阅读说明：本技术 一种利用脱硫副产物与钾矿石生产矿物质肥的方法 (Method for producing mineral fertilizer by using desulfurization by-products and potassium ore ) 是由 石林 蓝建锋 于 2021-06-24 设计创作，主要内容包括：本发明公开一种利用脱硫副产物与钾矿石生产矿物质肥的方法,所述方法包括：将脱硫副产物与钾矿石、添加剂和水,通过物料混合、过滤、烘干、焙烧、冷却、粉碎步骤,制备出矿物质肥中间体；然后加入腐殖酸、硫酸锌、硫酸铁、亚硒酸钠和硼砂,并加入水搅拌,一起进行造粒,即为一种矿物质肥。本发明的原辅料来源广泛,成本低廉,有利于实现固体废弃物的高效利用和实现经济效益的最大化。本发明的矿物质肥矿物质养分全面和平衡,养分种类齐全,可达到营养平衡的效果；对于酸性土壤的改良、补充缺失土壤矿物质以及防止土壤板结等等都具有很好的功能。(The invention discloses a method for producing mineral fertilizer by using desulfurization byproducts and potassium ore, which comprises the following steps: mixing the desulfurization by-products with potassium ore, additives and water, filtering, drying, roasting, cooling and crushing to prepare a mineral fertilizer intermediate; then adding humic acid, zinc sulfate, ferric sulfate, sodium selenite and borax, adding water, stirring, and granulating to obtain the mineral fertilizer. The invention has wide source of raw materials and auxiliary materials and low cost, and is beneficial to realizing the high-efficiency utilization of solid wastes and the maximization of economic benefits. The mineral fertilizer has comprehensive and balanced mineral nutrients and complete nutrient varieties, and can achieve the effect of nutrient balance; has good functions of improving acid soil, supplementing deficient soil minerals, preventing soil hardening and the like.)

1. A method for producing mineral fertilizer by using desulfurization byproducts and potassium ore is characterized by comprising the following steps:

(1) mixing the desulfurization by-products with potassium ore, additives and water, filtering, drying, roasting, cooling and crushing to prepare a mineral fertilizer intermediate;

(2) and (2) adding humic acid, zinc sulfate, ferric sulfate, sodium selenite and borax into the mineral fertilizer intermediate prepared in the step (1), adding water, stirring, and then granulating to obtain the mineral fertilizer.

2. The method according to claim 1, wherein in step (1), the desulfurization by-products include dry/semi-dry desulfurization ash, wet desulfurization gypsum; the potassium ore is rock containing potassium feldspar, illite, muscovite, and leucite aluminosilicate minerals, wherein 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 2, wherein the dry/semi-dry desulfurized fly ash, wet desulfurized gypsum and potassium ore are, in mass percent: 5-50% of dry/semi-dry desulfurized fly ash, 5-50% of wet desulfurized gypsum and 5-70% of potassium ore.

4. The method according to claim 1, wherein the additive in the step (1) is prepared by mixing two of sodium sulfate, potassium chloride, sodium carbonate and potassium carbonate according to a mass ratio of 1: 1.0 to 1.5; the addition amount of the additive is 3.0-5.0% of the total weight of the desulphurization by-product and the potassium ore.

5. 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 desulfurization by-products, the potassium ore and the additives; 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.

6. The method of claim 1, wherein the filtered drainage of step (1) is reused; and drying the filtered filter residue until the moisture content is 5.0-8.0%, wherein the roasting temperature is 850-1050 ℃, and the roasting time is 0.5-2.0 hours.

7. The method of claim 1, wherein the mass ratio of the mineral fertilizer intermediate in step (2) to humic acid, zinc sulfate, ferric sulfate, sodium selenite and borax is 100: 20-85: 1.0-5.0: 2-10: 1.0-5.0: 1.5-7.5.

8. The method according to claim 1, wherein the water in the step (2) is added in an amount of 3.0-8.0% of the total mass of the mineral fertilizer intermediate and humic acid, zinc sulfate, ferric sulfate, sodium selenite and borax.

