CN108473380A - NPK fertilizer containing phosphorus potassium nitrogen and the method for being used to prepare the granulated NPK fertilizer containing phosphorus potassium nitrogen - Google Patents
NPK fertilizer containing phosphorus potassium nitrogen and the method for being used to prepare the granulated NPK fertilizer containing phosphorus potassium nitrogen Download PDFInfo
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- CN108473380A CN108473380A CN201780005551.9A CN201780005551A CN108473380A CN 108473380 A CN108473380 A CN 108473380A CN 201780005551 A CN201780005551 A CN 201780005551A CN 108473380 A CN108473380 A CN 108473380A
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B11/00—Fertilisers produced by wet-treating or leaching raw materials either with acids in such amounts and concentrations as to yield solutions followed by neutralisation, or with alkaline lyes
- C05B11/04—Fertilisers produced by wet-treating or leaching raw materials either with acids in such amounts and concentrations as to yield solutions followed by neutralisation, or with alkaline lyes using mineral acid
- C05B11/08—Fertilisers produced by wet-treating or leaching raw materials either with acids in such amounts and concentrations as to yield solutions followed by neutralisation, or with alkaline lyes using mineral acid using sulfuric acid
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C1/00—Ammonium nitrate fertilisers
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B1/00—Superphosphates, i.e. fertilisers produced by reacting rock or bone phosphates with sulfuric or phosphoric acid in such amounts and concentrations as to yield solid products directly
- C05B1/04—Double-superphosphate; Triple-superphosphate; Other fertilisers based essentially on monocalcium phosphate
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G1/00—Mixtures of fertilisers belonging individually to different subclasses of C05
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Abstract
The present invention relates to a kind of compound N P and K NPK fertilizer, wherein total nitrogen content is 13 15%, with P2O5The total phosphate mass fraction of meter is 11 15%, with K2The potassium mass fraction of O meters is 7 8%, and it further relates to use various sylvite, especially potassium chloride and ammonium salt are as the nutrient source in the fertilizer, the method that the fertilizer is prepared by solid phosphate, the solid phosphate is the mixture of fluor-apatite Ca5 (PO4) 3F and calcium monohydrogen phosphate CaHPO4nH2O, wherein n is 0 to 2, and fluor-apatite Cas (PO4) 3F contents are 27% to 99%.The technical result is to provide the enhancing performance of NPK fertilizer; especially preparation method allows to improve granule strength; the water solubility of phosphorus related with the granulation plasticity of composite fertilizer, to contain in improvement fertilizer is solved the problems, such as to 98%, so as to improve the consumer goods performance of NPK fertilizer.
Description
Technical field
The present invention relates to chemical industry, and can be used for the field of composite inorganic NPK fertilizer production technologies.NPK fertilizer
(" nitrogen, phosphorus and potassium fertilizer (azophoska) ", " nitroammophoska (nitroammophoska) ") is that have high economic benefit and envision use
In the composite fertilizer of growing different crops and substantially any soil.The mass fraction that the type of NPK passes through nitrogen, phosphorus and potassium in fertilizer
Characterization.
Modern agricultural chemical science is advocated using the nutritive proportion N with different range:P:K, i.e. N:P2O5:K2The fertilizer of O
Material, this, which needs to develop to provide, produces according to consumer demand and the technology of the possibility of the fertilizer with controlled nutritive proportion
Method.
It is specifically, described the present invention relates to the phosphate production granulation NPK fertilizer by the fluor-apatite containing up to 99%
Phosphate is the CaHPO that wherein n is 0 to 24×nH2O (calcium monohydrogen phosphate) and Ca5(PO4)3The mixture of F (fluor-apatite), phosphoric acid
Fluor-apatite Ca in salt5(PO4)3F contents are 27% to 99%, and wherein this method allows to use various sylvite and ammonium salt as fertilizer
The source of nutrients in material.
The invention further relates to the continuation methods that NPK fertilizer is granulated by the phosphate production containing the fluor-apatite.As potassium
Source has used sylvite, is the raw material being easy to get in the market, especially potassium chloride (KCl).As nitrogen source, ammonium nitrate has been used
NH4NO3With ammonium sulfate (NH4)2SO4.When using KCl as potassium resource in claimed NPK, using ammonium sulfate as stabilization
Agent.
Background technology
RU 2216526 is disclosed has adjustable N for obtaining:P2O5:K2The method of the NPK fertilizer of O ratio, the side
Method includes using nitric acid solution phosphatic raw materials, and nitrogen component is added, is neutralized with ammonia, NP slurries is mixed with potassium chloride and sulfate
It closes.
Patent RU 2439039 and RU 2223933 is also disclosed to be reduced phosphate mine with nitric acid, in adjoint ammonia and slurries
With the method that sylvite is added.
The shortcomings that these methods is：Use expensive and rare component i.e. nitric acid as acid, due to using potassium chloride
Low-intensity and hydrochloric acid release, the property of pellet in the case of as raw material during its storage do not enable consumer satisfaction.Product steams
The hair stage obtains remaining moisture, leads to additional energy consumption, at the same using in ammonia and remaining acid can cause can in product
The reduction of dissolubility microcosmic salt content.
Patent RU2107055 is disclosed for rock and using alkalescence potassium by being reduced phosphate with the mixture of phosphoric acid and sulfuric acid
In salt such as potassium carbonate and mixture, then neutralized with ammonia and the method for preparing compound fertilizer.The disadvantages of this method is to have used to carry
Phosphoric acid is taken, this is a kind of product of costliness, produces the generation along with a large amount of waste, that is, ardealites, and a large amount of water and phosphorus
Acid is introduced into system together, this needs evaporation stage to obtain final product.
