CN1239627C - Preparing process and agricultural application of nano-class humic acid polymer mixture - Google Patents
Preparing process and agricultural application of nano-class humic acid polymer mixture Download PDFInfo
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Abstract
The present invention relates to a new production process and an application technique on agriculture. Weathered coal, coal gangue, pulverized coal ash and peat are used as raw materials, organic matter in the weathered coal, the coal gangue and the peat is processed into nano-level humic acid by a chemical reaction and high shearing technology, a micro-emulsifying technology and a microcapsule technology, compounds in the pulverized coal ash and the coal gangue, including silicon, calcium, etc., are processed into nano-level silicon and calcium compounds, and finally, a nano-lelve solid sand water-keeping agent, an anti-draught and water-keeping liquid mulching film, a soil structure conditioner, a multifunctional dressing agent, a slow/controlled release fertilizer, etc. are produced.
Description
It is being raw material with weathered coal, peat, coal gangue, flyash that nano level humic acids involved in the present invention mixes polymers, and the series products that the employing nano material technology processes is used for agricultural and ecotope.
The coal waste refers to weathered coal, coal gangue and fly ash in electric power plant.About 82,300,000,000 tons of China's weathered coal resource; About 1.5 hundred million tons of annual coal gangue generation is stored up coal gangue over the years and has been reached nearly 2,000,000,000 tons; About 1.5 hundred million tons of the annual discharge coal ash in fuel-burning power plant, nearly 70% flyash is deposited in the ash field; 12,400,000,000 tons of China's peat reserves.Except peat be embedded in underground, the equal land occupation of weathered coal, coal gangue and flyash, influence ecological environment.
Coal waste and peat utilize present situation as follows with existing problems:
Weathered coal mainly is processed as the humic acids product, comprises humic acid fertilizer, and the humic acid combined fertilizer improves soil physical property, xanthohumic acid drought resistance agent, fodder additives etc.; Though part test is pharmaceutically being arranged, is not generally using.The utilization of coal gangue is mainly two aspects, and the one, as inferior fuel, the 2nd, produce building materials, as cement, Industrial Residue Brick, refractory materials, casting model powder etc.Whole nation coal gangue comprehensive utilization ratio 17.16%.Flyash is mainly used in paves the way, and building materials (brick, cement, concrete admixture) float pearl; On agricultural, mainly be applied to heavy soil and alkali-affected soil, occurred magnetized fly-ash composite fertilizer in recent years, very big in the dispute of fertilizer circle.Peat claims the peat composed of rotten mosses again, is mainly used in the livestock packing ring, humic acid fertilizer, organic-inorganic compound mixed fertilizer filler, industrialized agriculture substrate material, peat nutrition soil etc.
China's coal waste and peat aboundresources, but utilization ratio is not high; There is very big problem in complete processing, shows as follows:
The humic acid complete processing exists problem nineteen seventies once started popularization humic acid heat in the whole nation, held the national meeting of promoting humic acid fertilizer in 1975 in Zhanjiang, the time spend 27 years, use the still few of humic acid fertilizer separately.It mainly is the production technique imperfection.Utilize the weathered coal and the peat composed of rotten mosses to produce humic acid one and have three cover technologies: sulfuric acid acetone method, exchange resin method and acid (or alkali) is extraction process directly.Acetone reclaims difficulty in the sulfuric acid acetone method, and resin is broken serious in the exchange resin method, all has the high problem of cost, can't use in practice.Acid (or alkali) the directly shortcoming of extraction process is that the humic acid sucrose extraction is low, and flocculation resistance is poor, solid-liquid separation difficulty etc.
The agricultural pressure that alleviates the fuel-burning power plant of the problem flyash of the agricultural existence of flyash, but no matter be directly to be applied to soil, still manufacture magnetic compound fertiliser, all are physics carryings, any chemical reaction does not take place, any variation is not arranged on matter, so effect is not good always.And, in applied basic research, do not prove the fertilizer efficiency of energy of magnetization reinforced soil magnetic field or raising N, P, K always, do not prove how the magnetizable powder coal ash produces electromagnetic induction to growth and development of plants yet, even do not prove what difference magnetizable powder coal ash and unmagnetized flyash have on fertilizer efficiency, owing in multiple fertilizer, add a large amount of flyash, obviously reduce multiple fertile NPK nutrient, improve the unit nutrient price, increase the production and selling cost, be difficult to large-scale promotion.(above reference: Lee is apt to auspicious ， Dou Xiu cloud, and 1996: China's weathered coal utilizes status and prospects, humic acid (2); P.1-4; Shao Yi, Wang Zhuokun, 1991: China's coal gangue, flyash discharging utilize present situation and countermeasure, Chinese population resource environment 1 (3-4), P.70-74; Li Guibao etc., 2000: flyash agricultural use progress, phosphate fertilizer and multiple fertilizer 15 (6), P.59-60; Guo Xiaofeng, 2001: also talk the production exploitation of xanthohumic acid liquid preparation, humic acids (1), P12-13; Li Shanxiang, 1999: the research and development progress (2) of humic acids, P.1-5.)
