WO2024037127A1 - 一种磷石膏脱色增白的方法 - Google Patents

一种磷石膏脱色增白的方法 Download PDF

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WO2024037127A1
WO2024037127A1 PCT/CN2023/098335 CN2023098335W WO2024037127A1 WO 2024037127 A1 WO2024037127 A1 WO 2024037127A1 CN 2023098335 W CN2023098335 W CN 2023098335W WO 2024037127 A1 WO2024037127 A1 WO 2024037127A1
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phosphogypsum
decolorizing
slurry
whitening
cyclone separator
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PCT/CN2023/098335
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English (en)
French (fr)
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曹龙
李长东
阮丁山
王威
郑海洋
毕真胜
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广东邦普循环科技有限公司
湖南邦普循环科技有限公司
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Priority to CN202380009608.8A priority Critical patent/CN116940419A/zh
Priority to PCT/CN2023/098335 priority patent/WO2024037127A1/zh
Publication of WO2024037127A1 publication Critical patent/WO2024037127A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
    • B03B7/00—Combinations of wet processes or apparatus with other processes or apparatus, e.g. for dressing ores or garbage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation

Definitions

  • the present disclosure belongs to the field of processing and resource utilization of phosphogypsum, and specifically relates to a method for decolorizing and whitening phosphogypsum.
  • Phosphogypsum refers to the solid waste residue produced by treating phosphate rock with sulfuric acid in the production of phosphoric acid. Its main component is calcium sulfate dihydrate. In the phosphoric acid production process, due to partially undecomposed phosphate rock, incomplete washing and filtration of phosphates and fluorides, or additives used in the production process, phosphogypsum will contain phosphorus, fluorine, etc. Impurities; and the existence of these impurities affects the performance of phosphogypsum, making it unable to be directly used in the production of gypsum building materials, restricting the use of phosphogypsum.
  • Impurities in phosphogypsum are divided into two categories: (1) Insoluble impurities: such as quartz, undecomposed apatite, insoluble P 2 O 5 , eutectic P 2 O 5 , fluoride and phosphates and sulfuric acid of fluorine, aluminum and magnesium Salt; (2) Soluble impurities: such as water-soluble P 2 O 5 , fluoride and sulfate with low solubility.
  • Flotation is a technology for separating minerals at the gas-liquid-solid three-phase interface. Flotation is a more suitable and efficient method for separating phosphogypsum.
  • the main methods for treating phosphogypsum are multiple washings, reverse selection first and then forward selection.
  • the effects of phosphogypsum treatment are not ideal.
  • the purpose of this disclosure is to provide a method for decolorizing and whitening phosphogypsum to remove organic matter, soluble phosphorus, fluorine, silicate, etc. in phosphogypsum to meet the requirements of industrial gypsum.
  • the method has a simple process, high efficiency in purifying phosphogypsum, low cost, and is easy to be industrialized.
  • a method for decolorizing and whitening phosphogypsum including the following steps:
  • S1 Slurry the phosphogypsum raw ore, add sulfuric acid to adjust the pH to below 2, add a decolorizing collector, inflate, perform reverse flotation, and flotate the organic slurry. The remaining slurry is recorded as the first phosphogypsum slurry;
  • the decolorizing collector includes diesel, naphthenic acid soap and foaming agent
  • step S2 Add lime to the first phosphogypsum slurry in step S1 to adjust the pH to above 11, and then pass it into the first cyclone separator and the second cyclone separator in sequence; the first cyclone separator overflows Separate fine-grained slurry, the particle size of the fine particles in the fine-grained slurry is less than 20 ⁇ m, the second cyclone separator overflows the second phosphogypsum slurry, and the bottom of the second cyclone separator flows out of quartz mixture;
  • step S3 The second phosphogypsum slurry in step S2 is settled, concentrated, filtered, and dried to obtain phosphogypsum.
  • the decolorizing collector of the phosphogypsum of the present disclosure is produced by compounding different industrial-grade raw materials, and is mainly composed of diesel oil, foaming agent, and naphthenic acid soap.
  • diesel oil mainly hydrophobizes the slurry
  • naphthenic acid soap has a molecular
  • the particularity of the structure is that one end contains a polar carboxylic acid group, and the other end is a cycloalkane group connected to a methylene group. It is extremely hydrophobic and has a strong resistance to charged sludge and fine particles of carbon during the decolorization process.
  • decolorizing collectors are mainly mineral oil-based substances. During decolorization and desliming, they only serve to hydrophobize the slurry, and then separate the fine particles of slime and carbon under the action of aeration. Compared with conventional decolorizing collectors, the decolorizing collector described in the present disclosure has more advantages in decolorizing and desliming effects.
  • reverse flotation is first used to remove organic matter, and then the pH of the first phosphogypsum slurry is adjusted to above 11 to convert the water-soluble phosphorus and fluorine in the first phosphogypsum slurry.
  • It is composed of fine particles of calcium phosphate, calcium fluoride and other insoluble substances. Because the particles of these insoluble substances are relatively fine, the particle size is below 20 ⁇ m, the particle size of phosphogypsum is between 20-60 ⁇ m, and the quartz particle size is above 74 ⁇ m.