Titanium pigment part is set to decrease below 60% with mixture using in ammonia.
Also some research methods are implemented to produce the process of compound fertilizer by soluble phosphate.
Chinese patent CN 1113900 (1994) discloses the production of nitrogenous and phosphorus fertilizer, and wherein fertilizer is by phosphate rock
And nitric acid production, and the product obtained is the Ca (H of crystallization2PO4)2, NH4H2PO4It is obtained by mixing ammonium nitrate with mother liquor
, and the mother liquor ammonia of acquisition is bubbled and generates CaHPO4.The shortcomings that this method may include：There is evaporation rank in the process
Section, the phosphorus in product is not the water-soluble form of calcium monohydrogen phosphate, and the method that potassium introduces fertilizer is not disclosed.
Patent GB 662079 is disclosed based on coming from natural phosphate, DCP (calcium monohydrogen phosphate) or TCP's (tricalcium phosphate)
Decompose fertilizer of the slurries production containing soluble microcosmic salt generated.It is reduced phosphate by sulfuric acid treatment, then exposes mixture
MAP and calcium nitrate are obtained in nitric acid.By ammonium sulfate being added by stable prod, gypsum and nitric acid are thus formed by calcium nitrate
Ammonium.Due to the formation of ammonium sulfate and the geavy salt of two kinds of ammonium nitrate molecules, the ammonium sulfate of the addition of additional amount has favorably fertilizer
It influences.Finally ammonia is added in mixture and realizes and citrate-titanium pigment is formed by the residue of existing MCP
The formation of hydrochlorate-DCP.Disadvantage includes that there are hygroscopicity potassium nitrate in system, this makes it difficult to processing mixture and is granulated
Product, and there are calcium monohydrogen phosphates in product, reduce the content of water-soluble phosphorus form.
British patent GB 702 860 is disclosed prepares granulation NPK fertilizer by the raw material that phosphate decomposition obtains.According to retouching
State, MCP (calcium dihydrogen phosphate) by with nitric acid reduce phosphate rock by prepare.It decomposes and is occurred with two steps.It is granulated according to description
One of the shortcomings that compound NP fertilizer is their plasticity.This problem does not solve in process of production.
Patent CN 1220236 (1997) discloses a kind of method, including white lime and one or two kinds of following substances are mixed
It closes：Powdery Ca3(PO4)2And CaHPO4, it is added with stirring the phosphoric acid 20 to 60 seconds of concentration 62% to 85% at 80 DEG C and generates
MCP (calcium dihydrogen phosphate) then cures 8-100 hours, spontaneously dries and grind to obtain product.H3PO4/Ca3(PO4)2Or
H3PO4/CaHPO4Ratio is identical (7 to 16):100.Ca (the H of powdered2PO4)2With the Ca (OH) of powdered2Reaction generates
CaHPO4, and Ca (OH)2/Ca(H2PO4)2Ratio is (10 to 22):100.The shortcomings that this method, include the use of white lime,
It is periodic (there are product maturation stages) that production, which needs the additional energy, process,.
Method of the another kind for producing MCP is the method with acid decomposed by phosphoric acid apatite.Apatite and phosphatase reaction：
Ca5(PO4)3F+7H3PO4→5Ca(H2PO4)2+HF
Which kind of acid process, method and the form of major product can depend on using：HCl, HNO3, H2SO4Make with acid blend
Change for starting material.
Chinese patent CN 1305946 is disclosed from apatite and is obtained calcium dihydrogen phosphate (MCP).This method includes phosphorus ash
Stone and sulfuric acid react 2-8 hours at a temperature in the range of 70 DEG C to 95 DEG C；The phosphoric acid of filtering and acquisition 10% to 30%；It will
CaCO3It is added in phosphoric acid and removes impurity；With Ca (OH)2It neutralizes and filters；CaHPO is added4And CaO；It is obtained with spray drying
Obtain Ca (H2PO4)2With the product (core of the calcium salt of phosphoric acid, the phosphorus of 19%-22%) with high content of phosphorus.The shortcomings that this method
It is the production of phosphate aqueous solution in one of the stage of process to be, therefore the needs of water evaporation cause and carry out the process relevant additional
Cost.
The author of patent MX NL03000044 (2003) considers calcium dihydrogen phosphate (MCP), the calcium contained in calcium superphosphate
Conversion.This product is obtained using 98% sulfuric acid, anhydrous ammonia, calcium oxide and MCP, DCP or TCP.During the first stage, phosphorus
Acid dihydride calcium and phosphoric acid obtain together with the water from starting calcium superphosphate, and solid indissolvable component (calcium sulfate, calcium phosphate,
Ferric phosphate and aluminum phosphate, fluorine compounds, unreacted starting phosphate material and other insoluble compounds such as silica and silicic acid
Salt) it is detached by being decanted in water.The solution of purifying is reacted with calcium hydroxide suspension, obtains the Crystal suspensions in DCP,
Then it is isolated by decantation.Then the crystal of acquisition is reacted with acid ammonium sulfate and generates mono phosphoric acid ester ammonium salt solution, and led to
It is separated by filtration the insoluble crystal of calcium sulfate dihydrate.In the final stage of reaction, concentrated hydrochloric acid and ammonia are added to DCP and hanged
In supernatant liquid.Filtering generates the solution that MCP concentration is more than 48%.Disadvantage includes：Implement the technical complexity of this method, use is a variety of
Reagent, product loses in precipitation during filtering and decantation, and obtains the MCP of solution form and keep its further processing multiple
Hydridization.
