WO2021017215A1 - 一种利用粉煤灰生产的矿物质土壤调理剂及其制备方法 - Google Patents

一种利用粉煤灰生产的矿物质土壤调理剂及其制备方法 Download PDF

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WO2021017215A1
WO2021017215A1 PCT/CN2019/113504 CN2019113504W WO2021017215A1 WO 2021017215 A1 WO2021017215 A1 WO 2021017215A1 CN 2019113504 W CN2019113504 W CN 2019113504W WO 2021017215 A1 WO2021017215 A1 WO 2021017215A1
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fly ash
acid
soil conditioner
content
based compound
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French (fr)
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石林
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华南理工大学
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    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D1/00—Fertilisers containing potassium
    • C05D1/005—Fertilisers containing potassium post-treatment
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01B—SOIL WORKING IN AGRICULTURE OR FORESTRY; PARTS, DETAILS, OR ACCESSORIES OF AGRICULTURAL MACHINES OR IMPLEMENTS, IN GENERAL
    • A01B79/00—Methods for working soil
    • A01B79/02—Methods for working soil combined with other agricultural processing, e.g. fertilising, planting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C1/00—Reclamation of contaminated soil
    • B09C1/08—Reclamation of contaminated soil chemically
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D1/00—Fertilisers containing potassium
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D1/00—Fertilisers containing potassium
    • C05D1/02—Manufacture from potassium chloride or sulfate or double or mixed salts thereof
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D3/00—Calcareous fertilisers
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/80—Soil conditioners
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00—Soil-conditioning materials or soil-stabilising materials
    • C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
    • C09K17/04—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only applied in a physical form other than a solution or a grout, e.g. as granules or gases
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00—Soil-conditioning materials or soil-stabilising materials
    • C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2101/00—Agricultural use
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2109/00—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE pH regulation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Definitions

  • the invention relates to the technical field of agricultural resource utilization of fly ash, in particular to a mineral soil conditioner produced by using fly ash and a preparation method thereof.
  • fly ash contains a large amount of heavy metals such as arsenic, lead, cadmium, chromium and mercury that are harmful to human health, it has caused great harm to the environment, and its low effective nutrients limit its comprehensive utilization in agriculture. effectiveness.
  • the pollution caused by fly ash is mainly manifested in the following aspects: (1) Polluted soil: When the heavy metal elements of fly ash enter the soil and exceed its critical value, the soil will output pollutants to the environment and pollute other environmental elements. , Soil composition, structure and function will change, which may eventually lead to the depletion and destruction of soil resources. The results of the study showed that compared with the blank group, the contents of various heavy metals in the experimental group with fly ash were generally increased, and the soil air permeability and drainage became worse.
  • Polluted water bodies Fly ash enters rivers and lakes with rainwater, surface runoff or wind, will pollute surface water, and rainwater will infiltrate the soil, causing groundwater pollution.
  • fly ash Due to its fine particle size, developed pores, large specific surface area, and strong water absorption, fly ash can improve soil structure, reduce bulk density, increase porosity, increase ground temperature, and reduce expansion rate, especially for improving the physical properties of clayey soil. It is also conducive to moisture preservation, enhancement of microbial activity in the soil and promotion of nutrient conversion, so that water, fertilizer, gas and heat tend to be coordinated, and create a good soil environment for crop growth.
  • Nanchang Power Plant's fly ash soil modification test showed that: the weight ratio of ash-soil ratio of 6.5% can reduce the soil bulk density from 1.36g/cm 3 to 1.26g/cm 3 .
  • fly ash can improve the soil structure by increasing the number of> 1mm water-stable aggregates in the soil.
  • the pot experiment of rice shows that applying 5000 kg fly ash per mu can reduce the physical clay particles ⁇ 0.01 mm in the clay soil from 44.65% to 41.97%, and the content of soil clay particles decreases with the increase of ash application, showing significant The linear negative correlation.
  • the soil porosity decreases with the increase of ash application, and there is a significant positive correlation.
  • Measurements by Northwest Agricultural College showed that: applying 1.5 tons of fly ash per mu, the soil expansion rate was reduced from 7.1% to 4.99%, which helped prevent soil loss.
  • Studies in the states of Pennsylvania and Delaware in the United States show that fly ash can improve the water holding capacity of sandy soil and increase its drought resistance.
  • fly ash contains Si, Al, Fe, Ca, Mg, K, Na, Ti, P, B, Cu, Mo, Zn, Mn and many other large, medium and trace mineral elements, which affect the soil nutrients.
  • the increase in content is beneficial.
  • Shanxi Province applied 5 to 60 tons of ash per mu on the fluvo-aquic soil.
  • the average available phosphorus content measured in 94 fly ash soils was 26.2 mg/kg, which was an increase of 35.1% compared to the ash-free control soil (average 19.4 mg/kg).
  • fly ash is rich in boron and is a good source of fertilizer for oil crops, the yield and quality of peanuts and soybeans grown on the soil improved by fly ash have been significantly improved.
  • the combined application of fly ash and humic acid can increase the content of available silicon in the soil.
  • the available silicon content in the soil increased from 1.07, 0.52, and 1.4 mg/kg to 1.9, 2.0, and 7.4 mg/kg, respectively.
  • the application of fly ash can improve the soil microbial activity.
  • the albic soil test shows that the microbial activity of the soil root layer during the flowering period of soybeans is significantly enhanced, and continues to the seed maturity period. Bacteria, actinomycetes and fungi all show a consistent growth trend , Is conducive to promoting the humification process of the organic components of grass carbon in the soil, creating good soil environmental conditions for the growth and development of crops.
  • Northwest Agricultural College applied 5 to 15 tons of fly ash per mu on the cinnamon soil, which increased the yield of wheat by 10.2% and corn by 8.4%.
