WO2024040893A1 - 一种磷石膏提纯增白的方法 - Google Patents
一种磷石膏提纯增白的方法 Download PDFInfo
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- WO2024040893A1 WO2024040893A1 PCT/CN2023/077582 CN2023077582W WO2024040893A1 WO 2024040893 A1 WO2024040893 A1 WO 2024040893A1 CN 2023077582 W CN2023077582 W CN 2023077582W WO 2024040893 A1 WO2024040893 A1 WO 2024040893A1
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- WIPO (PCT)
- Prior art keywords
- phosphogypsum
- flotation
- whitening
- purifying
- add
- Prior art date
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- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 title claims abstract description 96
- 238000000034 method Methods 0.000 title claims abstract description 30
- 230000002087 whitening effect Effects 0.000 title claims abstract description 27
- 238000005188 flotation Methods 0.000 claims abstract description 109
- 238000001035 drying Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 44
- 239000002002 slurry Substances 0.000 claims description 41
- 239000007788 liquid Substances 0.000 claims description 32
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 21
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 14
- 239000004088 foaming agent Substances 0.000 claims description 11
- 239000012141 concentrate Substances 0.000 claims description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 238000004042 decolorization Methods 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 2
- 229940077388 benzenesulfonate Drugs 0.000 claims description 2
- 125000005587 carbonate group Chemical group 0.000 claims description 2
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000002910 solid waste Substances 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 9
- 239000012535 impurity Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 6
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 6
- 238000009825 accumulation Methods 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000003002 pH adjusting agent Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 239000010459 dolomite Substances 0.000 description 2
- 229910000514 dolomite Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- -1 ammonium 3-hydroxycaproate Chemical compound 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- FOBPTJZYDGNHLR-UHFFFAOYSA-N diphosphorus Chemical compound P#P FOBPTJZYDGNHLR-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002686 phosphate fertilizer Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
Classifications
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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
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/02—Froth-flotation processes
-
- 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
- B03B1/00—Conditioning for facilitating separation by altering physical properties of the matter to be treated
- B03B1/04—Conditioning for facilitating separation by altering physical properties of the matter to be treated by additives
-
- 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
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/007—Modifying reagents for adjusting pH or conductivity
Definitions
- This application relates to the technical field of comprehensive utilization of solid waste, and specifically relates to a method for purifying and whitening phosphogypsum.
- Phosphogypsum is a kind of industrial solid waste in the phosphate fertilizer chemical industry. The accumulation of phosphogypsum will bring many hidden dangers. Phosphogypsum is in powder form and can easily form dust when exposed to the sun for a long time, which affects the atmospheric environment. If it is wetted by rain, it will cause phosphogypsum to become contaminated. Harmful impurities such as various salts containing water-soluble P 2 O 5 and F ions flow out; phosphogypsum is a flow-shaped object, and if it is not handled properly, acidic polluted water containing impurities will leak or overflow and enter surface water and groundwater. Or soil, will cause irreversible water, soil, plant pollution.
- Phosphogypsum is also listed as a major source of danger by the national safety supervision department. Once the phosphogypsum reservoir dam fails, it will cause huge losses to life and property downstream. The large accumulation of phosphogypsum has caused serious social and environmental problems, and its comprehensive utilization and management are urgent. Solving the problem of comprehensive utilization of phosphogypsum is of great significance.
- Treating phosphogypsum as a building material is an important means to reduce the accumulation of phosphogypsum.
- phosphogypsum cannot be directly used as a building material. It needs to be purified before use to improve its purity and whiteness so that it can be used in In the construction field, therefore, how to improve the whiteness and purity of phosphogypsum has become an urgent technical problem to be solved by those skilled in the art.
- the purpose of this application is to overcome the shortcomings of the existing technology and provide a method for purifying and whitening phosphogypsum, which can prepare high-purity and high-whiteness phosphogypsum, effectively reduce the accumulation of phosphogypsum, and alleviate the environment. pressure.
