CN105601345A - Method for preparing calcium nitrate and magnesium fertilizer from coarse calcium nitrate as by-product of nitrophosphate fertilizer - Google Patents
Method for preparing calcium nitrate and magnesium fertilizer from coarse calcium nitrate as by-product of nitrophosphate fertilizer Download PDFInfo
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- CN105601345A CN105601345A CN201510988950.4A CN201510988950A CN105601345A CN 105601345 A CN105601345 A CN 105601345A CN 201510988950 A CN201510988950 A CN 201510988950A CN 105601345 A CN105601345 A CN 105601345A
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C5/00—Fertilisers containing other nitrates
- C05C5/04—Fertilisers containing other nitrates containing calcium nitrate
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Abstract
The invention is applied to the technical field of fertilizer preparation and provides a method for preparing calcium nitrate and magnesium fertilizer from coarse calcium nitrate as a by-product of nitrophosphate fertilizer. The method comprises the following steps: coarse calcium nitrate as the by-product of the nitrophosphate fertilizer is provided; magnesium oxide or magnesium hydroxide is added to calcium nitrate and mixed, and a calcium nitrate and magnesium mixed solution is obtained; the calcium nitrate and magnesium mixed solution is filtered, concentrated and granulated sequentially, and the water-soluble granular calcium nitrate and magnesium fertilizer is obtained. According to the method, coarse calcium nitrate as the by-product of the nitrophosphate fertilizer is directly used as a calcium source, the calcium source is not needed to be introduced from outside, and nitric acid raw materials are not needed to be consumed, so that the raw material cost is reduced greatly; meanwhile, magnesium oxide or magnesium hydroxide is adopted to neutralize free acid in coarse calcium nitrate, production and emission of residues are avoided, load of production equipment is reduced, the yield is increased, the environmental protection concept is met, the process of the method is simple and easy to control, and industrialization is realized easily.
Description
Technical field
The invention belongs to fertilizer preparing technical field, relate in particular to the thick calcium nitrate system of nitrophosphate fertilizer accessory substance of utilizingThe method of standby calcium nitrate fertiliser containing magnesium.
Background technology
Calcium nitrate fertiliser containing magnesium is a kind of important water soluble fertilizer, and it mainly comprises calcium nitrate and two kinds of water of magnesium nitrateSoluble. Wherein, the nitrate nitrogen containing in calcium nitrate fertiliser containing magnesium can directly be absorbed by plants, fast for plant is mendedFill nutrition; Water-soluble calcium can promote the absorption of Nitrogen In Soils, phosphorus, potassium, increases the resistance of crop; WaterDissolubility magnesium can improve the content of making object inner chlorophyll, promotes photosynthesis.
The existing method of preparing calcium nitrate fertiliser containing magnesium, is generally and uses calcium Mg nitrate raw material mixing post processingAfter, in patent of invention CN103833444A, the preparation method of calcium nitrate magnesium double salt type composite fertilizer is: willMass ratio is (3.5～0.1): 1 magnesium nitrate and calcium nitrate are configured to mixed aqueous solution; Then by mixing waterThe concentrate that solution simmer down to total mass ratio is 50～90%; Concentrate is delivered in 30～110M head tankUnder 85～130 DEG C of conditions, the shower nozzle ejection from 0.5～3.0MM continuously, after air is cooling, makes calcium nitrateMagnesium compound fertilizer product. This product feature is magnesium nitrate in composite fertilizer, the total mass ratio 50～90% of calcium nitrate,The mass ratio of the crystallization water is 10～50%, the mass ratio 3.5～0.1:1 of magnesium nitrate and calcium nitrate. And inventionIn the multifunctional high-calcium fertilizer that patent CN104211482A provides, by 50～70% parts of calcium ammonium nitrates, magnesium nitrate 30～60% and boric acid 1～5% mix, after heating, drying, make height thereby grind to form 50～200 object powderCalcareous fertilisers. Said method is produced calcium nitrate fertiliser containing magnesium and is all adopted directly by granulation system after magnesium nitrate and calcium nitrate mixtureObtain calcium nitrate fertiliser containing magnesium, therefore energy consumption and integrated cost are high, and automaticity is low. Therefore, how to optimize nitreThe preparation method of acid ca and mg fertilizer, the production cost that reduces calcium nitrate fertiliser containing magnesium is to advance calcium nitrate fertiliser containing magnesium extensively to quoteKey factor.
