CN103436266A - Method for producing secondary element acid-soil conditioning agent by using industrial calcium silicate board waste materials - Google Patents
Method for producing secondary element acid-soil conditioning agent by using industrial calcium silicate board waste materials Download PDFInfo
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Abstract
The invention discloses a method for producing a secondary element acid-soil conditioning agent by using industrial calcium silicate board waste materials. The method mainly comprises the following steps of: mixing calcium silicate boards, white mud, dolomite and the like as well as additives A and B, ball-milling, drying, forming, machining, baking, activating, cooling and crushing, thus obtaining the mineral substance nutritional type acid-soil conditioning agent. The acid-soil conditioning agent comprises more than 60% of available nutrients, more than 25% of available calcium oxide, more than 20% of available silicon dioxide, more than 5% of available magnesium oxide, more than 5% of available sulfur trioxide, more than 2% of available chlorine and multiple trace element components. The secondary element acid-soil conditioning agent is weakly basic (pH is 9-12). The method belongs to the subject of the high-efficiency agriculture resource utilization of industry soil wastes and covers the scientific idea of circular economy and sustainable development. The prepared acid-soil conditioning agent can be used for adjusting the physical and chemical property of acid or saline-alkali soil and comprehensively increasing the level of the medium trace elements in the soil.
Description
Technical field
The present invention relates to the new-type fertilizer field, belong to agricultural sciences.Be specifically related to a kind of method that the moderate-element acidic soil conditioner is produced in industrial silico-calcium board waste material activation.
Background technology
Soil pH value is extremely important to the growth of plant.What suitable most of farm crop grew up strong and sturdy is neutral soil, and its pH value is 7 or is slightly less than 7.Soil acidification (soil acidification) refers to the process that in soil, hydrogen ion concentration increases or soil acidity strengthens, show as the remarkable reduction of soil pH value, form acid soil, affect activity biological in soil, change the form of nutrient in soil, reduce nutrient availability, impel free manganese, aluminum ion to dissolve in the soil solution, poison making deposits yields.At occurring in nature, acid soil accounts for the whole world can utilize 30% of soil.Under field conditions (factors), soil acidification is a mechanism relatively slowly, and as the carbonic acid that animals and plants respiration in soil forms, the organic acid that plant and animal residues produces through microbial decomposition can slowly cause soil acidification.But from the eighties in last century so far in early days, China's nearly all topsoil (top soils) mean ph value 0.13 to 0.80 unit that descended, although the mean ph value of southern area red soil 0.23 unit that only descended wherein, but acid the strongest, arrive aluminium and manganese element and produced the environmentally hazardous stage of activation.
Soil acidification is a continual natural process, and in soil, the existence of some natural acids is being carried out this Formation history very slowly, but the impact of human factor makes this process greatly accelerate.Wherein mainly contain two aspects:
(1) Atmospheric acid deposition
Acid rain is the main inducing that causes soil acidification.China's Acid Rain Zone main body is positioned at the wide geographic area on the south the Changjiang river, and also there is Acid Rain Zone among a small circle in the north.But from national acid rain occurrence scope: be generally expansion trend, northern acid rain occurrence scope enlarges obviously, and south remains unchanged substantially.And the acid rain pollution severely afflicated area progressively is transferred to Central China and middle part, south China by southwest.In Europe, the United States, the large Acid Rain Zone of subepoch circle three, the strongly-acid Acid Rain Zone of China (pH<4.5) area maximum, the areas to the south, the Changjiang river is the global strong acid heart in the rain.It is acid that the south China Soils In The Region mostly is originally, the shower of acid rain in recent years in addition, and acidization is accelerated; And northern area soil mostly is alkalescence, acid rain is had to certain surge capability.After soil acidification, can accelerate in soil contain primary mineral and the secondary mineral weathering of aluminium and discharge a large amount of aluminum ions, form the absorbable aluminium of plant.The absorption aluminium that plant is long-term and excessive, can produce poisoning, the phenomena of mortality even.In addition, acid rain still can accelerate the loss of soil mineral nutritive element; Change Soil structure, cause the poor ridge of soil, affect the plant normal development, and the inducing plant disease and pest, make crop failure.