  • the field test of using fly ash to improve the salinized moist initiation soil showed that: applying 20 tons of fly ash per hectare, rice and wheat have a very significant yield increase effect.
  • fly ash can not only increase the yield by 5%, but also increase the crude protein and fat content of soybeans.
  • fly ash contains trace elements such as zinc, copper, boron, molybdenum, iron, etc., it can be processed into high-efficiency compound fertilizer.
  • Japan uses fly ash to make silicic acid fertilizers, such as fly ash potassium silicate fertilizer prepared by mixing fly ash and caustic potash, containing K 2 O 20%, SiO 2 35%, MgO 4%, B 2 O 3 0.1%, CaO 8%, the fertilizer is easily soluble in acid but not water, non-hygroscopic, not lost due to rain, and has a long fertilizer effect.
  • fly ash compound fertilizer produced by the Henan Academy of Agricultural Sciences can increase the yield of wheat by 17.7-88%, corn by 26.5-67.2%, rice by 2.8-25.6%, and peanut by 12-24.2%; Compared with compound fertilizer, the yield of various crops increased between 2.0% and 13.5%.
  • the fly ash multi-element compound fertilizer developed by Hefei University of Technology is superior to conventional fertilization with equal nutrients and 25% low-concentration three-element compound fertilizer through field experiments, increasing the production by 19.1% and 8.9%, respectively.
  • fly ash contains heavy metal elements such as arsenic, mercury, chromium, cadmium, and lead, and often exceeds the limit standard value of heavy metal in agricultural fly ash. Large amounts of farmland use will pollute the soil and enter the human body through the food chain.
  • Low mineral active ingredients Although fly ash contains a lot of mineral elements, its effectiveness is poor. The nutrients in fly ash are almost completely insoluble in water, and the solubility in weakly acidic solutions does not exceed 20%, which greatly increases the amount of use in farmland. .
  • the purpose of the present invention is to aim at the low efficiency of existing fly ash resource utilization and insufficient technological level.
  • the present invention provides a mineral soil conditioner produced by using fly ash and a preparation method thereof. It can be summarized as follows: by adding various heteroacidic solvents to fly ash to dissolve heavy metal elements in fly ash, and then using sodium sulfide solution to precipitate acid-soluble heavy metal ions, so that the acidic heteroacid solvent is reused.
  • the selected fly ash after removing heavy metals, and then adding calcium-based compounds, potassium-based compounds and other substances to it, together with mixing, drying and roasting activation, to obtain silicon calcium potassium magnesium as the main mineral nutrients, with weak alkali characteristics Mineral soil conditioner.
  • a preparation method of a mineral soil conditioner produced by using fly ash includes the following steps:
  • step (1) Fully mix the selected fly ash obtained by filtration in step (1) with calcium-based compounds and potassium-based compounds, and then dry them after granulation;
  • the hetero acid is a mixed acid of any two or more of humic acid, hydrochloric acid, hydrofluoric acid, sulfuric acid, nitric acid, perchloric acid, citric acid, formic acid, acetic acid, or tartaric acid, and
  • concentration of each acid is 0.1 ⁇ 1mol/L.
  • the miscellaneous acid can dissolve the heavy metals in the fly ash and convert them into water-soluble heavy metals; the solid-liquid mixing ratio of the fly ash and the miscellaneous acid is 1:0.1 ⁇ 1:10g/ mL;
  • the ultrasound time is 1-30 minutes.
  • step (1) in order to remove heavy metals and recover miscellaneous acids, it also includes adding sodium sulfide solution to the filtrate obtained in step (1), conditioning and stirring, and filtering, and heavy metals are removed in the form of heavy metal sulfide precipitation; the concentration of the sodium sulfide solution It is 0.1-5mol/L, and the pH of the filtrate after conditioning is 4.0-9.5.
  • the filtrate obtained after adding the sodium sulfide solution is recycled for secondary use, supplemented with miscellaneous acid to restore the concentration of miscellaneous acid in step (1), and then continue to implement the ultrasonic stirring filtration in step (1) to dissolve the fly ash again
  • the heavy metals are selected from fly ash.
  • the heavy metal-containing filter residue obtained after sodium sulfide precipitation and filtration is washed at least 3 times with water, and then the filter residue is treated as hazardous industrial solid waste for landfill treatment, and the water content of the filter residue is limited to below 40%.
  • the precipitation rate of heavy metals precipitated into filter residue reaches more than 90%.
  • the mass ratio of the washing amount to the heavy metal sulfide precipitate that is, the liquid/solid ratio is 0.1:1 to 1:10.
  • the stirring rate is 50-200 r/min, and the stirring time is 10-120 minutes.
  • the calcium-based compound is a mixture of two or more CaCO 3 , Ca(OH) 2 , CaCl 2 or CaMg[CO 3 ] 2 ;
  • the potassium-based compound is KOH, KCl, K 2 SO 4 or K 2 CO 3 ;
  • the mixed mass fraction of the filter residue, calcium-based compound and potassium-based compound obtained after step (1) filtration is: the filter residue obtained after step (1) filtration is 10% ⁇ 70 %, add calcium-based compound 10% ⁇ 70%, potassium-based compound 10% ⁇ 70%.
  • the mixing time of the filter residue, the calcium-based compound, and the potassium-based compound obtained after the step (1) suction filtration is 10 to 120 minutes; water is added before the granulation to the step (1) after the suction filtration
  • the filter residue, calcium-based compound and potassium-based compound are granulated when the water content of the filter residue, calcium-based compound and potassium-based compound is 5-8wt%, the particle size is 0.3-5.5 cm, and the drying time is 30-300 minutes, so that the moisture content of the dried material is less than 1.5wt%.
