogypsum
结论：原磷石膏经过本申请所述的方法处理后，其抗压强度、抗折强度大幅提高。Conclusion: After the original phosphogypsum is treated by the method described in this application, its compressive strength and flexural strength are greatly improved.
实施例8Example 8
原料成分：磷石膏渣中含17%固体杂质、8%的SO3、75%的CaSO4·2H2O。Raw material composition: Phosphogypsum slag contains 17% solid impurities, 8% SO3 , and 75% CaSO4 ·2H2 O.
工艺流程：Process flow:
1）筛选：收集磷酸和/或磷肥生产过程中从排渣口排出的磷石膏，用5倍量的水在常温下进行冲洗，然后使用12目的筛网进行初步过滤，得到粗石膏，然后将粗石膏使用80目的筛网进行2次分选，得到精石膏；1) Screening: Collect the phosphogypsum discharged from the slag outlet during the production of phosphoric acid and/or phosphate fertilizer, wash it with 5 times the amount of water at room temperature, and then use a 12-mesh screen for preliminary filtration to obtain coarse gypsum, and then Coarse gypsum is sorted twice with an 80-mesh screen to obtain refined gypsum;
2）添加增强增韧材料：在精石膏中加入增强增韧材料，将其搅拌均匀，所述的增强增韧材料与磷石膏的质量比为4：100；所述的增强增韧材料为丝状棉。所述的丝状棉为棉花、硅酸铝棉的多种混合；2) Add reinforcement and toughening material: add reinforcement and toughening material to fine gypsum, stir it evenly, the mass ratio of the reinforcement and toughening material to phosphogypsum is 4:100; the reinforcement and toughening material is silk shaped cotton. Described silky cotton is the multiple mixing of cotton, aluminum silicate cotton;
3）陈化：将经过步骤（2）处理的精石膏在室温下陈化，陈化的时间为6天，陈化至附着水含量10%；3) Aging: Aging the refined gypsum treated in step (2) at room temperature for 6 days until the attached water content is 10%;
4）烘干：将陈化后的精石膏烘干，所述的烘干的温度保持在70℃，烘干至含水量1.5%；4) Drying: Dry the aged refined gypsum at a temperature of 70°C until the water content is 1.5%;
5）脱硫：将烘干后的精石膏加热16分钟脱硫，脱硫的温度保持在170℃，脱硫后磷石膏含硫1%，即可。5) Desulfurization: Heat the dried fine gypsum for 16 minutes to desulfurize. The desulfurization temperature is kept at 170°C. After desulfurization, the sulfur content of phosphogypsum is 1%.
表8：实施例8得到的增强增韧的磷石膏与原有磷石膏的抗折强度和抗压强度对比Table 8: Comparison of flexural strength and compressive strength between the reinforced and toughened phosphogypsum obtained in Example 8 and the original phosphogypsum
结论：原磷石膏经过本申请所述的方法处理后，其抗压强度、抗折强度大幅提高。Conclusion: After the original phosphogypsum is treated by the method described in this application, its compressive strength and flexural strength are greatly improved.
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| CN201710873171.9ACN107572847B (en) | 2017-09-25 | 2017-09-25 | Reinforced and toughened phosphogypsum and preparation method thereof |
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| CN201710873171.9ACN107572847B (en) | 2017-09-25 | 2017-09-25 | Reinforced and toughened phosphogypsum and preparation method thereof |
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| CN201710873171.9AActiveCN107572847B (en) | 2017-09-25 | 2017-09-25 | Reinforced and toughened phosphogypsum and preparation method thereof |
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