Purpose of the present invention: in view of the problem of present China coal waste and the existence of peat agricultural application, the present invention intends adopting nano material technology, existing production technique is transformed, with weathered coal, coal gangue, flyash and peat is raw material, the agent of development nano level sand-fixation, water-keeping, the water conservation liquid ground film of taking precautions against drought, soil conditioner, multi-function seed coating agent, new process of production such as slowly/controlled releasing fertilizer coating agent and the utilisation technology on agricultural, the resource utilization of raising coal waste and peat.
Main technological route of the present invention:
Adopt chemical reaction and high-shear technology, micro-emulsion technology, microcapsulary, the organic matter in weathered coal, coal gangue and the peat is processed as the nano level humic acid, compounds such as the silicon in flyash and the coal gangue, calcium are processed as nano silicone, calcium cpd.
Flow process of the present invention is seen accompanying drawing 1.
Detailed description of the present invention:
To the material composition analysis, the mensuration project must meet above standard by " pollutent control criterion in the agricultural flyash of GB8173-87 ".
Assay determination project: organic matter, silicon, calcium, iron, lead, mercury, chromium, nickel, cadmium, arsenic.
1 nano level humic acids polymer production technology
1.1 raw material stoving, ball mill is pulverized, and crosses 200 mesh sieve holes;
1.2 in having the reactor of whipping device, add weathered coal, peat, coal gangue, the flyash of pulverizing, add the diluted acid reaction:
(1) weathered coal and peat add 45%～50%H
2SO
4Or HNO
3, add-on 1: 0.2～0.25 (weight ratio), 1 hour reaction times;
(2) coal gangue and flyash add HCl-H
2SO
4Mixing acid, hydrochloric acid and vitriolic ratio are decided on the form of silicone content in the raw material and silicon compound, and silicone content is high more, and the difficult silicate content that decomposes is high more, and the hydrochloric acid ratio is big more.
(3) after chemical reaction finishes, be neutralized to about pH7.0 with liming or ammoniacal liquor.
(4) add the dispersion agent Sodium dodecylbenzene sulfonate, add-on 5%～10% stirs.1.3 above-mentioned resultant of reaction is put into High shear device (seeing 02123522.8 application for a patent for invention that the inventor submitted on July 2nd, 2002), rotating speed 20,000 r/min, high-shear time 5～10min, promptly generate nano level humic acids compound, this compound is actually the aggregate of classes of compounds micelle, comprises the nano level humate, all kinds of nano grade inorganic compounds, the complexing of humic acid and each metallic element (chelating) things etc., their common feature is to have colloid property.
2 starch-acrylonitrile copolymer production technique
2.1 starch pasting
With cold water yam starch is disperseed (starch is 10%～15%), under agitation be heated to 65～75 ℃ of gelatinizations 1 hour, be cooled to room temperature (25～30 ℃) again.
2.2 starch-acrylonitrile compolymer
Cooled pasted starch liquid adds ceric ammonium nitrate and nitric acid mixed solution (cerium ion that contains 1mol nitric acid and 0.1mol in every L mixed solution) in polymerization reactor, stir 10～15min, adds vinyl cyanide, and add-on is 50%～120% of an amount of starch, at N
2Gas shiled continues down to stir 70～75 ℃ of temperature of reaction 3～4 hours.Add KOH water-methanol mixing solutions then, be heated to 95 ℃ of saponification hydrolysis 2～3 hours, again with in sulfuric acid or the hydrochloric acid and the pH value be about 7.0.
Starting material consumption: yam starch 150kg, water 1000kg, vinyl cyanide 150kg, ceric ammonium nitrate solution 12～15L (cerium ion that contains 1mol nitric acid and 0.1mol in every L mixed solution), potassium hydroxide 40～42kg, methyl alcohol 180～200L.
Classical starch-acrylonitrile copolymer preparation is still needed and is wanted repetitive scrubbing, filtration, drying, pulverizing, and present method is saved subsequent handling.
3 nano level humic acidses mix the preparation of polymers
With nano level humic acid polymkeric substance and starch-acrylonitrile copolymer (5: 1) thorough mixing in proportion, (mass ratio 5-10: 1) solution stirring is disperseed (add-on be said mixture 5%～10%) to add Sodium dodecylbenzene sulfonate and OP-10, fully emulsified through the high speed dispersion device, disperseed 0.5 hour, two kinds of composition uniform mixing are formed mix polymers finished product, barrelling.