  • the roasting temperature is 800-1050°C, take it out and cool it, ball mill it into a powdery mineral soil conditioner, or continue to add 5-8wt% water after cooling.
  • the disc is granulated into a granular mineral soil conditioner, and the particle size of the soil conditioner is 0.3-5.5 cm.
  • the water content is less than 2wt%, the content of citrate soluble silica is more than 15wt%, the content of citrate soluble calcium oxide is more than 25wt%, the content of citrate soluble potassium oxide is more than 4wt%, and the content of citrate soluble magnesium oxide is more than 4wt%.
  • the content is greater than 2wt%, the content of citrate soluble sulfur trioxide is greater than 2wt%, the total effective components of nutrients are not less than 80wt%, and the pH is 9-12.
  • the particle size of the obtained mineral soil conditioner is 0.5-2 cm.
  • the present invention has the following advantages and innovations:
  • the main raw material of the present invention is fly ash, which is industrial solid waste obtained after coal combustion.
  • the heavy metals contained in the fly ash are extracted and the residue is made into a mineral soil conditioner, which can reduce the content of fly ash.
  • Heavy metal content (the removal rate of heavy metals in the present invention is as high as 50% or more), reaching the limit standard for agricultural fly ash; improve the efficient comprehensive utilization of fly ash, reduce the harm of heavy metals in fly ash, and increase the level of mineral content to reduce The amount of farmland, thereby generating greater economic benefits;
  • the selected fly ash after heavy metal removal is made into a mineral soil conditioner to realize the secondary utilization of pollutants and conform to the scientific concept of circular economy development and sustainable development.
  • the mineral soil conditioner prepared by the present invention contains silicon, calcium, magnesium, potassium, sodium, sulfur and many trace elements.
  • the nutrient types are complete, which can achieve the effect of balanced fertilization, thereby comprehensively improving the soil
  • the content of mineral elements and the quality of the soil environment reduce the amount of farmland, resulting in greater economic benefits.
  • the mineral soil conditioner product prepared by the present invention is weakly alkaline and has obvious improvement and restoration effects on acid soil.
  • Fig. 1 is a schematic diagram of a process flow diagram of using fly ash to produce a mineral soil conditioner in an embodiment.
  • FIG. 1 it is a schematic diagram of the process flow of the present invention for producing mineral soil conditioner by using fly ash.
  • the specific flow is as follows:
  • the obtained filtrate can be reused after supplementing a part of the consumption of 3-6% of the miscellaneous acid, and the filter residue containing heavy metal sulfide can be discarded as a hazardous solid
  • the material is processed and disposed; in the selected fly ash, calcium-based compounds and potassium-based compounds are added and mixed uniformly, dried, granulated, activated, cooled, crushed and packaged to obtain mineral soil conditioners.
  • fly ash is used to produce mineral soil conditioners.
  • a thermal power plant in Inner Mongolia has an annual output of 1 million tons of fly ash, of which the content of silica is 57.67wt%, the content of potassium oxide is 0.42wt%, the content of alumina is as high as 17.32wt%, the content of calcium oxide is 2.15wt%, and the content of iron oxide It is 1.35% by weight, and the heavy metal content is: lead content 121.73mg/kg, cadmium content 2.15mg/kg, mercury content 0.74mg/kg, copper content 7.97mg/kg.
  • the operation process is:
  • step (2) Add a sodium sulfide solution with a concentration of 0.15 mol/L to the filtrate obtained after filtration in step (1), and the pH after conditioning is 5.5. After stirring for 85 minutes at the speed of 150r/min stirrer, filter it; then wash the sulfide heavy metal slag with clean water 3 times. The precipitation rate of lead, cadmium, mercury and copper in the filtrate reaches more than 90%; the filtrate needs to remove heavy metals The miscellaneous acid is supplemented to restore the concentration of the miscellaneous acid in step (1) for recycling.
  • step (3) For the selected fly ash filter residue obtained after filtration in step (1), calcium carbonate, calcium hydroxide and potassium hydroxide are added and mixed, and the mixing mass ratio is: the filter residue obtained after step (1) suction filtration 45 %, calcium carbonate 25%, calcium hydroxide 20%, and potassium hydroxide 10%; after stirring evenly, use the kiln exhaust gas to dry for 70 minutes, roast the dried sample at 900°C for 30 minutes, and cool to room temperature. After crushing and sieving 100 meshes, a soil conditioner rich in mineral elements is obtained.
  • the total mineral nutrient content of the soil conditioner produced is 84.35wt%, of which the effective silica content is 15.34wt%, the effective calcium oxide content is 26.87wt%, and the effective magnesium oxide is 5.82wt%.
  • the potassium oxide content is 4.75 wt%, the effective sodium oxide content is 2.74 wt%, and the pH value is 10.5. It is a soil conditioner containing a variety of minerals.
  • a thermal power plant in Liaoning has an annual output of 1.6 million tons of fly ash, of which silica content is 52.67 wt%, alumina content is 21.76 wt%, potassium oxide content is 0.72 wt%, calcium oxide content is 3.15 wt%, and iron oxide content is 3.57% by weight, of which heavy metal content is: lead content 101.30mg/kg, cadmium content 1.71mg/kg, mercury content 0.78mg/kg, copper content 19.48mg/kg.
  • the operation process is:
  • step (2) Add a sodium sulfide solution with a concentration of 0.25 mol/L to the filtrate obtained in step (1), control the pH of the conditioning solution to be 6.7, stir for 25 minutes at a 90r/min stirrer speed, and then filter;
  • the sulfide heavy metal slag was washed with clean water three times, and the precipitation rate of lead, cadmium, mercury, and copper in the filtrate reached 92% or more; the filtrate after removing heavy metals needs to be supplemented with miscellaneous acid to restore to the concentration of miscellaneous acid mentioned in step (1) recycle.
