CN104311190A - Method for producing high concentration chlorine-based composite fertilizer by partially decalcifying hydrochloric acid decomposed phosphorite - Google Patents
Method for producing high concentration chlorine-based composite fertilizer by partially decalcifying hydrochloric acid decomposed phosphorite Download PDFInfo
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- CN104311190A CN104311190A CN201410525643.8A CN201410525643A CN104311190A CN 104311190 A CN104311190 A CN 104311190A CN 201410525643 A CN201410525643 A CN 201410525643A CN 104311190 A CN104311190 A CN 104311190A
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- composite fertilizer
- high concentration
- acid
- hydrochloric acid
- decalcifying
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
Abstract
The invention discloses a method for producing a high concentration chlorine-based composite fertilizer by partially decalcifying hydrochloric acid decomposed phosphorite. The method comprises the following steps: using a byproduct hydrochloric acid in industrial production for decomposing phosphorite; and defluorinating, partially decalcifying the obtained acidolysis liquid and carrying out solid-liquid separation to obtain a phosphorus and nitrogen containing solution; introducing ammonia to neutralize; and concentrating and adding potassium and granulating to produce the high concentration chlorine-based composite fertilizer. The method specifically comprises the following steps: A) carrying out acidolysis on phosphorite; B) defluorinating and partially decalcifying the obtained acidolysis liquid; C) ammonification; D) concentration; and E) adding potassium and granulating to produce the high concentration chlorine-based composite fertilizer. The method disclosed by the invention can be used for consuming hydrochloric acid on a large scale, so that the problem that industrial byproduct hydrochloric acid is hard to use is effectively solved. Compared with sulfuric acid decomposed phosphorite, the hydrochloric acid decomposed phosphorite has the advantages of being fast in reaction, high in decomposition rate, wide in application range of phosphorite raw materials, low in cost and the like. Therefore, rich low and medium-grade phosphorite sources in China are fully utilized, and the total nutrient of the obtained product nitrogen phosphorus and potassium composite fertilizer is greater than or equal to 40%.
Description
Technical field
The present invention relates to a kind of method that decomposing phosphate rock by chlorhydric acid partly decalcifying produces high concentration cl base composite fertilizer, particularly one utilizes industrial by-product decomposing phosphate rock by chlorhydric acid, and the acid hydrolysis solution partly decalcifying obtained is for the preparation of the method for high concentration cl base composite fertilizer.Belong to composite fertilizer producing process technical field.
Background technology
There is abundant phosphate rock resource in China, reserves are only second to Morocco, occupy second place of the world, but compared with world's concerned countries, it has larger gap in ore quality, washability and Rock Phosphate (72Min BPL) exploitation etc., wherein can be relatively low for the Rock Phosphate (72Min BPL) basic unit price of processing and utilization, only have 40.54 hundred million tons, P
2o
5the rich ore that massfraction is greater than 30% only has 11.08 hundred million tons, and national Rock Phosphate (72Min BPL) P
2o
5average mass fraction only has 17%.In recent years, along with the excessive use of abundant ore source, now increasingly exhausted, how effective exploitation, utilize Mid-and low-grade phosphate rock resources to become particularly important for the Sustainable development of China's sulphur dioxide of phosphor chemical industry.
About the correlative study of decomposing phosphate rock by chlorhydric acid, research history existing very long both at home and abroad, because there is the problem of calcium chloride and phosphoric acid separation difficulty in this route, generally be divided into two lines: one is utilize decomposing phosphate rock by chlorhydric acid, with an organic solvent phosphoric acid by wet process is extracted, and then through back extraction, evaporation, concentrated obtain purification of phosphoric acid and reclaim organic solvent, there is the shortcomings such as flow process complexity, investment is large, energy consumption is high in this route.Two is utilize decomposing phosphate rock by chlorhydric acid to produce secondary calcium phosphate, normally adopt in lime slurry or calcium carbonate and acid hydrolysis solution, calcium in acid hydrolysis solution is separated out with the form of secondary calcium phosphate, although this technique flow process is simple, be convenient to control, but also there is a large amount of calcium chloride solutions to be wasted, the problems such as economy is not high.