- a method for purifying and whitening phosphogypsum including the following steps:
- This application can effectively remove impurities and decolorize phosphogypsum by decolorizing (reverse flotation) phosphogypsum, and then through three forward flotation processes, so that organic matter, carbon residue, silicon and other impurities in phosphogypsum can be effectively removed. Therefore, high-purity phosphogypsum with high whiteness and purity can be prepared.
- the unreacted phosphorus pentoxide and metal oxides in the phosphogypsum can be dissolved, thereby further improving the whiteness and purity of the phosphogypsum.
- the inventor of this application found in a large number of studies that in the process of positive flotation purification and whitening, the pH is a key parameter affecting purification and whitening. If the pH is too low or too high, it will lead to pentoxidation. The dissolution effect of diphosphorus and metal oxides is not good, thus reducing the whiteness and purity of phosphogypsum.
- forward flotation is carried out in ordinary flotation cells.
- the forward flotation and reverse flotation described in this application are forward flotation and reverse flotation that are commonly understood by those skilled in the art.
- Flotation that is, forward flotation, refers to discharging useless minerals along with the slurry as tailings; reverse flotation refers to leaving the required minerals in the flotation tank and scraping the unwanted minerals with the foam. out.
- the CaSO 4 ⁇ 2H 2 O content of the phosphogypsum is 70 to 92%, the whiteness is 20 to 40%, and the SiO 2 content is 4 to 8%.
- the purification and whitening method of the present application has a good effect and can effectively remove impurities and whiten it at the same time.
- the mass fraction of the slurry is 20 to 40%
- the decolorization treatment includes adding a decolorizing collector and a foaming agent to the slurry to perform reverse flotation.
- the decolorizing collector is a trihydroxypolyammonium collector, and its dosage is 0.48 to 1kg/t. It should be noted that the dosage of decolorizing collector kg/t refers to the dosage relative to phosphogypsum, that is, 0.48 to 1 kg of trihydroxypolyammonium type collector is used for 1 ton of phosphogypsum, the same below.
- the foaming agent is a carbonate foaming agent, and its dosage is 0.18 to 0.24kg/t.
- the above-mentioned specific polyammonium type containing three hydroxyl groups as the collector, use carbonate as the foaming agent, and control its dosage. Under their interaction and mutual influence, it can be effectively removed in just one step. Organic matter, carbon residue, dolomite and other gangue minerals can effectively improve the whiteness and purity of phosphogypsum.
- the trihydroxypolyammonium collector is at least one of 3-hydroxyammonium hexanoate and 3-hydroxyammonium dodecanoate.
- the foaming agent is at least one of sodium carbonate and calcium carbonate.
- the collector is at least one of sodium linear alkyl benzene sulfonate and sodium ⁇ -alkenyl sulfonate, and its dosage is 0.15 to 0.25kg/t.
- the pH adjuster is a sulfuric acid solution with a volume concentration of 20 to 40%.
- the pH adjuster is a sulfuric acid solution with a volume concentration of 20 to 40%, it can dissolve unreacted phosphorus pentoxide and metal oxides in the phosphogypsum, while also avoiding corrosion of the equipment.
- the pH adjuster is a sulfuric acid solution with a volume concentration of 30 to 40%.
- the drying temperature is 100 to 200°C.
- the drying temperature can significantly affect the whiteness of phosphogypsum. By controlling the drying temperature at 100 to 200°C, the whiteness of phosphogypsum can be significantly improved.
- the drying temperature is 200°C.
- the beneficial effects of this application are: (1)
- the method for purifying and whitening phosphogypsum described in this application can prepare high-purity and high-whiteness phosphogypsum, effectively reduce the accumulation of phosphogypsum, and relieve environmental pressure; It has broad application prospects.
- the prepared refined phosphogypsum can replace desulfurized gypsum to prepare building gypsum powder;
- the phosphogypsum is decolorized and then subjected to three positive flotation processes to effectively remove impurities from the phosphogypsum.