In patent of invention CN104326771A, utilize phosphorus mine tailing to add in lime and calcium hydroxide neutralization filtrateFree acid, make PH be adjusted to 6.5～7, after filtration, make calcium nitrate magnesium after the operation such as Vacuum Concentration is dryFertilizer product. But the method is produced calcium nitrate fertiliser containing magnesium, has following problem: first, in phosphorus mine tailingResidue is many, causes that machine utilization is large, and output is lower; Secondly, this method fails to make the calcium salt in mine tailing fully aliveChange, so that need to be reintroduced back to outside calcium salt, calcium utilization deficiency; Again, need consumption nitric acid and mine tailing anti-Should, acid consumption is large, and cost is higher.
Summary of the invention
The object of the present invention is to provide one to utilize the thick calcium nitrate of nitrophosphate fertilizer accessory substance to prepare calcium nitrate fertiliser containing magnesiumMethod, the preparation method who is intended to solve existing calcium nitrate fertiliser containing magnesium need to introduce outside calcium salt, its cost of materialDrop into problems high and that finished product residue is many.
The method of utilizing the thick calcium nitrate of nitrophosphate fertilizer accessory substance to prepare calcium nitrate fertiliser containing magnesium provided by the invention, comprisesFollowing steps:
The thick calcium nitrate of accessory substance of preparing nitrophosphate fertilizer is provided;
In described calcium nitrate, add magnesia or magnesium hydroxide, be mixed to get calcium nitrate magnesium mixed solution;
Described calcium nitrate magnesium mixed solution is filtered successively, concentrated and granulation processing, obtain water-soluble nitreAcid calcium magnesium granules fertilizer.
Particularly, taking the gross weight of described calcium nitrate magnesium granules fertilizer as 100%, in described calcium nitrate magnesium granules fertilizerThe weight percentage of magnesium is 1.0～6.5%; The quality percentage composition of calcium is 10～18.5%.
Particularly, the pH value of described calcium nitrate magnesium mixed solution is 6.0～7.0.
In above-mentioned steps, also comprise the pH value of described calcium nitrate magnesium mixed solution is regulated to processing.
Particularly, the evaporating temperature of described concentration is 150～155 DEG C.
Particularly, the temperature of described granulation processing is 50～90 DEG C, and pressure is ﹣ 100～﹣ 500Pa.
Particularly, after described granulation treatment step, also comprise described calcium nitrate magnesium granules fertilizer is sievedProcess, obtaining particle diameter is the calcium nitrate magnesium granules fertilizer of 1～4mm.
Particularly, after described granulation treatment step, also comprise and carry out cooling processing, described cooling processingTemperature is 30～50 DEG C, and pressure is ﹣ 100～﹣ 500Pa, humidity≤60%.
The method of utilizing the thick calcium nitrate of nitrophosphate fertilizer accessory substance to prepare calcium nitrate fertiliser containing magnesium provided by the invention, directlyUse the thick calcium nitrate of nitrophosphate fertilizer accessory substance as calcium source, do not need to introduce calcium source by outside again, reduced formerMaterial cost; Meanwhile, adopt the free acid in magnesia or magnesium hydroxide and in described thick calcium nitrate, avoidedThe generation of waste residue and discharge, reduced the load of production equipment, improved output, meets environmental protection theory;In addition, the present invention utilizes the thick calcium nitrate of nitrophosphate fertilizer accessory substance to prepare the method for calcium nitrate fertiliser containing magnesium, does not need to disappearConsumption nitric acid material, cost of material is further reduced, and technological process is simple and easy to control, is easy to realize industryChange.
Brief description of the drawings
Fig. 1 is that the thick calcium nitrate of nitrophosphate fertilizer accessory substance that utilizes that the embodiment of the present invention provides is prepared calcium nitrate fertiliser containing magnesiumMethod flow schematic diagram;
Fig. 2 is that the thick calcium nitrate of nitrophosphate fertilizer accessory substance that utilizes that the embodiment of the present invention 1 provides is prepared calcium nitrate magnesiumFertile method flow schematic diagram.