Summary of the invention
The object of the invention is to the defect overcoming prior art, there is provided a kind of hydrochloric acid of industrial production by-product that utilizes as acid hydrolysis solution decomposing phosphate rock, and added value is high, effluent discharge is few, the decomposing phosphate rock by chlorhydric acid acid hydrolysis solution that phosphorus, nitrogen recovery are high prepares the method for chlorine-based compound fertilizer.
Decomposing phosphate rock by chlorhydric acid acid hydrolysis solution of the present invention prepares the method for chlorine-based compound fertilizer, is achieved in that
Comprise the following steps:
A. adopt industrial by-product hydrochloric acid to be used for decomposing phosphate rock as acid hydrolysis solution, phosphorus ore raw material is mid low grade phosphate rock and phosphorus concentrate;
B. the phosphorus ore acid hydrolysis liquid obtained by step a adds defluorinating agent defluorinate, and separating acid insolubles obtains defluorinate acid hydrolysis solution;
C. the defluorinate acid hydrolysis solution obtained by step b adds calcium remover precipitated calcium ion, and filter the solid gypsum generated, filtrate is partly decalcifying acid hydrolysis solution;
D. the partly decalcifying acid hydrolysis solution obtained by step c leads in ammonia and ammonification, concentrated, adds potash fertilizer, granulation production chloro NPK composite fertilizer;
E. the solid gypsum obtained by step c obtains high purity gypsum product through washing, vacuum evaporation drying treatment.
In step a, phosphorus ore globule size is 1 ~ 5mm, phosphorus ore P
2o
5content is 15% ~ 30%.
In step a, the weight fraction of hydrochloric acid is 20 ~ 35%; Hydrochloric acid consumption is 100 ~ 105% of theoretical amount, temperature of reaction 25 ~ 50 DEG C, reaction times 0.5 ~ 2.0h.
In step b, defluorinating agent is the one in sodium sulfate, sodium-chlor, potassium sulfate, Repone K; Consumption is 50 ~ 80% of theoretical amount; Temperature of reaction is 30 ~ 50 DEG C, and the reaction times is 1.0 ~ 2.5h.
Calcium remover in step c is the mixture of a kind of or ammonium sulfate in ammonium sulfate, potassium sulfate and potassium sulfate, and calcium remover consumption is sulfate radical and calcium ion mol ratio 0.6-0.85:1 in defluorinate acid hydrolysis solution, and temperature of reaction is 30-60 DEG C, and the reaction times is 1.0-4.0h.
Ammonia used with ammonification in steps d is liquefied ammonia, and potash fertilizer raw material is Repone K.
The neutralization reaction terminal pH of steps d is 3.8 ~ 4.2, degree of neutralization 1.0-1.2.
In step e, the condition of vacuum evaporation is temperature 60-80 DEG C, pressure 0.04 ~ 0.08MPa.
Instant invention overcomes the drawback that the above-mentioned operational path of background technology exists, with ammonium sulfate, potassium sulfate as the calcium ion in heavy calcium agent partial removal acid hydrolysis solution, by-product high purity gypsum, process discharge refuse is few, added value of product is high, can utilize industrial by-product hydrochloric acid and domestic abundant Mid-and low-grade phosphate rock resources cost-effectively.
The present invention can consume industrial by-product hydrochloric acid on a large scale, and the chlorine-based compound fertilizer added value of product obtained is high, and economic benefit is good, has important reality and economic implications to effectively utilizing industrial by-product hydrochloric acid and domestic abundant Mid-and low-grade phosphate rock resources.
Accompanying drawing explanation
Fig. 1 is present invention process schema.
Embodiment
Be described below in detail embodiments of the invention, the example of described embodiment is shown in the drawings.Described embodiment, only for explaining the present invention, and can not be interpreted as limitation of the present invention.