  • the formed insoluble substances such as calcium phosphate, calcium fluoride, phosphogypsum, and quartz are separated by the cyclone classification effect of the first cyclone separator and the second cyclone separator, and
  • the residual decolorizing collector plays a positive role in separating insoluble substances; the residual foaming agent will generate certain bubbles under the action of the cyclone, and the residual diesel oil will (Non-polar oil) reduces the force between slurry particles and can quickly separate insoluble substances such as calcium phosphate and calcium fluoride with particle sizes less than 20 ⁇ m, phosphogypsum and quartz mixtures.
  • the method for decolorizing and whitening phosphogypsum described in the present disclosure directly uses the decolorizing collector to perform reverse flotation of phosphogypsum, and then uses a chemical precipitation method to remove soluble phosphorus, Fluorine settles down in the form of insoluble matter, and the insoluble phosphorus, fluorine precipitates, undecomposed phosphate rock, and quartz are separated through two cyclonic classifications.
  • the method for decolorizing and whitening phosphogypsum described in the present disclosure is suitable for pharmaceutical use. The amount is small, and the obtained phosphogypsum CaSO 4 ⁇ 2H 2 O has high content and good whiteness.
  • step S1 the whiteness of the raw phosphogypsum ore is 15%-25%. More preferably, the whiteness of the raw phosphogypsum ore is 20%-25%.
  • step S1 the mass concentration of the slurry after the raw phosphogypsum ore is slurried is 30 wt%.
  • step S1 the mass concentration of sulfuric acid added is 20-40 wt%.
  • step S1 the added amount of sulfuric acid is 1.4-2.08kg/t of raw ore.
  • step S1 the added amount of the decolorizing collector is 0.2-0.4kg/t of raw ore.
  • the mass ratio of diesel, naphthenic acid soap, and foaming agent in the decolorizing collector is 1:7:2.
  • the foaming agent includes a nonionic surfactant.
  • the nonionic surfactant includes a polyoxyethylene nonionic surfactant
  • the polyoxyethylene nonionic surfactant is a long-chain fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene One or more of vinyl ether, fatty acid polyoxyethylene ester, polyoxyethylene alkyl amine, polyoxyethylene alkyl amide.
  • step S1 the inflation volume during inflation is 80m 3 /h.
  • step S1 after flotating the organic matter slurry, the organic matter slurry is settled, concentrated, and filtered to obtain solid organic matter.
  • step S2 the quicklime added is industrial calcium oxide, and the mass content of calcium oxide is ⁇ 90wt%.
  • the amount of lime added is 4.2-6.67kg/t of raw ore.
  • the first cyclone separator is an LZFX50 cyclone separator and the second cyclone separator is an LZFX100 cyclone separator; the LZFX50 cyclone separator and the LZFX100 cyclone separator are Cyclone separators are developed and produced by Oasis Mineral Processing Equipment Preparation Co., Ltd.
  • step S3 the drying temperature during drying is 45°C.
  • the phosphogypsum raw ore with a whiteness of about 20% can be recycled and reused. It has high purity and can effectively remove water-soluble phosphorus and fluorine in the phosphogypsum raw ore.
  • the finished phosphogypsum meets the requirements of CaSO 4 ⁇ 2H 2 O content ⁇ 90wt%, water-soluble phosphorus pentoxide (P 2 O 5 ) ⁇ 0.20wt%, water-soluble fluoride ion (F - ) ⁇ 0.10wt%, and phosphogypsum The different components in the raw ore are separated, making it easier to prepare for recycling.
  • the main methods for treating phosphogypsum include multiple water washings, first reverse selection and then forward selection.
  • the raw materials of the flotation agent (i.e., the decolorizing collector) used in this solution are partly waste materials generated in industry, and Using lime neutralization and sedimentation separation, the dosage of chemicals is small and the treatment cost is low; then through sedimentation defluoridation and phosphorus post-cyclone classification, phosphogypsum with high whiteness is obtained.
  • This solution can avoid the large amount of wastewater generated through water washing and the use of high-cost cationic decolorization collectors.
  • the mass concentration of sulfuric acid used was 20wt%.
  • the added amount of sulfuric acid used is 1.4kg/t raw ore.
  • the decolorizing collector used includes diesel, naphthenic acid soap, and foaming agent; the ratio of diesel, naphthenic acid soap, and foaming agent is 1:7:2.
  • the foaming agent is OP-10.
  • the above-mentioned decolorizing collector is recorded as decolorizing collector ZC-1.
  • the added quicklime is industrial calcium oxide, with a mass content of calcium oxide ⁇ 90wt%; the amount of lime added is 6.67kg/t of raw ore.
  • LZFX50 cyclone separator and LZFX100 cyclone separator are both developed and produced by Oasis Mineral Processing Equipment Preparation Co., Ltd.
  • the raw phosphogypsum ore from Yichang, Hubei is decolorized and whitened; in the raw phosphogypsum ore: the content of CaSO 4 ⁇ 2H 2 O is 88.43wt%, the whiteness of phosphogypsum is 22.16%, and the content of SiO 2 is 3.68wt% .
