WO2022227181A1 - Method for preparing silicon-potassium-calcium compound fertilizer by using calcium-containing red mud - Google Patents
Method for preparing silicon-potassium-calcium compound fertilizer by using calcium-containing red mud Download PDFInfo
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- WO2022227181A1 WO2022227181A1 PCT/CN2021/096795 CN2021096795W WO2022227181A1 WO 2022227181 A1 WO2022227181 A1 WO 2022227181A1 CN 2021096795 W CN2021096795 W CN 2021096795W WO 2022227181 A1 WO2022227181 A1 WO 2022227181A1
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- Prior art keywords
- potassium
- calcium
- red mud
- compound fertilizer
- containing red
- Prior art date
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000011575 calcium Substances 0.000 title claims abstract description 29
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000003337 fertilizer Substances 0.000 title claims abstract description 25
- 229940043430 calcium compound Drugs 0.000 title claims abstract description 20
- JOOKTTKZGRVHOQ-UHFFFAOYSA-N [Ca].[K].[Si] Chemical compound [Ca].[K].[Si] JOOKTTKZGRVHOQ-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000002386 leaching Methods 0.000 claims abstract description 25
- WPUINVXKIPAAHK-UHFFFAOYSA-N aluminum;potassium;oxygen(2-) Chemical compound [O-2].[O-2].[Al+3].[K+] WPUINVXKIPAAHK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000009466 transformation Effects 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000011084 recovery Methods 0.000 claims abstract description 14
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001948 sodium oxide Inorganic materials 0.000 claims abstract description 13
- 239000011734 sodium Substances 0.000 claims abstract description 12
- 239000002893 slag Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000011268 mixed slurry Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 10
- 239000007790 solid phase Substances 0.000 claims abstract description 10
- 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 abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 5
- SXQXMCWCWVCFPC-UHFFFAOYSA-N aluminum;potassium;dioxido(oxo)silane Chemical compound [Al+3].[K+].[O-][Si]([O-])=O.[O-][Si]([O-])=O SXQXMCWCWVCFPC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000012452 mother liquor Substances 0.000 claims description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000004131 Bayer process Methods 0.000 claims description 7
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 7
- 239000007791 liquid phase Substances 0.000 claims description 7
- 239000000292 calcium oxide Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 3
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 3
- 239000010413 mother solution Substances 0.000 abstract 3
- 238000001704 evaporation Methods 0.000 abstract 1
- 230000008020 evaporation Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 239000002689 soil Substances 0.000 description 5
- 229910018626 Al(OH) Inorganic materials 0.000 description 4
- 238000000855 fermentation Methods 0.000 description 4
- 230000004151 fermentation Effects 0.000 description 4
- 239000006210 lotion Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 3
- 229910001950 potassium oxide Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000005067 remediation Methods 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000010903 husk Substances 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 244000146553 Ceiba pentandra Species 0.000 description 1
- 235000003301 Ceiba pentandra Nutrition 0.000 description 1
- 108010068370 Glutens Proteins 0.000 description 1
- 244000017020 Ipomoea batatas Species 0.000 description 1
- 235000002678 Ipomoea batatas Nutrition 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001674 calcium compounds Chemical class 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 238000012272 crop production Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- RNGFNLJMTFPHBS-UHFFFAOYSA-L dipotassium;selenite Chemical compound [K+].[K+].[O-][Se]([O-])=O RNGFNLJMTFPHBS-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000021312 gluten Nutrition 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 239000003864 humus Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000002054 inoculum Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910021646 siderite Inorganic materials 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D1/00—Fertilisers containing potassium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D1/00—Oxides or hydroxides of sodium, potassium or alkali metals in general
- C01D1/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
Definitions
- the invention belongs to the technical field of comprehensive utilization of red mud, and particularly relates to a method for preparing a silicon-potassium-calcium compound fertilizer by utilizing calcium-containing red mud.
- Red mud is a solid waste produced in the process of producing alumina from bauxite. Due to the high alkali content in it and it is difficult to remove, most of the red mud is stored in the form of stacking, and the comprehensive utilization rate is insufficient. A lot of land resources pollute the environment. Analysis of the composition of red mud can reveal that it contains some nutrient elements required for crop growth, and red mud has the advantages of good particle distribution and dispersion. It can be considered as fertilizer for crop production to improve its utilization rate.