- a method for purifying and whitening phosphogypsum including the following steps:
- the CaSO 4 ⁇ 2H 2 O content of the obtained refined phosphogypsum was 96.17%, the yield was 79.99%, the whiteness was 67.12%, and the SiO 2 content was 0.57%.
- Example 2 The difference between Example 2 and Example 1 is that the drying temperature is different, and everything else is the same.
- Example 2 The drying temperature of Example 2 is 200°C.
- the CaSO 4 ⁇ 2H 2 O content of the obtained refined phosphogypsum is 96.17%, the yield is 79.99%, the whiteness is 73.71%, and the SiO 2 content is 0.57%.
- a method for purifying and whitening phosphogypsum including the following steps:
- the CaSO 4 ⁇ 2H 2 O content of the obtained refined phosphogypsum was 96.56%, the yield was 78.84%, the whiteness was 65.74%, and the SiO 2 content was 0.77%.
- Example 4 The difference between Example 4 and Example 3 is that the drying temperature is different, and everything else is the same.
- Example 4 The drying temperature of Example 4 is 200°C.
- the CaSO 4 ⁇ 2H 2 O content of the obtained refined phosphogypsum is 96.56%, the yield is 78.84%, the whiteness is 76.46%, and the SiO 2 content is 0.77%.
- a method for purifying and whitening phosphogypsum including the following steps:
- the CaSO 4 ⁇ 2H 2 O content of the obtained refined phosphogypsum was 97.71%, the yield was 79.40%, the whiteness was 65.50%, and the SiO 2 content was 0.66%.
- Example 6 The difference between Example 6 and Example 5 is that the drying temperature is different, and everything else is the same.
- Example 6 The drying temperature of Example 6 is 200°C.
- the CaSO 4 ⁇ 2H 2 O content of the obtained refined phosphogypsum is 97.71%, the yield is 79.40%, the whiteness is 73.46%, and the SiO 2 content is 0.66%.
- a method for purifying and whitening phosphogypsum including the following steps:
- the CaSO 4 ⁇ 2H 2 O content of the obtained refined phosphogypsum was 97.71%, the yield was 78.93%, the whiteness was 62.42%, and the SiO 2 content was 0.82%.
- Example 8 The difference between Example 8 and Example 7 is that the drying temperature is different, and everything else is the same.
- Example 8 The drying temperature of Example 8 is 200°C.
- the CaSO 4 ⁇ 2H 2 O content of the obtained refined phosphogypsum is 97.71%, the yield is 78.93%, the whiteness is 67.99%, and the SiO 2 content is 0.82%.
- Comparative Example 1 adopts positive flotation once, and everything else is the same.
- a method for purifying and whitening phosphogypsum including the following steps:
- the resulting refined phosphogypsum has a CaSO 4 ⁇ 2H 2 O content of 93%, a yield of 83%, a whiteness of 42%, and a SiO 2 content of 1.5%.
- Comparative Example 2 The difference between Comparative Example 2 and Example 7 is that the pH adjusted in the positive flotation process of Comparative Example 2 is different, and everything else is the same.
- a method for purifying and whitening phosphogypsum including the following steps:
- the resulting refined phosphogypsum has a CaSO 4 ⁇ 2H 2 O content of 93%, a yield of 86%, a whiteness of 45%, and a SiO 2 content of 3.5%.
- Comparative Example 3 The difference between Comparative Example 3 and Example 7 is that the decolorizing collector and foaming agent in Comparative Example 3 are different from those in Example 7, and the others are the same.
- a method for purifying and whitening phosphogypsum including the following steps:
- the CaSO 4 ⁇ 2H 2 O content of the obtained refined phosphogypsum was 92%, the yield was 88%, the whiteness was 34%, and the SiO 2 content was 4.8%.