  • S1 Slurry the above-mentioned phosphogypsum raw ore, and adjust the mass concentration of the phosphogypsum slurry to 30wt% and place it in the flotation tank.
  • the stirring rate is 1860 rpm, so that the raw phosphogypsum ore is fully dispersed in the water.
  • reverse float at an aeration volume of 80m 3 /h After the agent is fully dispersed, reverse float at an aeration volume of 80m 3 /h.
  • the organic matter slurry extracted from the flotation is settled, concentrated and filtered to obtain solid organic matter; the remaining slurry in the flotation tank is recorded as the first phosphogypsum slurry.
  • the raw phosphogypsum ore from Yichang, Hubei is decolorized and whitened; in the raw phosphogypsum ore: the content of CaSO 4 ⁇ 2H 2 O is 88.43wt%, the whiteness of phosphogypsum is 22.16%, and the content of SiO 2 is 3.68wt% .
  • S1 Slurry the above-mentioned phosphogypsum raw ore. Adjust the mass concentration of the phosphogypsum slurry to 30wt% and place it in a flotation tank. The stirring rate is 1860 rpm to allow the phosphogypsum raw ore to be fully dispersed in the water. Add dilute sulfuric acid with a mass fraction of 20wt% to adjust the pH to below 2, stir for 2 minutes, and then add the decolorizing collector ZC-10.2kg/t raw ore. After the agent is fully dispersed, reverse float at an aeration volume of 80m 3 /h. The organic matter slurry extracted from the flotation is settled, concentrated and filtered to obtain solid organic matter; the remaining slurry in the flotation tank is recorded as the first phosphogypsum slurry.
  • the raw phosphogypsum ore from Yichang, Hubei is decolorized and whitened; in the raw phosphogypsum ore: the content of CaSO 4 ⁇ 2H 2 O is 88.43wt%, the whiteness of phosphogypsum is 22.16%, and the content of SiO 2 is 3.68wt% .
  • S1 Slurry the above-mentioned phosphogypsum raw ore. Adjust the mass concentration of the phosphogypsum slurry to 30wt% and place it in a flotation tank. The stirring rate is 1860 rpm to allow the phosphogypsum raw ore to be fully dispersed in the water. Add dilute sulfuric acid with a mass fraction of 20wt% to adjust the pH to below 2, stir for 2 minutes, and then add the decolorizing collector ZC-10.4kg/t raw ore. After the agent is fully dispersed, reverse float at an aeration volume of 80m 3 /h. The organic matter slurry extracted from the flotation is settled, concentrated and filtered to obtain solid organic matter; the remaining slurry in the flotation tank is recorded as the first phosphogypsum slurry.
  • This comparative example decolorizes and whitens the phosphogypsum raw ore from Yichang, Hubei; in the phosphogypsum raw ore: the CaSO 4 ⁇ 2H 2 O content is 88.43wt%, the phosphogypsum whiteness is 22.16%, and the SiO 2 content is 3.68wt% .
  • a method for decolorizing and whitening phosphogypsum in this comparative example includes the following steps:
  • S1 Slurry the above-mentioned phosphogypsum raw ore. Adjust the mass concentration of the phosphogypsum slurry to 30wt% and place it in a flotation tank. The stirring rate is 1860 rpm to allow the phosphogypsum raw ore to be fully dispersed in the water. Add 20wt% dilute sulfuric acid to adjust the pH to below 2, stir for 2 minutes, and then add the decolorizing collector ZC-10.3kg/t raw ore. After the agent is fully dispersed, flotation is carried out at an aeration volume of 80m 3 /h. , the flotated organic matter slurry is settled, concentrated, and filtered to obtain solid organic matter; the remaining slurry in the flotation tank is recorded as the first phosphogypsum slurry.
  • This comparative example decolorizes and whitens the phosphogypsum raw ore from Yichang, Hubei; in the phosphogypsum raw ore: the CaSO 4 ⁇ 2H 2 O content is 88.43wt%, the phosphogypsum whiteness is 22.16%, and the SiO 2 content is 3.68wt% .
  • a method for decolorizing and whitening phosphogypsum in this comparative example includes the following steps:
  • S1 Slurry the above-mentioned phosphogypsum raw ore. Adjust the mass concentration of the phosphogypsum slurry to 30wt% and place it in a flotation tank. The stirring rate is 1860 rpm to allow the phosphogypsum raw ore to be fully dispersed in the water. Add 20wt% dilute sulfuric acid to adjust the pH to below 2, stir for 2 minutes, and then add the decolorizing collector ZC-10.3kg/t raw ore. After the agent is fully dispersed, flotation is carried out at an aeration volume of 80m 3 /h. The flotated organic matter slurry is settled, concentrated, and filtered to obtain solid organic matter; the remaining slurry in the flotation tank is recorded as the first phosphogypsum slurry.
  • the method for decolorizing and whitening phosphogypsum described in the present disclosure can remove organic matter, soluble phosphorus, fluorine, silicate, etc. in phosphogypsum and meet the requirements of industrial gypsum.
  • the method has a simple process, high efficiency in purifying phosphogypsum, low cost, and is easy to be industrialized.
  • Decolorizing collector ZC-1 is produced by compounding different industrial-grade raw materials, mainly composed of diesel oil, foaming agent, and naphthenic acid soap.