- the main steps include: (1) The orange peel and kapok husk are dried, mixed with siderite slag and calcined, and sieved to obtain magnetic biochar powder; (2) mixed and fermented with wheat gluten, humus and cottonseed cake to obtain fermented solid residue and fermentation liquid (3) Mixing and heating the fermentation broth with potassium selenite and ammonium humate, and then adding biochar powder for impregnation to obtain impregnated biochar; (4) calcining and pulverizing the red mud and passing through a 50-mesh sieve to obtain red mud particles (5) Mix the impregnated biochar with fermentation solid residues, red mud particles, EM composite microbial inoculants and other remaining materials for granulation; (6) Use ultra
- the purpose of the present invention is to provide a kind of method that utilizes calcium-containing red mud to prepare silicon-potassium-calcium compound fertilizer, overcomes the deficiencies existing in the prior art, improves the comprehensive utilization rate of red mud, adopts potassium metaaluminate mother liquor to leach calcium-containing red mud,
- the leaching solution can be recovered and crystallized to separate out part of sodium hydroxide and aluminum hydroxide, and the mixed mother liquor containing potassium metaaluminate solution can be obtained by separation, wherein sodium hydroxide and aluminum hydroxide can be returned to the Bayer process system to produce alumina, containing potassium metaaluminate
- the mixed mother liquor of the solution is supplemented with potassium hydroxide to adjust the molar ratio of the mother liquor, and is recycled in the return process.
- the leaching residue can be used as a silicon-potassium-calcium compound calcium fertilizer for crop growth.
- the method of the present invention comprises the following steps:
- transformation liquid and transformation slag After flashing the leaching material, carry out solid-liquid separation to obtain transformation liquid and transformation slag; the solid phase in the transformation slag is mainly hydrated potassium aluminosilicate, which is washed and dried to make silicon-potassium-calcium compound fertilizer.
- step 2 the main reaction formula of leaching reaction is:
- the silicon-potassium-calcium compound fertilizer contains K 2 O ⁇ 15% by mass percentage.
- step 3 the transformation liquid separates out part of sodium hydroxide and aluminum hydroxide through cooling, and then separates solid phase and liquid phase by filtration; After adding potassium hydroxide solution, return to step 1 for recycling.
- the recovery rate of alumina is 10-25%, and the recovery rate of sodium oxide is 93-96%.
- the content of K 2 O in the transformation slag is increased by leaching the mother liquor
- the Al 2 O 3 in the red mud is partially dissolved in the liquid phase after being dissolved by the alkali
- the solution containing part of the alkali and aluminum is recovered and then passed through
- Aluminum hydroxide and sodium hydroxide are precipitated by cooling and crystallization, and returned to the Bayer process system to produce alumina.
- potassium hydroxide solution is added to the mother liquor and returned to the process for recycling; part of sodium hydroxide and aluminum hydroxide solids are precipitated by cooling and crystallization.
- the present invention adopts potassium metaaluminate mother liquor to directly leaching calcium-containing red mud, and combines the process of producing alumina by Bayer process to realize the harmless treatment of red mud .
- the features and beneficial effects of the present invention are as follows: (1) the method of leaching calcium-containing red mud from potassium metaaluminate mother liquor can prepare silicon-potassium-calcium compound fertilizer and realize the harmless utilization of red mud. ; (2) Leaching calcium-containing red mud from potassium metaaluminate mother liquor can extract some alumina and a large amount of sodium oxide in the red mud, and realize the recovery of valuable components.
- Fig. 1 is the schematic flow chart of the method for preparing silicon-potassium-calcium compound fertilizer using calcium-containing red mud according to the present invention.
- the calcium-containing red mud in the embodiment of the present invention is the red mud produced in the process of producing alumina by the Bayer process.
- the solute of the potassium metaaluminate mother liquor includes KOH and KAl(OH) 4 , the concentration of KOH is 200-240 g/L, and the molar ratio of K + to Al(OH) 4 - in the solution is 3-7.
- the solutes of the mixed mother liquor containing potassium metaaluminate and sodium metaaluminate include KOH, NaOH, KAl(OH) 4 and NaAl(OH) 4 , the concentration of KOH is 200-240 g/L, (K + The molar ratio of +Na + ) to Al(OH) 4 - is 3-7.
- the stirring speed of the leaching reaction is 200-400 rpm.
- water is washed until the lotion is neutral, and the obtained lotion is mixed with the filtrate, and then cooled and precipitated.
- the recovery rate of alumina in the examples of the present invention is the rate at which the alumina in the red mud is converted into the alumina in the solid phase.
- the recovery rate of sodium oxide is the rate at which sodium oxide in red mud is converted into sodium hydroxide in the liquid phase.
- the flashed material is separated from solid and liquid by means of filtration or sedimentation.
- the mixed mother liquor containing potassium metaaluminate and sodium metaaluminate is mixed with calcium-containing red mud, and the mixing ratio is 3 mL/g according to the liquid-solid ratio to obtain a mixed slurry;
- the calcium-containing red mud contains Al 2 O 3 22.25%, CaO 13.31%, SiO 2 19.58%, Na 2 O 6.85%, K 2 O 1.82% by mass percentage;
- the potassium hydroxide concentration of the mixed mother liquor containing potassium metaaluminate and sodium metaaluminate is 200 g/L;
- the mixed slurry is heated to 210 ° C, and the leaching reaction is carried out under stirring conditions, and the leaching reaction time is 55 minutes to obtain the leaching material;
- transformation liquid and transformation slag After flashing the leaching material, carry out filtration and solid-liquid separation (filtering method is selected) to obtain transformation liquid and transformation slag;
- the solid phase in the transformation slag is mainly hydrated potassium aluminosilicate, which is made into potassium silicate after washing and drying.