  • step (3) Add calcium chloride, dolomite and potassium carbonate to the selected fly ash filter residue obtained after filtration in step (1), and the mixing mass ratio is: 35% of the filter residue obtained after step (1) suction filtration , Calcium chloride 35%, dolomite 20%, potassium carbonate 10%; after stirring evenly, dry at 105°C for 45 minutes, roast the dried sample at 870°C for 2h, cool to room temperature, break it Sieve 100 meshes to obtain a soil conditioner rich in mineral elements.
  • the total mineral nutrient content of the soil conditioner produced is 82.01wt%, of which the effective silica content is 17.98wt%, the effective calcium oxide content is 31.09wt%, and the effective magnesium oxide is 6.16wt%.
  • the potassium oxide content is 6.21wt% and the pH value is 11.1. It is a soil conditioner containing a variety of minerals.
  • a thermal power plant in Hebei province has an annual output of 3 million tons of fly ash, of which the silica content is 46.67wt%, alumina content is 15wt%, potassium oxide content is 0.92wt%, calcium oxide content is 6.15wt%, and iron oxide content is 2.71wt%, of which heavy metal content is: lead content 71.73mg/kg, cadmium content 1.13mg/kg, mercury content 1.07mg/kg, copper content 38.02mg/kg.
  • the operation process is:
  • step (2) Add a sodium sulfide solution with a concentration of 2mol/l to the filtrate obtained in step (1), and control the pH of the conditioning solution to be 7.2 (after stirring at 77r/min agitator speed for 45 minutes, then filter; then use clean water) Washing the sulfide heavy metal residue 3 times, the precipitation rate of lead, cadmium, mercury, and copper in the filtrate reaches 91% or more, and then is landfilled, and the water content of the filter residue is limited to 40wt% or less; the filtrate after removing heavy metals needs The miscellaneous acid is supplemented to restore the concentration of the miscellaneous acid in step (1) for recycling.
  • the total mineral nutrients in the soil conditioner produced are 82.93wt%, of which the effective silica content is 17.46wt%, the effective calcium oxide content is 31.04wt%, and the effective magnesium oxide is 8.12wt%.
  • the potassium oxide content is 5.18 wt%, the effective sodium oxide content is 1.94 wt%, and the pH value is 11.8. It is a soil conditioner containing a variety of mineral nutrients.