Within 2005, China's acid rain range of distribution has accounted for 28% of territory total area, and expands to 40% in 2010, and areas to the south, the middle and lower reach of Yangtze River average annual Precipitation pH of the area more than at least 50%, lower than 4.5, is the acid rain seriously polluted area.And, according to Guangdong Province's environment communique in 2010, city precipitation mean ph value is 4.86 at present, the acid rain frequency is 45.9%, and there are 5, Shaoguan, Shenzhen, Foshan, Zhaoqing and Huizhou etc. in the city that belongs to heavy Acid Rain Zone (pH<4.5).
(2) excessive applied nitrogen
Except Atmospheric acid deposition can bring out soil acidification, excessive the using of nitrogenous fertilizer is also the arch-criminal who causes soil acidification.Still the cacodoxy of ubiquity " the more many more high yields of nitrogenous fertilizer " at present China's agriculture production.Since the eighties in last century, China's amount of application of nitrogen fertilizer rapid growth, to the mid-90, China has become the first big country of world's nitrogen fertilizer production and consumption, has consumed the nitrogenous fertilizer in the whole world 35% on the arable land that accounts for the world 7%.Due to the particularly use of ammonium fertilizer of nitrogenous fertilizer, cause ammonium nitrogen (NH
4escaping and nitric nitrogen (NO-N)
3-N) Soil accumulation, the plantation of leguminous crop in addition, rate of fertilizer application and fertilization mode, crop harvesting are removed alkaline matter in soil etc. improperly, have all accelerated the acidifying of soil.
The acidifying of soil has not only brought the increase of soil acidity, and more main is runs off the nutrition compositions such as potassium in soil, calcium, silicon, magnesium in a large number; Promote aluminium, manganese and heavy metal element activation, aluminium poison and heavy metallic poison phenomenon occur; The lasting acidifying of soil, also changed population and the activity of soil microorganisms; Affect that crop root is grown and to the absorption of nutrient; And grow various disease and pests.
For a long time, for the general acidifying of soil and the adverse consequences brought thereof, except controlling Atmospheric Acid Deposition, reduce chemical fertilizer particularly outside the amount of application of nitrogenous fertilizer, also develop some acidic soil conditioners both at home and abroad.Traditional as lime or limestone powder soil conditioner, also have in addition some as alkaline residue, peat, flyash, rhombspar, phosphogypsum, ground phosphate rock, carbon method filter mud, Yellow Phosphorous Slag powder etc.
Lime or limestone powder are after acid soil is used, and the acidity of topsoil is easy to improve by using, and the concentration of soil plough horizon exchangeable calcium ion also can increase to some extent.Blessing in the Meng waits and finds at Middle Part of Zhejiang red soil region liming: topsoil exchangeable calcium ion reaches maximum in time a year and a half after liming, slow decreasing again subsequently, and multiple acidifying phenomenon appears in soil, a large amount of or long-term application lime not only can cause soil compaction and form " lime harden field ", and easily causes the dysequilibrium of the elements such as soil calcium, potassium, magnesium and cause the underproduction.Therefore, during with lime improvement acid soil, must be noted that liming continually, in liming improvement soil, should be in other alkaline acidic soil conditioner as plant ash, burn native compounding application.
It is raw material that Guangdong Dazhong Agriculture Science Ltd. utilizes south, Guangdong alkali industry Group Plc to utilize " solvay soda process " to produce the alkaline residue produced in the soda ash process, produce the acidic soil conditioner of a kind of " field master worker " brand, annual production at present reaches 150,000 tons, product has 17 kinds, and sales range extends to Guangxi, Hunan, Jiangxi, Fujian, Zhejiang, Hainan, Hubei, Shandong etc. from Guangdong.The main insolubles of solvay soda process alkaline residue comprises calcium carbonate, calcium hydroxide, magnesium hydroxide and terra alba (gypsum), and solvend comprises calcium chloride and sodium-chlor, and wherein solvend accounts for 10～15%.But due to chlorion too high in alkaline residue, excessive viscosity and excessive inactivation calcium carbonate (CaCO
350%), all directly having limited as the using of acid soil improving agent, peasant household generally reflects to exist and continues result of use phenomenon worse and worse.
