CN113502164A - Method for producing mineral soil conditioner by utilizing desulfurized gypsum, phosphogypsum and potassium ore and product - Google Patents
Method for producing mineral soil conditioner by utilizing desulfurized gypsum, phosphogypsum and potassium ore and product Download PDFInfo
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Abstract
The invention discloses a method for producing a mineral soil conditioner by utilizing desulfurized gypsum, phosphogypsum and potassium ore and a product, wherein the method comprises the following steps: mixing desulfurized gypsum, phosphogypsum, potassium ore, an additive and water, filtering, drying, calcining, cooling and crushing to prepare a mineral substance soil conditioner intermediate; then adding zinc sulfate, sodium selenite and borax, adding water, fully stirring, granulating, and drying the granules to obtain the mineral soil conditioner. The mineral soil conditioner produced by the invention has comprehensive and balanced mineral nutrients, the mineral contains calcium, potassium, sodium, silicon, magnesium, sulfur, selenium, zinc, boron, iron and other trace element components, the nutrient types are complete, the effect of nutrient balance can be achieved, and the mineral soil conditioner has good functions of improving acid soil, supplementing missing soil minerals, preventing soil hardening and the like.
Description
Technical Field
The invention belongs to the field of agricultural resource utilization of industrial gypsum solid wastes, and particularly relates to a method for producing a mineral soil conditioner by utilizing desulfurized gypsum, phosphogypsum and potassium ore and a product.
Background
The desulfurized gypsum is industrial solid waste produced by using sulfur dioxide-containing flue gas discharged by combustion of fossil fuel and performing wet flue gas desulfurization by limestone-gypsum method, and its main component is calcium sulfate dihydrate (CaSO)4·2H2O), a free water content of generally around 10% or even higher, and poor flowability. By 2019, the annual output of the desulfurized gypsum in China reaches 71.5 Mt. At present, the comprehensive utilization way of the desulfurized gypsum in China is single, and the desulfurized gypsum is mainly used as a cement retarder and used for producing novel wall materials such as gypsum boards, gypsum blocks and the like; meanwhile, the method is gradually popularized and applied in the production of gypsum-based dry-mixed mortar, high-strength gypsum and other products (research review on resource utilization of solid wastes in enterprises of coal-fired power generation, northeast electric power technology 2020, 41 (7): 27-30 to 59). (1) Used as a cement retarder. This is currently the most dominant way of utilizing desulfurized gypsum. The desulfurized gypsum has similar components with natural gypsum and higher purity than the natural gypsum, and can completely replace the natural gypsum to be used as a cement retarder from the aspect of performance. However, the desulfurized gypsum has high water content, and if the desulfurized gypsum is directly used as a cement retarder, the desulfurized gypsum can not only be bonded and blocked in the transportation and storage processes, but also cause inaccurate metering and unstable production and influence on the cement quality. Therefore, before being used as a cement retarder, the cement retarder needs to be dried at low temperature, the water content is controlled to be about 3.0 percent, desulfurized gypsum can be made into small balls or blocks of 5-40 mm through granulation, and environmental pollution caused by flying of fine powder is eliminated (P.Tesarek, J.Drchalova, J.kolisko, et al.fluent gas desuifugation and typing strain, study of basic mechanical, hydraulic and thermal properties.construction and Building Material, 2007,21: 1500-assistant 1509.). (2) A paper-faced gypsum board. Before 2004, the production of paper-surface gypsum boards in China mainly takes natural gypsum as a raw material, and most production enterprises are distributed in areas with rich gypsum mineral resources. With the continuous development of desulfurization gypsum treatment technology and equipment and the great increase of desulfurization gypsum, the desulfurization gypsum is newly built in China after 2006The large thistle board production line basically uses the desulfurized gypsum as a raw material, so the thistle board can utilize 100 percent of the desulfurized gypsum, the thistle board is suitable for the large-industry high-standard automatic production line, the product transportation radius is large, the energy consumption is low, the technical content and the additional value are high, and the thistle board is one of the best directions for the comprehensive utilization of the desulfurized gypsum. (3) A gypsum block. The gypsum block is a light partition wall block material, belongs to green wall material, has good technical economy and strong market competitiveness, and is also one of the main ways for comprehensive utilization of the desulfurized gypsum. (4) Gypsum based dry mixed mortar. The desulfurized gypsum can be used for producing the desulfurized building gypsum with good quality after being dried, calcined, cooled and modified. The desulfurized gypsum is used as a main raw material, and different fillers and additives are added, so that the gypsum-based dry-mixed mortar including whitewash gypsum, gypsum putty, bonding gypsum, caulking gypsum and the like can be produced, and the method is also one of the ways for comprehensively utilizing the desulfurized gypsum. In the eastern area of China, particularly in Guangdong, Jiangsu, Shanghai and Zhejiang, the economic development level is high, natural gypsum resources are lacked, the application amount of the desulfurized gypsum is large, and the utilization rate is high. In the middle and western regions, the application level of the desulfurized gypsum is poor, the utilization rate is low, and some regions are not utilized at all. At present, most of gypsum products produced by medium and small enterprises are concentrated in the fields of gypsum plasterboards, gypsum blocks, gypsum mortar and the like (Yuancui, the comprehensive utilization of desulfurized gypsum of coal-fired power plants in China is summarized, and the research of contemporary chemical industry, 2019, (04): 39-40). In the high-end product market, for example, alpha high-strength gypsum, self-leveling gypsum, gypsum whiskers and the like almost have no Chinese brand. The self-leveling gypsum has been popularized and applied abroad for decades, and has mature production technology and matched machines. The self-leveling gypsum is developed in China from the 80 th of the 20 th century, but the market popularization is still in the starting stage at present. Gypsum product production enterprises are scattered, small and many, price competition is serious, and profit margin is very low.