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- Paper (AREA)
Abstract
本申请公开了一种磷石膏提纯增白的方法,属于固体废弃物综合利用技术领域,所述的磷石膏提纯增白的方法,包括以下步骤:(1)将磷石膏加水配制成矿浆,将矿浆进行脱色处理,得到脱色矿浆;(2)将捕收剂加入到脱色矿浆中,加入pH调节剂,调节pH至2.0~2.5,进行第一次正浮选,得到第一次浮选液;(3)将所述pH调节剂加入到第一次浮选液中,调节pH至2.0~2.5,进行第二次正浮选,得到第二次浮选液;(4)将所述pH调节剂加入到第二次浮选液中,调节pH至2.0~2.5,进行第三次正浮选,浓缩,过滤,干燥,得到精制磷石膏。能够制备得到高纯度和高白度的磷石膏,有效的减少磷石膏的堆存,缓解环境的压力。
Description
本申请涉及固体废弃物综合利用技术领域,具体涉及一种磷石膏提纯增白的方法。
磷石膏是磷肥化工行业的一种工业固废,磷石膏的堆放会带来许多隐患,磷石膏呈粉末状,长久日晒易形成扬尘,影响大气环境;若被雨水淋漓,会造成磷石膏中含有水溶性P2O5、F离子的多种盐类等有害杂质流出;磷石膏呈流塑状物体,稍有处置不当,含有杂质的酸性污染水出现渗漏或外溢,进入地表水、地下水或土壤,将会造成不可逆转的水体、土壤、植物污染。磷石膏同时被国家安监部门列为重大危险源,一旦磷石膏库溃坝将对下游生命财产造成巨大的损失。磷石膏的大量堆积已引起严重的社会、环境问题,其综合利用与治理已刻不容缓,解决磷石膏的综合利用问题具有重要意义。
将磷石膏经过处理作为建筑材料是减少磷石膏的堆存的重要手段,但是磷石膏不能直接作为建筑材料,在使用前需要对其提纯处理,提高其纯度和白度,从而使其能够应用于建筑领域,因此,如何提高磷石膏的白度和纯度成为了本领域技术人员亟待解决的技术问题。
发明内容
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。
本申请的目的在于克服现有技术存在的不足之处而提供一种磷石膏提纯增白的方法,能够制备得到高纯度和高白度的磷石膏,有效的减少磷石膏的堆存,缓解环境的压力。
为实现上述目的,本申请采取的技术方案为:
一种磷石膏提纯增白的方法,包括以下步骤:
(1)将磷石膏加水配制成矿浆,将矿浆进行脱色处理,得到脱色矿浆;
(2)将捕收剂加入到脱色矿浆中,加入pH调节剂,调节pH至2.0~2.5,进行第一次正浮选,得到第一次浮选液;
(3)将所述pH调节剂加入到第一次浮选液中,调节pH至2.0~2.5,进行第二次正浮选,得到第二次浮选液;
(4)将所述pH调节剂加入到第二次浮选液中,调节pH至2.0~2.5,进行第三次正浮选,浓缩,过滤,干燥,得到精制磷石膏。
本申请通过将磷石膏进行脱色处理(反浮选),再通过三次正浮选,能够有效的对磷石膏进行除杂和脱色,使磷石膏中的有机质、碳渣、硅和其他杂质有效脱除,从而能够制备得到高白度和纯度的高纯磷石膏。
本申请在三次正浮选中,通过将pH至2.0~2.5,能够将磷石膏中未反应的五氧化二磷和金属氧化物溶解出来,从而进一步提高磷石膏的白度和纯度。
本申请的发明人在大量的研究中发现,在正浮选提纯和增白的过程中,所述的pH是影响提纯和增白的关键参数,若pH过低或者过高均会导致五氧化二磷和金属氧化物溶出效果不好,从而降低磷石膏的白度和纯度。