Peat and flyash all can be used for improveing soil, increase the content of soil with organic matter, promote the moisture in the soil value of soil, but their pH values own are lower or be neutral, can not be used for nursing one's health the acidity of soil, and in general, in itself, the content of heavy metal is not low, may bring secondary pollution to soil.
Rhombspar is used and can be promoted significantly growing and improving output of crop in acid soil, and the research of Zhu Hongbin etc. is found: use the rhombspar acidic soil conditioner, wheat increase yield 11.6%～13.4%, rape yield increasing 9.4～27.2%.But the long-term application rhombspar also can make soil the phenomenon that hardens occur, and causes crop failure.
Phosphogypsum not only can be improved saltings, can also be as a kind of cubsoil modifying agent of acid soil.For Sumner etc. propose, the theory of phosphogypsum improvement cubsoil, can be summarized as " automatically adding liming effect ", and soil is with after calcium sulfate reacts, because surperficial replacement reaction produces basicity.Spoito specializes " automatically adding lime ", and its reaction is:
Al?(OH)?
3+CaSO
4==Al?(OH)?SO
4+Ca?(OH)
?2
Al
2SiO
3(OH)
4+2CaSO
4+5H
2O==2Al(OH)SO
4+2H
2SiO
4+2Ca(OH)
2
The result of above-mentioned reaction, owing to having produced calcium hydroxide, make the pH of soil be worth improving, and cause the content of Exchangeable Al to descend.
Ground phosphate rock is a kind of important raw and processed materials of phosphorous chemical industry, thereby can increase the output of the content raising crop of available phosphorus in soil, and improves the pH value of soil.Increase the content of exchangeable calcium, reduce the content of exchange state aluminium.But ground phosphate rock mainly is comprised of phosphatic rock, in raw ore, the content of heavy metal and radioelement is generally higher.
Carbon method filter mud is the industrial solid castoff of sugar refinery output, temperature will gentle Liu Shu base by the red earth oranges and tangerines show after using sugar refinery carbon method filter mud: use carbon method filter mud and can obviously improve the pH value of soil and the content of soil quick-effective phosphor, join potassium application and can significantly improve orange yield, obviously improve its Vc and citric acid content, and its effect to join potassium application than the lime of equivalent good, think that carbon method filter mud can be through replacing the improvement of lime for red earth.
Except independent use or these soil conditioners of mixing use, also has at present the research report of some nutritional type type soil conditioners.Untie in the acid soil improvement of the development such as controlling containing N 1.08g/kg P
2o
53.27g/kg, K
2o1.33g/kg, CaO 432.7g/kg, MgO 14.04g/kg, by 5 processing, effect of increasing production 9.5～19.6%, the quality of peanut all has raising in various degree.Chen Fuxing etc. are used four kinds of traditional Agricultural breezes as main raw material, according to the red soil characteristic, in conjunction with the demand of crop nutrition content element, are mixed with the red soil improving agent series product, have the effects such as the soil acidity of reduction, supply nutrient, chessom.Guo Rongfa also uses the macromolecular organic compound of 97% ground phosphate rock+3%, through processing treatment, becomes activating phosphorite powder, on latosol, uses, and result shows: its fertilizer efficiency of administration of activated ground phosphate rock is low unlike the calcium superphosphate fertilizer efficiency.
Although above amendment can play certain improved effect to acid soil, has following problem: (1) mostly is primary raw material, the process of manufacture simple coarse, active constituent content is not high and fluctuation is large, the too strong problem of also existence alkalescence had.Raw materials used from above acidic soil conditioner: as to be mainly mineral substance or industrial solid castoff, as lime or Wingdale, rhombspar, phosphogypsum, ground phosphate rock, zeolite, Calucium Silicate powder, serpentine, flyash, carbon method filter mud, Yellow Phosphorous Slag powder etc., production process is that simple mechanical abrasive dust mixes.Because these materials mostly are insolubles, this has just caused in amendment active constituent content low, and the content fluctuation is large and composition is unstable, and the alkalescence of lime is too strong, can bring to the growth of crop harm; (2) tend to cause soil compaction or heavy metal contamination.As lime or Wingdale, using in a large number of rhombspar can be caused soil compaction; All contain heavy metal and the radioelement such as a certain amount of lead, cadmium, mercury, arsenic, chromium in phosphogypsum, ground phosphate rock and flyash, can be to soil---farm crop---food safety is brought harm.