Phosphogypsum is an industrial byproduct gypsum generated in the industrial production of high-concentration phosphate fertilizer, and the main component of phosphogypsum is calcium sulfate dihydrate (CaSO)4·2H2O). For each 1 ton of phosphoric acid (100% P)2O5Meter) will yield 4.8-5.0 tons of phosphogypsum; the phosphogypsum is grey white or grey black, contains 10.0-30.0% of water, has a pH value of 1.9-5.3, contains less than or equal to 0.5% of fluorine and has a particle diameter of 5-50 mu m generally. And residual organic phosphorus, inorganic phosphorus, fluoride, silicon, aluminum, potassium, sodium and other components. The phosphogypsum yield of 10 provinces such as Yunnan, Hubei, Guizhou, Shandong, Anhui, Chongqing, Jiangsu, Sichuan, Guangdong, Shaanxi and the like in China accounts for 91.5 percent of the total yield of the phosphogypsum in China. However, the comprehensive utilization rate is low at present, and effective treatment and resource utilization are urgently needed (Le national Peng, the technical difficulty discussion of comprehensive utilization of phosphogypsum, sulfuric acid industry, 2019, (10): 20-21 turns to 27).
The potassium ore mainly contains aluminosilicate minerals such as potassium feldspar, illite, muscovite, leucite, etc., and generally requires K2The content of O is more than or equal to 8 percent, and the rock types comprise volcanic rock, volcanic sedimentary rock, metamorphic rock and the like. These rocks are widely distributed in most parts of our country and it is estimated that: the total potassium-containing reserves of potassium-rich rocks in China are at least 200 hundred million tons, which is far higher than 8291.6 million tons of water-soluble potassium reserves in China. Due to K in potassium-rich rocks2O is fixed in aluminosilicate crystal lattices and is difficult to be directly absorbed by plants under natural conditions, and how to produce potash fertilizers by using potassium ores and corresponding soil conditioners has become a current research hotspot.
From the beginning of the 60 th of the 20 th century, China develops research work for preparing potash fertilizer by using potash feldspar in sequence, and the preparation method can be comprehensively divided into the following steps: sintering process, high-temperature melting process, hydrothermal process, blast furnace smelting process, low-temperature decomposition process, and the like. However, only sintering processes have been used industrially up to now. The reaction principle is as follows: limestone and coal are used as auxiliary materials, and are mixed with potassium feldspar, and after the mixture is crushed, pelletized and calcined, macromolecular potassium feldspar is converted into micromolecular potassium silicate, potassium carbonate and the like, so that the limestone and coal are widely adopted by enterprises, such as Shanxi 'Fulibang' and Shanxi 'Rongchang'. The method has low production cost, can resolve the silicon in the potassium feldspar and the calcium in the limestone together to obtain the alkalescent potassium, silicon, calcium and other large and medium element mineral soil conditioners, is favorable for comprehensively utilizing various mineral nutrients in rocks, has good market prospect, and has obvious improvement effect on acid soil in the south; however, the prior art has the problems that the calcination temperature is higher, the calcination temperature of the method is generally over 1200 ℃, the water solubility of the product is lower, the product has hydraulicity, and the soil is hardened by adding water and caking.
