CN113337295A - Method for producing soil conditioner by utilizing bulk industrial solid wastes and product - Google Patents
Method for producing soil conditioner by utilizing bulk industrial solid wastes and product Download PDFInfo
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Abstract
The invention discloses a method for producing a soil conditioner by utilizing bulk industrial solid wastes and a product, wherein the method comprises the following steps: preparing an active mineral soil conditioner intermediate by adopting soda white mud, desulfurized gypsum, phosphogypsum, potassium ore, an additive and water through the steps of material mixing, drying, roasting, cooling and crushing; then adding the auxiliary materials of potassium fulvate, zinc sulfate, ferric sulfate, sodium selenite and borax, adding water, stirring, granulating, drying and packaging the mixture 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, iron, selenium, zinc, boron, organic matters and other trace elements, and has complete nutrients and balanced nutrients. The product has good effects and promotion functions on the improvement of acid soil, the prevention of soil hardening and the supplementation of deficient soil minerals.
Description
Technical Field
The invention belongs to the field of agricultural resource utilization of bulk industrial solid wastes, and particularly relates to a method for producing a soil conditioner by utilizing bulk industrial solid wastes and a product.
Background
Soda ash production white mud (referred to as soda ash production white mud) is industrial solid waste containing a large amount of water generated in the process of producing soda ash by an ammonia-soda process. With the annual industrial development of soda ash in China, the discharge amount of white mud for producing soda is larger and larger. The components of the soda lime mud are approximately: CaCO3 39.5～60.0％；CaSO4 2.8～20.0％；CaCl2 9.8～14.0％；NaCl 2.4～8.0％；CaO 3.0～8.3％；Mg(OH)2 2.0～15.4％；SiO2 2.5～9.1％；R2O33.1-6.9%; 6.0-10.0% of acid-insoluble substance. The particles are fine, and the particle size of more than 65 percent (volume fraction) is less than or equal to 10 mu m. The alkaline residue has a high pH value, generally 10.0-12.0, and is a high alkaline substance, and contains 5-15% chloride including CaCl2And NaCl, which makes it extremely hygroscopic, deliquescent and corrosive. These have all seriously hindered the application of caustic sludge in the construction industry. Therefore, most of the caustic sludge can be treated only by adopting surface accumulation and discharge. The stacked caustic sludge occupies a large amount of land resources, dust pollution can be caused after surface weathering, and easily soluble components permeate underground water and soil through leaching, surface runoff and erosion and can cause secondary pollution. When the alkaline residue is discharged outside the sea, a 'white sea' is formed, which causes pollution to the surrounding sea area, damages the marine ecological environment and endangers aquaculture, and a channel can be blocked after deposition. Therefore, the treatment problem of the white mud for producing soda always restricts the further development of soda enterprises, and is a great technical problem and potential safety hazard in the production process of the ammonia-soda process (the technology for producing calcium-magnesium multi-element compound fertilizer by yellow senega red and soda residue [ J)]Soda industry, 2000, (1): 20-22.).
The comprehensive utilization approaches of the soda white mud mainly comprise:
(1) dechlorinating with water, and adding chalk to reduce the chlorine content to 2.0%, and the fertilizer is used as calcium magnesium fertilizer, and is especially suitable for acid soil (Lin Xiao Ming. method for producing granular fertilizer by using waste residue from alkali production [ P ]. Chinese patent publication No. CN1580011, 2005-02-16.);
(2) preparing an adhesive from the alkali-making white mud, quartz sand, gypsum and the like, and then making bricks, tiles and the like by using the adhesive;
(3) mixing the soda white mud with blast furnace slag, quartz sand and dihydrate gypsum to produce clinker-free cement;
(4) the CaCl2 in the soda lime mud is reduced to be below 4.0 percent, and the NaCl is reduced to be below 3.0 percent, so that the soda lime mud can be used As an additive for poultry or livestock, but the concentration of toxic metals such As Pb, As and the like is required to meet the standard requirement;
(5) and preparing chlorine-containing cement by using the alkali-making white mud instead of limestone.
However, the above treatment methods are not widely and comprehensively applied due to high treatment cost, limited use amount or immature technology. Therefore, most countries still adopt a treatment method of stockpiling and clear liquid discharging of soda white mud.
