CN101434495A - Phosphogypsum sustained-controlled compound fertilizer - Google Patents
Phosphogypsum sustained-controlled compound fertilizer Download PDFInfo
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- CN101434495A CN101434495A CNA2007100663739A CN200710066373A CN101434495A CN 101434495 A CN101434495 A CN 101434495A CN A2007100663739 A CNA2007100663739 A CN A2007100663739A CN 200710066373 A CN200710066373 A CN 200710066373A CN 101434495 A CN101434495 A CN 101434495A
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Abstract
The invention relates to a controlled and sustained phosphogypsum compound fertilizer. The phosphogypsum is a chemical waste with enormous emission. The controlled and sustained compound fertilizer is mainly manufactured by processing the phosphogypsum and carbamide or urea resin, and other traditional fertilizer components can be added according to requirements. The fertilizer is comprehensive in efficiency and can control the process of fertilizer efficiency release in accordance with plant needs, thus improving the effective utilization rate of fertilizers, being widely used in plant cultivation and being especially suitable for sandy soil, sulfur deficient soil, perennial plants and alkaline soil. The fertilizer is also more suitable for cruciferae, leguminous crop and tobacco and cotton and the like. The fertilizer is simple in production process, low in energy consumption and low in cost and can be used as field fertilizers, thus having significance to energy saving and emission reducing and environmental protection.
Description
1, technical field: the present invention is a kind of phosphogypsum sustained-controlled compound fertilizer, belongs to the farming, forestry, animal husbandry, sideline production and fishery field.
2, background technology: chemical fertilizer is a readily avaiable fertilizer, plays an important role in modern agriculture.But nitrogenous fertilizer such as urea, soluble in water, it is bigger to run off in soil, waste more, traditional fertilizer nutrient effective rate of utilization is low, life-time service not only causes a large amount of losses of fertilizer nutrient, cause a large amount of wastes of social resources such as coal, electricity, Sweet natural gas in the chemical fertilizers production process, even more serious, using traditional fertilizer has for a long time in a large number caused groundwater azotate content to improve, disastrous effects such as water body in lake eutrophication and atmosphere Greenhouse effect are serious day by day make human life quality and living environment be subjected to serious challenge.
Nineteen forty-seven, the Rohner of the U.S. and wood propose to generate methylene urea as slow acting fertilizer with urea and formaldehyde reaction, by the polymer nitride in the organic synthesis formation fertilizer, its release rate has obtained the patent of first slow acting fertilizer much smaller than the release rate of instant fertilizer in soil.The U.S., Japan and every Western Europe country.Successively this fertilizer is used for the cereal experiment in cultivation.Subsequently, slow-acting fertilizer has obtained bigger development, becomes " slow-release or control-release fertilizer " of seriation, and has formed industrialization, now is widely used.
Slow-release or control-release fertilizer as its name suggests, can delay, and the control fertilizer nutrient discharges, and promptly discharges nutrient according to the crop demand, and to improve the fertilizer rate, it comprises two types: the one, and synthetic organic amino nitrogenous fertilizer comprises urea formaldehyde, urea acetaldehyde; The 2nd, coated fertilizer, as sulfur coated urea, slow inorganic nitrogenous fertilizer, long-term efficiency bicarbonate ammonium etc.
Urea formaldehyde be above-mentioned be basic raw material with urea, in addition certain formaldehyde is called urea-formaldehyde resin again through a series of straight chain compounds of catalyst synthetic, is called for short UF.Now be widely used on meadow, the trees.At present, urea-formaldehyde resin is huge in global output, existing tackiness agent mainly as artificial board, about 1,000,000 tons of Chinese annual production, about 750,000 tons of U.S.'s annual production.
The coating controlled availability fertilizer is to be coated with one deck inert substance on the particle of instant nitrogenousfertilizer, for paraffin, sulphur, resin, polyethylene, pitch, grease etc., by small hole in the inert substance of top layer, realizes the purpose of slowly release and sustained release nutrient.
But the long-acting nitrogen fertilizer cost is higher, is called as " noble's fertilizer " always.Because cost is higher than common fertilizer, generally can only be used at present the crop of high economic worth, be golf turf, gardening and the box thing of planting, nursery, vegetables, fruit etc.Still can not be widely used in field crop.