Disclosure of Invention
In order to solve the problems of the defects and the shortcomings and improve the resource utilization efficiency of gypsum industrial solid wastes and potassium ores thereof, the invention aims to provide a method for producing a mineral soil conditioner by compounding desulfurized gypsum, phosphogypsum and potassium ores and a product thereof.
The invention decomposes the desulfurized gypsum and the phosphogypsum by high-temperature calcination to generate calcium oxide, and the calcium oxide and a part of the rest calcium sulfate and potassium ore form CaO-CaSO4The potassium feldspar reaction system converts potassium in the potassium ore into potassium sulfate, calcium into calcium silicate and calcium aluminate, and magnesium into small molecular compounds with citrate solubility characteristics, such as calcium magnesium silicate and the like, namely into a mineral soil conditioner; in the calcining process, part of calcium sulfate is subjected to thermal decomposition, the generated waste gas containing sulfur dioxide can be effectively absorbed by limestone slurry, the obtained desulfurization product gypsum can be added into the material for reuse after dehydration, and the purified flue gas reaches the standard and is discharged; the addition of the additive increases the contents of magnesium and microelements such as zinc, selenium, boron, iron and the like, so that medium and trace element nutrients of the conditioner are more complete and balanced.
The raw and auxiliary materials used for production are phosphogypsum generated in the production process of desulfurized gypsum phosphate fertilizer generated by flue gas desulfurization, and the phosphogypsum, potassium ore and additives are mixed, and are subjected to material stirring, filtering, drying, calcining, cooling and crushing to prepare a mineral substance soil conditioner intermediate; then adding zinc sulfate, sodium selenite, borax and other auxiliary materials, adding a proper amount of water, stirring, granulating, drying and packaging to obtain the mineral soil conditioner. The produced product can be used for soil conditioning and repairing, particularly provides a large amount of large, medium and trace element minerals for soil, and is a powerful supplement for the nutrient deficiency of a large amount of chemical elements of nitrogen, phosphorus and potassium chemical fertilizers. Meanwhile, the implementation of the technology realizes the change of waste into valuable and promotes the development of circular economy.
The invention can realize the high-efficiency agricultural resource utilization of the wet desulfurization gypsum, the phosphogypsum and the potassium ore with lower utilization degree at present, solves the problems of large accumulation of the bulk solid wastes and environmental pollution caused by the bulk solid wastes, and simultaneously, the produced mineral soil conditioner can be used for conditioning and repairing soil and solves the problems of acidification, hardening and low mineral nutrients commonly existing in the soil in China at present.
The purpose of the invention is realized by the following technical scheme:
a method for producing a mineral soil conditioner by utilizing desulfurized gypsum, phosphogypsum and potassium ore comprises the following steps:
(1) mixing desulfurized gypsum, phosphogypsum, potassium ore, an additive and water, filtering, drying, calcining, cooling and crushing to prepare a mineral substance soil conditioner intermediate;
(2) and (2) adding zinc sulfate, sodium selenite and borax into the mineral soil conditioner intermediate prepared in the step (1), adding water, fully stirring (fully wetting the mixture; fully dissolving, reacting and chelating various compounds through the wetting action of water), granulating, and drying the granules to obtain the mineral soil conditioner.
Preferably, in the process of calcining and preparing the soil conditioner intermediate in the step (1), sulfur dioxide flue gas generated by pyrolysis of gypsum is absorbed by a limestone slurry absorbent, namely, flue gas desulfurization is carried out by a wet limestone-gypsum method, the obtained desulfurization byproduct, namely dihydrate gypsum, is dehydrated and then is reused as desulfurization gypsum, and the purified flue gas containing sulfur dioxide is discharged after reaching the standard.
Preferably, the dihydrate gypsum content of the desulfurized gypsum in the step (1) is more than or equal to 98.0 percent, and the dihydrate gypsum content of the phosphogypsum is more than or equal to 95.0 percent;
preferably, in the step (1), the desulfurized gypsum is wet flue gasDesulfurized gypsum produced during the desulfurization process; the phosphogypsum is a byproduct phosphogypsum in the production process of phosphate fertilizer; the potassium ore is potassium-containing aluminosilicate rock containing potassium feldspar, illite, muscovite and leucite, wherein K is2The content of O is more than or equal to 8.0 percent, and the rock types comprise volcanic rock, volcanic sedimentary rock, sedimentary rock and metamorphic rock.
Preferably, the mass percentages of the desulfurized gypsum, the phosphogypsum and the potassium ore in the step (1) are as follows: 0-80% of desulfurized gypsum, 0-80% of phosphogypsum and 5-70% of potassium ore.