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Abstract

本发明公开一种利用粉煤灰生产矿物质土壤调理剂及其制备方法。所述制备方法包括：（1）将粉煤灰与杂酸混合，在超声作用下，搅拌过滤，得到精选粉煤灰和滤液；（2）将步骤（1）滤得的精选粉煤灰与钙基化合物、钾基化合物充分混合，造粒后再用窑炉尾气余热烘干；（3）在步骤（2）中造粒烘干后继续在窑炉中焙烧活化，经冷却、球磨、成型加工，得到上述的矿物质土壤调理剂。本发明实现了燃煤副产物——粉煤灰的农业高效利用，减少了粉煤灰中重金属含量及其带来的环境毒害；制得的矿物质土壤调理剂矿质养分齐全，达到了平衡施肥的目的。

Description

一种利用粉煤灰生产的矿物质土壤调理剂及其制备方法 技术领域
本发明涉及粉煤灰的农业资源化利用技术领域，具体涉及一种利用粉煤灰生产的矿物质土壤调理剂及其制备方法。
背景技术
我国是一个产煤大国，煤炭占全国能源总量的2/3以上，每年烧掉的煤炭在30亿吨以上，按4吨煤炭产生1吨粉煤灰计算，每年产生的粉煤灰总量高达1.2亿吨以上，已成为我国工业固体废物的最大单一污染源。由于粉煤灰中富集了大量的砷、铅、镉、铬和汞等危害人体健康的重金属物质，对环境造成了极大的危害，加之有效养分低，限制了其在农业上的综合利用效率。粉煤灰带来的污染主要表现在以下几个方面：(1)污染土壤：当粉煤灰重金属元素进入土壤且超过其临界值时，土壤会向环境输出污染物，使其它环境要素受到污染，土壤组成、结构和功能等均会发生变化，最终可导致土壤资源枯竭和破坏。研究结果显示，相比空白组，施用粉煤灰的实验组中各种重金属含量均普遍提高，并造成土壤透气性、排水性变差。(2)污染水体：粉煤灰随雨水地表径流或随风进入河流、湖泊会污染地表水，并附雨水渗透到土壤中，造成地下水污染。比较明显的会使水体pH值升高，有毒有害元素Cr、As等增加，粉煤灰直接排入河道还会阻塞河道。(3)污染大气：由于粉煤灰颗粒细小，露天堆放时会在风力作用下产生扬尘，扬灰高度可达40～50m，不仅影响大气能见度，而且在潮湿环境中粉尘的聚集对建筑物、自然景观等形貌还会造成严重破坏。(4)危害人类健康：粉煤灰对水资源、土壤以及空气的污染直接影响到人们身体健康和日常生活。长期生活在高粉煤灰粉尘环境中的居民，鼻咽炎、上呼吸道感染等发病率很高。粉煤灰中的放射性元素也会影响到人体健康。因此，开展粉煤灰的综合利用，变废为宝、变害为利，已成为我国经济建设中一项重要的技术经济政策，也是煤电行业迫切需要解决的技术难题之一。
粉煤灰由于粒度细小，孔隙发育、比表面积大、吸水性强，能起到改善土壤结 构，降低容重，增加孔隙率，提高地温，缩小膨胀率，特别是对改善粘质土壤的物理性质，也利于保湿保墒、增强土壤中微生物活性与促进养分转化，使水、肥、气、热趋向协调，为作物生长创造良好的土壤环境。河南农大和河南省农科院土肥所在砂姜黑土上所做田间试验表明：施用粉煤灰后土壤容重降低、孔隙度增大，且随着用灰量增加，土壤容重逐渐下降，土壤孔隙度逐渐增大，其相关系数分别为-0.97和0.98，对土壤温度的连续观测表明，粉煤灰对砂姜黑土有明显的增温作用，特别是对5cm和10cm深度的增温效应随粉煤灰用量的增加而增加；对播种后15天土壤10cm深度含水量的测定表明，施用粉煤灰的比对照田含水量增加23.7～36.4％。印度坎普尔地区试验表明：每公顷施灰20吨，土壤导水率由0.076增加至0.55mm/h，土壤稳定性指标从12.51增至14.08。南昌发电厂粉煤灰改土试验表明：灰土比为6.5％的重量比可使土壤容重由1.36g/cm 3降至1.26g/cm 3。另外，粉煤灰可通过增加土壤中＞1mm水稳性团聚体的数量，改善土壤结构。水稻盆栽试验表明：每亩施5000公斤粉煤灰，可使粘质土壤中＜0.01mm的物理性粘粒由44.65％降至41.97％，土壤粘粒含量随施灰量增加而递减，呈显著的直线负相关。在每亩施灰量4000公斤以内，土壤孔隙度随施灰量增加而递减，有显著的正相关性。西北农学院测定表明：亩施粉煤灰1.5吨，土壤膨胀率由7.1％降为4.99％，从而有利于防止土壤流失。美国Pennsylvania州及Delaware州研究表明：粉煤灰可改善砂质土壤的持水性，提高其抗旱能力。另一方面，在粉煤灰中含有Si、Al、Fe、Ca、Mg、K、Na、Ti、P、B、Cu、Mo、Zn、Mn等诸多大、中微量矿物质元素，对土壤养分含量的提升大有益出。纽约州立大学Malanchuk研究表明：在温室条件下，每公顷施用224吨粉煤灰，莲藕产量显著增加。山西省在潮土上亩施灰5～60吨，94个施粉煤灰土壤测定的平均有效磷含量为26.2mg/kg，比无灰对照土壤(平均19.4mg/kg)增加35.1％。由于粉煤灰富含硼，是油料作物的良好肥源，生长在粉煤灰改良的土壤上的花生、大豆的产量及品质均有明显提高。加拿大安大略省Simcoe地区自1996年开始为期5年的研究项目——“粉煤灰作为果树钙和硼的资源评价”。粉煤灰同腐殖酸结合施用，可以提高土壤中有效硅的含量。吉林市农科所在三种土壤上种植水稻，亩施粉煤灰1.5～3吨，土壤有效硅含量由1.07、0.52、1.4mg/kg，分别提高到1.9、2.0 、7.4mg/kg。施用粉煤灰可以改善土壤微生物活性，白浆土试验表明：大豆自开花期土壤根系层的微生物活性明显增强，一直延续到籽实成熟期，细菌、放线菌和真菌都表现有一致的增长趋势，有利于促进草碳有机成分在土壤中的腐殖化过程，为农作物生长发育创造良好的土壤环境条件。