需要说明的是,在本申请中,正浮选均是在普通的浮选槽中进行的,本申请所述的正浮选和反浮选为本领域技术人员常理解的正浮选和反浮选,即正浮选指的是:将无用的矿物面随矿浆作为尾矿排出;反浮选指的是:将需要的矿物留在浮选槽中,而将不需要的矿物随泡沫刮出。
作为本申请的优选实施方案,所述磷石膏的CaSO4·2H2O含量为70~92%,白度为20~40%,SiO2含量为4~8%。
针对上述特定的白度和CaSO4·2H2O、SiO2含量的磷石膏,采用本申请的提纯增白方法效果好,能够将杂质有效去除的同时增白。
作为本申请的优选实施方案,所述矿浆的质量分数为20~40%,所述脱色处理包含将脱色捕收剂、起泡剂加入到所述矿浆中进行反浮选。
作为本申请的优选实施方案,所述脱色捕收剂为三羟基聚铵型捕收剂,其用量为0.48~1kg/t。需要说明的是,关于脱色捕收剂的用量kg/t指的是相对于磷石膏的用量,即1t磷石膏用0.48~1kg三羟基聚铵型捕收剂,下同。
作为本申请的优选实施方案,所述起泡剂为碳酸盐类起泡剂,其用量为0.18~0.24kg/t。采用上述特定的含有三个羟基的聚铵型作为捕收剂,以碳酸盐为起泡剂,并控制其用量,在其相互作用,互相影响下,只需一步处理,即可有效的去除有机质、碳渣、白云石等脉石矿物,从而有效的提高磷石膏的白度和纯度。
作为本申请的优选实施方案,所述三羟基聚铵型捕收剂为3-羟基己酸铵、3-羟基十二碳酸铵中的至少一种。
作为本申请的优选实施方案,所述起泡剂为碳酸钠、碳酸钙中的至少一种。
作为本申请的优选实施方案,所述捕收剂为直链烷基苯磺酸钠、α-烯基磺酸钠中的至少一种,其用量为0.15~0.25kg/t。
作为本申请的优选实施方案,所述pH调节剂为体积浓度为20~40%硫酸溶液。所述的pH调节剂为体积浓度为20~40%硫酸溶液时,能够使磷石膏中未反应的五氧化二磷和金属氧化物溶出,同时还能避免对设备的腐蚀。
作为本申请的优选实施方案,所述pH调节剂为体积浓度为30~40%硫酸溶液。
作为本申请的优选实施方案,所述干燥温度为100~200℃。本申请的发明
人在大量的研究中发现,所述的干燥温度能够显著影响到磷石膏的白度,通过将干燥温度控制在100~200℃时,能够显著提高磷石膏的白度。
作为本申请的优选实施方案,所述干燥温度为200℃。
本申请的有益效果在于:(1)本申请所述的磷石膏提纯增白的方法,能够制备得到高纯度和高白度的磷石膏,有效的减少磷石膏的堆存,缓解环境的压力,具有广泛的应用前景,所制备得到的精制磷石膏可代替脱硫石膏制备建筑石膏粉;(2)本申请将磷石膏进行脱色处理,再通过三次正浮选,能够有效的对磷石膏进行除杂和脱色,使磷石膏中的有机质、碳渣、硅和其他杂质有效脱除,从而能够制备得到高白度和纯度的高纯磷石膏;(3)本申请通过采用含有三个羟基的聚铵型作为捕收剂,以碳酸盐为起泡剂,并控制其用量,在其相互作用,互相影响下,只需一步处理,即可有效的去除有机质、碳渣、白云石等脉石矿物,从而有效的提高磷石膏的白度和纯度。
在阅读并理解了详细描述后,可以明白其他方面。
为使本申请实施例的目的、技术方案和优点更加清楚,下面将对本申请实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例是本申请一部分实施例,而不是全部的实施例。基于本申请中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都属于本申请保护的范围。
在本申请中,具体的分散、搅拌处理方式没有特别限制。
实施例1
一种磷石膏提纯增白的方法,包括以下步骤:
(1)在搅拌桶中将磷石膏(CaSO4·2H2O含量为91.89%,白度为31.03%,
SiO2含量为5.87%)加水配制成质量浓度为35%的矿浆,将1kg/t的3-羟基十二碳酸铵、0.26kg/t的碳酸钙加入到矿浆中,进行反浮选,得到脱色矿浆;
(2)将脱色矿浆加入到粗选浮选槽中,加入0.2kg/t的十二烷基苯磺酸钠,并加入体积浓度为35%的硫酸溶液,调节pH至2.4,进行第一次正浮选,得到第一次浮选液;
(3)将第一次浮选液加入到精选浮选槽,并加入体积浓度为35%的硫酸溶液,调节pH至2.4,进行第二次正浮选,得到第二次浮选液;
(4)将第二次浮选液加入到另一精选浮选槽,并加入体积浓度为35%的硫酸溶液,调节pH至2.4,进行第三次正浮选,浓缩,过滤,在100℃下烘干,得到精制磷石膏。
所得精制磷石膏的CaSO4·2H2O含量为96.17%,产率为79.99%,白度为67.12%,SiO2含量为0.57%。
实施例2
实施例2与实施例1不同之处在于,烘干温度不同,其他都相同。
实施例2的烘干温度为200℃,所得精制磷石膏的CaSO4·2H2O含量为96.17%,产率为79.99%,白度为73.71%,SiO2含量为0.57%。
实施例3
一种磷石膏提纯增白的方法,包括以下步骤:
(1)在搅拌桶中将磷石膏(CaSO4·2H2O含量为91.89%,白度为31.03%,SiO2含量为5.87%)加水配制成质量浓度为35%的矿浆,将0.8kg/t的3-羟基己酸铵、0.24kg/t的碳酸钙加入到矿浆中,进行反浮选,得到脱色矿浆;
(2)将脱色矿浆加入到粗选浮选槽中,加入0.15kg/t的α-烯基磺酸钠,并加入体积浓度为30%的硫酸溶液,调节pH至2.2,进行第一次正浮选,得到第
一次浮选液;
(3)将第一次浮选液加入到精选浮选槽,并加入体积浓度为30%的硫酸溶液,调节pH至2.2,进行第二次正浮选,得到第二次浮选液;
(4)将第二次浮选液加入到另一精选浮选槽,并加入体积浓度为30%的硫酸溶液,调节pH至2.2,进行第三次正浮选,浓缩,过滤,在100℃下烘干,得到精制磷石膏。
所得精制磷石膏的CaSO4·2H2O含量为96.56%,产率为78.84%,白度为65.74%,SiO2含量为0.77%。
实施例4
实施例4与实施例3不同之处在于,烘干温度不同,其他都相同。
实施例4的烘干温度为200℃,所得精制磷石膏的CaSO4·2H2O含量为96.56%,产率为78.84%,白度为76.46%,SiO2含量为0.77%。
实施例5
一种磷石膏提纯增白的方法,包括以下步骤:
(1)在搅拌桶中将磷石膏(CaSO4·2H2O含量为91.89%,白度为31.03%,SiO2含量为5.87%)加水配制成质量浓度为35%的矿浆,将0.6kg/t的3-羟基十二碳酸铵、0.22kg/t的碳酸钠加入到矿浆中,进行反浮选,得到脱色矿浆;
(2)将脱色矿浆加入到粗选浮选槽中,加入0.1kg/t的十二烷基苯磺酸钠,并加入体积浓度为40%的硫酸溶液,调节pH至2.5,进行第一次正浮选,得到第一次浮选液;
(3)将第一次浮选液加入到精选浮选槽,并加入体积浓度为40%的硫酸溶液,调节pH至2.5,进行第二次正浮选,得到第二次浮选液;
(4)将第二次浮选液加入到另一精选浮选槽,并加入体积浓度为40%的硫
酸溶液,调节pH至2.5,进行第三次正浮选,浓缩,过滤,在100℃下烘干,得到精制磷石膏。