Further preferably, in the step (1), the mass percentages of the desulfurized gypsum, the phosphogypsum and the potassium ore are as follows: 5-80% of desulfurized gypsum, 5-80% of phosphogypsum and 5-70% of potassium ore.
Preferably, the additive in the step (1) is any two of magnesium chloride, potassium chloride, dolomite and magnesite, and the addition amount of the additive is 3.0-15.0% of the total mass of the desulfurized gypsum, the phosphogypsum and the potassium ore.
Preferably, the adding amount of the water in the step (1) is 50-70% of the total mass of the desulfurized gypsum ardealite, the potassium ore and the additive; the material mixing is wet ball milling, the stirring speed of the ball milling is 50-90r/min, and the stirring time is 20-120 min.
Preferably, the filtered water of step (1) is reusable; drying the filtered filter residue until the water content is 5.0-8.0%; the calcination temperature is 925-1250 ℃ and the calcination time is 1.0-2.0 hours.
Preferably, the mass ratio of the mineral soil conditioner intermediate in the step (2) to zinc sulfate, sodium selenite and borax is 100: 1.0-5.0: 1.0-5.0: 1.5-7.5; the addition amount of the water is 3.0-8.0% of the total mass of the mineral soil conditioner intermediate, the zinc sulfate, the sodium selenite and the borax.
Preferably, the stirring speed in the step (2) is 100-145r/min, and the stirring time is 20-45 min; the granulation is disc granulation, and the granularity is controlled to be 3.0-15.0 mm; the granules are dried by hot air and then packaged into bags.
The mineral soil conditioner prepared by the method is characterized in that K is added into the mineral soil conditioner2The potassium content is more than or equal to 4.0w percent calculated by O, the citrate soluble silicon dioxide content is more than or equal to 18.0w percent, the citrate soluble calcium oxide content is more than or equal to 35.0w percent, the citrate soluble magnesium oxide content is more than or equal to 5.0w percent, the available sulfur is more than or equal to 7.5w percent, the total available nutrient is more than or equal to 80w percent, and the pH value is 9.0-12.0.
The reaction mechanism created by the invention is as follows: the desulfurized gypsum and the phosphogypsum are calcined at high temperature, a part of calcium sulfate is decomposed to release sulfur dioxide gas and solid calcium oxide, and the sulfur dioxide gas and the solid calcium oxide are combined with potassium ore to form potassium ore-CaSO4A CaO reaction system, under the condition that the reaction temperature is 925 to 1250 ℃, the collected relevant potassium ore-CaSO4Delta G of a series of chemical reactions which may occur in CaO systemsT 0The value calculation shows that: delta G thereofT 0The values are all less than-400 kJ/mol, reaction products mainly comprise potassium sulfate, dicalcium silicate, tricalcium aluminate, other calcium magnesium silicate, calcium magnesium aluminosilicate and the like, and the minerals have the characteristics of citrate solubility and alkalescence and can be used for regulating and improving acid soil.
By implementing the process, the desulfurized gypsum, the phosphogypsum and the potassium ore with low utilization value can be converted into a mineral soil conditioner product with higher added value, and trace element components such as zinc, selenium, boron, iron and the like are mixed, so that a new soil conditioner product with higher cost performance can be prepared. The energy consumption for producing each ton of product is 100-150 kilograms of standard coal, and the power consumption is 50-70 degrees per ton of product. The total production cost is lower than 500 yuan, and the market price of the soil conditioner is at least more than 1500 yuan/ton, thereby generating greater economic benefit, environmental protection benefit and social benefit.
Compared with the prior art, the invention has the following advantages and innovations:
(1) the raw and auxiliary materials for production are mainly bulk industrial solid wastes, including desulfurized gypsum, phosphogypsum, potassium ore and the like. The raw materials and auxiliary materials have wide sources and low cost, and are beneficial to realizing the high-efficiency utilization of the solid waste and the maximization of the economic benefit.
(2) The mineral soil conditioner produced by the invention has comprehensive and balanced mineral nutrients. The mineral contains calcium, potassium, sodium, silicon, magnesium, sulfur, selenium, zinc, boron, iron and other trace elements, and has complete nutrients and balanced nutrients. The product has good functions of improving acid soil, supplementing deficient soil minerals, preventing soil hardening and the like.
Drawings
FIG. 1 is a schematic diagram of the process flow of producing mineral soil conditioner and product by using desulfurized gypsum, phosphogypsum and potassium ore raw and auxiliary materials.