西北农学院在褐土生土上亩施粉煤灰5～15吨，小麦比对照增产10.2％，玉米比对照增产8.4％。用粉煤灰改良盐化潮湿始成土的田间试验表明：每公顷施粉煤灰20吨，水稻、小麦均有极显著的增产效果。大豆盆栽试验表明：施用粉煤灰不仅可使产量增加5％，而且可以提高大豆的粗蛋白及脂肪含量。近几年来，用粉煤灰制作多元素复混肥和将粉煤灰磁化或磁化后制作复混肥受到越来越多生产厂家的重视。粉煤灰由于含有锌、铜、硼、钼、铁等微量元素，可将其加工成高效复合肥。日本利用粉煤灰制造硅酸质肥料，如粉煤灰与苛性钾混合造粒制得的粉煤灰硅酸钾肥料，含K 2O 20％、SiO 235％、MgO 4％、B 2O 30.1％、CaO 8％，该肥料易溶于酸而不溶于水，无吸湿性，不因雨水而流失，肥效期长。河南农科院土肥所制作的粉煤灰复混肥与对照相比可使小麦增产17.7～88％，玉米增产26.5～67.2％，水稻增产2.8～25.6％，花生增产12～24.2％；与普通复肥比较，各种作物增产幅度在2.0～13.5％之间。合肥工业大学研制的粉煤灰多元素复混肥经大田试验，优于等养分的常规施肥，也优于25％低浓度三元素复混肥，分别增产19.1％和8.9％。
但粉煤灰的农业作用也存在以下问题：(1)重金属超标。粉煤灰中含有砷、汞、铬、镉、铅等重金属元素，而且往往超过农用粉煤灰重金属限量标准值，大量农田使用会污染土壤，进而通过食物链进入人体。(2)矿物质有效成分低。虽然粉煤灰中含有大量的矿质元素，但有效性差，粉煤灰中的养分在水中几乎完全不溶解，在弱酸性溶液中的溶解度也不超过20％，这大大增加了在农田的使用量。
发明概述
技术问题
问题的解决方案
技术解决方案
本发明的目的在于针对现有粉煤灰资源化利用效率低下和技术水平不够先进而提出的，本发明提供了一种利用粉煤灰生产的矿物质土壤调理剂及其制备方法，所述方法概括为：通过在粉煤灰中加入各种杂酸性溶剂溶解粉煤灰中的重金属元素，再利用硫化钠溶液使酸溶的重金属离子产生沉淀，使得酸性杂酸溶剂重复使用。去除重金属后的精选粉煤灰，再在其中加入钙基化合物、钾基化合物等物质，一起经混合、烘干和焙烧活化，得到以硅钙钾镁为主要矿质养分、带有弱碱特性的矿物质土壤调理剂。
本发明的目的至少通过如下之一的技术方案实现。
一种利用粉煤灰生产的矿物质土壤调理剂的制备方法，包括如下步骤：
(1)将粉煤灰与杂酸混合均匀后，在超声作用下，经搅拌后过滤，得到精选粉煤灰和滤液；
(2)将步骤(1)过滤得到的精选粉煤灰与钙基化合物、钾基化合物充分混合，造粒后再烘干；
(3)造粒烘干后继续经焙烧活化，取出冷却，经球磨或成型加工，得到上述矿物质土壤调理剂。
进一步的，所述步骤(1)中，杂酸为腐殖酸、盐酸、氢氟酸、硫酸、硝酸、高氯酸、柠檬酸、甲酸、乙酸或酒石酸中任意两种以上的混合酸，且各酸浓度均为0.1～1mol/L，杂酸可将粉煤灰中的重金属溶出转化成水溶态重金属；所述粉煤灰与杂酸的固液混合比为1∶0.1～1∶10g/mL；所述超声时间为1-30分钟。
进一步的，为去除重金属回收杂酸，还包括向步骤(1)中得到的滤液中加入硫化钠溶液，调质搅拌后过滤，重金属以重金属硫化物沉淀的形式去除；所述硫化钠溶液的浓度为0.1～5mol/L，调质后滤液pH为4.0-9.5。
进一步的，加入硫化钠溶液后过滤得到的滤液二次循环使用，补充杂酸使恢复至步骤(1)中杂酸浓度，然后继续实施步骤(1)中的超声搅拌过滤再次溶出粉煤灰中的重金属，得到精选粉煤灰。
进一步的，将通过硫化钠沉淀过滤后得到的含重金属滤渣水洗至少3次以上，然后滤渣做为危险工业固体废弃物做填埋处理，且所述滤渣含水量限制在40％以下。其中，重金属沉淀成滤渣的沉淀率达到90％以上。
进一步的，所述水洗量与重金属硫化物沉淀物的质量比，即液/固比为0.1∶1～1∶10。
进一步的，所述步骤(1)中，搅拌速率为50～200r/min，搅拌时间为10-120分钟。
进一步的，步骤(2)中，所述钙基化合物为CaCO 3、Ca(OH) 2、CaCl 2或CaMg[CO 3] 2两种以上的混合物；所述钾基化合物为KOH、KCl、K 2SO 4或K 2CO 3；步骤(2)中，步骤(1)过滤后得到的滤渣、钙基化合物以及钾基化合物混合质量分数为：步骤(1)过滤后得到的滤渣10％～70％，添加钙基化合物10％～70％，钾基化合物10％～70％。
进一步的，所述步骤(2)中，步骤(1)抽滤后得到的滤渣、钙基化合物以及钾基化合物混合时间为10～120分钟；造粒前加水至步骤(1)抽滤后得到的滤渣、钙基化合物以及钾基化合物的含水量为5-8wt％时进行造粒，粒度0.3-5.5厘米，烘干时间30～300分钟，使得烘干物料水分含量低于1.5wt％。
进一步的，所述步骤(3)中，活化30-60分钟，焙烧温度800-1050℃，取出冷却，经球磨成粉状矿物质土壤调理剂，或冷却后继续加入5-8wt％的水经圆盘造粒成为颗粒矿物质土壤调理剂，且所述土壤调理剂粒度为0.3-5.5厘米。
上述方法得到的酸性土壤调理剂中，含水率低于2wt％，枸溶性二氧化硅含量在15wt％以上，枸溶性氧化钙含量大于25wt％，枸溶性氧化钾含量大于4wt％，枸溶性氧化镁含量大于2wt％，枸溶三氧化硫含量大于2wt％，养分总有效成分不低于80wt％，pH值为9-12。
进一步地，得到的矿物质土壤调理剂的颗粒粒径为0.5-2cm。
发明的有益效果
有益效果