所得精制磷石膏的CaSO4·2H2O含量为97.71%,产率为79.40%,白度为65.50%,SiO2含量为0.66%。
实施例6
实施例6与实施例5不同之处在于,烘干温度不同,其他都相同。
实施例6的烘干温度为200℃,所得精制磷石膏的CaSO4·2H2O含量为97.71%,产率为79.40%,白度为73.46%,SiO2含量为0.66%。
实施例7
一种磷石膏提纯增白的方法,包括以下步骤:
(1)在搅拌桶中将磷石膏(CaSO4·2H2O含量为91.89%,白度为31.03%,SiO2含量为5.87%)加水配制成质量浓度为35%的矿浆,将0.48kg/t的3-羟基十二碳酸铵、0.2kg/t的碳酸钙加入到矿浆中,进行反浮选,得到脱色矿浆;
(2)将脱色矿浆加入到粗选浮选槽中,加入0.1kg/t的十二烷基苯磺酸钠,并加入体积浓度为35%的硫酸溶液,调节pH至2.3,进行第一次正浮选,得到第一次浮选液;
(3)将第一次浮选液加入到精选浮选槽,并加入体积浓度为35%的硫酸溶液,调节pH至2.3,进行第二次正浮选,得到第二次浮选液;
(4)将第二次浮选液加入到另一精选浮选槽,并加入体积浓度为35%的硫酸溶液,调节pH至2.3,进行第三次正浮选,浓缩,过滤,在100℃下烘干,得到精制磷石膏。
所得精制磷石膏的CaSO4·2H2O含量为97.71%,产率为78.93%,白度为62.42%,SiO2含量为0.82%。
实施例8
实施例8与实施例7不同之处在于,烘干温度不同,其他都相同。
实施例8的烘干温度为200℃,所得精制磷石膏的CaSO4·2H2O含量为97.71%,产率为78.93%,白度为67.99%,SiO2含量为0.82%。
对比例1
对比例1与实施例7不同之处在于,对比例1经采用一次正浮选,其他都相同。
一种磷石膏提纯增白的方法,包括以下步骤:
(1)在搅拌桶中将磷石膏(CaSO4·2H2O含量为91.89%,白度为31.03%,SiO2含量为5.87%)加水配制成质量浓度为35%的矿浆,将0.48kg/t的3-羟基十二碳酸铵、0.2kg/t的碳酸钙加入到矿浆中,进行反浮选,得到脱色矿浆;
(2)将脱色矿浆加入到粗选浮选槽中,加入0.1kg/t的十二烷基苯磺酸钠,并加入体积浓度为35%的硫酸溶液,调节pH至2.3,进行第一次正浮选,浓缩,过滤,在100℃下烘干,得到精制磷石膏。
所得精制磷石膏的CaSO4·2H2O含量为93%,产率为83%,白度为42%,SiO2含量为1.5%。
对比例2
对比例2与实施例7不同之处在于,对比例2正浮选过程中调节的pH不同,其他都相同。
一种磷石膏提纯增白的方法,包括以下步骤:
(1)在搅拌桶中将磷石膏(CaSO4·2H2O含量为91.89%,白度为31.03%,SiO2含量为5.87%)加水配制成质量浓度为35%的矿浆,将0.48kg/t的3-羟基十二碳酸铵、0.2kg/t的碳酸钙加入到矿浆中,进行反浮选,得到脱色矿浆;
(2)将脱色矿浆加入到粗选浮选槽中,加入0.1kg/t的十二烷基苯磺酸钠,并加入体积浓度为35%的硫酸溶液,调节pH至3.5,进行第一次正浮选,得到第一次浮选液;
(3)将第一次浮选液加入到精选浮选槽,并加入体积浓度为35%的硫酸溶液,调节pH至3.5,进行第二次正浮选,得到第二次浮选液;
(4)将第二次浮选液加入到另一精选浮选槽,并加入体积浓度为35%的硫酸溶液,调节pH至3.5,进行第三次正浮选,浓缩,过滤,在100℃下烘干,得到精制磷石膏。
所得精制磷石膏的CaSO4·2H2O含量为93%,产率为86%,白度为45%,SiO2含量为3.5%。