Detailed Description
The technical solution of the present invention is further described in detail below with reference to the specific embodiments and the accompanying drawings, but the scope and the implementation manner of the present invention are not limited thereto.
As shown in fig. 1, a process flow diagram of a method for producing a mineral soil conditioner by using desulfurized gypsum, phosphogypsum and potassium ore raw and auxiliary materials and a product thereof is described in detail as follows:
step 1: preparing a mineral substance soil conditioner intermediate by adopting raw and auxiliary materials such as wet desulfurization gypsum, phosphogypsum, potassium ore, an additive and the like through the steps of material mixing (wet ball milling), filtering, drying, calcining, cooling, crushing and the like;
step 2: and (2) adding auxiliary materials such as zinc sulfate, sodium selenite, borax and the like into the active mineral soil conditioner intermediate prepared in the step (1), adding a proper amount of water, stirring, fully wetting, granulating and drying to obtain the mineral soil conditioner. The new variety contains a large amount of mineral elements of silicon, calcium, magnesium, sulfur, potassium and sodium, and trace elements of zinc, selenium, boron and iron, has complete nutrient components, and is a new variety of mineral soil conditioners with extremely high cost performance.
Further, in the step 1, the desulfurized gypsum and the phosphogypsum are respectively industrial by-products phosphogypsum generated in the production process of by-product phosphate fertilizer generated in the wet flue gas desulfurization process; the potassium ore is mainly rock containing aluminosilicate minerals such as potassium feldspar, illite, muscovite, leucite, etc., and generally requires K2The content of O is more than or equal to 8.0 percentThe rock types include volcanic rock, volcanic sedimentary rock, metamorphic rock, and the like. The used additives are four kinds of materials such as magnesium chloride, potassium chloride, dolomite, magnesite and the like, the adding amount of the additives is 3.0-15.0% of the sum of the mass of other materials, water accounting for 50-70% of the total mass is added into the additives, the materials are fully and uniformly stirred (wet ball milling), the stirring speed is 50-90r/min, the stirring time is 20-120min, then filtration is carried out, the water filtration is repeatedly used, filter residues are dried to the water content of 5.0-8.0% by using hot tail gas discharged by calcination, then the materials are calcined, the temperature is 925 DEG 1250 ℃, and the time is 1.0-2.0 hours. The mineral substance soil conditioner intermediate is prepared by the steps of material mixing, filtering, drying, calcining, cooling, crushing and the like.
Further, mixing the mineral soil conditioner intermediate prepared in the step 1 with zinc sulfate, sodium selenite, borax and the like in a mass ratio of 100: 1.0-5.0: 1.0-5.0 and 1.5-7.5, adding water with the total mass of 3.0-8.0%, stirring uniformly and fully at the stirring speed of 100-; fully dissolving, reacting and chelating various compounds through the wetting action of moisture, then carrying out disc granulation, controlling the granularity to be 3.0-15.0mm, drying and packaging into bags. The new mineral soil conditioner is a new mineral soil conditioner variety.
Further, the new mineral soil conditioner variety prepared in the step (2) contains potassium (K)2O) content is more than or equal to 4.0 percent, citrate soluble silicon dioxide content is more than or equal to 18.0 percent, citrate soluble calcium oxide content is more than or equal to 35.0 percent, citrate soluble magnesium oxide content is more than or equal to 5.0 percent, available sulfur is more than or equal to 7.5 percent, the mineral soil conditioner contains zinc, selenium, boron and iron effective components, total effective nutrients are more than or equal to 80 percent, and the pH value is 9.0-12.0, thus being a new mineral soil conditioner variety with weak alkaline property.