9. The method as claimed in claim 1, wherein the stirring rate 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 2-12 mm; the granules are dried and bagged.

10. The mineral fertilizer prepared by the method of any one of claims 1 to 9, wherein the content of organic matters in the mineral fertilizer is not less than 5.0% by 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 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 40 percent.

Technical Field

The invention belongs to the field of agricultural resource utilization of industrial solid wastes, and particularly relates to a method for producing a mineral fertilizer by utilizing desulfurization byproducts and potassium ore.

Background

With the comprehensive development and large-scale implementation of flue gas desulfurization nationwide, a novel industrial solid waste, i.e., a desulfurization byproduct, is produced in large quantities. Of the produced desulfurization by-products, wet lime (limestone), a by-product of gypsum process (WFGD), desulfurized gypsum (CaSO)₄·2H₂O), a large amount of desulfurized ash produced by dry and semi-dry methods (including Circulating Fluidized Bed (CFB), in-furnace limestone and calcium oxide activated desulfurization (LIFAC), Novel Integrated Desulfurization (NID), in-furnace calcium injection and multistage combustor (LIMB), rotary Spray Drying (SDA), charged dry flue gas desulfurization system (CDSI), double alkali method (sodium alkali and calcium alkali), simple limestone-gypsum method, and the like. The desulfurized fly ash not only contains gypsum (CaSO) generated in the desulfurization process₄·2H₂O) and also contains incompletely oxidized calcium sulfite hemihydrate (CaSO)₃·1/2H₂O), unreacted desulfurizing agent including CaCO)₃、Ca(OH)₂、Mg(OH)₂And CaO and coal-fired fly ash components including quartz, feldspar, mullite, hematite, calcium halide (CaCl)₂And CaF₂) And unburned carbon particles, hollow microspheres, and glass bodies (wanngwenlong, trelein, machunyuan, etc. characteristics and comprehensive utilization of dry and semi-dry desulfurization ash, power plant system engineering, 2005, phase 5: 27-29).

The compositional characteristics of these desulfurized ashes greatly limit the extent and scope of their resource utilization. Firstly, as far as the application of this type of desulfurized fly ash in the cement and concrete industry is concerned, the desulfurized fly ash is produced according to the current national standard GB/T1596-2017 "fly ash for cement and concrete": SO in grade I and II ash used as active mixed material in cement production₃The content is not more than 3%; SO in grade I, II, III ashes as admixtures for the preparation of cement concretes and mortars₃The content of the organic acid is not more than 3%. SO in dry and semi-dry desulfurized fly ash₃In terms of SO₂With SO₃Total) is generally up to 6% or more, and mostly with incomplete oxygenModified CaSO₃·1/2H₂The O form exists, and great potential safety hazard exists. Secondly, in the engineering application process of using the desulfurized ash as a blending material, the existence of high content of free calcium oxide (f-CaO) can also cause the building material to absorb water and expand, emit heat and influence the stability of engineering. Thirdly, the desulfurized fly ash contains higher content of soluble compounds, including CaCl₂、CaF₂And magnesium compounds including Mg (OH)₂、MgSO₃、MgSO₄And the like, the existence of the soluble substances can reduce the gelling property and the hardening process of the cement material, so that the constructional engineering structure is damaged, and the phenomenon of 'blooming' occurs. Finally, the unburned carbon particles can reduce the stacking density of the building materials, increase the water absorption capacity, deepen the color, cause the phenomenon of uneven structure and influence the beauty and texture of the building.

Based on the reasons, the desulfurization ash can only be used for some applications with low added values, such as roadbed filling, dam cushion layer, pit and low-lying pit land backfilling, and more desulfurization ash is directly discarded or accumulated on the spot, which not only causes huge resource waste and occupies a large amount of farmlands, but also causes dust emission and causes atmospheric environmental pollution in the drought wind and sand season in the north.