与已有技术相比，本发明具有以下优点和创新之处：
(1)本发明的主要原料为粉煤灰，是煤燃烧之后得到的工业固体废物，将粉煤灰中含有的重金属提取出来并将残渣制作矿物质土壤调理剂，可降低粉煤灰中的重金属含量(本发明中重金属去除率高达50％以上)，达到农用粉煤灰的限值标准；提高粉煤灰的高效综合利用水平，减轻粉煤灰重金属危害，并提高矿 物质含量水平，减少农田用量，从而产生更大的经济效益；
(2)本发明用粉煤灰去除重金属后的精选粉煤灰制作成矿物质土壤调理剂，实现污染物的二次利用，符合循环经济发展和可持续发展的科学理念。
(3)本发明制得的矿物质土壤调理剂中，含有硅、钙、镁、钾、钠、硫以及诸多的微量元素成分，养分种类齐全，可达到平衡施肥的效果，从而全面提升土壤中的矿质元素含量和土壤环境质量，减少农田用量，从而产生更大的经济效益。
(4)本发明制得的矿物质土壤调理剂产品为弱碱性，对于酸性土壤的改良和修复效果明显。
(5)重金属以硫化物稳定态形式加以去除，最终通过填埋方式处置；杂酸溶剂可重复使用。从而达绿色循环经济生产模式。
对附图的简要说明
附图说明
图1为实施例中一种利用粉煤灰生产矿物质土壤调理剂的工艺流程示意图。
发明实施例
本发明的实施方式
以下结合具体实施案例及附图对本发明技术方案作进一步详细描述，但本发明的保护范围和实施方式不限于此。
如图1所示，为本发明一种利用粉煤灰生产矿物质土壤调理剂的工艺流程示意图，具体流程如下：
配制各种酸洗溶液，包括腐殖酸、盐酸、硫酸、硝酸、高氯酸、柠檬酸、甲酸、乙酸、酒石酸等等，混合浓度为0.1～10mol/L，并与粉煤灰进行混合、搅拌、过滤，使粉煤灰中的重金属溶出和分离，达到农用粉煤灰重金属限值标准，分离后得到含重金属的滤液和去除重金属的粉煤灰——精选粉煤灰；在得到的含重金属的滤液中加入硫化钠溶液将重金属沉淀下来并进行过滤，得到的滤液，补充一部分消耗量3-6％的杂酸后可重复使用，而含有重金属硫化物的滤渣可做为危险固体废弃物进行处理处置；在精选的粉煤灰中，加入钙基化合物、钾基化合物一起混合均匀、烘干、造粒、活化、冷却、破碎和包装，得到矿物质土 壤调理剂。
按照图1所示工艺流程，利用粉煤灰生产矿物质土壤调理剂。
实施例1
内蒙某火力发电厂，年产粉煤灰100万吨，其中二氧化硅含量为57.67wt％，氧化钾含量0.42wt％，氧化铝含量高达17.32wt％，氧化钙含量2.15wt％，氧化铁含量为1.35wt％，其中重金属含量为：铅含量121.73mg/kg，镉含量2.15mg/kg，汞含量0.74mg/kg，铜含量7.97mg/kg。
其操作工艺为：
(1)将粉煤灰与浓度均为0.2mol/L的腐殖酸、盐酸、硫酸、硝酸、高氯酸的混合酸液按固/液比1∶1g/mL混合后，超声20分钟后，在85r/min搅拌器转速下搅拌55分钟，使其充分混合均匀，然后进行过滤，得到粉煤灰中重金属的去除率分别为：铅67％、镉86％、汞66％、铜87％；
(2)在步骤(1)过滤后得到的滤液中加入浓度0.15mol/L的硫化钠溶液，调质后的PH＝5.5。经150r/min搅拌器转速下搅拌85分钟后进行过滤；再用清水洗涤硫化物重金属渣3次，滤液中铅、镉、汞、铜的沉淀率均达到90％以上；除去重金属后的滤液需要补充杂酸使恢复至步骤(1)中所述杂酸浓度以循环使用。
(3)对于步骤(1)过滤后得到的精选粉煤灰滤渣，在其中加入碳酸钙、氢氧化钙以及氢氧化钾混合，混合质量比例为：步骤(1)抽滤后得到的滤渣45％、碳酸钙25％、氢氧化钙20％以及氢氧化钾10％；搅拌均匀后，用窑炉尾气烘干70分钟，将烘干后样品于900℃下焙烧30分钟，冷却至室温后，经破碎、过筛100目，得到富含矿物质元素的土壤调理剂。
经第三方检测得知：生产的土壤调理剂中，总矿物质养分84.35wt％，其中有效二氧化硅含量为15.34wt％，有效氧化钙含量为26.87wt％，有效氧化镁5.82wt％，有效氧化钾含量为4.75wt％，有效氧化钠含量为2.74wt％，pH值10.5，是一种含有多种矿物质营分的土壤调理剂。
实施例2
辽宁某火力发电厂，年产粉煤灰160万吨，其中二氧化硅含量为52.67wt％，氧化铝含量21.76wt％，氧化钾含量0.72wt％，氧化钙含量3.15 wt％，氧化铁含量为3.57wt％，其中重金属含量为：铅含量101.30mg/kg，镉含量1.71mg/kg，汞含量0.78mg/kg，铜含量19.48mg/kg。
其操作工艺为：
(1)将粉煤灰与浓度均为0.57mol/L的腐殖酸、盐酸、硫酸、氢氟酸、硝酸、高氯酸的混合酸液，按固/液比1∶2.5g/mL混合后，在超声波作用下15分钟后，在150r/min搅拌器转速下搅拌60分钟，使其充分混合均匀，然后进行过滤，得到粉煤灰中重金属的去除率分别为：铅78％、镉82％、汞49％、铜70％；
(2)在步骤(1)过滤后得到的滤液中加入浓度0.25mol/L的硫化钠溶液，控制调质液pH＝6.7，经90r/min搅拌器转速下搅拌25分钟后进行过滤；再用清水洗涤硫化物重金属渣3次，滤液中铅、镉、汞、铜的沉淀率均达到92％以上；除去重金属后的滤液需要补充杂酸使恢复至步骤(1)中所述杂酸浓度以循环使用。
(3)将步骤(1)过滤后得到的精选粉煤灰滤渣，在其中加入氯化钙、白云石以及碳酸钾混合，混合质量比例为：步骤(1)抽滤后得到的滤渣35％、氯化钙35％、白云石20％、碳酸钾10％；搅拌均匀后，再105℃烘干45分钟，将烘干后样品于870℃下焙烧2h，冷却至室温后，经破碎、过筛100目，得到富含矿物质元素的土壤调理剂。