Example 1
In certain coal-fired power plants in Shandong, flue gas desulfurization is carried out by a limestone-gypsum method, and a large amount of industrial desulfurization gypsum is generated. Meanwhile, a large amount of phosphogypsum is generated in the process of producing phosphate fertilizer by a phosphate fertilizer plant nearby. The Shandong tobacco platform contains a large amount of potassium feldspar, wherein the content of potassium oxide is 14.35%, 66.59% of silicon dioxide, 17.16% of aluminum oxide, and about 2% of sodium oxide, iron oxide, and the like, the total content of each oxide being 100%. The three raw materials and auxiliary materials are mixed according to the mass ratio: desulfurized gypsum: phosphogypsum: potassium feldspar 34.5: 25.8: 29.7. and then adding two additives such as magnesium chloride and dolomite, wherein the mass ratio of the two additives is 1:1, the adding amount of the water-soluble organic silicon material is 10.0 percent of the total mass of other raw and auxiliary materials, the total composition is 100 percent, then 60 percent of water is added, the materials are fully and uniformly stirred, the stirring speed is 75r/min, the stirring time is 65min, then the water is filtered, the filtered water is repeatedly used, the filter residue is dried to the water content of 6.5 percent, then the calcination is carried out, the calcination temperature is 950 ℃, and the calcination time is 1.5 hours. Taking out, cooling to room temperature, crushing, sieving with a 100-mesh (0.15mm) sieve to obtain a mineral soil conditioner intermediate, desulfurizing the flue gas of the discharged calcined waste gas containing sulfur dioxide by a limestone-gypsum method, and filtering and drying the obtained desulfurized gypsum for reuse; and mixing the obtained mineral soil conditioner intermediate with zinc sulfate, sodium selenite, borax and the like in a mass ratio of 100: 3.5: 3.5 and 5.5, adding water with the total mass of 6.0 percent, fully and uniformly stirring at the stirring speed of 115r/min for 30 min; fully dissolving, reacting and chelating various compounds through the wetting action of moisture, then carrying out disc granulation, controlling the particle size to be 13.5mm, drying and packaging into bags. Namely a new mineral soil conditioner. Wherein the product contains potassium (K)2O) content of 6.05 percent, citrate soluble silicon dioxide content of 21.85 percent, effective calcium oxide content of 37.02.0 percent, citrate soluble magnesium oxide content of 5.05 percent, effective sulfur of 7.50 percent, zinc, selenium and boron effective components and about 5.5 percent, total available nutrient of 82.97 percent, and pH value of 9.91, and is a new mineral soil conditioner with weak alkaline property.
Example 2
The coal-fired boiler in Shanxi adopts limestone-gypsum wet method to implement desulfurization, and produces a large quantity of desulfurized gypsum (CaSO)4.2H2O), the nearby Xiyang county also contains a large amount of potassium-containing shale, and the sorted ore contains 8.75% of potassium oxide, 62.12% of silicon dioxide and 15% of aluminum oxide23% and about 13.90% of sodium oxide, iron oxide, phosphorus pentoxide, manganese oxide and the like, and the total content of the oxides is close to 100%. And (3) mixing desulfurized gypsum: the mass ratio of the two materials of the shale containing potassium is 57.5: 33.5, adding potassium chloride and magnesite, wherein the mass ratio of the potassium chloride to the magnesite is 1:1, adding 4.5% of water, respectively, weighing and mixing the components to form 100% of the total mass, adding 55% of water of the total mass of the materials, performing wet ball milling together, wherein the ball milling stone is high-alumina ball milling stone, fully homogenizing, stirring at a speed of 90r/min for 45min, filtering, repeatedly using filtered water, drying filter residues until the water content is 7.5%, putting the filter residues into an activation kiln for high-temperature calcination, controlling the temperature at 1025 ℃ for 60 min, taking out a calcined product, cooling to room temperature, crushing, sieving all the crushed calcined products by a 100-mesh (0.15mm) sieve to obtain a mineral soil conditioner intermediate, desulfurizing the sulfur dioxide-containing calcined waste gas discharged by limestone by a limestone-gypsum method for flue gas desulfurization, and filtering and drying the obtained desulfurized gypsum for repeated use; then mixing with zinc sulfate, sodium selenite, borax and other auxiliary materials according to the mass ratio of 100: 3.5: 2.0: 5.0, adding water accounting for 6.5 percent of the total mass fraction, and fully and uniformly stirring at the stirring speed of 95r/min for 35 min; and (3) fully dissolving, reacting and chelating various compounds through wetting, then carrying out disc granulation, controlling the granularity to be 6.0mm, drying and packaging into bags, thus obtaining the new mineral soil conditioner variety. Wherein the product contains potassium (K)2O) content of 5.10 percent, citrate soluble silicon dioxide content of 19.32 percent, effective calcium oxide content of 35.95.0 percent, citrate soluble magnesium oxide content of 7.34 percent, effective sulfur of 6.25 percent, zinc, selenium and boron effective components of 7.5 percent, total available nutrient of 81.46 percent and pH value of 11.02, and is a new mineral soil conditioner with weak alkaline property.