The industry calcium silicate board with microporous is as a kind of New Building Materials, the widespread use building material industry, but, as preparing the raw material of moderate-element acidic soil conditioner, rarely have research both at home and abroad.This,, for the added value that improves industrial silico-calcium board waste material, develops a circular economy, and the road of walking Sustainable development is significant.
The present invention will be devoted to improve the resource utilization degree of calcium silicon plate.Specifically in industrial silico-calcium board waste material, add the compounds such as calcium, magnesium, sulphur, and adopt homemade low temperature additive, silicon in the calcium silicate board with microporous waste material is further activated, together with other component added, being combined into together the moderate-elements such as silicon that acid soil is badly in need of, calcium, magnesium, sulphur is main nutrient type acid soil amendment.
Summary of the invention
A kind of method of utilizing the calcium silicate board with microporous activation to produce the moderate-element acidic soil conditioner of the present invention, by add the components such as white clay, rhombspar in calcium silicate board with microporous, and under the effect that helps additive, make calcium, silicon components activation in calcium silicate board with microporous, together with the calcium in white clay and rhombspar, sulphur, magnesium, chlorine, be combined into take that calcium, silicon, magnesium, sulphur, chlorine are main component, with the moderate-element acidic soil conditioner of weakly alkaline feature.
The present invention has taked following technical process:
According to the mass percent meter, calcium silicate board with microporous waste material 20%～80%, white clay 6%～60%, rhombspar 5%～65%, help additive A and B 1%～5%, the composition mixture material, wherein helping additive A is more than one in potassium felspar sand, white mica, illite or salt of wormwood; Helping additive B is more than one in saltcake, salt or Sodium Fluoride, and helping the mass ratio between additive A and B is 1:0.5～1:2.Mixture is carried out to ball milling, be milled to particle diameter and be less than 0.10mm; Then mixture is dried to water ratio and be less than 6%; Mixture forming process after drying is become to the spherolite that particle diameter is 1～2cm, and enter in the activation kiln and carry out calcination activation, temperature is controlled at 800～1100 ℃, roasting time 0.5～4 hour; Cooling, pulverizing that spherolite after activation carries out, make mineral matter nutritional type acidic soil conditioner; And be packaged into bag.
Compared with the prior art, the present invention has following advantage:
(1) raw materials for production are comprised of natural mineral mostly, have convenience of drawing materials, with low cost, than existing production cost, reduce more than 50%;
(2) in the nutrient type acid soil amendment of producing, the moderate-element component is complete, can reach the effect of balance fertilizing.
(3) utilize the special additive that helps, can make activation temperature from traditional 1200 ℃, the reaction times, more than 5 hours, shortens to 800～1100 ℃, roasting time 0.5～4 hour, and the energy consumption in production process reduces greatly.
The accompanying drawing explanation
Fig. 1 is for utilizing calcium silicate board with microporous to produce moderate-element acidic soil conditioner process flow diagram.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.