Mexican patent MX NL0500002, which are disclosed, is used to prepare calcium dihydrogen phosphate MCP, sodium phosphate, the side of potassium and MAP
Method, wherein using phosphate rock, sulfuric acid, calcium oxide, ammonium sulfate or potassium sulfate are as raw material.Part and parcel is for producing phosphorus
The method of hydrochlorate, by making DCP (calcium monohydrogen phosphate) with the bisulphate reactant salt appropriate of corresponding (magnesium, ammonium, potassium) salt and
It prepares.When filtering gypsum, the MAP of acquisition or other salt is concentrated and is crystallized in evaporator.The shortcomings that method is salting liquid system
The stage of standby and gypsum filtering causes and the product solidified relevant extra cost by evaporation.Use natural phosphate rock salt
Decompose can cause to generate a large amount of waste ardealite.
In industrial practice, MCP (calcium dihydrogen phosphate) is mainly prepared by calcium salt with phosphatase reaction.One example is
H3PO4With calcium containing compound such as milk of lime reacting at low temperature.In addition it is possible to use Ground limestone and phosphoric acid react.
Another method include by with the mixture of sulfuric acid treatment calcium sulfate and phosphoric acid or by sulfuric acid and calcium sulfate and
Calcium dihydrogen phosphate Ca (H2PO4)2Mixture reaction and prepare the tricalcium orthophosphate Ca of referred to as calcium phosphate3(PO4)2。
It is mainly carried out by decomposing natural phosphate with acid in fact, prepared by NPK.The prior art includes passing through phosphate
The method that the material of simple calcium superphosphate (SSP) or triple superphosphate (TSP) is prepared with sulfuric acid or phosphatase reaction.Soluble part
It is mainly made of single calcium phosphate, and insoluble part is gypsum (and other than the insoluble impurities contained in gypsum in SSP
Other insoluble impurities).
During the processing for obtaining compound fertilizer, raw material in drum granulator using adding a small amount of alkali (for example, ammonia) and
It is granulated.Therefore, it during up to 5% free phosphoric acid content is due in granulation process in the calcium superphosphate of powdered and and drops
Low 1-2%.Meanwhile water-soluble portion reduction reaches 60% level in this process.
The above-mentioned prior art discloses the main aspect and disadvantage of the reaction system of granulation of compound fertilizer.
The shortcomings that known method further includes the current generation in technological development, relevant with NPK compound fertilizer production technologies
Problems with is still the problematic or unsolved fact：
Technically there is problem in the compound fertilizer based on MCP (calcium dihydrogen phosphate) and ammonium nitrate, observe that caking is asked
Topic.The particle obtained is flexible, this makes it difficult to manufacture using conventional granulation processes,
There is reaction release gaseous state HCl in a certain amount of moisture in-MCP and KCl,
MCP may be dissolved in the water of " oneself " during heating.
There is presently no existing including phosphate moiety or with calcium dihydrogen phosphate MCP, that is, it is based on calcium superphosphate or three
The known method for commercial scale compound fertilizer of calcium superphosphate.
Therefore, the present invention is directed to develop with P2O5Highly-water-soluble NEW TYPE OF COMPOSITE NPK fertilizer.
By using potassium chloride (KCl) to be used as potassium resource in the presence of MCP (calcium dihydrogen phosphate) and gypsum and ammonium nitrate being used to make
NPK- fertilizer, which is produced, for nitrogen source solves the problems, such as this.
Since a requirement of the fertilizer of acquisition is P2O5Highly-water-soluble, it is important that have substantially with biphosphate
Phosphatic decompose of the complexity of the phosphatic forms of calcium MCP or other obtains all products, this will provide water solubility.MCP
It should keep stablizing and it being prevented to be converted into calcium monohydrogen phosphate and phosphoric acid.
It should be noted that be presently believed that sulphur be the type fertilizer in important one of nutrient.According to the present invention,
Final products include anhydrous microlith cream (calcium sulfate), provide the channel (be used for plant) of this element of sulphur, required and deposit
It is in the target fertilizer being introduced into soil.
Therefore, the present invention provides the improvement of NPK fertilizer properties, and its production method can improve granule strength simultaneously,
So that solving the problems, such as related to the plasticity of compound fertilizer is granulated, and the consumption performance of NPK fertilizer is thereby enhanced.
The solution of problem causes obtained product to have high efficiency, reduces the cost of final products and is significantly expanded
Raw material basis.
The present invention provides the compound N P and Ks containing ammonium nitrate, monoammonium phosphate, dead plaster, potassium nitrate, ammonium chloride
Fertile (NPK), the wherein mass fraction of total nitrogen are 13%-15%, and the mass fraction of total phosphate is with P2O5It is calculated as 11%-15%, potassium
Mass fraction with K2O is calculated as 7%-8%.
The solution for obtaining the technical problem of this fertilizer is, the side of compound NPK fertilizer is prepared by solid phosphate
Method, the solid phosphate are the mixtures of fluor-apatite and calcium monohydrogen phosphate, and method includes according to described in semidry method sulfuric acid decomposition
Potassium chloride is added as potassium resource in solid phosphate, and ammonium nitrate prepares NPK slurries, granulation and dry final products as nitrogen source.