In view of the application status and development trend of the flue gas desulfurization technology at home and abroad: although the limestone-gypsum method (wet method) flue gas desulfurization technology still occupies the market leading position, the problems of large investment of disposable equipment, high operating cost, difficult treatment of desulfurization waste water and the like are still very prominent. The dry and semi-dry method and the simple limestone-gypsum method desulfurization technology have the advantages of small floor area, low manufacturing cost, easy adjustment and maintenance, no desulfurization waste water discharge and the like, and are particularly suitable for small and medium boilers and old boilers needing to be reconstructed and expanded. The treatment and disposal of the desulfurized fly ash generated by the desulfurization of the flue gas always become one of the main bottlenecks which restrict the deep development and market popularization of the desulfurization technology. Therefore, the research and development of the high-efficiency utilization technology of the dry and semi-dry desulfurization ash and the wet desulfurization gypsum are significant (Yuancuoxia, summary of comprehensive utilization of the desulfurization gypsum in coal-fired power plants in China, and contemporary chemical research, 2019 (4): 39-40).

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 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 fertilizer, is beneficial to comprehensively utilizing various mineral nutrients in rocks, has good market prospect, and has obvious improvement effect on acid soil in the south; however, the calcination temperature is higher, the calcination temperature of the method is generally over 1200 ℃, the product has low water solubility and hydraulic property, and the soil is hardened by adding water and caking (dawn slow, Yongqianxi, Qimenyao, and the like, potassium feldspar potassium extraction technology advances, mineral product protection and utilization, 2020 No. 4, 172-.

Disclosure of Invention

In order to solve the defects, the invention realizes the high-efficiency resource utilization of the dry-process and semi-dry-process desulfurized fly ash, the wet-process desulfurized gypsum and the potassium ore with extremely low utilization degree at present, solves the problems of large accumulation of the desulfurized fly ash and environmental pollution, and simultaneously, the produced mineral fertilizer can be used for repairing and conditioning soil and solves the problems of acidification, hardening and low mineral nutrients of the soil.

The invention utilizes the desulfurization by-product and potassium ore to compound and produce mineral fertilizer. By introducing desulfurized ash including desulfurized gypsum, controlling working condition in combustion process, making desulfurized ash and desulfurized gypsum become auxiliary agent for decomposing potassium ore, and making potassium feldspar-CaSO₄-CaO or CaCO₃The system is carried out, so that potassium of 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 characteristic, such as calcium magnesium silicate, and the like, the reaction temperature is reduced from the original temperature of more than 1200 ℃ to 950-1050 ℃, the nutrients of the obtained roasted product are more balanced, and the mineral solubility of the product is increased.

The invention aims to provide a method for producing mineral fertilizer by using desulfurization byproducts and potassium ore; the production raw materials are raw and auxiliary materials such as desulfurization by-products and potassium ores generated by flue gas desulfurization, and the produced product can be used for soil conditioning, particularly provides a large amount of medium and trace element minerals and organic matters for soil, and is a powerful supplement for 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 purpose of the invention is realized by the following technical scheme:

a method for producing mineral fertilizer by using desulfurization byproducts and potassium ore comprises the following steps:

(1) mixing the desulfurization by-products with potassium ore, additives and water, filtering, drying, roasting, cooling and crushing to prepare a mineral fertilizer intermediate;

(2) and (2) adding humic acid, zinc sulfate, ferric sulfate, sodium selenite and borax into the mineral fertilizer intermediate prepared in the step (1), adding water, stirring, and then granulating to obtain the mineral fertilizer.

Preferably, in step (1), theThe desulfurization byproducts comprise dry method/semi-dry method desulfurization ash and wet method desulfurization gypsum; the potassium ore is rock containing potassium feldspar, illite, muscovite, and leucite aluminosilicate minerals, wherein 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.

Further preferably, the dry/semi-dry desulfurization ash, the wet desulfurization gypsum and the potassium ore are as follows by mass percent: 5-50% of dry/semi-dry desulfurized fly ash, 5-50% of wet desulfurized gypsum and 5-70% of potassium ore.