Desulfurized gypsum is a by-product of Flue Gas Desulfurization (FGD) processes using lime-limestone. It is prepared by grinding lime-limestone into slurry, and removing dust to obtain SO-containing product2The flue gas is passed through a slurry scrubber to remove SO2. Lime slurry and SO2The reaction generates calcium sulfate and calcium sulfite, and the calcium sulfite is oxidized and converted into calcium sulfate to obtain an industrial byproduct gypsum, which is called desulfurized gypsum and widely used in industries such as building materials and the like. Can also be applied to cement retarders, production of alpha gypsum powder and beta gypsum powder and the like (Yuancaoxia, the summary of comprehensive utilization of desulfurized gypsum of coal-fired power plants in China, the research of contemporary chemical engineering, 2019 (4): 39-40).
Phosphogypsum is an industrial byproduct gypsum generated in the 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)2O5Metering) will yield 4.8-5.0 tons of phosphogypsum; phosphogypsumIs gray white or gray black, contains 10.0-30.0% of water, has a pH value of 1.9-5.3, contains fluorine less than or equal to 0.5%, and has a particle diameter of 5-50 μm. And residual organic phosphorus, inorganic phosphorus, fluoride, fluorine, silicon, aluminum, potassium, sodium and other inorganic substances. 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, at present, the comprehensive utilization rate is low, and effective treatment and resource utilization are urgently needed (the way and prospect of resource utilization of phosphogypsum in hoard morning, the stage 8 of 2020: 30-33. for chemical mineral processing).
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 6 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 potassium fertilizer and a corresponding soil conditioner by using potassium ore has become a current research hotspot (Zhang Xiao, Yongqianxi, Qimengyao, and the like, the potassium feldspar potassium-extracting technology advances, mineral protection and utilization, 2020 No. 4, 172-. 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, and can resolve silicon in potassium feldspar and calcium in limestone together to obtain alkalescent potassium, silicon, calcium and other large and medium elementsThe mineral soil conditioner is beneficial to comprehensively utilizing various mineral nutrients in rocks, has good market prospect and has obvious improvement effect on acid soil in south China; however, this method has problems that the calcination temperature is generally 1200 ℃ or higher, the water solubility of the product is low, the product is hydraulic, and the soil is hardened by adding water.
On the premise that the heavy metal elements contained in the raw and auxiliary materials meet the ecological indexes of arsenic, cadmium, lead, chromium and mercury in the national standard of the national silicon-calcium-potassium-magnesium fertilizer (GB/T36207-2018), and the contents (unit: mg/kg) of the heavy metal elements are respectively less than or equal to 50, less than or equal to 10, less than or equal to 200, less than or equal to 500 and less than or equal to 5, the problem of efficient resource utilization of various large-scale industrial solid wastes is solved, and the method is a prominent environmental problem to be solved in the current economic high-quality development process of China.
Disclosure of Invention
In order to solve the defects, the invention can realize the high-efficiency resource utilization of the existing large amount of industrial solid wastes with extremely low utilization degree, large quantity and wide range, including soda-making white mud, desulfurized gypsum, phosphogypsum and potassium ore, solves the problems of large accumulation of the wastes and environmental pollution, and simultaneously, the produced mineral soil conditioner can be used for soil restoration and conditioning, and solves the problems of soil acidification, hardening and low mineral nutrients.
The invention relates to a technology for producing a mineral soil conditioner by compounding soda white mud, desulfurized gypsum, phosphogypsum and potassium ore. The main raw material of the potassium ore is introduced into the bulk industrial solid wastes as auxiliary materials, and working conditions in the combustion process are controlled in a combined manner, so that potassium in the potassium ore is converted into potassium sulfate, calcium is converted into calcium silicate and calcium aluminate, magnesium is converted into small molecular compounds with citrate solubility characteristics such as calcium magnesium silicate, and the like, the reaction temperature is reduced to 950-1025 ℃ from the original temperature of over 1200 ℃, and the obtained roasted product has more balanced nutrients, no hydraulic property and higher mineral solubility.
The invention aims to provide a method for producing a soil conditioner by utilizing bulk industrial solid wastes and a product; the production raw materials are soda white mud, desulfurized gypsum, phosphogypsum and potassium ore, and the produced product can be used for conditioning and improving soil and has great effects on inhibiting soil acidification, preventing hardening and improving medium and trace element mineral substance nutrient content. Meanwhile, the comprehensive implementation of the technology realizes the change of waste into valuable and promotes the healthy development of circular economy and agriculture.
The purpose of the invention is realized by the following technical scheme:
a method for producing a mineral soil conditioner by utilizing bulk industrial solid wastes comprises the following steps:
(1) preparing an active mineral soil conditioner intermediate by adopting soda white mud, desulfurized gypsum, phosphogypsum, potassium ore, an additive and water through the steps of material mixing, drying, roasting, cooling and crushing;
(2) and (2) adding potassium fulvate, zinc sulfate, ferric sulfate, sodium selenite and borax auxiliary materials into the active mineral soil conditioner intermediate prepared in the step (1), adding water, stirring (fully wetting the mixture to dissolve, react and chelate mineral nutrients), and then granulating, drying and packaging the mixture to obtain the mineral soil conditioner.