  • diesel oil mainly hydrophobizes the slurry
  • naphthenic acid soap has a polar carboxylic acid group on one end due to the particularity of its molecular structure, and a naphthenic group connected to a methylene group on the other end, which is hydrophobic.
  • Extremely strong During the decolorization process, it has a strong adsorption effect on charged slime and fine-grained carbon.
  • a certain foaming agent is added to the decolorization collector to provide a large amount of stable foam during flotation and aeration, making the decolorization more efficient. , the mud removal effect is better.
  • Adding lime to the first phosphogypsum slurry not only adjusts the pH in the phosphogypsum aqueous solution, but also precipitates the water-soluble phosphorus and fluorine in the second phosphogypsum slurry in the form of insoluble calcium salts such as calcium phosphate and calcium fluoride. Because these insoluble calcium salt particles are relatively fine, the particle size is about 20 ⁇ m or less, the particle size of phosphogypsum is between 20-60 ⁇ m, and the quartz particle size is above 74 ⁇ m.
  • the formed poorly soluble calcium salts, phosphogypsum, and quartz are separated through the effect of cyclone classification, and the residual decolorizing collector ZC-1 in the slurry plays an active role in separating the poorly soluble calcium salts; the remaining The foaming agent will generate certain bubbles under the action of cyclone, and the remaining non-polar oil will reduce the force between the slurry particles, which can quickly separate the insoluble calcium salt particles, phosphogypsum and quartz mixture. Come on.

Abstract

本公开属于磷石膏的处理和资源化利用领域，具体涉及一种磷石膏脱色增白的方法。本公开所述的磷石膏脱色增白的方法，利用脱色捕收剂对磷石膏进行反浮选去除有机质，再通过调节pH将可溶性的磷、氟沉降下来，经过两次旋流分级将难溶的磷、氟沉淀物、未分解的磷矿石、石英分别分离，得到磷石膏CaSO4·2H2O含量高、白度好。本公开的脱色捕收剂主要由柴油、起泡剂、环烷酸皂组成，柴油使矿浆起到疏水化的作用，而环烷酸皂一端含有极性的羧酸基团，另一端为环烷基团连接着亚甲基，疏水性极强，在脱色过程中对带电荷的矿泥和细颗粒的碳具有很强的吸附作用，同时脱色捕收剂中还加入了起泡剂，在反浮选充气时提供大量稳定的泡沫，使脱色、脱泥的效果更好。

Description

一种磷石膏脱色增白的方法 技术领域
本公开属于磷石膏的处理和资源化利用领域，具体涉及一种磷石膏脱色增白的方法。
背景技术