- Calcium compound fertilizer by mass percentage, contains 15% potassium oxide, 21.91% silicon oxide, 15.69% calcium oxide, 0.33% sodium oxide, and 18.82% aluminum oxide;
- the transformation liquid is cooled to separate out part of sodium hydroxide and aluminum hydroxide, and then the solid phase and the liquid phase are separated by filtration; the solid phase is used for the production of alumina by the Bayer process, and the liquid phase is used as the mother liquor containing potassium chlorate, and potassium hydroxide solution is added. Then, it is recycled in the preparation process of returning to the mixed slurry;
- the potassium hydroxide concentration in the potassium metaaluminate mother liquor is 220g/L;
- the silicon-potassium-calcium compound fertilizer contains 20.69% silicon oxide, 15.49% potassium oxide, 14.47% calcium oxide, 0.5% sodium oxide, and 19.37% aluminum oxide by mass percentage;
- the potassium hydroxide concentration in the potassium metaaluminate mother liquor is 240g/L;
- the silicon-potassium-calcium compound fertilizer contains 21.65% silicon oxide, 15.35% potassium oxide, 14.23% calcium oxide, 0.51% sodium oxide, and 19.78% aluminum oxide by mass percentage.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Fertilizers (AREA)
Abstract
A method for preparing a silicon-potassium-calcium compound fertilizer by using calcium-containing red mud, comprising the following steps: (1) mixing a mother solution containing potassium metaaluminate with the calcium-containing red mud, or mixing a mixed mother solution containing potassium metaaluminate and sodium metaaluminate with the calcium-containing red mud; (2) heating the mixed slurry to 210-260°C, stirring and leaching; (3) performing flash evaporation on the leached material, and then performing solid-liquid separation to obtain a transformation liquid and transformation slag; and a solid phase in the transformation slag being mainly potassium aluminosilicate hydrate, washing and drying to prepare the silicon-potassium-calcium compound fertilizer. According to the method in the present invention, an approach in which the calcium-containing red mud is leached by using the potassium metaaluminate mother solution is used, so that the silicon-potassium-calcium compound fertilizer can be prepared, and harmless utilization of the red mud is achieved; part of aluminum oxide and a large amount of sodium oxide in the red mud can be extracted, and valuable component recovery is achieved.
Description
本发明属于赤泥综合利用技术领域，特别涉及一种利用含钙赤泥制备硅钾钙复合肥的方法。 The invention belongs to the technical field of comprehensive utilization of red mud, and particularly relates to a method for preparing a silicon-potassium-calcium compound fertilizer by utilizing calcium-containing red mud.
赤泥是铝土矿生产氧化铝过程中产生的固体废弃物，由于其中的碱含量高且难以脱除，大部分赤泥都采用堆存的方式，综合利用率不足，长期堆存处理既占用了大量的土地资源又污染环境。分析赤泥成分组成可以得到其中含有农作物生长所需的一些营养元素，且赤泥具有颗粒分布与分散性好的优势，可以考虑将其做成肥料用于农作物生产，提高其利用率。Red mud is a solid waste produced in the process of producing alumina from bauxite. Due to the high alkali content in it and it is difficult to remove, most of the red mud is stored in the form of stacking, and the comprehensive utilization rate is insufficient. A lot of land resources pollute the environment. Analysis of the composition of red mud can reveal that it contains some nutrient elements required for crop growth, and red mud has the advantages of good particle distribution and dispersion. It can be considered as fertilizer for crop production to improve its utilization rate.
近年来，相关从业者针对赤泥的综合利用进行了大量的研究工作，如孙仁贵提出的“一种赤泥辅助土壤修复肥料，公开号：CN 105330476 A”的方法，主要步骤包括：（1）将桔皮、木棉壳干燥后与菱铁矿渣混合煅烧，过筛后得到磁性生物炭粉末；（2）将小麦谷朊粉、腐殖土、棉籽饼混合发酵，得到发酵固体残渣和发酵液；（3）将发酵液与亚硒酸钾、腐殖酸铵混合加热后再加入生物炭粉末浸渍，得到浸渍生物炭；（4）将赤泥煅烧粉碎后过50目筛，得到赤泥颗粒；（5）将浸渍生物炭与发酵固体残渣、赤泥颗粒、EM复合微生物菌剂以及其他剩余物料混合后造粒用；（6）使用超声波对步骤（5）中所得颗粒辐照40~60分钟，得到土壤修复肥料。In recent years, relevant practitioners have carried out a lot of research work on the comprehensive utilization of red mud. For example, the method of "A Red Mud-assisted Soil Repair Fertilizer, Publication Number: CN 105330476 A" proposed by Sun Rengui, the main steps include: (1) The orange peel and kapok husk are dried, mixed with siderite slag and calcined, and sieved to obtain magnetic biochar powder; (2) mixed and fermented with wheat gluten, humus and cottonseed cake to obtain fermented solid residue and fermentation liquid (3) Mixing and heating the fermentation broth with potassium selenite and ammonium humate, and then adding biochar powder for impregnation to obtain impregnated biochar; (4) calcining and pulverizing the red mud and passing through a 50-mesh sieve to obtain red mud particles (5) Mix the impregnated biochar with fermentation solid residues, red mud particles, EM composite microbial inoculants and other remaining materials for granulation; (6) Use ultrasonic waves to irradiate the particles obtained in step (5) for 40-60 minutes Minutes to get soil remediation fertilizer.