This solid phosphate is fluor-apatite Ca5(PO4)3F and calcium monohydrogen phosphate CaHPO4×nH2The mixture of O, wherein n
It is 0 to 2, fluor-apatite Ca5(PO4)3F contents are 27% to 99%.
The technical result for implementing this method is P2O5Water-soluble form reach 98%.In other words, the phosphorus contained in fertilizer
98% is water-soluble.The more important for solving technical problem is to implement the technical process to cause by reacting with monohydrate
Form (i.e. it keeps stablizing) obtains MCP (calcium dihydrogen phosphate).To this purpose, the temperature during calcium monohydrogen phosphate decomposes should not surpass
Cross 120 DEG C.Start to be dehydrated at this temperature.
In other words, important aspect be for production process be related at a temperature of no more than 120 DEG C use monohydrate
The MCP of object form, this, which transfers to avoid MCP, is degraded into calcium monohydrogen phosphate and phosphoric acid.
In addition, during NPK is produced, sulfate, especially ammonium sulfate are added, MCP can be made to be converted to phosphoric acid one
Ammonium, to avoid there is remaining reactive MCP in final products, which solve, with HCl is discharged, NPK components are divided during storage
The problem of solution, and the problem of also avoid the plasticity in pelletization stage.
Another importance that claimed method is realized is that sulfate is added to MCP, this can under certain conditions
Anhydrous gypsum is provided.That is, MCP can provide substantially anhydrous gypsum with reacting for sulfate at a temperature of not less than 120 DEG C.
When the technical conditions of acquisition anhydrous gypsum further ensure in the soil using fertilizer in the form of finely dispersed
The availability of basic fertilizer element sulphur.
To sum up, it should be emphasised that, the condition of the method proposed prepares MCP and is fed to and obtains after reactor
The temperature of slurries is not lower than 120 DEG C so that avoiding the formation of the form of gypsum hemihydrate, (it is for the fertilizer right and wrong that are obtained
It is often undesirable).
Therefore, the present invention solves the problems, such as that the plasticity for being granulated compound NPK fertilizer is related.
Invention content
The process that calcium monohydrogen phosphate (DCP) decomposes：
Contact of the concentrated sulfuric acid with calcium monohydrogen phosphate results in calcium dihydrogen phosphate (MCP).By ingredient with relative to the calcium in DCP
Equimolar than mixing (sulfuric acid of equimolar amounts according in chemical reaction (1) and (4) DCP composition calculating).
It is the DCP not instead of pure materials because as starting material, mixture, wherein with DCP mono- to select this method
Rise at least there is also fluor-apatites.
The process that mixing periods occur can be by the system representation of following equation：
H2SO4+2CaHPO4+H2O→Ca(H2PO4)2+CaSO4-71.2kJ/mol (1)
More specifically, reaction enthalpy refers to following general formula：
2CaHPO4·2H2O+H2SO4=CaSO4+Ca(H2PO4)2·H2O+3H2O
In terms of mineralogy, DCP is commonly known as " brushite (brushite) ", is dicalcium phosphate dihydrate.
According to the RTG of the sample DCP of offer measure as a result, it exists with " monetite (monetite) " of anhydrous form, because
This DCP in equation (1) is shown with anhydrous form.The RTG records after reaction are prepared according to MCP, the gypsum of acquisition is anhydrous
Object form and react be exothermic.
Therefore, the formation of 1MCP is reacted to carry out with two stages：
H2SO4+CaHPO4·H3PO4+CaSO4 (2)
H3PO4+CaHPO4→Ca(H2PO4)2 (3)
Parallel with the phosphate decomposition stage is sulfuric acid reacts with fluor-apatite.
7H2SO4+2Ca5F(PO4)3+3H2O→3Ca(H2PO4)2·H2O+7CaSO4+2HF-545.6kJ/mol (4)
Different from DCP conversions, this reaction is high exothermic heat.According to mechanism, phosphate decomposition was reacted with two stages
Occur；In practice, second stage is slow and reacts progress not fully：
Ca5F(PO4)3+5H2SO4→3H3PO4+5CaSO4+2HF (5)
Ca5F(PO4)3+7H3PO4+5H2O→5Ca(H2PO4)2·H2O+2HF (6)
So that the MCP obtained " degrades " and forms DCP and phosphoric acid in the presence of water, again thus then due to back reaction
Form MCP.The back reaction carries out in the presence of water, and therefore, it is difficult to realize high-caliber water-soluble phosphorus (MCP) in reaction mixture
Content.In practice, this by systems with low water content is decomposed by realize.
Ca(H2PO4)2·H2O←→CaHPO4+H3PO4+H2O (7)
It is necessary to obtain MCP in the form of monohydrate, because this temperature during DCP is decomposed should not be more than 120
DEG C, start to be dehydrated at this temperature.In the case of anhydrous MCP being formed under the high-temperature for lacking water or reaction mixture,
Slurries are hydrated during preparing, and are had adverse effect to water balance and reaction medium viscosity, and are in adjoint temperature
Under conditions of variation is difficult to control.