磷石膏是指在磷酸生产中用硫酸处理磷矿石产生的固体废渣，其主要成分为二水硫酸钙。在磷酸生产过程中，由于部分未分解的磷矿石、或是洗涤过滤不完全的磷酸盐和氟化物、或是生产过程中使用的添加剂，均会使磷石膏中含有磷、氟等多种杂质；而这些杂质的存在影响了磷石膏的性能，使其不能直接应用于石膏建材的生产，制约了磷石膏的使用。
磷石膏杂质分两大类：(1)不溶性杂质：如石英、未分解的磷灰石、不溶性P2O5、共晶P2O5、氟化物及氟、铝、镁的磷酸盐和硫酸盐；(2)可溶性杂质：如水溶性P2O5，溶解度较低的氟化物和硫酸盐。
目前国内对磷石膏的应用进行了大量的研究，也取得了一定的成果。浮选是在气-液-固三相界面分选矿物的技术，浮选是一种较为合适的高效分离磷石膏方法。目前磷石膏处理主要方法有多次水洗、先反选再正选，但磷石膏处理的效果均不理想。
发明内容
基于此，本公开的目的在于，提供一种磷石膏脱色增白的方法，去除磷石膏中的有机质、可溶性磷、氟、硅酸盐等，达到工业石膏的要求。该方法工艺简单、纯化磷石膏效率高、成本低、容易工业化。
为实现上述的目的，本公开提供如下技术方案：
一种磷石膏脱色增白的方法，包括以下步骤：
S1：将磷石膏原矿进行调浆，添加硫酸调节pH至2以下，添加脱色捕收剂，充气，进行反浮选，浮选出有机质矿浆，剩余的矿浆记为第一磷石膏矿浆；
其中，所述脱色捕收剂包括柴油、环烷酸皂和起泡剂；
S2：向步骤S1的所述第一磷石膏矿浆添加石灰调节pH至11以上，然后依次通入第一旋流分离器、第二旋流分离器中；所述第一旋流分离器溢流分离出细颗粒性矿浆，所述细颗粒性矿浆中的细颗粒的粒径小于20μm，所述第二旋流分离器溢流出第二磷石膏矿浆、所述第二旋流分离器底流出石英混合物；
S3：将步骤S2的所述第二磷石膏矿浆进行沉降、浓缩、压滤、烘干得到磷石膏。
本公开的磷石膏的所述脱色捕收剂是利用不同的工业级原料进行复配产生，主要由柴油、起泡剂、环烷酸皂组成。其中柴油主要使矿浆起到疏水化的作用，而环烷酸皂由于分子 结构的特殊性，一端含有极性的羧酸基团，另一端为环烷基团连接着亚甲基，疏水性极强，在脱色过程中对带电荷的矿泥和细颗粒的碳具有很强的吸附作用，同时所述脱色捕收剂中还加入了起泡剂，在反浮选充气时提供大量稳定的泡沫，使脱色、脱泥的效果更好。而常规的脱色捕收剂主要是矿物油类的物质，在脱色、脱泥时，只是起到矿浆的疏水化作用，再在充气的作用下将细颗粒物质矿泥、碳进行分离出来。对比常规的脱色捕收剂，本公开所述脱色捕收剂在脱色、脱泥的效果上更具有优势。
本公开所述的磷石膏脱色增白的方法中，先采用反浮选去除有机质，再通过调节第一磷石膏矿浆的pH至11以上，使第一磷石膏矿浆中的水溶性磷、氟转化为的细颗粒的磷酸钙、氟化钙等难溶性物质。由于这些难溶性物质的颗粒较为细，粒径在20μm以下，磷石膏的粒径在20-60μm之间，石英颗粒粒径在74μm以上。因此根据粒径的差异，通过第一旋流分离器、第二旋流分离器的旋流分级的效果将形成的磷酸钙、氟化钙等难溶性物质、磷石膏、石英分离开来，并且所述第一磷石膏矿浆中，残留的所述脱色捕收剂对分离难溶性物质起到了积极的作用；残留的起泡剂在旋流的作用下，会产生一定的气泡，同时残留的柴油(非极性油)使矿浆颗粒之间的作用力减小，能更快地将粒径小于20μm的磷酸钙、氟化钙等难溶性物质、磷石膏和石英混合物分离开来。
本公开所述的磷石膏脱色增白的方法，对比于其他磷石膏浮选的工艺，本公开直接利用所述脱色捕收剂对磷石膏进行反浮选，之后利用化学沉淀法将可溶性磷、氟以不溶物形式沉降下来，经过两次旋流分级将难溶的磷、氟沉淀物、未分解的磷矿石、石英分别分离，本公开所述的磷石膏脱色增白的方法，药剂用量少，得到磷石膏CaSO4·2H2O含量高、白度好。
在一个方案中，步骤S1中，所述磷石膏原矿的白度为15％-25％。更优选的，所述磷石膏原矿的白度为20％-25％。
在一个方案中，步骤S1中，磷石膏原矿进行调浆后的矿浆的质量浓度为30wt％。
在一个方案中，步骤S1中，添加的硫酸的质量浓度为20-40wt％。
在一个方案中，步骤S1中，所述硫酸的添加量为1.4-2.08kg/t原矿。
在一个方案中，步骤S1中，所述脱色捕收剂添加量为0.2-0.4kg/t原矿。
在一个方案中，所述脱色捕收剂中，柴油、环烷酸皂、起泡剂的质量比为1：7：2。
在一个方案中，所述起泡剂包括非离子型表面活性剂。
在一个方案中，所述非离子型表面活性剂包括聚氧乙烯型非离子表面活性剂，所述聚氧乙烯型非离子表面活性剂为长链脂肪醇聚氧乙烯醚、烷基酚聚氧乙烯醚、脂肪酸聚氧乙烯酯、聚氧乙烯烷基胺、聚氧乙烯烷基酰胺中的一种或多种。
在一个方案中，步骤S1中，充气时的充气量为80m3/h。
在一个方案中，步骤S1中，浮选出有机质矿浆后，将有机质矿浆进行沉降、浓缩、压滤得固体有机质。
在一个方案中，步骤S2中，添加的生石灰为工业氧化钙，氧化钙质量含量≥90wt％。
在一个方案中，石灰添加量为4.2-6.67kg/t原矿。