Preferably, the additive in the step (1) is formed by mixing two of sodium sulfate, potassium chloride, sodium carbonate and potassium carbonate, and the mixing ratio is 1: 1.0 to 1.5;

preferably, the additive is added in an amount of 3.0 to 5.0% by weight based on the total weight of the desulfurization by-products and the potassium ore.

Preferably, the adding amount of the water in the step (1) is 50-70% of the total mass of the desulfurization by-products, the potassium ore and the additives;

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 850-.

Preferably, the mass ratio of the mineral fertilizer intermediate in the step (2) to humic acid, zinc sulfate, ferric sulfate, sodium selenite and borax is 100: 20-85: 1.0-5.0: 2-10: 1.0-5.0: 1.5-7.5.

Preferably, the adding amount of the water in the step (2) is 3.0-8.0% of the total mass of the mineral fertilizer intermediate, humic acid, zinc sulfate, ferric sulfate, sodium selenite and borax.

Preferably, the stirring speed in the step (2) is 100-145r/min, and the stirring time is 20-45 min;

preferably, the granulation is disc granulation, and the granularity is controlled to be 2-12 mm; the granules are dried and bagged.

The mineral fertilizer prepared by the method has the organic matter content of more than or equal to 5.0 percent and 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 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 40 percent.

The reaction mechanism created by the invention is as follows: the dry and semi-dry desulfurized fly ash mainly comprises two types of calcium-based compounds, one type is CaCO₃、Ca(OH)₂And CaO, both of which undergo decarburization and dehydration reaction during calcination, 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), also including wet desulfurized gypsum and calcium sulfite hemihydrate (CaSO)₃.1/2H₂O), the compounds can realize desulfurization and oxidation in an oxidizing atmosphere at 450-600 ℃, and are converted into CaSO₄. Therefore, under the oxidizing roasting atmosphere below 1000 ℃, the final products of the dry-method and semi-dry-method desulfurized ash and the wet-method desulfurized gypsum are 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 that the reaction temperature is 950-1050 ℃, the collected related potassium ore-CaSO₄Delta G of a series of chemical reactions which may occur in CaO systems_T0The value calculation shows that: delta G thereof_T0The 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 desulfurized fly ash, desulfurized gypsum and potassium ore with low utilization value can be converted into mineral fertilizer intermediates with higher added value, and organic matters, zinc, iron, selenium, boron and other trace element components are mixed, so that a new variety of soil conditioner 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.

The invention can be applied to the treatment of the desulfurized ash and desulfurized gypsum which are produced in large quantity and wide range in the domestic calcium method flue gas desulfurization process. 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 produced raw and auxiliary materials are mainly bulk industrial solid wastes, including dry-method and semi-dry-method desulfurized ash, desulfurized gypsum, 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 fertilizer produced by the invention has comprehensive and balanced mineral nutrients. The mineral contains calcium, potassium, sodium, silicon, magnesium, sulfur, iron, selenium, zinc, boron, organic matter 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 process flow diagram of the method for producing mineral fertilizer by using raw and auxiliary materials such as desulfurization by-products and potassium ore.

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 schematic process flow diagram of a method for producing mineral fertilizer by using raw and auxiliary materials such as desulfurization by-products and potassium ore is described in detail as follows:

step 1: preparing a mineral fertilizer intermediate by mixing, filtering, drying, roasting, cooling, crushing and other steps of dry-process and semi-dry-process desulfurized ash, wet-process desulfurized gypsum and other raw and auxiliary materials such as potassium ore, additives and the like;

step 2: and (3) adding auxiliary materials such as humic acid, zinc sulfate, ferric sulfate, sodium selenite, borax and the like into the active mineral substance fertilizer intermediate prepared in the step (1), adding a proper amount of water, stirring, fully wetting, and then granulating to obtain the mineral substance fertilizer. 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 humus, has complete nutrient components and is a new variety of mineral fertilizers with extremely high cost performance.