embodiment 1
Certain fertilizer company is a kind of scale state owned enterprise of producing composite fertilizer.Adopt this explained hereafter moderate-element acidic soil conditioner, can be used as filling and join in composite fertilizer, make its nutritive ingredient more comprehensive and balanced, and production cost has descended nearly 55%.Its technical process as shown in Figure 1.The mineral raw material adopted (according to the mass percent meter) compatibility is: calcium silicate board with microporous waste material 50%, and white clay 37%, rhombspar 12%, helping additive A and B is 1%, wherein helping additive A is potassium felspar sand+white mica (mass ratio 1:1); Helping additive B is saltcake+salt (mass ratio 1:1), and helping the weight consumption ratio between additive A and B is also 1:1.Above-mentioned mineral raw material is fully mixed, and carry out ball milling, be milled to particle diameter and be less than 0.074mm; Then mixture is dried to water ratio and be less than 5%; Mixture forming process after drying is become to the spherolite of the about 2cm of particle diameter, and enter in the activation kiln and carry out calcination activation, temperature is controlled at 900 ℃, roasting time 1 hour.Carry out cooling, pulverizing after activation, can be made into mineral matter nutritional type acidic soil conditioner.Wherein by the check of third party's composition, learn: the available nutrient in the acidic soil conditioner of production is greater than 72%, wherein the efficient oxidation calcium is greater than 27%, effectively silicon-dioxide is greater than 22%, the efficient oxidation magnesium is greater than 6%, effectively sulphur trioxide is greater than 6%, available chlorine content is greater than 2.5%, and contains various trace elements.The pH=10.2 of product, production cost can be controlled in below 550 yuan/tons.It is a kind of nutrient type acid soil amendment that contains multiple moderate-element.
embodiment 2
Shanxi fertilizer company adopts material (according to the mass percent meter) compatibility of this explained hereafter moderate-element acidic soil conditioner to be: calcium silicate board with microporous waste material 37%, white clay 51%, rhombspar 10%, helping additive A and B is 2%, wherein helping additive A is illite+salt of wormwood (mass ratio 1:1); Helping additive B is salt+Sodium Fluoride (mass ratio 1:1), and helping the mass ratio between additive A and B is 1:2.Its technical process is: above-mentioned mineral raw material is fully mixed, and carry out ball milling, be milled to particle diameter and be less than 0.090mm; Then mixture is dried to water ratio and be less than 6%; Mixture forming process after drying is become to the spherolite of the about 1.5cm of particle diameter, and enter in the activation kiln and carry out calcination activation, temperature is controlled at 950 ℃, roasting time 1.5 hours.Cooling, pulverizing that spherolite after activation carries out, can be made into mineral matter nutritional type acidic soil conditioner.Wherein by the check of third party's composition, learn: in the product of production, available nutrient is greater than 65%, and wherein the efficient oxidation calcium is greater than 31%, and effectively silicon-dioxide is greater than 21%, the efficient oxidation magnesium is greater than 5.5%, effectively sulphur trioxide is greater than 5.4%, and available chlorine content is greater than 3.0%, and contains various trace elements.The pH=11.3 of product, production cost can be controlled in below 520 yuan/tons.It is a kind of nutrient type acid soil amendment that contains multiple moderate-element.
embodiment 3
Guangdong fertilizer company is a kind of large-scale private enterprise that produces soil conditioner.Adopt this explained hereafter moderate-element amendment, production cost has descended nearly 51%, the raw material adopted (according to the mass percent meter) compatibility is: calcium silicate board with microporous waste material 60%, white clay 28%, rhombspar 11%, helping additive A and B is 1%, and wherein helping additive A is illite+white mica (mass ratio 1:1); Helping additive B is saltcake+Sodium Fluoride (mass ratio 1:1), and helping the mass ratio between additive A and B is 1:0.75.Its technical process is: above-mentioned mineral raw material is fully mixed, and carry out ball milling, be milled to particle diameter and be less than 0.074mm; Then mixture is dried to water ratio and be less than 5%; Dry the powder forming process and become the spherolite of the about 2cm of particle diameter, and enter in the activation kiln and carry out calcination activation, temperature is controlled at 1050 ℃, roasting time 40 minutes.Cooling, pulverizing that spherolite after activation carries out, can be made into mineral matter nutritional type acidic soil conditioner.Wherein by the check of third party's composition, learn: the available nutrient in product is greater than 63%, and wherein the efficient oxidation calcium is greater than 27%, and effectively silicon-dioxide is greater than 22%, the efficient oxidation magnesium is greater than 6%, effectively sulphur trioxide is greater than 6%, and available chlorine content is greater than 2%, and contains various trace elements.The pH=11.2 of product, production cost can be controlled in 530 yuan/tons.It is a kind of nutrient type acid soil amendment.