Detailed description of the invention
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearer, withUnder by reference to the accompanying drawings and embodiment, the present invention is further elaborated. Should be appreciated that described hereinSpecific embodiment only in order to explain the present invention, be not intended to limit the present invention.
The embodiment of the present invention provides a kind of nitrophosphate fertilizer accessory substance thick calcium nitrate of utilizing to prepare calcium nitrate fertiliser containing magnesiumMethod, comprises the following steps, as shown in Figure 1:
S01., the thick calcium nitrate of accessory substance of preparing nitrophosphate fertilizer is provided;
S02. in described calcium nitrate, add magnesia or magnesium hydroxide, be mixed to get calcium nitrate magnesium and mix moltenLiquid;
S03. described calcium nitrate magnesium mixed solution filtered successively, concentrate and granulation processing, obtain water-solubleProperty calcium nitrate magnesium granules fertilizer.
Concrete, in above-mentioned steps S01, prepare in the process of nitrophosphate fertilizer, can produce a large amount of accessory substancesThick calcium nitrate. Particularly freezing is prepared the process of nitrophosphate fertilizer, 100 tons of about by-products of nitrophosphate fertilizer of every production60 tons, thick calcium nitrate. In described thick calcium nitrate, mainly contain a large amount of four water-calcium nitrate crystal, in addition, withThe gross weight of described thick calcium nitrate is 100%, also contains free nitric acid 6%, fluosilicic acid and phosphoric acid 0.6%, waterDivide 32%, magnesium nitrate, ferric nitrate and aluminum nitrate add up to 0.2%, acid non-soluble substance 0.09%. A large amount of thick nitric acidIf calcium is not processed, on the one hand, cause a large amount of wastes of resource, be unfavorable for the control of production cost;On the other hand, hoarding in a large number of thick calcium nitrate, easily increases the load of environment, does not meet environmental protection theory.The embodiment of the present invention, using the thick calcium nitrate of accessory substance of preparing nitrophosphate fertilizer as raw material, is described calcium nitrate fertiliser containing magnesiumPreparation calcium source and nitrogenous source are provided, making does not need to introduce outside calcium in the preparation process of described calcium nitrate fertiliser containing magnesiumSource and nitrogenous source, significantly reduced production cost.
In the embodiment of the present invention, the thick calcium nitrate of accessory substance of preparing nitrophosphate fertilizer is solution state. As onePreferred embodiment, the temperature of described thick calcium nitrate is 60～90 DEG C, this preferred temperature can ensure described thickCalcium nitrate solution has good mobility; Described calcium nitrate can be because of the too low formation calcium nitrate of temperature simultaneouslyCrystallization and cause line clogging.
In above-mentioned steps S02, in described calcium nitrate, add magnesia or magnesium hydroxide, on the one hand, utilizeMagnesia or magnesium hydroxide can neutralize the free acid (reaction equation is as follows) in described calcium nitrate, fully aliveChange the calcium ion in described calcium nitrate, meanwhile, reach the object of the pH value in coarse adjustment mixed solution; The opposing partyFace, by adding described magnesia or magnesium hydroxide, for the preparation of described calcium nitrate fertiliser containing magnesium provides magnesium source.
Reaction equation: 2H++MgO→Mg2++H2O
2H++Mg(OH)2→Mg2++2H2O
As preferred embodiment, the pH value of described calcium nitrate magnesium mixed solution is 6.0～7.0. This is preferredPH value scope, the fertilizer that can make the embodiment of the present invention obtain is not only applicable to northern basic soil, can yetBe suitable for southern acid ground, be difficult for causing soil compaction; In addition the described nitric acid of this preferred pH value scope,Ca and mg fertilizer material product can improve soil texture.
The amount that described magnesia or magnesium hydroxide add, with the concentration of calcium ion in described thick calcium nitrate andIn the product obtaining eventually, the content of water-soluble calcium, magnesium is specifically determined. As concrete preferred embodiment, withThe gross weight of the described calcium nitrate magnesium granules fertilizer obtaining is eventually 100%, the weight of magnesium in described calcium nitrate magnesium granules fertilizerAmount percentage composition is 1.0～6.5%; The quality percentage composition of calcium is 10～18.5%. Described magnesia or hydrogen-oxygenChange the amount that magnesium adds, can calculate successively.