在一个方案中，步骤S2中，所述第一旋流分离器为LZFX50旋流分离器、所述第二旋流分离器为LZFX100旋流分离器；所述LZFX50旋流分离器和所述LZFX100旋流分离器均由绿洲选矿设备制备有限公司研发生产。
在一个方案中，步骤S3中，烘干时的烘干温度为45℃。
本公开的有益效果：
经过本方案反浮选脱色、石灰中和沉降、旋流分级，可以将白度为20％左右的磷石膏原矿回收利用，纯度高，能够有效去除磷石膏原矿中的水溶性磷、氟，最终成品磷石膏满足CaSO4·2H2O含量≥90wt％，水溶性五氧化二磷(P2O5)≤0.20wt％，水溶性氟离子(F-)≤0.10wt％的要求，并且磷石膏原矿中的不同成分进行了分离，更利于回收利用做准备。
相对于现有技术：目前磷石膏处理主要方法有多次水洗、先反选再正选，而本方案采用的浮选药剂(即所述脱色捕收剂)原料部分为工业中产生的废料，并利用石灰中和沉降分离，药剂用量少，处理成本低；再通过沉降脱氟、磷后旋流分级，得到白度高的磷石膏。本方案可以避免通过水洗方式产生大量的废水和采用高成本的阳离子脱色捕收剂。
具体实施方式
以下实施例或对比例中：
使用的硫酸的质量浓度为20wt％。
使用硫酸的添加量为1.4kg/t原矿。
使用的脱色捕收剂包括柴油、环烷酸皂、起泡剂；其中柴油、环烷酸皂、起泡剂的比例为1：7：2。所述起泡剂为OP-10。将上述脱色捕收剂记为脱色捕收剂ZC-1。
添加的生石灰为工业氧化钙，氧化钙质量含量≥90wt％；石灰添加量为6.67kg/t原矿。
LZFX50旋流分离器和LZFX100旋流分离器均由绿洲选矿设备制备有限公司研发生产。
实施例1
本实施例对来自湖北宜昌的磷石膏原矿进行脱色增白；该磷石膏原矿中：CaSO4·2H2O含量为88.43wt％，磷石膏白度为22.16％，SiO2的含量为3.68wt％。
本实施例的一种磷石膏脱色增白的方法，包括以下步骤：
S1：将上述磷石膏原矿进行调浆，调节磷石膏的矿浆的质量浓度为30wt％置于浮选槽 中，搅拌速率为1860转/min，让磷石膏原矿充分分散于水中。加入质量分数为20wt％的稀硫酸调节pH至2以下，搅拌2min，再加入脱色捕收剂ZC-10.3kg/t原矿，待药剂充分分散后，在充气量为80m3/h，进行反浮选，将浮选出来的有机质矿浆进行沉降、浓缩、压滤得固体有机质；浮选槽中剩余的矿浆则记为第一磷石膏矿浆。
S2：向第一磷石膏矿浆中添加石灰使pH在11以上，使第一磷石膏矿浆中的水溶性氟、磷转化为磷酸钙、氟化钙等难溶性物质。反应过后的料浆依次通入LZFX50、LZFX100旋流分离器中，从LZFX50溢流分离出磷酸钙、氟化钙等粒径在20um以下细颗粒的难溶性物质、LZFX100溢流出第二磷石膏矿浆、LZFX100底流出石英混合物。
S3：将第二磷石膏矿浆进行沉降、浓缩、压滤、45℃烘干得磷石膏，磷石膏中CaSO4·2H2O的含量为95.23wt％，SiO2的含量为0.55wt％，磷石膏产率为77.77wt％，磷石膏白度为84.94％。
实施例2
本实施例对来自湖北宜昌的磷石膏原矿进行脱色增白；该磷石膏原矿中：CaSO4·2H2O含量为88.43wt％，磷石膏白度为22.16％，SiO2的含量为3.68wt％。
本实施例的一种磷石膏脱色增白的方法，包括以下步骤：
S1：将上述磷石膏原矿进行调浆，调节磷石膏的矿浆的质量浓度为30wt％置于浮选槽中，搅拌速率为1860转/min，让磷石膏原矿充分分散于水中。加入质量分数为20wt％的稀硫酸调节pH至2以下，搅拌2min，再加入脱色捕收剂ZC-10.2kg/t原矿，待药剂充分分散后，在充气量为80m3/h，进行反浮选，将浮选出来的有机质矿浆进行沉降、浓缩、压滤得固体有机质；浮选槽中剩余的矿浆则记为第一磷石膏矿浆。
S2：向第一磷石膏矿浆中添加石灰使pH在11以上，使第一磷石膏矿浆中的水溶性氟、磷转化为磷酸钙、氟化钙等难溶性物质。反应过后的料浆依次通入LZFX50、LZFX100旋流分离器中，从LZFX50溢流分离出磷酸钙、氟化钙等粒径在20um以下细颗粒的难溶性物质、LZFX100溢流出第二磷石膏矿浆、LZFX100底流出石英混合物。
S3：将第二磷石膏矿浆进行沉降、浓缩、压滤、45℃烘干得二水石膏，磷石膏中CaSO4·2H2O含量为94.51wt％，SiO2的含量为0.62wt％，磷石膏产率为78.67wt％，磷石膏白度为81.48％。
实施例3
本实施例对来自湖北宜昌的磷石膏原矿进行脱色增白；该磷石膏原矿中：CaSO4·2H2O含量为88.43wt％，磷石膏白度为22.16％，SiO2的含量为3.68wt％。
本实施例的一种磷石膏脱色增白的方法，包括以下步骤：
S1：将上述磷石膏原矿进行调浆，调节磷石膏的矿浆的质量浓度为30wt％置于浮选槽中，搅拌速率为1860转/min，让磷石膏原矿充分分散于水中。加入质量分数为20wt％的稀硫酸调节pH至2以下，搅拌2min，再加入脱色捕收剂ZC-10.4kg/t原矿，待药剂充分分散后，在充气量为80m3/h，进行反浮选，将浮选出来的有机质矿浆进行沉降、浓缩、压滤得固体有机质；浮选槽中剩余的矿浆则记为第一磷石膏矿浆。