刘凯平提出的“一种利用赤泥制造的复合肥料及其制备方法，公开号：CN 110590461 A”的方案，主要步骤为：（1）将赤泥烘干，与炉渣混合进行粉碎，加入有机酸、有机液体肥搅拌均匀，调节pH值为7~9，再向其中加入煤灰，控制温度及水分，得到赤泥混合物；（2）将赤泥混合物与蚯蚓粪或土、稻壳粉、红薯粉、秸秆粉、锯末和混合菌种进行混合，控制水分和温度，发酵，发酵结束后加入剩余原料混合均匀造粒，得到复合肥料。The scheme of "a compound fertilizer made from red mud and its preparation method, publication number: CN 110590461 A" proposed by Liu Kaiping, the main steps are: (1) drying the red mud, mixing it with slag for pulverization, adding organic acid , Stir the organic liquid fertilizer evenly, adjust the pH value to 7~9, then add coal ash to it, control the temperature and moisture to obtain a red mud mixture; (2) Mix the red mud mixture with vermicompost or soil, rice husk powder, sweet potato The powder, straw powder, sawdust and mixed bacteria are mixed, the moisture and temperature are controlled, and the fermentation is carried out.
赵光利等人提出的“一种赤泥颗粒土壤修复剂及其制备方法，公开号：CN 105316001 A”的方案，主要步骤为：S1.将赤泥、石膏和胶凝材料按比例混合粉碎，搅拌2~4 h后过60目筛，得到混合粉料；S2.将混合粉料造粒成球；S3.将S2得到的球风干12~48 h；S4.将S3风干后的生球烘干后自然冷却得到赤泥颗粒土壤修复剂。The scheme of "a kind of red mud granular soil remediation agent and its preparation method, publication number: CN 105316001 A" proposed by Zhao Guangli et al., the main steps are: S1. The red mud, gypsum and cementitious material are mixed and pulverized in proportion, and stirred. After 2~4 hours, pass through a 60-mesh sieve to obtain mixed powder; S2. Pellet the mixed powder into balls; S3. Air-dry the balls obtained from S2 for 12-48 h; S4. Dry the raw balls after air-drying of S3 After natural cooling, the red mud granular soil remediation agent is obtained.
现有的方法虽然也可以实现赤泥的综合利用，但多存在流程复杂，生产周期长、原料较多，导致生产成本增加等问题，且对于生产氧化铝产生的赤泥碱性较强，如不进行脱碱处理，则氧化钠也会为农作物生长带来危害。Although the existing method can also realize the comprehensive utilization of red mud, there are many problems such as complicated flow process, long production cycle, and many raw materials, which lead to increased production cost, and the red mud produced in the production of alumina is relatively alkaline, such as Without dealkalization treatment, sodium oxide will also bring harm to the growth of crops.
本发明的目的是提供一种利用含钙赤泥制备硅钾钙复合肥的方法，克服现有技术存在的不足，提高赤泥的综合利用率，采用偏铝酸钾母液浸出含钙赤泥，浸出液可回收经过降温结晶析出部分氢氧化钠和氢氧化铝，分离得到含偏铝酸钾溶液的混合母液，其中氢氧化钠和氢氧化铝可返回拜耳法系统生产氧化铝，含偏铝酸钾溶液的混合母液中补入氢氧化钾以调整母液摩尔比，返回流程中循环使用，浸出渣可作为硅钾钙复合钙肥用于农作物生长。The purpose of the present invention is to provide a kind of method that utilizes calcium-containing red mud to prepare silicon-potassium-calcium compound fertilizer, overcomes the deficiencies existing in the prior art, improves the comprehensive utilization rate of red mud, adopts potassium metaaluminate mother liquor to leach calcium-containing red mud, The leaching solution can be recovered and crystallized to separate out part of sodium hydroxide and aluminum hydroxide, and the mixed mother liquor containing potassium metaaluminate solution can be obtained by separation, wherein sodium hydroxide and aluminum hydroxide can be returned to the Bayer process system to produce alumina, containing potassium metaaluminate The mixed mother liquor of the solution is supplemented with potassium hydroxide to adjust the molar ratio of the mother liquor, and is recycled in the return process. The leaching residue can be used as a silicon-potassium-calcium compound calcium fertilizer for crop growth.