对比例3
对比例3与实施例7不同之处在于,对比例3中的脱色捕收剂与起泡剂不同于实施例7,其他都相同。
一种磷石膏提纯增白的方法,包括以下步骤:
(1)在搅拌桶中将磷石膏(CaSO4·2H2O含量为91.89%,白度为31.03%,SiO2含量为5.87%)加水配制成质量浓度为35%的矿浆,将0.48kg/t的十二烷基三甲基溴化铵、0.2kg/t的松醇油加入到矿浆中,进行反浮选,得到脱色矿浆;
(2)将脱色矿浆加入到粗选浮选槽中,加入0.1kg/t的十二烷基苯磺酸钠,并加入体积浓度为35%的硫酸溶液,调节pH至2.3,进行第一次正浮选,得到第一次浮选液;
(3)将第一次浮选液加入到精选浮选槽,并加入体积浓度为35%的硫酸溶液,调节pH至2.3,进行第二次正浮选,得到第二次浮选液;
(4)将第二次浮选液加入到另一精选浮选槽,并加入体积浓度为35%的硫
酸溶液,调节pH至2.3,进行第三次正浮选,浓缩,过滤,在100℃下烘干,得到精制磷石膏。
所得精制磷石膏的CaSO4·2H2O含量为92%,产率为88%,白度为34%,SiO2含量为4.8%。
最后应当说明的是,以上实施例仅用以说明本申请的技术方案而非对本申请保护范围的限制,尽管参照较佳实施例对本申请作了详细说明,本领域的普通技术人员应当理解,可以对本申请的技术方案进行修改或者等同替换,而不脱离本申请技术方案的实质和范围。
Claims (10)
- 一种磷石膏提纯增白的方法,其中,包括以下步骤:(1)将磷石膏加水配制成矿浆,将矿浆进行脱色处理,得到脱色矿浆;(2)将捕收剂加入到脱色矿浆中,加入pH调节剂,调节pH至2.0~2.5,进行第一次正浮选,得到第一次浮选液;(3)将所述pH调节剂加入到第一次浮选液中,调节pH至2.0~2.5,进行第二次正浮选,得到第二次浮选液;(4)将所述pH调节剂加入到第二次浮选液中,调节pH至2.0~2.5,进行第三次正浮选,浓缩,过滤,干燥,得到精制磷石膏。
- 根据权利要求1所述的磷石膏提纯增白的方法,其中,所述磷石膏的CaSO4·2H2O含量为70~92%,白度为20~40%,SiO2含量为4~8%。
- 根据权利要求1所述的磷石膏提纯增白的方法,其中,所述矿浆的质量分数为20~40%,所述脱色处理包含将脱色捕收剂、起泡剂加入到所述矿浆中进行反浮选。
- 根据权利要求3所述的磷石膏提纯增白的方法,其中,所述脱色捕收剂为三羟基聚铵型捕收剂,其用量为0.48~1kg/t;所述起泡剂为碳酸盐类起泡剂,其用量为0.18~0.24kg/t。
- 根据权利要求4所述的磷石膏提纯增白的方法,其中,所述三羟基聚铵型捕收剂为3-羟基己酸铵、3-羟基十二碳酸铵中的至少一种;所述起泡剂为碳酸钠、碳酸钙中的至少一种。
- 根据权利要求1所述的磷石膏提纯增白的方法,其中,所述捕收剂为直链烷基苯磺酸钠、α-烯基磺酸钠中的至少一种,其用量为0.15~0.25kg/t。
- 根据权利要求1所述的磷石膏提纯增白的方法,其中,所述pH调节剂为体积浓度为20~40%硫酸溶液。
- 根据权利要求1所述的磷石膏提纯增白的方法,其中,所述pH调节剂为体积浓度为30~40%硫酸溶液。
- 根据权利要求1所述的磷石膏提纯增白的方法,其中,所述干燥温度为100~200℃。
- 根据权利要求9所述的磷石膏提纯增白的方法,其中,所述干燥温度为200℃。
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