Preferably, the alkali-making white mud in the step (1) is alkaline residue generated in the process of producing sodium carbonate, is a bulk industrial solid waste with a water content of 50-60%, and comprises the following solid components in percentage by mass: CaCO3 39.5～60.0％，CaSO4 2.8～20.0％，CaCl2 9.8～14.0％，NaCl 2.4～8.0％，CaO 3.0～8.3％，Mg(OH)2 2.0～15.4％，SiO22.5 to 9.1 percent of the total weight of the catalyst, 3.1 to 6.9 percent of other oxides and 6.0 to 10.0 percent of acid insoluble substances; the desulfurized gypsum is a byproduct of flue gas desulfurization by a gypsum method, namely lime/limestone; the phosphogypsum is solid waste phosphogypsum generated in the process of producing phosphoric acid by using apatite; the potassium ore is rock containing potassium feldspar, illite, muscovite, and leucite aluminosilicate minerals, and K is2The content of O is more than or equal to 6 percent, and the rock types comprise volcanic rock, volcanic sedimentary rock, sedimentary rock and metamorphic rock.
Preferably, the heavy metal elements contained in the alkali-making white mud, the desulfurized gypsum, the phosphogypsum and the potassium ore in the step (1) meet the ecological indexes of arsenic, cadmium, lead, chromium and mercury in the national standard GB/T36207-2018 of the national silicon-calcium-potassium-magnesium fertilizer, and the contents of the heavy metal elements are respectively less than or equal to 50mg/kg, less than or equal to 10mg/kg, less than or equal to 200mg/kg, less than or equal to 500mg/kg and less than or equal to 5mg/kg, and the granularity is more than or equal to 200 meshes (less than or equal to 0.074 mm).
Preferably, the alkali-making white mud, the desulfurized gypsum, the phosphogypsum and the potassium ore in the step (1) are as follows by mass percent: 5-50% of soda white mud, 5-50% of desulfurized gypsum, 5-50% of phosphogypsum and 5-70% of potassium ore.
Preferably, the additive in the step (1) is formed by mixing two of potassium sulfate, potassium chloride, potassium carbonate, sodium sulfate, sodium chloride and sodium carbonate according to a mass ratio of 1: 1-1.5;
preferably, the addition amount of the additive is 3.0-5.0% of the total mass of the alkali-making white mud, 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 alkali making white mud, the desulfurized gypsum, the phosphogypsum, the potassium ore and the additive;
preferably, 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 drainage of step (1) is reused; drying the filtered filter residue until the water content is 5.0-8.0%;
preferably, the roasting temperature is 950-.
Preferably, the mass ratio of the active mineral soil conditioner intermediate in the step (2) to the potassium fulvate, the zinc sulfate, the ferric sulfate, the sodium selenite and the borax is 100: 20.0-85.0: 1.0-5.0: 2.0-10.0: 1.0-5.0: 1.5-7.5;
preferably, the adding amount of the water is 3.0-8.0% of the total mass of the active mineral substance soil conditioner intermediate and the potassium fulvate, the zinc sulfate, the ferric 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; through the wetting action, various compounds are fully dissolved, reacted and chelated.
Preferably, the granulation is disc granulation, and the particle size is controlled to be 2.0-12.0 mm.
The mineral soil conditioner prepared by the method is characterized in that the content of organic matters in the mineral soil conditioner is more than or equal to 15.0 percent, and K is used2The potassium content is more than or equal to 2.5 percent calculated by O, the citrate-soluble silicon dioxide content is more than or equal to 10.0 percent, the citrate-soluble calcium oxide content is more than or equal to 15.0 percent, the citrate-soluble magnesium oxide content is more than or equal to 2.0 percent, the available sulfur is more than or equal to 3.5 percent, the available chlorine is more than or equal to 3.5 percent, the available iron is more than or equal to 0.5 percent, the zinc, selenium and boron active ingredients are contained, and the total available nutrient is more than or equal to 52.0 percent.