本发明的方法包括以下步骤：The method of the present invention comprises the following steps:
1、将含偏铝酸钾母液与含钙赤泥混合，或者将含偏铝酸钾和偏铝酸钠的混合母液与含钙赤泥混合，混合比例按液固比为3~4.5mL/g，获得混合浆液；所述的含钙赤泥按质量百分比含Al
2O
3
10~25%，CaO 10~50%，SiO
2 15~25%，Na
2O 4~10%，K
2O 0.5~2.0%；
1. Mix the potassium metaaluminate-containing mother liquor with calcium-containing red mud, or mix the mixed mother liquor containing potassium meta-aluminate and sodium meta-aluminate with calcium-containing red mud, and the mixing ratio is 3~4.5mL/solid ratio. g, obtain a mixed slurry; the calcium-containing red mud contains Al 2 O 3 10~25%, CaO 10~50%, SiO 2 15~25%, Na 2 O 4~10%, K 2 O by mass percentage 0.5~2.0%;
2、将混合浆液加热至210~260℃，在搅拌条件下进行浸出反应，浸出反应时间10~55min，获得浸出物料；2. Heating the mixed slurry to 210~260°C, carry out the leaching reaction under stirring conditions, the leaching reaction time is 10~55min, and the leaching material is obtained;
3、将浸出物料进行闪蒸后，进行固液分离，获得转型液和转型渣；转型渣中固相主要为水合硅铝酸钾，经水洗和烘干后，制成硅钾钙复合肥。3. After flashing the leaching material, carry out solid-liquid separation to obtain transformation liquid and transformation slag; the solid phase in the transformation slag is mainly hydrated potassium aluminosilicate, which is washed and dried to make silicon-potassium-calcium compound fertilizer.
上述的步骤 2中，浸出反应的主要反应式为：In above-mentioned step 2, the main reaction formula of leaching reaction is:
Na
2O·Al
2O
3·SiO
2·nH
2O+2KAl(OH)
4→2KAl SiO
4+2 NaAl(OH)
4 + n H
2O （1）。
Na 2 O·Al 2 O 3 ·SiO 2 ·nH 2 O + 2KAl(OH) 4 → 2KAl SiO 4 +2 NaAl(OH) 4 + nH 2 O (1).
上述的步骤3中，硅钾钙复合肥按质量百分比含K
2O≥15%。
In the above-mentioned step 3, the silicon-potassium-calcium compound fertilizer contains K 2 O ≥ 15% by mass percentage.
上述的步骤3中，转型液经过降温析出部分氢氧化钠和氢氧化铝，然后过滤分离出固相和液相；固相用于拜尔法生产氧化铝，液相作为含骗氯酸钾的母液，补加氢氧化钾溶液后，返回步骤1循环使用。In the above-mentioned step 3, the transformation liquid separates out part of sodium hydroxide and aluminum hydroxide through cooling, and then separates solid phase and liquid phase by filtration; After adding potassium hydroxide solution, return to step 1 for recycling.
上述的降温析出的反应式为：The reaction formula that above-mentioned cooling is separated out is:
Al(OH)
4
+→Al(OH)
3↓+
OH
- （2）。
Al(OH) 4 + →Al(OH) 3 ↓+ OH - (2).
上述方法中，氧化铝的回收率为10~25%，氧化钠的回收率为93~96%。In the above method, the recovery rate of alumina is 10-25%, and the recovery rate of sodium oxide is 93-96%.
上述方法中，水洗至洗液为中性，获得的洗液与滤液混合后，进行降温析出。In the above method, washing with water until the lotion is neutral, and after mixing the obtained lotion and the filtrate, the temperature is lowered for precipitation.
本发明的方法通过母液浸出，使转型渣中中K
2O含量增加，赤泥中的Al
2O
3被碱溶后有部分进入液相中，且该含有部分碱和铝的溶液回收再经过降温结晶析出氢氧化铝和与氢氧化钠，返回拜耳法系统生产氧化铝，降温析出后母液中再补入氢氧化钾溶液返回流程中循环利用；降温结晶析出部分氢氧化钠与氢氧化铝固体，返回拜耳法系统生产氧化铝，达到含钙赤泥脱钠提铝的目的； 本发明采用偏铝酸钾母液直接浸出含钙赤泥，结合拜耳法生产氧化铝过程实现赤泥无害化处理。
In the method of the invention, the content of K 2 O in the transformation slag is increased by leaching the mother liquor, the Al 2 O 3 in the red mud is partially dissolved in the liquid phase after being dissolved by the alkali, and the solution containing part of the alkali and aluminum is recovered and then passed through Aluminum hydroxide and sodium hydroxide are precipitated by cooling and crystallization, and returned to the Bayer process system to produce alumina. After cooling and precipitation, potassium hydroxide solution is added to the mother liquor and returned to the process for recycling; part of sodium hydroxide and aluminum hydroxide solids are precipitated by cooling and crystallization. , return to the Bayer process system to produce alumina, to achieve the purpose of removing sodium and extracting aluminum from calcium-containing red mud; the present invention adopts potassium metaaluminate mother liquor to directly leaching calcium-containing red mud, and combines the process of producing alumina by Bayer process to realize the harmless treatment of red mud .