Example 3
50-ton coal-fired boiler of a chemical plant in Jiangsu province adopts a limestone-gypsum method to desulfurize flue gas, and a large amount of desulfurized gypsum (CaSO) is generated in the desulfurization process4.2H2O) having a moisture content of up to 54% and a moisture content of 7.6% after drying. The potassium ore is collected from Shandong Taian, and the potassium oxide content is 8.33% after ore separation66.14% of silicon dioxide, 13.56% of aluminum oxide, about 11.97% of sodium oxide, calcium oxide, magnesium oxide, iron oxide, phosphorus pentoxide, titanium dioxide, manganese dioxide and the like, and the total amount of the oxides is close to 100%. The desulfurization gypsum: the weight ratio of potassium ore is 54.23: 38.77, adding additives of potassium chloride and dolomite, wherein the mass ratio of the potassium chloride to the dolomite is 1:1, the addition amounts of the two are respectively 3.5% and 3.5%, the two are put into a ball mill for ball milling, water with the total mass of about 54% is added into the ball mill, wet ball milling is carried out on the ball mill, the ball mill adopts high-alumina ball mill, the stirring speed is 60r/min, the stirring time is 90min, then filtering is carried out, water filtration is repeatedly used, filter residues are dried until the water content is 8.0%, then the filter residues are put into a kiln for calcination, the temperature is controlled at 995 ℃, the calcination time is 45min, calcined substances are taken out and cooled to room temperature, then the calcined substances are crushed, and all the calcined substances pass through a 100-mesh (0.15mm) sieve, so that a mineral soil conditioner intermediate is obtained; the discharged waste gas containing sulfur dioxide is desulfurized by limestone-gypsum method to obtain desulfurized gypsum which is dried and reused; and mixing the obtained mineral soil conditioner intermediate with zinc sulfate, sodium selenite, borax and the like in a mass ratio of 100: 5.0: 5.0: 7.5, adding water accounting for 5.5 percent of the total mass amount, and fully and uniformly stirring at the stirring speed of 95r/min for 45 min; fully dissolving, reacting and chelating various compounds through the moisture wetting action, then carrying out disc granulation, controlling the granularity to be 3.5mm, drying and packaging into bags, thus obtaining the new mineral soil conditioner variety. Wherein the product contains potassium (K)24.05 percent of O), 20.15 percent of citrate soluble silicon dioxide, 35.25.0 percent of effective calcium oxide, 6.02 percent of citrate soluble magnesium oxide, 7.5 percent of effective sulfur, 8.0 percent of effective components of zinc, selenium and boron, 80.97 percent of total effective nutrient and 10.15 percent of pH value, and is a new mineral soil conditioner with weak alkaline property.
Example 4
Phosphoric acid is produced by phosphorite in a chemical plant of Zhanjiang city, Guangdong province, and a large amount of phosphogypsum (CaSO) is produced in the production process4.2H2O), piled up as a hill, affecting the production of surrounding plantsAnd residential environments of residents. The phosphogypsum is dried to reach the water content of 5.50 percent and the dihydrate gypsum content of 96.16 percent. The potassium ore is collected from potassium granite around production enterprises, the rock after separation contains 8.02% potassium oxide, 75.65% silicon dioxide, 9.68% aluminum oxide, and about 6.65% sodium oxide, calcium oxide, magnesium oxide, iron oxide, titanium dioxide, etc., and the total amount of various oxides in the ore is close to 100%. The phosphogypsum is prepared by mixing the following components: the mass ratio of potassium ore is 40.45: 50.05, and adding additives of magnesium chloride and magnesite, wherein the mass ratio of the magnesium chloride to the magnesite is 1:1, adding the two into a ball mill, wherein the adding amount of the two is 4.5% and 4.5%, ball milling the two together, adding water with the total mass of about 60%, putting ball milling stone into the ball mill for wet ball milling, wherein the ball milling stone is bauxite, the stirring speed is 55r/min, the stirring time is 65min, filtering, repeatedly using filtered water, drying filter residues until the moisture content is 5.6%, putting the filter residues into a kiln for calcination, controlling the temperature at 1200 ℃, the calcination time is 35min, taking out the calcined product, cooling to the room temperature, crushing, and sieving all the calcined products by a 100-mesh (0.15mm) sieve to obtain a mineral soil conditioner intermediate; the discharged calcining waste gas containing sulfur dioxide is subjected to flue gas desulfurization by a limestone-gypsum method, and the obtained desulfurization gypsum is filtered, dried and reused; mixing the mineral soil conditioner intermediate with zinc sulfate, sodium selenite, borax and the like in a mass ratio of 100: 3.5: 4.5: 5.5, adding water accounting for 6.0 percent of the total mass amount, and fully and uniformly stirring at a stirring speed of 105r/min for 38 min; fully dissolving, reacting and chelating various compounds through the moisture wetting action, then carrying out disc granulation, controlling the granularity to be 10.5mm, drying and packaging into bags, thus obtaining the new mineral soil conditioner variety. Wherein the product contains potassium (K)24.07 percent of O), 18.5 percent of citrate soluble silicon dioxide, 36.250 percent of effective calcium oxide, 5.26 percent of citrate soluble magnesium oxide, 7.70 percent of effective sulfur, 8.8 percent of effective components of zinc, selenium and boron, 80.52 percent of total effective nutrient and 11.38 of pH value, and is a new mineral soil conditioner with weak alkaline property.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A method for producing a mineral soil conditioner by utilizing desulfurized gypsum, phosphogypsum and potassium ore is characterized by comprising the following steps:
(1) mixing desulfurized gypsum, phosphogypsum, potassium ore, an additive and water, filtering, drying, calcining, cooling and crushing to prepare a mineral substance soil conditioner intermediate;
(2) and (2) adding zinc sulfate, sodium selenite and borax into the intermediate of the mineral soil conditioner prepared in the step (1), adding water, fully stirring, granulating, and drying the granules to obtain the mineral soil conditioner.