Further, in the step 1, the desulfurization byproducts include dry and semi-dry desulfurization ash, wet desulfurization gypsum, and the like; 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. The used additives comprise 6 of sodium sulfate, potassium chloride, sodium carbonate, potassium carbonate and a mixture thereof, and the mineral fertilizer intermediate is prepared by the steps of material mixing, filtering, drying, roasting, cooling, crushing and the like. Wherein the raw and auxiliary materials comprise the following components in percentage by mass: dry and semi-dry desulfurized fly ash: 5-50%, wet desulfurization gypsum: 5-50%, potassium ore: 5-70%, 6 additives of sodium sulfate, potassium chloride, sodium carbonate and potassium carbonate, wherein the used additive is prepared by mixing two of the 6 additives in a weight ratio of 1: 1 to 1.5 percent of additive, the addition amount of which is 3.0 to 5.0 percent of the total weight of other raw and auxiliary materials, and adding water accounting for 50 to 70 percent of the total mass, fully and uniformly stirring, the stirring speed is 50 to 90r/min, the stirring time is 20 to 120min, then filtering, filtering water for repeated use, drying filter residues until the water content is 5.0 to 8.0 percent, then roasting, the roasting temperature is 850 ℃ and 1050 ℃, and the roasting time is 0.5 to 2.0 hours.

Further, mixing the mineral fertilizer intermediate prepared in the step 1 with humic acid, zinc sulfate, ferric sulfate, sodium selenite, borax and the like in a weight ratio of 100: 20-85: 1.0-5.0: 2-10: 1.0-5.0 and 1.5-7.5, adding water accounting for 3.0-8.0 percent of the total mass amount, fully and uniformly stirring, wherein the stirring speed is 100-; fully dissolving, reacting and chelating various compounds through the wetting action, then carrying out disc granulation with the granularity controlled at 2-12mm, drying and packaging into bags. Namely a new mineral fertilizer variety.

Further, the new mineral fertilizer variety prepared in the step (2) is characterized in that the organic matter content in the variety is more than or equal to 5.0%, 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 iron is more than or equal to 0.5 percent, and the fertilizer contains trace element components such as zinc, selenium, boron and the like, and total available nutrients are more than or equal to 40 percent.

Example 1

In a coal-fired power plant in Shandong, dry-process/semi-dry-process flue gas desulfurization is carried out by adopting slaked lime, and desulfurized ash is obtained by collecting dust by a cloth bag; in addition, the lime/limestone-gypsum method is also adopted to implement wet flue gas desulfurization, and a large amount of desulfurized gypsum is also generated. The potassium ore is collected from Shandong tobacco platform, and contains potassium oxide 14.35%, silicon dioxide 66.59%, aluminum oxide 17.16%, sodium oxide, iron oxide, etc. about 2%, and total oxide content 100%. Dry/semi-dry desulfurized fly ash: wet desulfurization of gypsum: the two materials of the potassium ore are 21.0: 24.60: 54.40, adding 2.0% of calcium chloride and 2.5% of sodium sulfate as additives, metering and mixing the materials together, adding water accounting for 60% of the total mass of the materials, carrying out wet ball milling, wherein the ball milling stone is high-alumina ball milling stone, the stirring speed is 55r/min, the stirring time is 80min, filtering, repeatedly using filtered water, drying filter residues until the moisture content is 5.5%, roasting in a kiln, controlling the temperature at 1005 ℃ for 80min, taking out and cooling to room temperature, crushing, sieving by a 100-mesh (0.15mm) sieve to obtain a mineral fertilizer intermediate, mixing with humic acid, zinc sulfate, ferric sulfate, sodium selenite, borax and the like according to the mass ratio of 100: 25.60: 4.0: 3.0: 2.0 and 2.5, adding water accounting for 6.0 percent of the total mass amount, and fully and uniformly stirring at the stirring speed of 120r/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 5.0mm, drying and packaging into bags. Namely a new mineral fertilizer variety.