The reaction mechanism created by the invention is as follows: the alkali-making white mud, the desulfurized gypsum and the phosphogypsum all contain a large amount of calcium-based compounds, and the calcium-based compounds mainly comprise two types of calcium-based compounds, one type is CaCO3、Ca(OH)2And CaO, both of which are subjected to decarburization and dehydration reaction during oxidizing roasting, wherein CaCO3About 898 ℃ and Ca (OH)2The decomposition temperature of (A) is approximately 580 ℃. In conclusion, they will be converted to the form of CaO in the oxidizing roasting atmosphere below 1000 ℃; another calcium-based compound is gypsum (CaSO)4.2H2O), they are dehydrated by heating and finally converted into CaSO4. Therefore, it will be converted into CaO and CaSO4Two calcium-based compounds, which are blended with potassium ore and converted into potassium ore-CaSO4CaO reaction system. Under the condition of reaction temperature of 950-1025 ℃, collecting relevant potassium ore-CaSO4Delta G of a series of chemical reactions which may occur in CaO systemsT0The value calculation shows that: delta G thereofT0The values are all less than-400 kJ/mol, and the optimal molar ratio of the reaction is potassium ore: CaSO4: CaO 1: 1: 14. the reaction products mainly comprise potassium sulfate, dicalcium silicate, tricalcium aluminate and other compounds such as calcium magnesium silicate and calcium magnesium aluminosilicate.
By implementing the process, the alkali-making white mud, the desulfurized gypsum, the phosphogypsum and the potassium ore with low utilization value can be converted into mineral soil conditioner intermediates with high additional value, and organic matters, zinc, iron, selenium, boron and other trace element components are mixed, so that a new soil conditioner variety with high 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 600 yuan, and the market selling price of the soil conditioner is at least more than 1500 yuan/ton.
The achievement can be applied to the treatment of a large amount of solid wastes which are widely used at home and abroad at present, including soda white mud, desulfurized gypsum and phosphogypsum. The technical process is simple, the equipment investment is less, the equipment is conventional and standardized, the production cost is low, and the profit margin is larger, so the application prospect is very wide.
Compared with the prior art, the invention has the following advantages and innovations:
(1) the raw materials and auxiliary materials for production are mainly bulk industrial solid wastes, including soda white mud, 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, iron, selenium, zinc, boron, organic matters and other trace elements, and has complete nutrients and balanced nutrients. The product has good effects and promotion functions on the improvement of acid soil, the prevention of soil hardening and the supplementation of deficient soil minerals.
Drawings
FIG. 1 is a schematic process flow diagram of the method for producing a mineral soil conditioner from bulk industrial solid waste according to the present invention.
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.
Referring to fig. 1, a process flow diagram of a method for producing a mineral soil conditioner from bulk industrial solid wastes is shown, and the process flow diagram is described in detail as follows:
step 1: preparing a mineral substance soil conditioner intermediate by adopting raw and auxiliary materials such as soda white mud, desulfurized gypsum, phosphogypsum, potassium ore, additives and the like through the steps of material mixing, filtering, drying, roasting, cooling, crushing and the like;
step 2: and (2) adding auxiliary materials such as potassium fulvate, zinc sulfate, ferric sulfate, sodium selenite, borax and the like into the active mineral substance soil conditioner intermediate prepared in the step (1), adding a proper amount of water, stirring, fully wetting, and then granulating to obtain the mineral substance soil conditioner. The new variety contains a large amount of mineral elements of silicon, calcium, magnesium, sulfur, potassium and sodium, trace elements of zinc, iron, selenium and boron and organic fulvic acid, has complete nutrient components and is a new variety of mineral soil conditioner with extremely high cost performance.
Further, in the step 1, bulk solid wastes such as soda lime mud, desulfurized gypsum, phosphogypsum and the like are adopted; 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 6 percent, the types of rocks comprise volcanic rock, volcanic sedimentary rock, metamorphic rock and the like, and the raw and auxiliary materials all require that the contained heavy metal elements meet the ecological indexes of arsenic, cadmium, lead, chromium and mercury in the national standard (GB/T36207-2018) of the national silicon-calcium-potassium-magnesium fertilizer, the content (unit: mg/kg) of the heavy metal elements is respectively less than or equal to 50, less than or equal to 10, less than or equal to 200, less than or equal to 500 and less than or equal to 5, and the granularity is more than or equal to 200 meshes (less than or equal to 0.074 mm). The used additives comprise 6 kinds of potassium sulfate, potassium chloride, potassium carbonate, sodium sulfate, sodium chloride and sodium carbonate and a mixture thereof, and the intermediate of the mineral substance soil conditioner is prepared by the steps of material mixing, drying, roasting, cooling, crushing and the like. Wherein the raw and auxiliary materials comprise the following components in percentage by mass: preparing alkali white mud: 5-50%, desulfurized gypsum: 5-50%, phosphogypsum: 5-50%, potassium ore: 5-70%, 6 additives of potassium sulfate, potassium chloride, potassium carbonate, sodium sulfate, sodium chloride and sodium carbonate, wherein the used additive is prepared by mixing two of the 6 additives in a mass ratio of 1: 1 to 1.5 percent of additive, the adding amount of the additive is 3.0 to 5.0 percent of the total weight of other raw and auxiliary materials, water with the total mass amount of 50 to 70 percent is added, the mixture is fully and uniformly stirred, and the stirring speed is highStirring for 20-120min at 50-90r/min, filtering, repeatedly using filtered water, drying the filter residue until the water content is 5.0-8.0%, and roasting at the roasting temperature of 950-1025 ℃ for 0.5-1.5 h.