2. The method as claimed in claim 1, wherein in the process of calcining and preparing the soil conditioner intermediate in step (1), sulfur dioxide flue gas generated by pyrolysis of gypsum is absorbed by limestone slurry absorbent, namely flue gas desulfurization is carried out by a wet limestone-gypsum method, the obtained desulfurization byproduct, namely dihydrate gypsum, is dehydrated and then is reused as desulfurization gypsum, and the purified flue gas of sulfur dioxide reaches the standard and is discharged.
3. The method according to claim 1, wherein in step (1), the desulfurized gypsum is desulfurized gypsum produced in a wet flue gas desulfurization process; the phosphogypsum is a byproduct phosphogypsum in the production process of phosphate fertilizer; the potassium ore is potassium-containing aluminosilicate rock containing potassium feldspar, illite, muscovite and leucite, wherein K is2The content of O is more than or equal to 8.0 percent, and the rock types comprise volcanic rock, volcanic sedimentary rock, sedimentary rock and metamorphic rock.
4. The method according to claim 1, wherein the mass percentages of the desulfurized gypsum, the phosphogypsum and the potassium ore in the step (1) are as follows: desulfurized gypsum: 0-80%, phosphogypsum: 0-80%, potassium ore: 5 to 70 percent.
5. The method as claimed in claim 1, wherein the additive in step (1) is any two of magnesium chloride, potassium chloride, dolomite and magnesite, and the addition amount is 3.0-15.0% of the sum of the mass of the desulfurized gypsum and the phosphogypsum and the potassium ore.
6. The method according to claim 1, wherein the water in the step (1) is added in an amount of 50-70% of the total mass of the desulfurized gypsum and the phosphogypsum, the potassium ore and the additive; the material mixing is wet ball milling, the stirring speed of the ball milling is 50-90r/min, and the stirring time is 20-120 min.
7. The method of claim 1, wherein the filtered drainage of step (1) is reusable; drying the filtered filter residue until the water content is 5.0-8.0%; the calcination temperature is 925-1250 ℃ and the calcination time is 1.0-2.0 hours.
8. The method of claim 1, wherein the mass ratio of the mineral soil conditioner intermediate of step (2) to zinc sulfate, sodium selenite, and borax is 100: 1.0-5.0: 1.0-5.0: 1.5-7.5; the addition amount of the water is 3.0-8.0% of the total mass of the mineral soil conditioner intermediate, the zinc sulfate, the sodium selenite and the borax.
9. The method as claimed in claim 1, wherein the stirring speed in step (2) is 100-145r/min, and the stirring time is 20-45 min; the granulation is disc granulation, and the granularity is controlled to be 3.0-15.0 mm; the granules are dried by hot air and then packaged into bags.
10. A mineral soil conditioner prepared by the method of any one of claims 1 to 9, wherein said mineral soil conditioner is prepared by the method of any one of claims 1 to 9K in mineral soil conditioner2The potassium content is more than or equal to 4.0w percent calculated by O, the citrate soluble silicon dioxide content is more than or equal to 18.0w percent, the citrate soluble calcium oxide content is more than or equal to 35.0w percent, the citrate soluble magnesium oxide content is more than or equal to 5.0w percent, the available sulfur is more than or equal to 7.5w percent, the total available nutrient is more than or equal to 80w percent, and the pH value is 9.0-12.0.
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