NPK fertilizer is produced using potassium chloride as potassium resource：
Including reaction and ammonium nitrate and MCP intermediate of the system of MCP, ammonium nitrate and potassium chloride due to MCP and KCl
Formed and it is unstable.In order to avoid these are reacted and stablize the quality of final products, it is necessary to remove reactivity from system
MCP.This with gypsum and monoammonium phosphate is further formed by using sulfuric acid in a specific embodiment with sulfuric acid reactant salt
Ammonium and realize.Relative to the MCP obtained in system, equimolar ground dispensing ammonium sulfate：
Ca(H2PO4)2+(NH4)2SO4→2NH4H2PO4+CaSO4 (8)
After KCl is added into the slurries containing ammonium nitrate, conversion reaction is occurred according to time of contact and dose location：
NH4NO3+KCl→KNO3+NH4Cl (9)
For condition, these chemical changes betide at a temperature of 100 DEG C to 130 DEG C.Heat is externally supplied.Reaction
Depth and degree depend on the temperature in system and water content and mixed intensity, the residence time and influence its solubility
The fineness of feed particles.In view of the share of the relative purity of the component of process, other reactions can be ignored.
The NPK products prepared using DCP, sulfuric acid, ammonium nitrate and KCl include mainly following components：
Ammonium nitrate
Monoammonium phosphate
Dead plaster
Potassium nitrate
Ammonium chloride
In general, the technical process of claimed NPK fertilizer produced according to the invention includes the following steps：
1. prepared by Wet portion-slurries
2. stem portion-granulation
3. recycling exhaust gas and waste water
Wet portion is the system for causing to prepare the process for the NPK slurries for being suitble to granulation：
Phosphate (the especially mixture of DCP and fluor-apatite) obtains calcium dihydrogen phosphate (MCP) with sulfuric acid decomposition,
The process carries out in the mixer with fluid bed, the optimum contact for particle during reaction.It reacts in a mixer
Later, it terminates reaction and carries out exhaust gas release in curing unit；
Prepared by further slurries carries out in the cascade for preparing three reactors for having blender.
When using potassium chloride as potassium resource in NPK, the further scheme of method is as follows：
In the first reactor：The ammonium sulfate of grain refined is fed, gypsum and monoammonium phosphate is obtained by the reaction with ammonium sulfate in MCP.
In the second reactor：Feed ammonium nitrate.Ammonium nitrate is matched by batching equipment with melt or particle form
Material.
In third reactor：It feeds microlite potassium chloride and completes to react.
By the slurry feed of the Wet portion from the process to granulation step, in the comminutor of suitable design by
Agglomeration is carried out with being layered in fluid bed.Return to the front that object is input to comminutor.It is dried with hot-air.Carry out following behaviour
Make：Screening crushes, cooling, after being surface-treated with agglomeration resistance additive, obtains the final products for being suitble to storage and transport.
The gas discharged during the exhaust gas of dust containing the raw material used in product and production and production is in wet type
Use is added neutralizer into adsorbent and captures in washer.
The main object of the present invention is to use KCl as potassium resource and ammonium nitrate as nitrogen source in the presence of MCP and gypsum
NPK fertilizer productions.Due to being related to P2O5Water-soluble strict demand, it is necessary to essentially all of phosphorus raw material be made to be in MCP or phosphorus
The form of other sour salt, can provide water solubility.MCP should keep stable, to prevent it to be converted into DCP and phosphoric acid.
Different from other macronutrients, in the case where phosphorus compound to be administered in soil, main problem is them
For the serviceability of plant nutrient.Therefore, all phosphorous fertilizer all seldom assess total phosphorus content.However, being always to provide opposite
Solubility criteria, this standard measure under given conditions：(form of most snap action) in water, (2% lemon in weak acid
Lemon acid or formic acid) or can simulate in the solution of edaphic condition (for example, neutral or alkaline ammonium citrate solution).
Therefore, the NPK production processes entirely proposed can be divided into 2 Main Stages：Produce the process of water-soluble phosphate
With the process for producing compound fertilizer by the salt.According to the present invention, the production of compound NPK fertilizer is made of two main process：It is wet
Process (production of NPK slurries) and dry process (granulation of final products, grinding, screening and cooling).
1. Wet portion
Fig. 1 be using potassium chloride (KCl) as product in potassium resource and the wet processes of NPK slurries is provided.
Calcium phosphate and fluor-apatite (stream 1) are fed together with the phosphate of the mixture of sulfuric acid (stream 2) to flow device (list
First A), it is the mixer with quick rotating vane and reaction mass curing unit.Sulfuric acid with phosphate equimolar ratio
Dispensing.Process can lead to following chemical reaction in the reaction mass in unit A：
H2SO4+2CaHPO4+H2O=Ca (H2PO4)2+CaSO4
7H2SO4+2Ca5(PO4)3F+3H2O=3Ca (H2PO4)2·H2O+7CaSO4+2HF
In both cases, reaction occurs in two stages：Phosphate and sulfuric acid reaction simultaneously discharge phosphoric acid, phosphoric acid and phosphorus
Hydrochlorate reaction generates calcium dihydrogen phosphate (MCP).The reaction that MCP is formed, especially because MCP in the presence of water is decomposed, it may
It will not carry out completely.
Reaction 1 and reaction 2, especially react 2, are exothermic.Technical solution for removing reaction heat is complicated
's：Reactor equipped with water jacket, and some heat from system with exhaust remove and partial heat with dampening
Steam removes.In order to ensure steam and gas remove, mixed cell A is run under vacuum.Heat removal system parameter, which must be adjusted, to be made
The temperature for obtaining reaction mixture is no more than 120 DEG C.
After the mixer, it is with blender by the curing unit of reaction mixture feed a to part of unit A
Device.Following procedure betides in curing unit：
The completion of reaction process；
From the final gas removal in reaction mixture；
The chemical and physical features of reaction mass are averaged.
Further slurries prepare the heating mantle with blender and equipped with overflow mechanism three reactors (unit B,
C, D) cascade in carry out.