与现有技术相比，本发明的特点和有益效果是：（1）利用偏铝酸钾母液浸出含钙赤泥的方式，可制备硅钾钙复合肥，实现了赤泥的无害化利用；（2）利用偏铝酸钾母液浸出含钙赤泥，可以提取赤泥中的部分氧化铝及大量氧化钠，实现有价组元回收。Compared with the prior art, the features and beneficial effects of the present invention are as follows: (1) the method of leaching calcium-containing red mud from potassium metaaluminate mother liquor can prepare silicon-potassium-calcium compound fertilizer and realize the harmless utilization of red mud. ; (2) Leaching calcium-containing red mud from potassium metaaluminate mother liquor can extract some alumina and a large amount of sodium oxide in the red mud, and realize the recovery of valuable components.
图1为本发明的利用含钙赤泥制备硅钾钙复合肥的方法流程示意图。Fig. 1 is the schematic flow chart of the method for preparing silicon-potassium-calcium compound fertilizer using calcium-containing red mud according to the present invention.
本发明实施例中的含钙赤泥为拜耳法生产氧化铝过程中产生的赤泥。The calcium-containing red mud in the embodiment of the present invention is the red mud produced in the process of producing alumina by the Bayer process.
本发明实施例中偏铝酸钾母液的溶质包括KOH和KAl(OH)
4，KOH的浓度为200~240g/L，溶液中K
+与Al(OH)
4
-的摩尔比为3~7。
In the embodiment of the present invention, the solute of the potassium metaaluminate mother liquor includes KOH and KAl(OH) 4 , the concentration of KOH is 200-240 g/L, and the molar ratio of K + to Al(OH) 4 - in the solution is 3-7.
本发明实施例中含偏铝酸钾和偏铝酸钠的混合母液的溶质包括KOH、NaOH、KAl(OH)
4和NaAl(OH)
4，KOH的浓度为200~240g/L， (K
++Na
+)与Al(OH)
4
-的摩尔比为3~7。
In the embodiment of the present invention, the solutes of the mixed mother liquor containing potassium metaaluminate and sodium metaaluminate include KOH, NaOH, KAl(OH) 4 and NaAl(OH) 4 , the concentration of KOH is 200-240 g/L, (K + The molar ratio of +Na + ) to Al(OH) 4 - is 3-7.
本发明实施例中浸出反应的搅拌速度200~400rpm。In the embodiment of the present invention, the stirring speed of the leaching reaction is 200-400 rpm.
本发明实施例中水洗至洗液为中性，获得的洗液与滤液混合后，进行降温析出。In the embodiment of the present invention, water is washed until the lotion is neutral, and the obtained lotion is mixed with the filtrate, and then cooled and precipitated.
本发明实施例中的氧化铝的回收率为赤泥中的氧化铝转化为固相中的氧化铝的收率。The recovery rate of alumina in the examples of the present invention is the rate at which the alumina in the red mud is converted into the alumina in the solid phase.
本发明实施例中氧化钠的回收率为赤泥中的氧化钠转化为液相中的氢氧化钠的收率。In the embodiment of the present invention, the recovery rate of sodium oxide is the rate at which sodium oxide in red mud is converted into sodium hydroxide in the liquid phase.
本发明实施例中闪蒸后的物料采用过滤或沉降的方式进行固液分离。In the embodiment of the present invention, the flashed material is separated from solid and liquid by means of filtration or sedimentation.