Claims (8)
1. a method of utilizing industrial silico-calcium board waste material to produce the moderate-element acidic soil conditioner, is characterized by, and raw materials for production are in mass percent (%), by following material composition mixture material:
Industry silico-calcium board waste material 20～80
White clay 6～60
Rhombspar 5～65
Help additive A and B 1～5;
By said mixture material process ball milling, dry again, forming process, calcination activation, cooling, pulverize, make mineral matter nutritional type acidic soil conditioner, finally be packaged into bag.
2. a kind of method of utilizing industrial silico-calcium board waste material to produce the moderate-element acidic soil conditioner according to claim 1, is characterized by, and the described additive A that helps is more than one in potassium felspar sand, white mica, illite or salt of wormwood.
3. a kind of method of utilizing industrial silico-calcium board waste material to produce the moderate-element acidic soil conditioner according to claim 1, is characterized by, and the described additive B that helps is more than one in saltcake, salt or Sodium Fluoride.
4. a kind of method of utilizing industrial silico-calcium board waste material to produce the moderate-element acidic soil conditioner according to claim 1, is characterized by, and described to help the mass ratio between additive A and B be 1:0.5～1:2.
5. a kind of method of utilizing industrial silico-calcium board waste material to produce the moderate-element acidic soil conditioner according to claim 1, is characterized by, and described ball milling is less than 0.10mm for mixture is milled to particle diameter.
6. a kind of method of utilizing industrial silico-calcium board waste material to produce the moderate-element acidic soil conditioner according to claim 1, is characterized by, and described oven dry is that mixture is dried to water ratio and is less than 6%.
7. a kind of method of utilizing industrial silico-calcium board waste material to produce the moderate-element acidic soil conditioner according to claim 1, is characterized by, and described forming process is that the mixture forming process after drying is become to the spherolite that particle diameter is 1～2cm.
8. a kind of method of utilizing industrial silico-calcium board waste material to produce the moderate-element acidic soil conditioner according to claim 1, is characterized by, and the temperature of described calcination activation is controlled at 800～1100 ℃, and the time is 0.5～4 hour.
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| CN103771911A (en) * | 2013-12-20 | 2014-05-07 | 华南理工大学 | Method for producing medium element acid soil conditioner by utilizing waste industrial calcium silicate board |
| CN104230561A (en) * | 2014-09-02 | 2014-12-24 | 山西凯盛肥业有限公司 | Silicon, calcium and magnesium soil conditioner and production method of silicon, calcium and magnesium soil conditioner |
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| CN109652081A (en) * | 2019-01-24 | 2019-04-19 | 长江师范学院 | A kind of preparation method of acidic soil conditioner |
| CN111303887A (en) * | 2020-03-19 | 2020-06-19 | 武汉理工大学 | Soil conditioner prepared from calcium silicate board waste and preparation method thereof |
| CN112592721A (en) * | 2020-12-16 | 2021-04-02 | 华南理工大学 | Natural soil heavy metal restoration modifier, preparation method thereof and preparation equipment thereof |
| CN113337295A (en) * | 2021-06-24 | 2021-09-03 | 华南理工大学 | Method for producing soil conditioner by utilizing bulk industrial solid wastes and product |
| CN114317004A (en) * | 2022-01-28 | 2022-04-12 | 徐光� | Medium-element water-soluble fertilizer and soil conditioner and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104230561A (en) * | 2014-09-02 | 2014-12-24 | 山西凯盛肥业有限公司 | Silicon, calcium and magnesium soil conditioner and production method of silicon, calcium and magnesium soil conditioner |
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| CN111303887A (en) * | 2020-03-19 | 2020-06-19 | 武汉理工大学 | Soil conditioner prepared from calcium silicate board waste and preparation method thereof |
| CN112592721A (en) * | 2020-12-16 | 2021-04-02 | 华南理工大学 | Natural soil heavy metal restoration modifier, preparation method thereof and preparation equipment thereof |
| CN113337295A (en) * | 2021-06-24 | 2021-09-03 | 华南理工大学 | Method for producing soil conditioner by utilizing bulk industrial solid wastes and product |
| CN114317004A (en) * | 2022-01-28 | 2022-04-12 | 徐光� | Medium-element water-soluble fertilizer and soil conditioner and preparation method thereof |
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