The prepared new variety of mineral fertilizer contains 10.25 percent of organic matter and potassium (K)₂O) content of 5.52 percent, citrate soluble silicon dioxide content of 13.56 percent, citrate soluble calcium oxide content of 19.56 percent, citrate soluble magnesium oxide content of 4.32 percent, available sulfur of 4.90 percent, available iron of 0.75 percent, and trace elements such as zinc, selenium, boron and the like, wherein the total available nutrient is not less than 58.86 percent, and the pH value of the product is 10.85.

Example 2

A certain coal-fired boiler plant in Shanxi adopts a dry method/semi-dry method to implement flue gas desulfurization, and desulfurized ash generated by dust collection through a cloth bag; in addition, the lime/limestone-gypsum method is also adopted to implement wet flue gas desulfurization, and a large amount of desulfurized gypsum is generated. The potassium ore is collected from Shanxi Xiyang county, wherein the potassium oxide content is 6.75%, the silicon dioxide is 64.12%, the aluminum oxide content is 15.23%, and the potassium ore also contains about 13.90% of sodium oxide, ferric oxide, phosphorus pentoxide, manganese oxide and the like, and the total content is close to 100%. Dry/semi-dry desulfurized fly ash: wet desulfurization of gypsum: the mass ratio of two materials of potassium ore is 24.0: 32.83: 43.17, adding 1.5% of calcium fluoride and 3.5% of potassium sulfate, metering and mixing, adding water accounting for 55% of the total mass of the materials, performing wet ball milling, wherein the ball milling stone is high-alumina ball milling stone, homogenizing fully, stirring at a speed of 75r/min for 45min, filtering, reusing filtered water, drying filter residues until the water content is 7.5%, roasting in an activation kiln, controlling the temperature at 998 ℃, roasting for 80min, taking out the roasted product, cooling to room temperature, crushing, sieving all the roasted products with a 100-mesh (0.15mm) sieve to obtain a mineral fertilizer intermediate, mixing with humic acid, zinc sulfate, ferric sulfate, sodium selenite, borax and the like according to a mass ratio of 100: 15.30: 2.0: 5.0: 2.0 and 3.0, adding water accounting for 7.5 percent of the total mass amount, and fully and uniformly stirring at the stirring speed of 115r/min for 25 min; through wetting, various compounds are fully dissolved, reacted and chelated, then the disc granulation is carried out, the granularity is controlled to be 2.0mm, and the dried compound is packaged into a bag. Namely a new mineral fertilizer variety.

The prepared new variety of mineral fertilizer contains 8.85% of organic matter and potassium (K)₂O) content 3.14%, citrate soluble silicon dioxide content 12.78%, citrate soluble calcium oxide content 33.31%, citrate soluble magnesium oxide content 5.80%, available sulfur 10.54%, available iron 3.75%, and trace elements such as zinc, selenium, boron, etc., wherein the total available nutrient is more than or equal to 68.17%, and the pH value of the product is 9.95.

Example 3

50-ton coal-fired boilers of certain chemical plants in Jiangsu province adopt a dry method/semi-dry method (spray drying method (SDA)) to implement flue gas desulfurization; a certain nearby coal-fired power plant adopts a lime/limestone-gypsum method to implement wet flue gas desulfurization, so that a large amount of desulfurized gypsum is generated; the potassium ore is collected from Shandongtai' an, wherein the potassium oxide content is 6.33%, the silicon dioxide content is 68.14%, the aluminum oxide content is 13.56%, and the potassium ore also contains about 11.97% of sodium oxide, calcium oxide, magnesium oxide, iron oxide, phosphorus pentoxide, titanium dioxide, manganese dioxide and the like, and the total content of various oxides is close to 100%. Desulphurizing the ash according to a dry/semi-dry process: wet desulfurization gypsum: the mass ratio of potassium ore is 45.5: 7.2: 47.3, adding additives of sodium carbonate and potassium sulfate, wherein the contents of the sodium carbonate and the potassium sulfate are respectively 2.0% and 3.0%, ball-milling the mixture in a ball mill, adding water with the total mass of about 64%, putting ball-milling stones into the ball mill for wet ball-milling, wherein the ball-milling stones are high-alumina ball-milling stones, stirring at the speed of 80r/min for 110min, filtering, repeatedly using filtered water, drying filter residues to the moisture content of 6.0%, roasting in a kiln at the temperature of 1028 ℃ for 25min, taking out the roasted products, cooling to room temperature, crushing, sieving all the roasted products with a 100-mesh (0.15mm) sieve to obtain mineral fertilizer intermediates, and then mixing the mineral fertilizer intermediates with humic acid, zinc sulfate, ferric sulfate, sodium selenite, borax and the like according to the mass ratio of 100: 44.18: 1.5: 4.5: 1.5 and 2.5, adding 6.5 percent of water by mass, and fully and uniformly stirring at the stirring speed of 120r/min for 37 min; fully dissolving, reacting and chelating various compounds through the wetting action, then carrying out disc granulation, controlling the particle size to be 1.0mm, drying and packaging into bags. Namely a new mineral fertilizer variety.