实施例Example
11
流程如图1所示；The process is shown in Figure 1;
将含偏铝酸钾和偏铝酸钠的混合母液与含钙赤泥混合，混合比例按液固比为3mL/g，获得混合浆液； The mixed mother liquor containing potassium metaaluminate and sodium metaaluminate is mixed with calcium-containing red mud, and the mixing ratio is 3 mL/g according to the liquid-solid ratio to obtain a mixed slurry;
含钙赤泥按质量百分比含Al
2O
3
22.25%，CaO 13.31%，SiO
2 19.58%，Na
2O 6.85%，K
2O 1.82%；
The calcium-containing red mud contains Al 2 O 3 22.25%, CaO 13.31%, SiO 2 19.58%, Na 2 O 6.85%, K 2 O 1.82% by mass percentage;
含偏铝酸钾和偏铝酸钠的混合母液的氢氧化钾浓度200g/L；The potassium hydroxide concentration of the mixed mother liquor containing potassium metaaluminate and sodium metaaluminate is 200 g/L;
将混合浆液加热至210℃，在搅拌条件下进行浸出反应，浸出反应时间55min，获得浸出物料；The mixed slurry is heated to 210 ° C, and the leaching reaction is carried out under stirring conditions, and the leaching reaction time is 55 minutes to obtain the leaching material;
将浸出物料进行闪蒸后，进行过滤固液分离（选用过滤方式），获得转型液和转型渣；转型渣中固相主要为水合硅铝酸钾，经水洗和烘干后，制成硅钾钙复合肥，按质量百分比含氧化钾15%，氧化硅21.91%，氧化钙15.69%，氧化钠0.33%，氧化铝18.82%；After flashing the leaching material, carry out filtration and solid-liquid separation (filtering method is selected) to obtain transformation liquid and transformation slag; the solid phase in the transformation slag is mainly hydrated potassium aluminosilicate, which is made into potassium silicate after washing and drying. Calcium compound fertilizer, by mass percentage, contains 15% potassium oxide, 21.91% silicon oxide, 15.69% calcium oxide, 0.33% sodium oxide, and 18.82% aluminum oxide;
转型液经过降温析出部分氢氧化钠和氢氧化铝，然后过滤分离出固相和液相；固相用于拜尔法生产氧化铝，液相作为含骗氯酸钾的母液，补加氢氧化钾溶液后，返回混合浆液的制备过程中循环使用；The transformation liquid is cooled to separate out part of sodium hydroxide and aluminum hydroxide, and then the solid phase and the liquid phase are separated by filtration; the solid phase is used for the production of alumina by the Bayer process, and the liquid phase is used as the mother liquor containing potassium chlorate, and potassium hydroxide solution is added. Then, it is recycled in the preparation process of returning to the mixed slurry;
氧化铝的回收率为24%，氧化钠的回收率为93%。The recovery of alumina was 24% and the recovery of sodium oxide was 93%.
实施例Example
22
方法同实施例1，不同点在于：The method is the same as in Example 1, except that:
（1）将含偏铝酸钾母液与含钙赤泥混合，混合比例按液固比为4mL/g；(1) Mix the potassium metaaluminate-containing mother liquor with calcium-containing red mud, and the mixing ratio is 4 mL/g according to the liquid-solid ratio;
（2）含偏铝酸钾母液中的氢氧化钾浓度220g/L； (2) The potassium hydroxide concentration in the potassium metaaluminate mother liquor is 220g/L;
（3）将混合浆液加热至230℃进行浸出反应，浸出反应时间30min；(3) The mixed slurry was heated to 230°C for leaching reaction, and the leaching reaction time was 30min;
（4）硅钾钙复合肥按质量百分比含氧化硅 20.69%，氧化钾 15.49%，氧化钙14.47%，氧化钠 0.5%，氧化铝 19.37%；(4) The silicon-potassium-calcium compound fertilizer contains 20.69% silicon oxide, 15.49% potassium oxide, 14.47% calcium oxide, 0.5% sodium oxide, and 19.37% aluminum oxide by mass percentage;
（5）氧化铝的回收率为17.6%，氧化钠的回收率为95%。(5) The recovery rate of alumina was 17.6%, and the recovery rate of sodium oxide was 95%.
实施例Example
33
方法同实施例1，不同点在于：The method is the same as in Example 1, except that:
（1）将含偏铝酸钾母液与含钙赤泥混合，混合比例按液固比为4.5mL/g；(1) Mix the potassium metaaluminate-containing mother liquor with calcium-containing red mud, and the mixing ratio is 4.5 mL/g according to the liquid-solid ratio;
（2）含偏铝酸钾母液中的氢氧化钾浓度240g/L；(2) The potassium hydroxide concentration in the potassium metaaluminate mother liquor is 240g/L;
（3）将混合浆液加热至260℃进行浸出反应，浸出反应时间10min；(3) The mixed slurry was heated to 260°C for leaching reaction, and the leaching reaction time was 10min;
（4）硅钾钙复合肥按质量百分比含氧化硅21.65%，氧化钾15.35%，氧化钙14.23%，氧化钠0.51%，氧化铝19.78%(4) The silicon-potassium-calcium compound fertilizer contains 21.65% silicon oxide, 15.35% potassium oxide, 14.23% calcium oxide, 0.51% sodium oxide, and 19.78% aluminum oxide by mass percentage.
（5）氧化铝的回收率为19.6%，氧化钠的回收率为96%。(5) The recovery rate of alumina was 19.6%, and the recovery rate of sodium oxide was 96%.