Phosphogypsum is industrial Wet-process Phosphoric Acid Production waste material.Produce one ton of phosphoric acid and will discharge 5 tons of phosphogypsums.The industry phosphoric acid by wet process is the raw material of production of phosphate fertilizer, and phosphate fertilizer is indispensable fertilizer in the agriculture production.Phosphogypsum is emitted on many countries to be had, and the annual global total release of phosphogypsum is more than 200,000,000 tons now.All there is phosphorus industry in the most of provinces of China, the phosphorus industrial base of focus mostly in Yunnan, phosphate rock resources such as Guizhou, Hubei, Sichuan, Hunan are abundant.China's production of phosphate fertilizer has leapt to the whole world the first now, and domestic phosphogypsum and quantity discharged will break through 3,000 ten thousand tons, be more than three times of Chinese plaster of paris produced quantity.
In July, 2006, China national Environmental Protection Administration has classified phosphogypsum as " dangerous solid waste ".In today of paying attention to environmental protection, a lot of countries all relatively pay attention to the development and use to phosphogypsum.The whole world mainly is used in the building materials aspect with phosphogypsum, and the technology that relates to the utilization of agriculture aspect is few, mainly contains:
Phosphogypsum is produced the volatile salt jointly producing cement, but complex process, power consumption is high.
As soil improvement agent.Because southern rainwater is more, element sulphur runs off in the soil, so soil is low to the level of supply of the sulphur of plant, last century 70, the eighties, the expert of Kunming Ecology Inst., Chinese Academy of Science finds that the paddy soil element sulphur of Jiangchuan County, Yunnan Province is on the low side, impose phosphogypsum after, rice yield rises appreciably.The Yunnan peasant finds that phosphogypsum has certain fertilizer efficiency to farm crop, and phosphogypsum is imposed on the mountain region farm crop, as slowly-releasing poor efficiency fertilizer.North rainwater is less relatively, and the surface water evaporation is serious, and the saltings is many, and phosphogypsum also is used for the improvement in saltings.
At present, phosphogypsum utilization ratio in the whole world is less than 4%.
The applicant has carried out a large amount of scientific researches at phosphogypsum aspect utilizing during the last ten years, before in the building material field application three utilize the phosphogypsum patent, its application number is respectively: a kind of imitated wood material 031269540 (being authorized); A kind of phosphogypsum composite material 2007100656025, a kind of ardealite ceramic materials.200710066333.4 in the patent of invention of " a kind of imitated wood material ", the applicant proposes: form the good New Building Materials of a kind of physical strength with phosphogypsum and urea-formaldehyde resin hybrid reaction.
3, summary of the invention: the present invention is a kind of phosphogypsum sustained-controlled compound fertilizer, it is characterized in that: utilize the combination of phosphogypsum and urea combination or phosphogypsum and urea-formaldehyde resin through being processed to form.
1. utilize phosphogypsum to mix,, need earlier phosphogypsum to be sintered into half water phosphogypsum if phosphogypsum is a phosphogypsum dihydrate with urea, urea and water are formulated as urea soln in required ratio, press required mixed with urea soln and half water phosphogypsum again, then through granulation, solidify dry formation.Urea and water, phosphogypsum portfolio ratio are by the required nitrogen content of fertilizer and fertilizer slow control demand factor and select.The semi-hydrated gypsum aquation needs about 17% water (mass parts) in theory.
Principle: gypsum has a characteristic, and dihydrate gypsum can form semi-hydrated gypsum through 110-150 ℃ of calcinings:
And behind the semi-hydrated gypsum chance water, can aquation be dihydrate gypsum again at normal temperatures, and rapid solidification,
Phosphogypsum has the characteristic of gypsum.Gypsum is slightly soluble in water, easily moisture absorption.The gypsum voidage of casting is more than 40%.
Aqueous solution of urea can make half water phosphogypsum aquation, the solidify out into solid material, and also can increase the intensity that phosphogypsum solidifies.Urea soln is with after half water phosphogypsum mixes, and half water phosphogypsum aquation has absorbed the water in the aqueous solution of urea, forms crystallization, and the urea after the dehydration is inclusive among the crystal space and fine channel of phosphogypsum.This phosphogypsum mixed fertilizer after the granulation, structure is many porous bodies, imposes in the soil, begins slowly to dissolve decomposition from the surface under the effect of soil mineral, water and root system of plant, has discharged urea thereupon.The degree of calcination of phosphogypsum, extent of hydration and granularity can be controlled the dispose procedure of fertilizer efficiency.