First slurry phase reactor (unit B)：
It will be in MAP (monoammonium phosphate) (stream 6) and crystalline sulfuric acid ammonium (stream 5) charging to first reactor.
Including reaction and ammonium nitrate and MCP intermediate of the system of MCP, ammonium nitrate and potassium chloride due to MCP and KCl
Formed and it is unstable.In order to avoid these are reacted and stablize the quality of final product, it is necessary to by with sulfuric acid reactant salt, having
In the embodiment of body, it is further formed gypsum and monoammonium phosphate using ammonium sulfate, reactivity MCP is removed from system.Sulphur
Sour ammonium is relative to the MCP equimolar dispensings obtained in system：
Ca(H2PO4)2+(NH4)2SO4=2NH4H2PO4+CaSO4
Reaction mass (stream 6) containing monoammonium phosphate and gypsum is entered by overflow in next reactor
Second reactor slurries (unit C)：
The main agents of process in reactor are ammonium nitrate.It is provided in granular form.It can use two methods will
It is input in system：
1. before input system, ammonium nitrate is melted in individual reactor and generates melt, then at about 158 DEG C
In the lower aqueous solution dispensing to slurry reactor by the ammonium nitrate containing 93%-97%.
2., will be in its dispensing to slurry phase reactor using proportioner by ammonium nitrate in granular form input system.
It, will be in ammonium nitrate (stream 7) charging to reactor unit C of particle or melt form depending on product form.Reaction
At a temperature of device mixture is held in no more than 160 DEG C.Heat is transmitted by steam jacket and direct steam.In the reactor not
Chemical process, the homogeneous slurry being mixed to get in the ammonium nitrate solution of saturation occurs.
Third slurry phase reactor：
Slurries (stream 8) from second reactor are fed via overflow to third reactor (cells D), wherein crystallizing chlorine
Change potassium to provide by proportioner.When being contacted with nitrate, substitution reaction is carried out according to following equation：
NH4NO3+ KCl=KNO3+NH4Cl
Reaction is carried out very fast and is basically completed in the exit of reactor.Depending on the composition of final products, quality,
Specified conditions, a part of potassium chloride can be not only in dispensing to third slurry phase reactor, but also directly dispensing is into backflowing.Reaction
Device temperature is held in the range of 125 DEG C to 145 DEG C.After third reactor, slurries enter the process of doing (stream 9).
Hydrogen fluoride captures in unit F.
Stream (stream 3) charging of steam and low-pressure gas from mixer to absorption tower, is used into main solution (carbon wherein
The slurries of sour calcium or calcium hydroxide) capture hydrogen fluoride.Final product calcirm-fluoride is filtered, wash and is recycled according to application
Or dry and pack, it is then sent to warehouse.
Therefore, using phosphate, sulfuric acid, ammonium nitrate, ammonium sulfate and potassium chloride prepare this NPK products mainly include with
Lower component：
Ammonium nitrate
Ammonium phosphate
Dead plaster
Potassium nitrate
Ammonium chloride
Illustrate the range of the nutritive proportion of the NPK fertilizer types of production in the examples below.
2. stem portion
Slurries at a temperature of 125 DEG C to 145 DEG C flow to making for arm mixer type by gravity from third reactor
In grain machine.It backflows and is input to its front.Distributor will be in the material in distribution of slurry to comminutor.It is granulated by a fluidized bed
It coalesces and is layered and carries out, fluid bed is generated by the blade being installed on two axis.According to the quality of the compound fertilizer produced,
Pressure adjusts the optimum operation condition (temperature, humidity) of comminutor for 0.3 to 0.4Pa steam feed to comminutor.Temperature
Wet granular within the scope of 90 DEG C to 110 DEG C depends on the composition of fertilizer, water content 1.5-3wt%, by sliding slot from making
Grain machine pallet is slipped in drying cylinder.Last chemical reaction can occur during granulation and drying.
Specific implementation mode
Embodiment
Embodiment 1
The basic process used is described above by reference to the scheme in Fig. 1.
The product obtained described below is using multiple made of phosphate, sulfuric acid, ammonium nitrate and ammonium sulfate and potassium chloride
Npk fertilizer (NPK) is closed, following components is mainly contained：Ammonium nitrate, dead plaster, potassium nitrate, potassium dihydrogen phosphate, and it is total
Nitrogen content is 13-15%, with P2O5The total phosphate mass fraction of meter is 11-15%, with K2O meter potassium mass fraction be
7-8%.
In particular situations, the technical conditions that method is realized allow to obtain corresponding to total nitrogen content, with P2O5That counts is total
Phosphate mass fraction and with K2The 15 of the potassium mass fraction of O meters:15:The compound NPK fertilizer of 8 types.
According to embodiment of the present invention, it is based on fluor-apatite Ca5(PO4)3The fluorine phosphorus that F contents are 27% to 99%
Lime stone Ca5(PO4)3F and calcium monohydrogen phosphate CaHPO4×nH2The above-mentioned NPK of the solid phosphate of the mixture of O (wherein n is 0 to 2)
Production allow use potassium chloride and ammonium nitrate.