S2：向第一磷石膏矿浆中添加石灰使pH在11以上，使第一磷石膏矿浆中的水溶性氟、磷转化为磷酸钙、氟化钙等难溶性物质。反应过后的料浆依次通入LZFX50、LZFX100旋流分离器中，从LZFX50溢流分离出磷酸钙、氟化钙等粒径在20um以下细颗粒的难溶性物质、LZFX100溢流出第二磷石膏矿浆，LZFX100底流出石英混合物；
S3：将第二磷石膏矿浆进行沉降、浓缩、压滤、45℃烘干得二水石膏，磷石膏中CaSO4·2H2O含量为95.53wt％，SiO2的含量为0.53wt％，磷石膏产率为76.34wt％，磷石膏白度为84.86％。
对比例1
本对比例对来自湖北宜昌的磷石膏原矿进行脱色增白；该磷石膏原矿中：CaSO4·2H2O含量为88.43wt％，磷石膏白度为22.16％，SiO2的含量为3.68wt％。
本对比例的一种磷石膏脱色增白的方法，包括以下步骤：
S1：将上述磷石膏原矿进行调浆，调节磷石膏的矿浆的质量浓度为30wt％置于浮选槽中，搅拌速率为1860转/min，让磷石膏原矿充分分散于水中。加入质量分数为20wt％的稀硫酸调节pH至2以下，搅拌2min，再加入脱色捕收剂ZC-10.3kg/t原矿，待药剂充分分散后，在充气量为80m3/h，进行浮选，将浮选出来的有机质矿浆进行沉降、浓缩、压滤得固体有机质；浮选槽中剩余的矿浆则记为第一磷石膏矿浆。
S2：向第一磷石膏矿浆中添加石灰使pH在11以上，使第一磷石膏矿浆中的水溶性氟、磷转化为磷酸钙、氟化钙等难溶性物质。反应过后的料浆通入LZFX100旋流分离器中，从LZFX100溢流分离出磷酸钙、氟化钙等粒径在20um以下细颗粒的难溶性物质和磷石膏矿浆混合物，LZFX100底流出石英混合物；
S3：将溢流出的磷酸钙、氟化钙等粒径在20um以下细颗粒的难溶性物质和磷石膏矿浆混合物沉降、浓缩、压滤、45℃烘干得二水石膏，磷石膏中CaSO4·2H2O含量为93.42wt％，SiO2的含量为0.68wt％，磷石膏产率为80.36wt％，磷石膏白度为78.34％。
对比例2
本对比例对来自湖北宜昌的磷石膏原矿进行脱色增白；该磷石膏原矿中：CaSO4·2H2O含量为88.43wt％，磷石膏白度为22.16％，SiO2的含量为3.68wt％。
本对比例的一种磷石膏脱色增白的方法，包括以下步骤：
S1：将上述磷石膏原矿进行调浆，调节磷石膏的矿浆的质量浓度为30wt％置于浮选槽中，搅拌速率为1860转/min，让磷石膏原矿充分分散于水中。加入质量分数为20wt％稀硫酸调节pH至2以下，搅拌2min，在加入脱色捕收剂ZC-10.3kg/t原矿，待药剂充分分散后，在充气量为80m3/h，进行浮选，将浮选出来的有机质矿浆进行沉降、浓缩、压滤得固体有机质；浮选槽中剩余的矿浆则记为第一磷石膏矿浆。
S2：向第一磷石膏矿浆中添加石灰使pH在11以上，使第一磷石膏矿浆中的水溶性氟、磷转化为磷酸钙、氟化钙等粒径在20um以下细颗粒的难溶性物质。反应过后的料浆通入LZFX50旋流分离器中，从LZFX50溢流分离出磷酸钙、氟化钙等粒径在20um以下细颗粒的难溶性物质，LZFX50底流出磷石膏和石英矿浆混合物；
S3：将底流出的磷石膏和石英矿浆混合物沉降、浓缩、压滤、45℃烘干得二水石膏，磷石膏中CaSO4·2H2O含量为91.56wt％，SiO2的含量为2.72wt％，磷石膏产率为85.86wt％，磷石膏白度为65.37％。
相对于现有技术，本公开所述的磷石膏脱色增白的方法，能够去除磷石膏中的有机质、可溶性磷、氟、硅酸盐等，达到工业石膏的要求。该方法工艺简单、纯化磷石膏效率高、成本低、容易工业化。脱色捕收剂ZC-1是利用不同的工业级原料进行复配产生，主要由柴油、起泡剂、环烷酸皂组成。其中柴油主要使矿浆起到疏水化的作用，而环烷酸皂由于分子结构的特殊性，一端含有极性的羧酸基团，另一端是为环烷基团连接着亚甲基，疏水性极强。在脱色过程中对带电荷的矿泥和细颗粒的碳具有很强的吸附作用，同时脱色捕收剂中还加入了一定的起泡剂，在浮选充气时提供大量稳定的泡沫，使脱色、脱泥的效果更好。向第一磷石膏矿浆中添加石灰既调节了磷石膏水溶液中的pH，同时也使第二磷石膏矿浆中的水溶性磷、氟以磷酸钙、氟化钙等难溶性的钙盐形式沉淀。由于这些难溶性的钙盐颗粒较为细，粒径大概在20μm以下，磷石膏的粒径在20-60μm之间，石英颗粒粒径在74μm以上。因此通过旋流分级的效果将形成的难溶性钙盐、磷石膏、石英分离开来，并且矿浆中残留的脱色捕收剂ZC-1在分离难溶性钙盐起到了积极地作用；残留的起泡剂在旋流的作用下，会产生一定的气泡，同时残留的非极性油使矿浆颗粒之间的作用力减小，能更快地将难溶性钙盐颗粒、磷石膏和石英混合物分离开来。