In the embodiment of the present invention, institute may can't be realized by adding described magnesia or magnesium hydroxide merelyState the above-mentioned PH scope of calcium nitrate magnesium mixed solution. In this case, as preferred embodiment, add describedAdd after the step of magnesia or magnesium hydroxide, also comprise and use the PH of nitric acid to described calcium nitrate magnesium mixed solutionValue regulates processing, and the pH value that makes described calcium nitrate magnesium mixed solution is 6.0～7.0.
As further preferred embodiment, give in described calcium nitrate magnesium mixed solution each for fear of aforementioned processingThe content of component causes error or fluctuation, affects the performance of described calcium nitrate fertiliser containing magnesium, can adopt and addThe form of magnesia or magnesium hydroxide, thick calcium nitrate is carried out trim process to described calcium nitrate magnesium mixed solution,Make the content of each component more meet the instructions for use of described calcium nitrate fertiliser containing magnesium.
In above-mentioned steps S03, described calcium nitrate magnesium mixed solution is dried to processing, remove water-insoluble,Particularly acid non-soluble substance. As preferred embodiment, described dry processing adopts filter press to realize, described press filtrationIn machine, air pressure is set to 0.4-0.8MPa.
After described dry processing, the filtrate obtaining is carried out to concentration, the evaporating temperature of described concentrationIt is 150～155 DEG C. As concrete preferred embodiment, the method for described concentration is:
Described calcium nitrate magnesium mixed solution is placed in to evaporation feeder trough, and adjustment evaporimeter middle pressure steam temperature is190-215 DEG C, pressure are 1.8-2.0MPa.
Condensate liquid using middle pressure saturated vapor further heats described calcium nitrate magnesium mixed solution as thermal source, makesIts temperature rises to 130 DEG C of left and right by 100 DEG C, finally enters evaporimeter;
In evaporimeter with in press saturated vapor as thermal source, by adjusting middle pressure steam amount, by molten calcium nitrate magnesiumLiquid is heated to 150～155 DEG C of boiling points and evaporates, and the gas-liquid mixture that evaporation produces goes out evaporimeter and enters evaporationIn separator;
The flash distillation of expanding in vapor seperator, and carry out gas-liquid separation, the pressure in vapor seperator is:-0.008～-0.012MPa。
In the embodiment of the present invention, the calcium nitrate magnesium concentrate obtaining after described concentration is carried out to granulation processing.During described granulation is processed, the performance of the calcium nitrate magnesium granules fertilizer that temperature and pressure obtains granulation has certain influence.Concrete, the too low granulating weak effect of temperature; Excess Temperature fertiliser granulates intensity is low, easily efflorescence. When pressure mistakeWhen large, easily cause the fragmentation of described calcium nitrate magnesium granules fertilizer; In the time that pressure is too small, the described nitric acid obtainingThe fertile degree of packing of calcium magnesium granules is inadequate, easily efflorescence, particularly easily efflorescence in transportation. As preferablyEmbodiment, the temperature of described granulation processing is 50～90 DEG C, pressure is ﹣ 100～﹣ 500Pa.
As further preferred embodiment, in order to obtain even-grained described calcium nitrate magnesium granules fertilizer, in instituteState after granulation treatment step, also comprise the processing of sieving of described calcium nitrate magnesium granules fertilizer, obtain particle diameter and beThe calcium nitrate magnesium granules fertilizer of 1～4mm.
As another preferred embodiment, after described granulation treatment step, also comprise and carry out cooling processing,The temperature of described cooling processing is 30～50 DEG C, and pressure is ﹣ 100～﹣ 500Pa, humidity≤60%.
The described calcium nitrate magnesium granules fertilizer that further, can also obtain granulation carries out anti-compaction processing
The side that what the embodiment of the present invention provided utilize the thick calcium nitrate of nitrophosphate fertilizer accessory substance to prepare calcium nitrate fertiliser containing magnesiumMethod, is directly used the thick calcium nitrate of nitrophosphate fertilizer industrial by-products as calcium source, does not need to introduce calcium by outside againSource, has reduced cost of material; Meanwhile, adopt the trip in magnesia or magnesium hydroxide and in described thick calcium nitrateFrom acid, avoid generation and the discharge of waste residue, reduce the load of production equipment, improve output, meetEnvironmental protection theory; In addition, the present invention utilizes nitrophosphate fertilizer accessory substance thick calcium nitrate to prepare calcium nitrate fertiliser containing magnesiumMethod, does not need to consume nitric acid material, and cost of material is further reduced, and technological process is simple and easy to control,Be easy to realize industrialization. The calcium nitrate fertiliser containing magnesium of preparing by embodiment of the present invention method is full water soluble fertilizerProduct, can improve fruit appearance color and luster and fineness, improves fruit quality and output, improves fruit grade.