经第三方检测得知：生产的土壤调理剂中，总矿物质养分82.01wt％，其中有效二氧化硅含量为17.98wt％，有效氧化钙含量为31.09wt％，有效氧化镁6.16wt％，有效氧化钾含量为6.21wt％，pH值11.1，是一种含有多种矿物质营分的土壤调理剂。
实施例3
河北省某火力发电厂，年产粉煤灰300万吨，其中二氧化硅含量为46.67wt％，氧化铝含量15wt％，氧化钾含量0.92wt％，氧化钙含量6.15wt％，氧化铁含量为2.71wt％，其中重金属含量为：铅含量71.73mg/kg，镉含量1.13mg/kg，汞含量1.07mg/kg，铜含量38.02mg/kg。
其操作工艺为：
(1)将粉煤灰与浓度均为0.9mol/L的腐殖酸、盐酸、硫酸、氢氟酸、酸、高氯 酸的混合酸液按固/液比1∶5g/mL混合后，超声27分钟后，在195r/min搅拌器转速下搅拌115分钟，使其充分混合均匀，然后进行过滤，得到粉煤灰中重金属的去除率分别为：铅72％、镉73％、汞73％、铜79％；
(2)在步骤(1)过滤后得到的滤液中加入浓度2mol/l的硫化钠溶液，控制调质液PH＝7.2(经77r/min搅拌器转速下搅拌45分钟后进行过滤；再用清水洗涤硫化物重金属渣3次，滤液中铅、镉、汞、铜的沉淀率均达到91％以上，然后做填埋处理，且所述滤渣含水量限制在40wt％以下；除去重金属后的滤液需要补充杂酸使恢复至步骤(1)中所述杂酸浓度以循环使用。
(3)将步骤(1)过滤后得到的精选粉煤灰滤渣，在其中加入碳酸钙、氢氧化镁以及硫酸钾混合，混合质量比例为：步骤(1)抽滤后得到的滤渣45％、碳酸钙25％、氢氧化镁16％以及硫酸钾14％；搅拌均匀后，用窑炉尾气要105℃烘干50分钟，将烘干后样品于1000℃下焙烧30分钟，冷却至室温，经破碎、过筛100目，得到富含矿物质元素的土壤调理剂。
经第三方检测得知：生产的土壤调理剂中，总矿物质养分82.93wt％，其中有效二氧化硅含量为17.46wt％，有效氧化钙含量为31.04wt％，有效氧化镁8.12wt％，有效氧化钾含量为5.18wt％，有效氧化钠含量为1.94wt％，pH值11.8，是一种含有多种矿物质养分的土壤调理剂。
以上实施例仅为本发明较为优化的实施方式，仅用于解释本发明，而非限制本发明，本领域技术人员在未脱离本发明精神实质与原理下所作的任何改变、替换、组合、简化、修饰等，均应为等效的置换方式，均应包含在本发明的保护范围内。

Claims (10)

  1. 一种利用粉煤灰生产矿物质土壤调理剂的方法，其特征在于，包括以下步骤：
    (1)将粉煤灰与杂酸混合，在超声作用下，搅拌过滤，得到精选粉煤灰和滤液；
    (2)将步骤(1)中的精选粉煤灰与钙基化合物、钾基化合物充分混合，造粒后烘干；
    (3)造粒烘干后焙烧活化并冷却，经球磨或成型加工，得到所述矿物质土壤调理剂。
  2. 根据权利要求1所述的方法，其特征在于，所述步骤(1)中，杂酸为腐殖酸、盐酸、氢氟酸、硫酸、硝酸、高氯酸、柠檬酸、甲酸、乙酸或酒石酸中任意两种以上的混合酸，且各酸浓度均为0.1～1mol/L；所述的粉煤灰与杂酸的固液混合比为1∶0.1～1∶10g/mL；所述超声时间为1-30分钟。
  3. 根据权利要求1所述的方法，其特征在于，还包括向步骤(1)中得到的滤液中加入硫化钠溶液，调质搅拌后过滤；所述硫化钠溶液的浓度为0.1～5mol/L，调质后pH＝4.0-9.5。
  4. 根据权利要求1所述的方法，其特征在于，所述步骤(1)中，搅拌速率为50～200r/min，搅拌时间为10-120分钟。
  5. 根据权利要求1所述的方法，其特征在于，步骤(2)中，所述钙基化合物为CaCO 3、Ca(OH) 2、CaCl 2或CaMg[CO 3] 2中的两种以上的混合物；所述钾基化合物为KOH、KCl、K 2SO 4或K 2CO 3；步骤(2)中，步骤(1)过滤后得到的滤渣、钙基化合物以及钾基化合物混合质量分数为：步骤(1)过滤后得到的滤渣10％～70％，添加钙基化合物10％～70％，钾基化合物10％～70％。
  6. 根据权利要求1所述的方法，其特征在于，所述步骤(2)中，造粒前加水至含水量为5-6％时进行造粒，粒度0.3-5.5厘米，烘干时间30～300分钟。
  7. 根据权利要求1所述的方法，其特征在于，所述步骤(3)中，活化30-60分钟，焙烧温度800-1050℃，取出冷却至室温，经球磨成粉状矿物质土壤调理剂，或冷却至室温后继续加入5-8wt％的水经圆盘造粒成为颗粒矿物质土壤调理剂，且所述土壤调理剂粒度为0.3-5.5厘米。
  8. 根据权利要求3所述的方法，其特征在于，加入硫化钠溶液后过滤得到的滤液可二次循环使用，补充杂酸，使恢复至步骤(1)中所述杂酸浓度，继续实施步骤(1)中的超声搅拌过滤，用来提取重金属，得到精选粉煤灰。
  9. 根据权利要求3所述的方法，其特征在于，将通过硫化钠沉淀过滤后得到的含重金属滤渣水洗至少3次以上，然后做填埋处理，且所述滤渣含水量限制在40wt％以下。
  10. 由权利要求1～9任一项所述方法制得的所述矿物质土壤调理剂，其特征在于，所述矿物质土壤调理剂的含水率低于2wt％，枸溶性二氧化硅含量在15wt％以上，枸溶性氧化钙含量大于25wt％，枸溶性氧化钾含量大于4wt％，枸溶性氧化镁含量大于2wt％，养分总有效成分不低于80wt％，pH值为9-12。
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