Claims (4)
- 一种利用含钙赤泥制备硅钾钙复合肥的方法，其特征在于包括以下步骤：A method of utilizing calcium-containing red mud to prepare silicon-potassium-calcium compound fertilizer is characterized in that comprising the following steps:（1）将含偏铝酸钾母液与含钙赤泥混合，或者将含偏铝酸钾和偏铝酸钠的混合母液与含钙赤泥混合，混合比例按液固比为3~4.5mL/g，获得混合浆液；所述的含钙赤泥按质量百分比含Al 2O 3 10~25%，CaO 10~50%，SiO 2 15~25%，Na 2O 4~10%，K 2O 0.5~2.0%； (1) Mix the potassium metaaluminate-containing mother liquor with calcium-containing red mud, or mix the mixed mother liquor containing potassium meta-aluminate and sodium meta-aluminate with calcium-containing red mud, and the mixing ratio is 3~4.5mL according to the liquid-solid ratio /g, to obtain a mixed slurry; the calcium-containing red mud contains Al 2 O 3 10~25%, CaO 10~50%, SiO 2 15~25%, Na 2 O 4~10%, K 2 by mass percentage O 0.5~2.0%;（2）将混合浆液加热至210~260℃，在搅拌条件下进行浸出反应，浸出反应时间10~55min，获得浸出物料；(2) heating the mixed slurry to 210-260°C, and carrying out the leaching reaction under stirring conditions, the leaching reaction time is 10-55 minutes, and the leaching material is obtained;（3）将浸出物料进行闪蒸后，进行固液分离，获得转型液和转型渣；转型渣中固相主要为水合硅铝酸钾，经水洗和烘干后，制成硅钾钙复合肥。(3) After flashing the leaching material, carry out solid-liquid separation to obtain transformation liquid and transformation slag; the solid phase in the transformation slag is mainly hydrated potassium aluminosilicate, which is washed and dried to make silicon-potassium-calcium compound fertilizer .
- 根据权利要求1所述的利用含钙赤泥制备硅钾钙复合肥的方法，其特征在于步骤（3）中，硅钾钙复合肥按质量百分比含K 2O≥15%。 The method for preparing silicon-potassium-calcium compound fertilizer using calcium-containing red mud according to claim 1, characterized in that in step (3), the silicon-potassium-calcium compound fertilizer contains K 2 O ≥ 15% by mass percentage.
- 根据权利要求1所述的利用含钙赤泥制备硅钾钙复合肥的方法，其特征在于步骤（3）中，转型液经过降温析出部分氢氧化钠和氢氧化铝，然后过滤分离出固相和液相；固相用于拜尔法生产氧化铝，液相作为含骗氯酸钾的母液，补加氢氧化钾溶液后，返回步骤（1）循环使用。The method for preparing silicon-potassium-calcium compound fertilizer using calcium-containing red mud according to claim 1, is characterized in that in step (3), the transformation liquid is cooled to separate out part of sodium hydroxide and aluminum hydroxide, and then the solid phase is separated by filtration and the liquid phase; the solid phase is used for the production of alumina by the Bayer process, the liquid phase is used as the mother liquor containing potassium chlorate, and after adding potassium hydroxide solution, it is returned to step (1) for recycling.
- 根据权利要求3所述的利用含钙赤泥制备硅钾钙复合肥的方法，其特征在于氧化铝的回收率为10~25%，氧化钠的回收率为93~96%。The method for preparing silicon-potassium-calcium compound fertilizer using calcium-containing red mud according to claim 3 is characterized in that the recovery rate of alumina is 10-25%, and the recovery rate of sodium oxide is 93-96%.
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| CN101607725A (en) * | 2008-06-19 | 2009-12-23 | 中国科学院过程工程研究所 | A kind of method that reclaims aluminum oxide and sodium oxide in the Bayer process red mud |
| CN103030160A (en) * | 2012-12-11 | 2013-04-10 | 中国科学院过程工程研究所 | Method for recycling alumina and sodium oxide from bayer process red mud |
| CN103934258A (en) * | 2014-04-30 | 2014-07-23 | 东北大学 | Method for recycling alkali and aluminum in process of treating bayer red mud by calcification-carbonization method |
| CN106187550A (en) * | 2016-08-02 | 2016-12-07 | 中国地质大学（北京） | A kind of method utilizing red mud flocculation agent acid leaching residue to prepare siliceous fertilizer |
| CN107298452A (en) * | 2017-06-23 | 2017-10-27 | 东北大学 | The method that the hot method of the step alkali of andradite one handles Bayer process red mud production metallurgy grade aluminum oxide |
| CN107892630A (en) * | 2017-11-20 | 2018-04-10 | 曲方圆 | A kind of humic acid calcium silicate fertilizer based on red mud and preparation method thereof |
| CN108975364A (en) * | 2018-07-30 | 2018-12-11 | 中南大学 | A kind of method that the processing of Bayer process red mud acid removes alkali collection sodium |
| CN109250741A (en) * | 2018-10-08 | 2019-01-22 | 东北大学 | A method of comprehensive utilization iron red mud |
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| CN113105282B (en) | 2022-09-27 |
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