Describe below in conjunction with specific embodiment, should be understood that, following embodiment is only as a toolBody embodiment describes embodiment of the present invention technical scheme, is not expressed as the unique of the embodiment of the present inventionTechnical scheme.
One utilizes the thick calcium nitrate of nitrophosphate fertilizer accessory substance to prepare that calcium weight percentage is 16.8%, magnesium weightPercentage composition is the method for 2.2% calcium nitrate fertiliser containing magnesium, comprises the following steps, as shown in Figure 2:
S11. provide the thick calcium nitrate of accessory substance of preparing nitrophosphate fertilizer: by thick nitric acid after nitrophosphate fertilizer freezing and crystallizingCalcium, is separated by filtration and beats to thick nitre calcium liquid dashpot, is delivered to neutralization chamber 1 by thick nitre calcium pump;
S12. in described calcium nitrate, add magnesia or magnesium hydroxide, be mixed to get calcium nitrate magnesium and mix moltenLiquid, specifically comprises the following steps:
S121. in the thick calcium nitrate concentration obtaining according to detection, the content of calcium is (as thick calcium nitrate mass concentration is60%), set the addition of magnesia (or magnesium hydroxide), regulate thick calcium nitrate solution and magnesia qualityThan being 30.7:1 (calcium magnesium mass ratio is 4.5:1);
S122. by described magnesia (or magnesium hydroxide) from neutralization chamber top hopper down to belt scale meteringBe delivered to neutralization reaction groove, the free acid (trip in described magnesia (or magnesium hydroxide) and described thick calcium nitrateFrom sour mass concentration approximately 6%) generation neutralization reaction;
S13. described calcium nitrate magnesium mixed solution filtered successively, concentrate and granulation processing, obtain water-solubleProperty calcium nitrate magnesium granules fertilizer, specifically comprises the following steps:
S131. the filtrate after neutralization is squeezed into coarse filtration feeder trough 2, be delivered to plate compression by coarse filtration feed pumpMachine 3 carries out press filtration processing, isolates insoluble matter waste residue, obtains the first filtrate;
S132. described the first filtrate after press filtration enters clear liquid groove 4, is delivered to proportioning groove by the pumping of clear liquid groove5, according to calcium nitrate magnesium clear liquid calcium-magnesium content ratio, pH value, add magnesia, nitric acid, thick calcium nitrate solutionDescribed the first filtrate is finely tuned;
S133. carry described the first filtrate to filter press 6 filtration treatment again by essence filter feed pump, filter outAfter filter residue, obtain the second filtrate;
S134. described the second filtrate enters evaporation feeder trough 7, is delivered to preheater 8 pre-by evaporation feed pumpHeat, temperature rises to 110 degree by 90 degree;
S135. described the second filtrate after the pre-heat treatment enters heat exchanger 9, and evaporation feed temperature is by 110 degreeBe increased to 140 degree;
S136. described the second filtrate enters forced-circulation evaporator 10, makes described the second filtrate be heated to boiling point150～155 DEG C evaporate, evaporated laggard enter granulation feeder trough 12;
S137. granulation feeder trough is delivered to rotary drum granulator 13 feed liquid and carries out granulation; Through cooling 16, sieveDivide 14 (mesh size 1mm～4mm), anti-compaction to make calcium nitrate magnesium products 18 after processing 17.
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, not all at thisAny amendment of doing within bright spirit and principle, be equal to and replace and improvement etc., all should be included in the present inventionProtection domain within.
Claims (8)
1. utilize the thick calcium nitrate of nitrophosphate fertilizer accessory substance to prepare a method for calcium nitrate fertiliser containing magnesium, comprise following stepRapid:
The thick calcium nitrate of accessory substance of preparing nitrophosphate fertilizer is provided;
In described calcium nitrate, add magnesia or magnesium hydroxide, be mixed to get calcium nitrate magnesium mixed solution;
Described calcium nitrate magnesium mixed solution is filtered successively, concentrated and granulation processing, obtain water-soluble nitreAcid calcium magnesium granules fertilizer.