Further, mixing the mineral soil conditioner intermediate prepared in the step (1) and the mineral soil conditioner intermediate prepared in the step (2) with potassium fulvate, zinc sulfate, ferric sulfate, sodium selenite, borax and the like in a mass ratio of 100: 20-85: 1.0-5.0: 2.0-10.0: 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-; through the wetting action, various compounds are fully dissolved, reacted and chelated, then the mixture enters a disc for granulation, the granularity is controlled to be 2.0-12.0mm, and the mixture is dried and packaged into a new mineral soil conditioner variety.
Further, the new mineral soil conditioner variety prepared in the step (2) has the organic matter content of more than or equal to 15.0 percent and potassium (K)2O) content is more than or equal to 2.5 percent, citrate soluble silicon dioxide content is more than or equal to 10.0 percent, citrate soluble calcium oxide content is more than or equal to 15.0 percent, citrate soluble magnesium oxide content is more than or equal to 2.0 percent, available sulfur is more than or equal to 3.5 percent, available chlorine is more than or equal to 3.5 percent, available iron is more than or equal to 0.5 percent, the active ingredients of zinc, selenium and boron are contained, and the total available nutrient is more than or equal to 52 percent.
Example 1
In certain alkali-making enterprises in Shandong, a large amount of white mud (alkaline residue) for alkali making by an ammonia-soda process is generated, and a large amount of flue gas desulfurization gypsum and phosphogypsum are arranged nearby. The potassium ore is collected from Shandong tobacco platform, wherein the potassium oxide content is 13.98%, the silicon dioxide content is 65.32%, the aluminum oxide content is 18.01%, in addition, the potassium ore also contains 2.69% of sodium oxide, ferric oxide and the like, and the total content of various oxides is about 100%. White mud for alkali preparation: desulfurized gypsum: phosphogypsum: the potassium ore comprises the following components in percentage by mass of 28.89: 8.59: 10.95: 51.57, and the raw materials and the auxiliary materials are all required to contain heavy metal elements meeting ecological indexes of arsenic, cadmium, lead, chromium and mercury in national standard of silicon-calcium-potassium-magnesium fertilizer (GB/T36207-2018), wherein the content (unit: mg/kg) is respectively less than or equal to 50, less than or equal to 10, less than or equal to 200, less than or equal to 500 and less than or equal to 5, and the granularity is more than or equal to 200 meshes (less than or equal to 0.074 mm). On the basis, 2.5% of potassium chloride and 2.5% of sodium sulfate are added, the potassium chloride and the sodium sulfate are metered and mixed together, water with the total mass of about 58% of the materials is added for wet ball milling, the ball milling stone is high-alumina ball milling stone, the stirring speed is 65r/min, the stirring time is 60min, then the filtering is carried out, the filtered water is reused, the filter residue is dried until the moisture content is 6.2%, then the filter residue is put into a kiln for roasting, the temperature is controlled at 1005 ℃, the roasting time is 90min, the filter residue is taken out and cooled to the room temperature, then the filter residue is crushed, and is sieved by a 100-mesh (0.15mm) sieve to obtain a mineral soil conditioner intermediate, and then the mineral soil conditioner intermediate is mixed with potassium fulvate, zinc sulfate, ferric sulfate, sodium selenite, borax and the like according to the mass ratio of 100: 23.44: 3.2: 5.2: 1.5 and 1.75, adding water accounting for 5.8 percent of the total mass amount, and fully and uniformly stirring at a stirring speed of 112r/min for 45 min; fully dissolving, reacting and chelating various compounds through the wetting action, then carrying out disc granulation, controlling the granularity to be 7.5mm, drying and packaging into bags, thus obtaining the new mineral soil conditioner variety.
The organic matter content of the new variety of the mineral soil conditioner is 17.13 percent, and the potassium (K) content of the new variety of the mineral soil conditioner is 17.13 percent2O) content of 6.52 percent, citrate soluble silicon dioxide content of 12.85 percent, citrate soluble calcium oxide content of 14.32 percent, citrate soluble magnesium oxide content of 5.23 percent, available sulfur of 7.25 percent, available chlorine of 4.54 percent and available iron of 3.65 percent, and contains trace element components such as zinc, selenium, boron and the like, the total available nutrient is more than or equal to 71.49 percent, and the pH value of the product is 10.85.