4 solidify husky water-holding agent and slow-release fertilizer coating cementing agent
4.1 sand-fixation, water-keeping agent
During use, add 20 times of dilutions of water again, be sprayed on about desertification and sandy land soil layer 10cm, earlier sand is fixed, plant grass again and plant trees restore vegetation.The water conservation process is a running balance, and water is slowly siphoned away by soil, again water is sucked back during rainfall. permeate in soil again.
4.2 slowly/controlled releasing fertilizer coating cementing agent
Above-mentioned nano level humic acids is mixed 10 times of polymers dilute with waters, on garden dish or rotary drum granulator, with high pressure spray nozzle (greater than 3kg) spraying; the coating while spraying; to all wrapping up the back stop-spraying, with a little talcum powder face powder, the dry back of hot blast (80～100 ℃) packs the fertiliser granulates that is wrapped again.
4.3 liquid ground film
Above-mentioned nano level humic acids is mixed 5～10 times of polymers dilute with waters, be sprayed on dryland soil top layer 2～3cm, anti-moisture evaporation is arranged and keep the soil moisture effect.
5 multi-function seed coating agents
Above-mentioned nano level humic acids is mixed polymers and N, P, K chemical fertilizer element, insecticidal bactericide (deciding different pesticide species according to the type of different areas disease and pest) thorough mixing is even, ratio is (10: 2: 0.01), the parcel seed, hot-air seasoning (35～40 ℃), seed-coat forms film, and short root, water conservation, nutrition, anti-seedling stage diseases and pests effect are after planting arranged.
Advantage of the present invention:
Because small-size effect, tunnel effect and the surface interface effect of nano material, these nano level compounds have good bonding capacity, drought-resistant water-preserving performance, nutrient slowly-released performance.The field plot trial result:
1. sand-fixation, water-keeping agent: water-soluble fully, spray the back and infiltrate soil layer rapidly, form harder meshy surface overcoat, rainwater can enter soil layer from mesh, not the intensity of failure surface overcoat; Sand fixing strength: do not play dirt, not sand during wind speed 17.2～20.7m/s (strong gale).
2. multi-function seed coating agent: integrate short root, nutrition slow-release, preventing disease and pest, water retaining function, seedling rate improves more than 30% on the dryland soil, 30～50 times of suction multiples, N, P, 50～100 days nutrient slowly-released time of K.
3. the fertile coating consolidating material of slow/controlled release: membrane wrapping thickness: 10 μ m～100 μ m, encapsulation ratio is more than 95%, the nitrogen slow-release time is 30～100 days in soil, and utilization rate of nitrogen fertilizer improves 10 percentage points, and this coating agent is applicable to the special-purpose slowly/controlled releasing fertilizer coating of corn, vegetables and wheat.
Claims (7)
- (1) a kind of nano level humic acids mixes the polymers production method, it is characterized in that with weathered coal, peat, coal gangue, flyash as starting material; Raw material drying, crushing screening and diluted acid generate nano level humic acids compound through high-shear after reacting, neutralize, add dispersion agent and stirring again; In polymerization reactor, starch is handled through gelatinization, added ceric ammonium nitrate and nitric acid mixed solution again, add vinyl cyanide at N 2Gas shiled is reaction down, adds KOH water-methanol mixing solutions, is heated to 95 ℃ of saponification hydrolysis 2～3 hours, again with in sulfuric acid or the hydrochloric acid and the pH value be 7.0, make starch-acrylonitrile copolymer; With nano level humic acid compound and starch-acrylonitrile copolymer thorough mixing in proportion, add dispersion agent and disperse, fully emulsified through high-speed emulsifying machine, disperseed 0.5 hour, make two kinds of even fusion of composition and make the nano level humic acids and mix polymers.
- (2) according to the described production method of claim 1, it is characterized in that the technological process for preparing nano level humic acids compound is: raw material drying, ball mill are pulverized, and cross 200 mesh sieve holes; Weathered coal that input has been pulverized in the reactor that has whipping device or peat, coal gangue, flyash add the diluted acid reaction, and reaction is neutralized to pH7.0 with liming or ammoniacal liquor after finishing; Add 5%～10% dispersion agent Sodium dodecylbenzene sulfonate of above-mentioned reactant total mass, stir, put into High shear device, shear through 20,000 r/min, time 5～10min promptly generates nano level humic acids compound.
- (3) according to the described production method of claim 1, it is characterized in that nano level humic acids compound and starch-acrylonitrile copolymer 5: 1 thorough mixing in proportion, add and press mass ratio 5～10: the Sodium dodecylbenzene sulfonate of 1 proportional arrangement and OP-10 mixed solution dispersed with stirring, its add-on is 5%～10% of a said mixture, fully emulsified through the high speed dispersion device, disperseed 0.5 hour, make two kinds of composition uniform mixing, barrelling.