Phosphate has been used as raw material, and the salt is by the way that with decomposing phosphate rock by chlorhydric acid stone, then separatin non-soluble precipitation makes
It is obtained with calcium carbonate serosity precipitation solid phosphate.In order to produce phosphate, the rock from the mineral deposits Keysik has been used：
| Substance | Unit | Content |
| P2O5, total amount | % | 28.71 |
| Cl | % | 0.0783 |
| F | % | 2.9 |
| SO4 | % | 1.04 |
| Ca | % | 31.8 |
| SiO2 | mg/kg | 73285 |
| MgO | mg/kg | 33172 |
This method provides fluor-apatite Ca5(PO4)3F and calcium monohydrogen phosphate CaHPO4×nH2The mixture of O, wherein n are 0 to 2,
Fluor-apatite Ca5(PO4)3F contents are 27% to 99%, are used for the further production process of NPK compositions：
| Substance | Unit | Content |
| P2O5, total amount | % | 42 |
| Cl | % | 0.15 |
| F | % | 1.02 |
| CaO | % | 38 |
It is containing in phosphate and by with hydrochloric acid reduce phosphate mine acquisition fluorine be present in the form of fluor-apatite
In mixture, this analysis of control by sample by, confirms.Phosphate DCP containing 27% fluor-apatite is further used for NPK
Production.
The stage of the solid phosphate described in sulfuric acid decomposition is carried out at a temperature of 110 DEG C to 120 DEG C using semidry method,
Middle decomposition is carried out with low water content.This necessary condition is due to equimolar selection in system, to maintain in the form of monohydrate
MCP stability.
More specifically, being fed with equimolar ratio in phosphate [557kg/h] into the mixer with fluid bed
98% sulfuric acid [272kg/h].The process is carried out under vacuum preferably to remove discharged gas, mainly hydrogen fluoride.Instead
Answer material by curing in unit feed to the cascade reactor with blender.Gas, mainly hydrogen fluoride are provided to absorption
Step.The process carries out at a temperature of no more than 120 DEG C.
In addition, in first reactor in cascade reactor, ammonium sulfate [224kg/h] is fed with fine powder form, process
It is carried out at a temperature of 130 DEG C to ensure the condition of anhydrous gypsum formation.Instead by ammonium nitrate melt [726kg/h] charging to second
It answers in device, process carries out in the reactor at 160 DEG C.Grain refined potassium chloride [320kg/h] is fed into third reactor,
Being swift in response in third reactor occurs and is completed at 120 DEG C.
When completing the process in third reactor, mixture is fed to the stem portion of process；It is granulated and drying causes to give birth to
There is group to be grouped as N for production:P2O5:K2O=15:15:8 compound NPK fertilizer, contains finely dispersed anhydrous gypsum form
Sulphur.
Embodiment 2
Used basic process is described above with reference to the scheme in Fig. 1.
The compound nitrogen, phosphorus and potassium fertilizer (NPK) obtained contains ammonium nitrate, monoammonium phosphate, dead plaster, potassium nitrate, ammonium chloride,
Wherein total nitrogen content is 13-15%, and total phosphate mass fraction is with P2O5It is calculated as 11-15%, potassium mass fraction is with K2O is counted
For 7-8%.
In particular situations, the technical conditions that method is realized allow to obtain corresponding to total nitrogen content, with P2O5That counts is total
Phosphate mass fraction and with K2The potassium mass fraction 15 of O meters:15:The compound NPK fertilizer of 8 types.
According to embodiment of the present invention, above to be based on wherein fluor-apatite Ca5(PO4)3F contents be 27% to
99% fluor-apatite Ca5(PO4)3F and calcium monohydrogen phosphate CaHPO4×nH2The solid phosphate of the mixture of O (wherein n is 0 to 2)
NPK production allow use potassium chloride and ammonium nitrate.
Phosphate has been used as raw material, and the salt is by the way that with decomposing phosphate rock by chlorhydric acid stone, then separatin non-soluble precipitation makes
It is obtained with calcium carbonate serosity precipitation solid phosphate.It is similar to Example 1, in order to produce phosphate, uses and come from
The rock in the mineral deposits Keysik：
The process provides fluor-apatite Ca5(PO4)3F and calcium monohydrogen phosphate CaHPO4×nH2The mixture of O, wherein n be 0 to
2, fluor-apatite Ca5(PO4)3F contents are 27% to 99%, are used for the further production process of NPK compositions：
| Substance | Unit | Content |
| P2O5, total amount | % | 41 |
| Cl | % | 0.2 |
| F | % | 3.73 |
| CaO | % | 37 |
It is containing in phosphate and by with hydrochloric acid reduce phosphate mine acquisition fluorine be present in the form of fluor-apatite
In mixture, this analysis of control by sample by, confirms.Phosphate DCP containing 99% fluor-apatite is further used for NPK
Production.
The stage of the solid phosphate described in sulfuric acid decomposition is carried out at a temperature of 110 DEG C to 120 DEG C using semidry method,
Middle decomposition is carried out with low water content.This necessary condition is the selection due to the medium molar ratio of system, to maintain monohydrate shape
The stability of the MCP of formula.
More specifically, being fed with equimolar ratio in phosphate [557kg/h] into the mixer with fluid bed
98% sulfuric acid [272kg/h].The process is carried out under vacuum preferably to remove discharged gas, mainly hydrogen fluoride.Instead
Answer material by curing in unit feed to the cascade reactor with blender.Gas, mainly hydrogen fluoride are provided to absorption
Step.The process carries out at a temperature of no more than 120 DEG C.
In addition, in first reactor in cascade reactor, ammonium sulfate [224kg/h] is fed with fine powder form, process
It is carried out at a temperature of 130 DEG C to ensure the condition of anhydrous gypsum formation.Instead by ammonium nitrate melt [726kg/h] charging to second
It answers in device, process carries out in the reactor at 160 DEG C.Grain refined potassium chloride [320kg/h] is fed into third reactor,
Being swift in response in third reactor occurs and is completed at 120 DEG C.