Example 2
A large scale alkali production enterprise in Qinghai produces a large amount of alkali white mud (alkali slag) produced by an ammonia-soda process, a flue gas desulfurization facility of a factory also produces a large amount of desulfurized gypsum, and a peripheral phosphate fertilizer enterprise also has a large amount of phosphogypsum accumulation. The potassium ore is collected from Qinghai Guerba, and contains potassium oxide 9.56%, silicon dioxide 68.46%, aluminum oxide 15.67%, sodium oxide, ferric oxide 6.31%, and total oxide content about 100%. White mud for alkali preparation: desulfurized gypsum: phosphogypsum: the mass ratio of two materials of the potassium ore is 27.47: 7.52: 20.65: 44.36, and the raw materials and the auxiliary materials are required to contain heavy metal elements meeting ecological indexes of arsenic, cadmium, lead, chromium and mercury in national standard of silicon-calcium-potassium-magnesium fertilizer (GB/T36207-2018), wherein the content (unit: mg/kg) is respectively less than or equal to 50, less than or equal to 10, less than or equal to 200, less than or equal to 500 and less than or equal to 5, and the granularity is more than or equal to 200 meshes (less than or equal to 0.074 mm). On the basis, 1.5% of sodium carbonate and 2.0% of potassium chloride are added, water accounting for 65% of the total mass of the materials is added for wet ball milling after the sodium carbonate and the potassium chloride are metered and mixed together, the ball milling stone is made of high-alumina ball milling stone, the stirring speed is 85r/min, the stirring time is 38min, then the filtering is carried out, the filtered water is reused, the filter residue is dried to reach the moisture content of 7.1%, then the filter residue is put into a kiln for drying and roasting, the temperature is controlled at 1025 ℃, the roasting time is 35min, the filter residue is taken out and cooled to the room temperature, then the filter residue is crushed and sieved by a 100-mesh (0.15mm) sieve to obtain a mineral soil conditioner intermediate, and then the mineral soil conditioner intermediate is mixed with potassium fulvate, zinc sulfate, ferric sulfate, sodium selenite, borax and the like according to the mass ratio of 100: 38.35: 1.2: 4.6: 2.3 and 2.8, adding 6.3 percent of water by mass, and fully and uniformly stirring at the stirring speed of 125r/min for 30 min; fully dissolving, reacting and chelating various compounds through the wetting action, then carrying out disc granulation, controlling the particle size to be 8.5mm, drying and packaging into bags. Namely a new mineral soil conditioner.
The organic matter content of the new variety of the mineral soil conditioner is 19.35 percent, and the potassium (K) is2O) content of 3.58%, citric soluble silicon dioxide content of 10.68%, citric soluble calcium oxide content of 15.58%, citric soluble magnesium oxide content of 6.30%, available sulfur of 6.25%, available chlorine of 5.39%, available iron of 1.58%, and zinc, selenium and boron effective components, wherein the total available nutrient is more than or equal to 68.71%, and the pH value of the product is 10.85.
Example 3
In a large chemical enterprise in Hebei province, a large amount of ammonia-soda process soda white mud (caustic sludge) is produced, a limestone-gypsum method is adopted in the factory to carry out wet flue gas desulfurization, a large amount of desulfurized gypsum is produced, a compound fertilizer processing enterprise is nearby, and a large amount of phosphogypsum produced in the production process of phosphoric acid is accumulated. The potassium ore is collected from Hebei Tangshan, wherein the potassium oxide content is 9.28%, the silicon dioxide content is 64.23%, the aluminum oxide content is 13.58%, and the total content of oxides such as sodium oxide, ferric oxide, titanium dioxide, manganese dioxide, phosphorus pentoxide and the like is about 12.91%. Preparing alkali white mud according to the mass ratio: desulfurized gypsum: phosphogypsum: the mass ratio of two materials of potassium ore is 25.89: 34.59: 12.95: 26.57, and the raw materials and the auxiliary materials are all required to contain heavy metal elements meeting ecological indexes of arsenic, cadmium, lead, chromium and mercury in national standard of silicon-calcium-potassium-magnesium fertilizer (GB/T36207-2018), wherein the content (unit: mg/kg) is respectively less than or equal to 50, less than or equal to 10, less than or equal to 200, less than or equal to 500 and less than or equal to 5, and the granularity is more than or equal to 200 meshes (less than or equal to 0.074 mm). On the basis, 2.0% of sodium chloride and 3.0% of potassium carbonate are added, the sodium chloride and the potassium carbonate are metered and mixed together, water with the total material mass of about 58% is added for wet ball milling, the ball milling stone is high-alumina ball milling stone, the stirring speed is 75r/min, the stirring time is 75min, then the filtering is carried out, the filtered water can be reused, the filter residue is dried until the water content reaches 6.2%, then the filter residue is put into a kiln for drying and roasting, the roasting temperature is controlled at 998 ℃, the roasting time is 80min, the filter residue is taken out and cooled to the room temperature, then the filter residue is crushed, and the crushed filter residue is sieved by a 100-mesh (0.15mm) sieve to obtain a mineral soil conditioner intermediate, and then the mineral soil conditioner intermediate is mixed with potassium fulvate, zinc sulfate, ferric sulfate, sodium selenite, borax and the like according to the mass ratio of 100: 23.44: 3.2: 5.2: 3.5 and 5.75, adding water accounting for 5.8 percent of the total mass, and fully and uniformly stirring at the stirring speed of 140r/min for 30 min; fully dissolving, reacting and chelating various compounds through the wetting action, then carrying out disc granulation, controlling the particle size to be 11.5mm, drying and packaging into bags. Namely a new mineral soil conditioner.