以上所述实施例仅表达了本公开的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本公开构思的前提下，还可以做出若干变形和改进，则本公开也意图包含这些改动和变形。

Claims (15)

  1. 一种磷石膏脱色增白的方法，其特征在于：包括以下步骤：
    S1：将磷石膏原矿进行调浆，添加硫酸调节pH至2以下，添加脱色捕收剂，充气，进行反浮选，浮选出有机质矿浆，剩余的矿浆记为第一磷石膏矿浆；
    其中，所述脱色捕收剂包括柴油、环烷酸皂和起泡剂；
    S2：向步骤S1的所述第一磷石膏矿浆添加石灰调节pH至11以上，然后依次通入第一旋流分离器、第二旋流分离器中；所述第一旋流分离器溢流分离出细颗粒性矿浆，所述细颗粒性矿浆中的细颗粒的粒径小于20μm，所述第二旋流分离器溢流出第二磷石膏矿浆、所述第二旋流分离器底流出石英混合物；
    S3：将步骤S2的所述第二磷石膏矿浆进行沉降、浓缩、压滤、烘干得到磷石膏。
  2. 根据权利要求1所述的磷石膏脱色增白的方法，其特征在于：步骤S1中，所述磷石膏原矿的白度为15％-25％。
  3. 根据权利要求1所述的磷石膏脱色增白的方法，其特征在于：步骤S1中，磷石膏原矿进行调浆后的矿浆浓度为30wt％。
  4. 根据权利要求1所述的磷石膏脱色增白的方法，其特征在于：步骤S1中，添加的硫酸的质量浓度为20-40wt％。
  5. 根据权利要求1所述的磷石膏脱色增白的方法，其特征在于：所述硫酸的添加量为1.4-2.08kg/t原矿。
  6. 根据权利要求1所述的磷石膏脱色增白的方法，其特征在于：步骤S1中，所述脱色捕收剂添加量为0.2-0.4kg/t原矿。
  7. 根据权利要求1所述的磷石膏脱色增白的方法，其特征在于：所述脱色捕收剂中，柴油、环烷酸皂、起泡剂的质量比为1：7：2。
  8. 根据权利要求1所述的磷石膏脱色增白的方法，其特征在于：所述起泡剂包括非离子型表面活性剂。
  9. 根据权利要求8所述的磷石膏脱色增白的方法，其特征在于：所述非离子型表面活性剂包括聚氧乙烯型非离子表面活性剂，所述聚氧乙烯型非离子表面活性剂为长链脂肪醇聚氧乙烯醚、烷基酚聚氧乙烯醚、脂肪酸聚氧乙烯酯、聚氧乙烯烷基胺、聚氧乙烯烷基酰胺中的一种或多种。
  10. 根据权利要求1所述的磷石膏脱色增白的方法，其特征在于：步骤S1中，充气时的充气量为80m3/h。
  11. 根据权利要求1所述的磷石膏脱色增白的方法，其特征在于：步骤S1中，浮选出有机质矿浆后，将有机质矿浆进行沉降、浓缩、压滤得固体有机质。
  12. 根据权利要求1所述的磷石膏脱色增白的方法，其特征在于：步骤S2中，添加的生石灰为工业氧化钙，氧化钙含量≥90wt％。
  13. 根据权利要求1所述的磷石膏脱色增白的方法，其特征在于：石灰添加量为4.2-6.67kg/t原矿。
  14. 根据权利要求1所述的磷石膏脱色增白的方法，其特征在于：步骤S2中，所述第一旋流分离器为LZFX50旋流分离器、所述第二旋流分离器为LZFX100旋流分离器；所述LZFX50旋流分离器和所述LZFX100旋流分离器均由绿洲选矿设备制备有限公司研发生产。
  15. 根据权利要求1所述的磷石膏脱色增白的方法，其特征在于：步骤S3中，烘干时的烘干温度为45℃。
PCT/CN2023/098335 2023-06-05 2023-06-05 一种磷石膏脱色增白的方法 WO2024037127A1 (zh)

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CN114653473A (zh) * 2022-03-30 2022-06-24 云南磷化集团有限公司 一种高效净化磷石膏的浮选方法
CN115400881A (zh) * 2022-08-26 2022-11-29 广东邦普循环科技有限公司 一种磷石膏提纯增白的方法
CN115780096A (zh) * 2022-11-04 2023-03-14 矿冶科技集团有限公司 一种反浮选捕收碳硅的捕收剂及其制备方法和用途
CN115957894A (zh) * 2022-10-24 2023-04-14 郑州大学 一种磷石膏增白提纯工艺
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WO2021140073A1 (de) * 2020-01-08 2021-07-15 Thyssenkrupp Industrial Solutions Ag Integriertes verfahren zur herstellung eines baustoffs aus phosphorgips
CN114653473A (zh) * 2022-03-30 2022-06-24 云南磷化集团有限公司 一种高效净化磷石膏的浮选方法
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