2. the nitrophosphate fertilizer accessory substance thick calcium nitrate of utilizing as claimed in claim 1 is prepared calcium nitrate fertiliser containing magnesiumMethod, is characterized in that, taking the gross weight of described calcium nitrate magnesium granules fertilizer as 100%, and described calcium nitrate magnesiumIn granulated fertilizer, the weight percentage of magnesium is 1.0～6.5%; The quality percentage composition of calcium is 10～18.5%.
3. the nitrophosphate fertilizer accessory substance thick calcium nitrate of utilizing as claimed in claim 1 is prepared calcium nitrate fertiliser containing magnesiumMethod, is characterized in that, the pH value of described calcium nitrate magnesium mixed solution is 6.0～7.0.
4. the nitrophosphate fertilizer accessory substance thick calcium nitrate of utilizing as claimed in claim 3 is prepared calcium nitrate fertiliser containing magnesiumMethod, is characterized in that, also comprises the pH value of described calcium nitrate magnesium mixed solution is regulated to processing.
5. the thick calcium nitrate of nitrophosphate fertilizer accessory substance that utilizes as described in as arbitrary in claim 1-3 is prepared calcium nitrateThe method of fertiliser containing magnesium, is characterized in that, the evaporating temperature of described concentration is 150～155 DEG C.
6. the thick calcium nitrate of nitrophosphate fertilizer accessory substance that utilizes as described in as arbitrary in claim 1-3 is prepared calcium nitrateThe method of fertiliser containing magnesium, is characterized in that, the temperature of described granulation processing is 50～90 DEG C, and pressure is ﹣ 100～﹣500Pa。
7. the thick calcium nitrate of nitrophosphate fertilizer accessory substance that utilizes as described in as arbitrary in claim 1-3 is prepared calcium nitrateThe method of fertiliser containing magnesium, is characterized in that, after described granulation treatment step, also comprises described calcium nitrate magnesiumThe granulated fertilizer processing of sieving, obtaining particle diameter is the calcium nitrate magnesium granules fertilizer of 1～4mm.
8. the thick calcium nitrate of nitrophosphate fertilizer accessory substance that utilizes as described in as arbitrary in claim 1-3 is prepared calcium nitrateThe method of fertiliser containing magnesium, is characterized in that, after described granulation treatment step, also comprises and carries out cooling processing, instituteThe temperature of stating cooling processing is 30～50 DEG C, and pressure is ﹣ 100～﹣ 500Pa, humidity≤60%.
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| CN201510988950.4A CN105601345A (en) | 2015-12-25 | 2015-12-25 | Method for preparing calcium nitrate and magnesium fertilizer from coarse calcium nitrate as by-product of nitrophosphate fertilizer |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108147859A (en) * | 2016-12-02 | 2018-06-12 | 贵州芭田生态工程有限公司 | Nitric acid ca and mg fertilizer and preparation method thereof |
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| CN104326771A (en) * | 2014-10-22 | 2015-02-04 | 瓮福（集团）有限责任公司 | Method for preparing calcium-magnesium nitrate fertilizer by utilizing phosphate tailings |
| CN104744100A (en) * | 2015-03-20 | 2015-07-01 | 路永宽 | Method for full water-soluble calcium and magnesium ammonium nitrate by disc granulation |
| CN104829271A (en) * | 2015-05-06 | 2015-08-12 | 贵州省化工研究院 | Method for preparing calcium magnesium ammonium phosphate and calcium magnesium ammonium nitrate from phosphor tailings |
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| CN103833444A (en) * | 2014-03-14 | 2014-06-04 | 交城县金兰化工有限公司 | Magnesium nitrate-calcium nitrate complex salt type compound fertilizer and preparation method thereof |
| CN104326771A (en) * | 2014-10-22 | 2015-02-04 | 瓮福（集团）有限责任公司 | Method for preparing calcium-magnesium nitrate fertilizer by utilizing phosphate tailings |
| CN104744100A (en) * | 2015-03-20 | 2015-07-01 | 路永宽 | Method for full water-soluble calcium and magnesium ammonium nitrate by disc granulation |
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