The organic matter content of the new variety of the mineral soil conditioner is 17.13 percent, and the potassium (K) content of the new variety of the mineral soil conditioner is 17.13 percent2O) content of 5.52 percent, citrate soluble silicon dioxide content of 10.85 percent, citrate soluble calcium oxide content of 15.32 percent, citrate soluble magnesium oxide content of 3.23 percent, available sulfur of 4.25 percent, available chlorine of 4.78 percent, available iron of 1.65 percent, and trace element active ingredients such as zinc, selenium, boron and the like, wherein the total available nutrient is more than or equal to 62.73 percent, and the pH value of the product is 11.25.
Example 4
The enterprises of ammonia-soda process alkali production in Guangdong produce a large amount of white mud for alkali production, flue gas desulfurization facilities in factories also produce a large amount of desulfurized gypsum, and a large amount of phosphogypsum is accumulated nearby. Potassium ore is collected from the remote place, and contains 6.32% of potassium oxide, 65.11% of silicon dioxide, 17.37% of aluminum oxide, 11.2% of sodium oxide, ferric oxide and the like, and the total content of various oxides is about 100%. White mud for alkali preparation: desulfurized gypsum: phosphogypsum: the mass ratio of two materials of potassium ore is 38.46: 10.55: 5.69: 69.19, and the raw materials and the auxiliary materials are all required to contain heavy metal elements meeting ecological indexes of arsenic, cadmium, lead, chromium and mercury in national standard of silicon-calcium-potassium-magnesium fertilizer (GB/T36207-2018), wherein the content (unit: mg/kg) is respectively less than or equal to 50, less than or equal to 10, less than or equal to 200, less than or equal to 500 and less than or equal to 5, and the granularity is more than or equal to 200 meshes (less than or equal to 0.074 mm). On the basis, 1.5% of sodium carbonate and 2.0% of potassium sulfate are added, water accounting for 60% of the total mass of the materials is added after the sodium carbonate and the potassium sulfate are metered and mixed together for wet ball milling, the ball milling stone is high-alumina ball milling stone, the stirring speed is 55r/min, the stirring time is 80min, then the filtering is carried out, the filtered water is reused, the filter residue is dried to the moisture content of 6.5%, then the filter residue is put into a kiln for drying and roasting, the temperature is controlled at 975 ℃, the roasting time is 60min, the filter residue is taken out and cooled to the room temperature, then the filter residue is crushed and sieved by a 100-mesh (0.15mm) sieve to obtain a mineral soil conditioner intermediate, and then the mineral soil conditioner intermediate is mixed with potassium fulvate, zinc sulfate, ferric sulfate, sodium selenite, borax and the like according to the mass ratio of 100: 50.15: 4.5: 7.6: 4.2 and 5.5, adding water accounting for 7.5 percent of the total mass amount, and fully and uniformly stirring at the stirring speed of 140r/min for 45 min; fully dissolving, reacting and chelating various compounds through the wetting action, then carrying out disc granulation with the granularity controlled at 11mm, drying and packaging into bags. Namely a new mineral soil conditioner.
The organic matter content of the new variety of the mineral soil conditioner is 23.15 percent, and the potassium (K) is2O) content of 2.55%, citric soluble silicon dioxide content of 13.38%, citric soluble calcium oxide content of 19.18%, citric soluble magnesium oxide content of 3.59%, available sulfur of 5.27%, available chlorine of 3.78%, available iron of 0.86%, and zinc, selenium and boron effective components, wherein the total available nutrient is more than or equal to 71.76%, and the pH value of the product is 11.05.