When completing the process in third reactor, mixture is fed to the stem portion of process；It is granulated and drying is led
Cause production there is group to be grouped into N:P2O5:K2O=13:11:7 compound NPK fertilizer, contains finely dispersed anhydrous gypsum
The sulphur of form.
Embodiment 3
Used basic process is described above by reference to the scheme in Fig. 1.
According to embodiment of the present invention, above to be based on wherein fluor-apatite Ca5(PO4)3F contents be 27% to
99% fluor-apatite Ca5(PO4)3F and calcium monohydrogen phosphate CaHPO4×nH2The solid phosphate of the mixture of O (wherein n is 0 to 2)
NPK production allow use potassium chloride and ammonium nitrate.
Phosphate, the salt is used to be obtained by using decomposing phosphate rock by chlorhydric acid stone similar to Examples 1 and 2 as raw material
.
The compound nitrogen, phosphorus and potassium fertilizer (NPK) obtained contains ammonium nitrate, monoammonium phosphate, dead plaster, potassium nitrate, chlorination
Ammonium, wherein total nitrogen content is 13-14%, total phosphate mass fraction is with P2O5It is calculated as 12-13%, potassium mass fraction is with K2O
It is calculated as 7-8%.
Claims (14)
1. a kind of compound npk fertilizer (NPK), it is characterised in that it contains ammonium nitrate, monoammonium phosphate, dead plaster, nitric acid
Potassium, ammonium chloride, the wherein mass fraction of total nitrogen are 13-15%, with P2O5The mass fraction of the total phosphate of meter is 11-15%, with
K2The mass fraction of the potassium of O meters is 7-8%.
2. a kind of method preparing compound NPK fertilizer described in claim 1 by solid phosphate, the solid phosphate is it
Middle fluor-apatite Ca5(PO4)3The fluor-apatite Ca that F contents are 27% to 99%5(PO4)3The calcium monohydrogen phosphate that F and wherein n are 0 to 2
CaHPO4×nH2The mixture of O, including with the next stage：
The stage of the solid phosphate is decomposed using semidry method with sulfuric acid,
Potassium chloride of the addition as potassium resource, the stage of the ammonium nitrate as nitrogen source,
Prepare the stage of NPK slurries and the stage of the granulation of final product and drying.
3. according to the method described in claim 2, wherein, process is continuous.
4. according to the method described in claim 2, wherein, capture decomposes the hydrogen fluoride generated by the solid phosphate.
5. according to the method described in claim 2, wherein, the decomposition of the solid phosphate uses the sulphur of a concentration of 96-98%
Acid carries out.
6. according to the method described in claim 2, wherein, the sulfuric acid and the solid phosphate are fed with equimolar ratio to anti-
It answers in material.
7. according to the method described in claim 2, wherein, the semidry method is to use sulfuric acid in low water content condition in systems
It is lower to decompose the phosphate.
8. according to the method described in claim 2, wherein, temperature of the solid phosphate described in sulfuric acid decomposition at 110 DEG C to 120 DEG C
Degree is lower to carry out.
9. according to the method described in claim 2, wherein, the product that the solid phosphate decomposes is deposited in the form of monohydrate
Calcium dihydrogen phosphate (MCP).
10. according to the method described in claim 2, wherein, the solid phosphate described in sulfuric acid decomposition carries out in a fluidized bed.
11. according to the method described in claim 2, wherein, the solid phosphate described in sulfuric acid decomposition carries out under vacuum, and can
Removing hydrogen fluoride to absorption system.
12. according to the method described in claim 2, wherein, due to the solid phosphate, especially its fluor-apatite part
Gypsum (the CaSO for decomposing and being formed4) mainly with anhydrous form be present in reaction mass and final product in.
13. according to the method described in claim 2, wherein, using potassium chloride, using sulfate, especially sulphur
Sour ammonium removes reactivity MCP from system.
14. according to the method for claim 13, wherein ammonium sulfate with the equimolar of MCP ratio to feed into reaction mass.
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| RU2016107776 | 2016-03-03 | ||
| RU2016107776A RU2626947C1 (en) | 2016-03-03 | 2016-03-03 | Phosphorus-potassuim-nitrogen-containing npk-fertiliser and method for producing granulated phosphorus-potassuim-nitrogen-containing npk-fertiliser |
| PCT/RU2017/000108 WO2017151017A1 (en) | 2016-03-03 | 2017-03-01 | Phosphorus-potassium-nitrogen-containing npk-fertilizer and a method for the preparation of granulated phosphorus-potassium-nitrogen-containing npk-fertilizer |
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| CN (1) | CN108473380A (en) |
| EA (1) | EA030295B1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108698948A (en) * | 2015-12-21 | 2018-10-23 | 亚拉国际有限公司 | ammonium nitrate fertilizer composition and preparation method thereof |
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| NO344285B1 (en) * | 2017-11-20 | 2019-10-28 | Elkem Materials | NPK-Si fertilizer and method for production thereof |
| EP4317119A1 (en) * | 2022-08-04 | 2024-02-07 | SABIC Global Technologies B.V. | Complex fertilizer comprising nitrogen, phosphorous, sulfur, calcium and magnesium nutrients |
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| RU2626947C1 (en) | 2017-08-02 |
| WO2017151017A1 (en) | 2017-09-08 |
| EA030295B1 (en) | 2018-07-31 |
| EA201692457A1 (en) | 2017-09-29 |
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