- (4) the nano level humic acids for preparing according to the described method of claim 1 mixes the application of polymers, it is characterized in that the nano level humic acids is mixed polymers directly as the sand-fixation, water-keeping agent, during use, add 20 times of dilutions of water, be sprayed on desertification and sandy land soil layer 10cm, earlier sand is fixed, planted grass again and plant trees restore vegetation.
- (5) the nano level humic acids for preparing according to the described method of claim 1 mixes the application of polymers; it is characterized in that above-mentioned nano level humic acids is mixed 10 times of polymers dilute with waters; on garden dish or rotary drum granulator; by it being sprayed greater than the 3kg pressure nozzle; the coating while spraying, to all wrapping up the back stop-spraying, the fertiliser granulates that is wrapped is again with a little talcum powder face powder; pack after 80～100 ℃ of warm air dryings, and as the slow release fertilizer coating jointing compound.
- (6) the nano level humic acids for preparing according to the described method of claim 1 mixes the application of polymers, it is characterized in that the nano level humic acids is mixed polymers directly as liquid ground film, during use,, be sprayed on dryland soil top layer 2～3cm with 5～10 times of above-mentioned mixed polymers dilute with waters.
- (7) the nano level humic acids for preparing according to the described method of claim 1 mixes the application of polymers, it is characterized in that the nano level humic acids is mixed polymers is prepared into multi-function seed coating agent, method is: with above-mentioned mixed polymers and N, P, K chemical fertilizer element, the insecticidal bactericide thorough mixing is even, its weight ratio is 10: 2: 0.01, the parcel seed, 35～40 ℃ of hot-air seasonings, seed-coat forms film, wherein, the process of the mixed polymers of preparation nano level humic acids comprises: (1) adds 45%～50%H in weathered coal and peat 2SO 4Or HNO 3, its weight ratio of add-on is 1: 0.2～0.25,1 hour reaction times; (2) in coal gangue and flyash, add HCl and H 2SO 4Mixing acid, hydrochloric acid and vitriolic ratio are decided on the form of silicone content in the raw material and silicon compound, and silicone content is high more, and the difficult silicate content that decomposes is high more, and the hydrochloric acid ratio is big more.
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100363460C (en) * | 2004-02-20 | 2008-01-23 | 中国农业科学院土壤肥料研究所 | Production process for mixing polymer of nano-subnano grade marsh dregs-gangue compound |
| CN100549100C (en) * | 2005-08-12 | 2009-10-14 | 中国矿业大学(北京) | Humate compound water retaining agent and preparation method thereof |
| KR20090083441A (en) * | 2006-11-06 | 2009-08-03 | 비잼 바이오사이언시스 프라이빗 리미티드 | Production of novel precision customized control release fertilizers |
| CN102001886B (en) * | 2010-11-02 | 2013-01-16 | 湖北富邦科技股份有限公司 | Fertilizer additive using pulverized fuel ash as raw material and preparation method thereof |
| CN102093129B (en) * | 2010-12-03 | 2013-03-13 | 湖北富邦科技股份有限公司 | Method for preparing compound controlled-release fertilizer from pulverized fuel ash serving as raw material |
| CN102612955B (en) * | 2012-03-28 | 2014-02-26 | 常熟市润丰农业有限公司 | Method for promoting leaf vegetable yield increasing using fly ash |
| CN105237190A (en) * | 2015-10-08 | 2016-01-13 | 定远县蒋集镇丰润蔬菜种植专业合作社 | Insect pest resistant sustain-released fertilizer for peanut planting and preparation method thereof |
| CN105237196A (en) * | 2015-10-08 | 2016-01-13 | 定远县蒋集镇丰润蔬菜种植专业合作社 | Cucumber fertilizer prepared from modified peat and preparation method thereof |
| CN105237191A (en) * | 2015-10-08 | 2016-01-13 | 定远县蒋集镇丰润蔬菜种植专业合作社 | Environment-friendly fertilizer for potato planting and preparation method thereof |
| CN105237299A (en) * | 2015-10-08 | 2016-01-13 | 定远县蒋集镇丰润蔬菜种植专业合作社 | Green and environment-friendly paddy rice nitrogen fertilizer and preparation method thereof |
| CN105272694A (en) * | 2015-10-08 | 2016-01-27 | 定远县蒋集镇丰润蔬菜种植专业合作社 | Leek fertilizer prepared from modified peat and preparation method thereof |
| CN107266690B (en) * | 2017-06-08 | 2019-07-23 | 申建立 | A kind of nanometer of humic acid potassium and its production method |
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