The prepared new variety of mineral fertilizer has 28.11 percent of organic matter content and potassium (K)₂O) content is 2.78%, citrate soluble silicon dioxide content is 11.68%, citrate soluble calcium oxide content is 15.57%, citrate soluble magnesium oxide content is 4.37%, available sulfur is 5.31%, available iron is 2.05%, and the product is rich in microelements of zinc, selenium and boron, total available nutrient is not less than 69.87%, and pH value of the product is 10.88.

Example 4

A certain papermaking enterprise in Guangdong adopts a dry method/semi-dry method to implement flue gas desulfurization, and generates a large amount of desulfurized ash; a certain nearby coal-fired power plant adopts a lime/limestone-gypsum method to implement wet flue gas desulfurization, so that a large amount of desulfurized gypsum is generated; the potassium ore is collected from Guangdong Qingyuan, wherein the potassium oxide content is 5.44%, the silicon dioxide content is 70.65%, the aluminum oxide content is 18.79%, the potassium ore also contains about 5.12% of sodium oxide, calcium oxide, magnesium oxide, iron oxide, phosphorus pentoxide, titanium dioxide, manganese dioxide and the like, and the total content of various oxides is close to 100%. According to the desulfurization ash: desulfurized gypsum: the mass ratio of potassium ore is 31.5: 27.3: 41.2, adding additives of sodium carbonate and potassium sulfate, wherein the contents of the sodium carbonate and the potassium sulfate are respectively 2.0% and 3.0%, ball-milling the mixture in a ball mill, adding water with the total mass of about 55%, putting ball-milling stones into the ball mill for wet ball-milling, wherein the ball-milling stones are high-alumina ball-milling stones, the stirring speed is 75r/min, the stirring time is 100min, filtering, repeatedly using filtered water, drying filter residues to the moisture content of 5.7%, then putting the filter residues into a kiln for roasting, controlling the temperature at 1005 ℃, controlling the roasting time to be 37min, taking out the roasted products, cooling the roasted products to the room temperature, crushing, sieving all the roasted products with a 100-mesh (0.15mm) sieve to obtain mineral fertilizer intermediates, and then mixing the mineral fertilizer intermediates with humic acid, zinc sulfate, ferric sulfate, sodium selenite, borax and the like according to the mass ratio of 100: 45.2: 2.3: 5.5: 1.8 and 2.9, adding water accounting for 5.5 percent of the total mass amount, and fully and uniformly stirring at the stirring speed of 115r/min for 40 min; fully dissolving, reacting and chelating various compounds through the wetting action, then carrying out disc granulation, controlling the particle size to be 5.0mm, drying and packaging into bags. Namely a new mineral fertilizer variety.

The prepared new variety of mineral fertilizer has the organic matter content of 21.32 percent and potassium (K)₂O) content of 3.89%, citric soluble silicon dioxide content of 14.78%, citric soluble calcium oxide content of 17.98%, citric soluble magnesium oxide content of 5.44%, available sulfur of 5.28%, available iron of 1.35%, and rich in microelements zinc, selenium and boron, wherein the total available nutrient is not less than 70.04%, and the pH value of the product is 10.75.

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.