2. utilize phosphogypsum to mix with urea-formaldehyde resin.The urea-formaldehyde resin form that is used as slow acting fertilizer in the already mentioned prior art in front is the powder or the particle of urea-formaldehyde resin, is to form through spraying, granulation, drying with urea-formaldehyde resin solution.The present invention then directly utilizes urea-formaldehyde resin solution, makes powder with phosphogypsum dihydrate or half water phosphogypsum or mixes back granulation, dry formation.The mol ratio of urea and formaldehyde in the urea-formaldehyde resin process for preparation needs to select by required nitrogen content of fertilizer and slow control.The portfolio ratio of urea-formaldehyde resin and phosphogypsum also needs to select by the gentle control of nitrogen content.
Principle: urea-formaldehyde resin itself is a kind of slow-acting fertilizer.Propose in the patent of the former application of the applicant: phosphogypsum is a kind of mixture, pH value is 1.5-4 in the phosphogypsum, be sour environment, some in this sour environment and the phosphogypsum can make urea-formaldehyde resin fast setting at normal temperatures as compositions such as aluminum phosphates.Urea-formaldehyde resin is a water soluble resin, and solid content is common 50-65%, and the moisture content in the urea-formaldehyde resin also can make half water phosphogypsum fast setting at normal temperatures.Gypsum and urea-formaldehyde resin can be solidified into the good material of physical strength.Urea-formaldehyde resin has two kinds of viewpoints to enhancing, the academia of gypsum: the one, and chemical reaction has taken place in gypsum and urea-formaldehyde resin; Another kind of viewpoint thinks that urea-formaldehyde resin clogged space and the trickle duct between gypsum crystal.The material that phosphogypsum and urea-formaldehyde resin form is many porous bodies structure.
The applicant finds in the matrix material processing waste of handling the formation of phosphogypsum and urea-formaldehyde resin, this waste material can slowly decompose under the acting in conjunction of root system of plant, microorganism, soil and water, and plant had good fertilizer efficiency, and this fertilizer efficiency is a kind of comprehensive fertilizer efficiency.Because in this fertilizer, except urea-formaldehyde resin was a kind of generally acknowledged fertilizer, from the theoretical analysis of fertilizer science, phosphogypsum itself also was a fertilizer.
Phosphogypsum is said so a kind of composition exactly than complicated mixture, removes and contains
CaSO
4, also have 20% impurity outward, wherein contain free phosphoric acid and sulfuric acid, mono-calcium phosphate, Lin Suanergai, fluorophosphate, potassium, sodium salt, in addition undecomposed phosphorus ore mountain powder and organic matter also have F
2O
5, AL
2O
3, MgO, multiple metallic element such as ZnO.Wherein gypsum is the general middle amount fertilizer of plant, and phosphide, sulfide, phosphide, sylvite and metal-salt all are that plant-growth can not obtain scarce element.
YUNLAN Phosphor Fertilizer Plant phosphogypsum main ingredient:
Component CaO SO
3Fe
2O
5Al
2O
3Total total F of P
Content 29.0 41.5 0.07 0.105 2.0 0.304
The compound manure that phosphogypsum and urea-formaldehyde resin form can also be controlled the dispose procedure of fertilizer efficiency effectively, can be for the sport technique segment of control: the mol ratio of urea and formaldehyde, the condensation level of urea-formaldehyde resin, the ratio of urea-formaldehyde resin and phosphogypsum.Phosphogypsum is not calcined and degree of calcination, grasps link, just can make it to become the fertilizer of " allowing the crops want to eat just eats ", and above-mentioned sport technique segment is the ordinary skill that the preparation urea-formaldehyde resin becomes gesso.
Phosphogypsum sustained-controlled compound fertilizer of the present invention except that above intrinsic component, if desired, can also the phosphogypsum curing molding or with urea-formaldehyde resin and the common curing molding of phosphogypsum as carrier, add other fertilizer components.
The performance of phosphogypsum sustained-controlled compound fertilizer: fertilizer efficiency is comprehensive, and the dispose procedure of may command fertilizer, and production technique is simple, energy-conservation consumption, and cost is low.
Phosphogypsum sustained controlled release fertilizer can the mass consumption industrial waste, realizes reducing discharging purpose, with the protection environment.Population expansion, shortage of resources, environmental degradation are current Sustainable development three big problems, China is with the arable land of less than 10% in the world, supported the population more than 20% in the world, also consumed and accounted for the world's 30% above chemical fertilizer, unit surface arable land chemical fertilizer usage quantity reaches more than 3 times of world average level especially.China depends on the problem that chemical fertilizer promotes agricultural development to bring unduly and seems more and more outstanding now: produce between grain output and the chemical fertilizer income and throw than descending, utilization rate of fertilizer is low, and chemical fertilizer resources such as oil and phosphorus ore are in short supply gradually.China is large agricultural country, how effectively to improve the chemical fertilizer rate of utilization in agricultural development, and saving and using natural resources and production factors is major issues that China faces.The phosphogypsum sustained-controlled compound fertilizer material has found a science, simple and easy, effective new way for addressing the above problem.