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 soil conditioner by utilizing bulk industrial solid wastes is characterized by comprising the following steps:
(1) preparing an active mineral soil conditioner intermediate by adopting soda white mud, desulfurized gypsum, phosphogypsum, potassium ore, an additive and water through the steps of material mixing, drying, roasting, cooling and crushing;
(2) and (2) adding potassium fulvate, zinc sulfate, ferric sulfate, sodium selenite and borax auxiliary materials into the active mineral soil conditioner intermediate prepared in the step (1), adding water, stirring, and then granulating, drying and packaging the mixture to obtain the mineral soil conditioner.
2. The method according to claim 1, wherein the soda ash produced in the step (1) is caustic sludge produced in the process of producing sodium carbonate, and is a bulk industrial solid waste with a water content of 50-60%, and the solid content of the solid waste is as follows by mass percent: CaCO3 39.5～60.0％，CaSO4 2.8～20.0％，CaCl29.8～14.0％，NaCl 2.4～8.0％，CaO 3.0～8.3％，Mg(OH)2 2.0～15.4％，SiO22.5 to 9.1 percent of the total weight of the catalyst, 3.1 to 6.9 percent of other oxides and 6.0 to 10.0 percent of acid insoluble substances; the desulfurized gypsum is a byproduct of flue gas desulfurization by a gypsum method, namely lime/limestone; the phosphogypsum is solid waste phosphogypsum generated in the process of producing phosphoric acid by using apatite; the potassium ore is rock containing potassium feldspar, illite, muscovite, and leucite aluminosilicate minerals, and K is2The content of O is more than or equal to 6 percent, and the rock types comprise volcanic rock, volcanic sedimentary rock, sedimentary rock and metamorphic rock.
3. The method according to claim 1, wherein the heavy metal elements contained in the alkali-making white mud, the desulfurized gypsum, the phosphogypsum and the potassium ore in the step (1) meet the ecological indexes of arsenic, cadmium, lead, chromium and mercury in the national standard GB/T36207-2018 of the national silicon-calcium-potassium-magnesium fertilizer, the contents of the heavy metal elements are respectively less than or equal to 50mg/kg, less than or equal to 10mg/kg, less than or equal to 200mg/kg, less than or equal to 500mg/kg and less than or equal to 5mg/kg, and the granularity of the heavy metal elements is more than or equal to 200 meshes.
4. The method according to claim 1, wherein the alkali-making white mud, the desulfurized gypsum, the phosphogypsum and the potassium ore in the step (1) comprise the following components in percentage by mass: 5-50% of soda white mud, 5-50% of desulfurized gypsum, 5-50% of phosphogypsum and 5-70% of potassium ore.
5. The method according to claim 1, wherein the additive in the step (1) is prepared by mixing two of potassium sulfate, potassium chloride, potassium carbonate, sodium sulfate, sodium chloride and sodium carbonate according to a mass ratio of 1: 1-1.5, and the addition amount of the additive is 3.0-5.0 percent of the total mass of the alkali-making white mud, the desulfurized gypsum, 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 soda lime mud, the desulfurized gypsum, 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 reused; drying the filtered filter residue until the water content is 5.0-8.0%; the roasting temperature is 950 ℃ and 1025 ℃, and the roasting time is 0.5-1.5 hours.
8. The method of claim 1, wherein the mass ratio of the activated mineral soil conditioner intermediate of step (2) to the potassium fulvate, zinc sulfate, iron sulfate, sodium selenite, and borax is 100: 20.0-85.0: 1.0-5.0: 2.0-10.0: 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 active mineral substance soil conditioner intermediate, the potassium fulvate, the zinc sulfate, the ferric 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 2.0-12.0 mm.
10. A mineral soil conditioner prepared by the method of any one of claims 1 to 9, wherein the mineral soil conditioner has an organic matter content of 15.0% or more, expressed as K2The potassium content is more than or equal to 2.5 percent calculated by O, the citrate-soluble silicon dioxide content is more than or equal to 10.0 percent, the citrate-soluble calcium oxide content is more than or equal to 15.0 percent, the citrate-soluble magnesium oxide content is more than or equal to 2.0 percent, the available sulfur is more than or equal to 3.5 percent, the available chlorine is more than or equal to 3.5 percent, the available iron is more than or equal to 0.5 percent, the zinc, selenium and boron active ingredients are contained, and the total available nutrient is more than or equal to 52.0 percent.
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