From the component of phosphogypsum sustained-controlled compound fertilizer just as can be seen: wherein fertilizer component is more comprehensive, can be widely used in plant.Because it is a kind of acidic fertilizier, and has a slow control performance, so but emphasis imposes on alkaline earth and rate of decay height, eluviation is strong, organic content is low soil, and the low soil of this effective sulfur content is at the regional ubiquity that influenced by strong eluviation, as the southern area of China.Also but emphasis imposes on the northern China saltings, there is the phenomenon of sulfosalt accumulation in the saltings, though sulphur content is higher, but also contain higher magnesium particle concentration, plant-growth there is disadvantageous effect, so need execute gypsum to produce calcium ion etc., when calcium ion concn increases around the plant, because calcium is to the antagonistic action of magnesium, magnesium ion just is not easy to enter in the root.Also but emphasis imposes on sandy soil and perennial plant, as meadow, trees etc.More suitable to acid resistance plant such as cuckoo, tea tree, pineapple etc., in addition to cress, as rape, summer and winter radish, leaf mustard, garlic; Leguminous plants, as peanut, Kidney bean, careless cigarette, cotton also have effect preferably.For acid soil and acid nonfast plant such as alfalfa, beet, oranges and tangerines, tomato etc., then can cooperate alkaline matter such as lime to implement.
The front is mentioned, and the material that phosphogypsum and urea-formaldehyde resin form is the good material of construction of a kind of physical strength, also is a kind of sustained-controlled compound fertilizer material simultaneously.Therefore the material of phosphogypsum and urea-formaldehyde resin formation can be made into the container that cultivates plants, as flowerpot, vase etc.This container itself can slowly be decomposed into plant nutrient is provided, and damaged container gets final product as fertilizer sources after pulverizing.
4, specific embodiment.
1. prepare urea-formaldehyde resin, compound method is the urea-formaldehyde resin traditional technology.The mol ratio of formaldehyde/urea is 1.2, and urea divides three addings in process for preparation.
2. the calcined phosphogypsum powder is selected new phosphogypsum for use, 135 ℃ of calcined dehydration temperature.
3. phosphogypsum and urea-formaldehyde resin capacity ratio are 2:1.
Operation: A, phosphogypsum and urea-formaldehyde resin stir, and make 2mm left and right sides size particles, curing, drying for standby.
B, select the capsicum and the Sunflower Receptacle of Yunnan Yuxi mountain planting to make contrast test of fertilizer efficiency.Respectively select 5 strains, test group imposes on above-mentioned slow control fertilizer in the root soil when transplanting seedlings.Comparative group is not executed.After the seedling strain survives, execute urea one time, test group and comparative group are finally eaten the nitrogen amount and are equated that other management are identical.
The result: the test group Sunflower Receptacle is on average become civilized 5 days in advance time, highly increases 10cm, the big 2cm of seed dish diameter.32 of the average every strains of capsicum comparative group result, 39 of the average every strains of test group result prove obvious effect of increasing production.
Claims (5)
1, a kind of phosphogypsum sustained-controlled compound fertilizer is characterized in that: phosphogypsum mixes with aqueous solution of urea or urea-formaldehyde resin, through powder process or granulation, curing, dry formation.
2, aforesaid right requires 1 described phosphogypsum sustained-controlled compound fertilizer to it is characterized in that can adding other fertilizer components as required.
3, aforesaid right requires 1,2 any described phosphogypsum sustained-controlled compound fertilizer, and its component ratio can be selected prescription according to the needs of fertilizer performance and control fertilizer efficiency dispose procedure.
4, aforesaid right require in 1,2 any described phosphogypsum sustained-controlled compound fertilizer with aqueous solution of urea blended phosphogypsum need be with half water phosphogypsum
And with urea-formaldehyde resin blended phosphogypsum can be half water phosphogypsum or 2 water phosphogypsum (CaSo
42H
2O).
5, aforesaid right requires the material of 1,2 any described phosphogypsum and urea-formaldehyde resin formation, can make both to have can be plant fertilizer efficiency is provided, again the container that can cultivate plants.
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