Using industrial by-product hydrochloric acid as acid hydrolysis solution decomposing phosphate rock, the acid hydrolysis solution obtained through defluorinate, partly decalcifying, solid-liquid separation, phosphorous, the nitrogen solution that obtain lead to ammonia neutralization, concentrate, add potassium granulation produce chlorine-based compound fertilizer, concrete grammar is as follows:
A. adopt industrial by-product hydrochloric acid to be used for decomposing phosphate rock as acid hydrolysis solution, phosphorus ore raw material is mid low grade phosphate rock and phosphorus concentrate;
B. the phosphorus ore acid hydrolysis liquid obtained by step a adds defluorinating agent defluorinate, and separating acid insolubles obtains defluorinate acid hydrolysis solution;
C. the defluorinate acid hydrolysis solution obtained by step b adds calcium remover precipitated calcium ion, and filter the solid gypsum generated, filtrate is partly decalcifying acid hydrolysis solution;
D. the partly decalcifying acid hydrolysis solution obtained by step c leads in ammonia and ammonification, concentrated, adds potash fertilizer, granulation production chloro NPK composite fertilizer;
E. the solid gypsum obtained by step c obtains high purity gypsum product through washing, vacuum evaporation drying treatment.
In step a, phosphorus ore globule size is 1 ~ 5mm, phosphorus ore P
2o
5content is 15% ~ 30%.
In step a, the weight fraction of hydrochloric acid is 20 ~ 35%; Hydrochloric acid consumption is 100 ~ 105% of theoretical amount, temperature of reaction 25 ~ 50 DEG C, reaction times 0.5 ~ 2.0h.
In step b, defluorinating agent is the one in sodium sulfate, sodium-chlor, potassium sulfate, Repone K; Consumption is 50 ~ 80% of theoretical amount; Temperature of reaction is 30 ~ 50 DEG C, and the reaction times is 1.0 ~ 2.5h.
Calcium remover in step c is the mixture of a kind of or ammonium sulfate in ammonium sulfate, potassium sulfate and potassium sulfate, and calcium remover consumption is sulfate radical and calcium ion mol ratio 0.6-0.85:1 in defluorinate acid hydrolysis solution, and temperature of reaction is 30-60 DEG C, and the reaction times is 1.0-4.0h.
Ammonia used with ammonification in steps d is liquefied ammonia, and potash fertilizer raw material is Repone K.
The neutralization reaction terminal pH of steps d is 3.8 ~ 4.2, degree of neutralization 1.0-1.2.
In step e, the condition of vacuum evaporation is temperature 60-80 DEG C, pressure 0.04 ~ 0.08MPa.
embodiment 1
(1) by P
2o
5content is the ground phosphate rock that 24.74% Rock Phosphate (72Min BPL) is broken for globule size 2mm, washing lotion when being filtered with acidolysis section acid non-soluble substance by industrial by-product hydrochloric acid mixes, be mixed with the hydrochloric acid soln that weight fraction is 25%, above-mentioned hydrochloric acid soln is added acidolysis groove under agitation and ground phosphate rock carries out acidolysis reaction, hydrochloric acid consumption is 100% of theoretical amount, temperature of reaction is 40 DEG C, and the reaction times is 1.0h;
(2) under agitation, in step (1) acidolysis gained slip, add anhydrous sodium sulphate carry out defluorination reaction, its consumption is 60% of theoretical amount, temperature of reaction is 40 DEG C, reaction times is 1.5h, then filters slip, and filtrate is the acid hydrolysis solution through defluorinate process;
(3) under agitation, filter in gained filtrate toward step (2) and add ammonium sulfate partly decalcifying, ammonium sulfate consumption is sulfate radical and calcium ion mol ratio 0.65 in acid hydrolysis solution, temperature of reaction is 50 DEG C, reaction times is 2.5h, remove gypsum by solid-liquid separation, liquid phase is the acid hydrolysis solution after partly decalcifying, gained gypsum 100g wash water/100g(gypsum) washing, under 100 DEG C of conditions drying can obtain high purity gypsum product;
(4) step (3) gained acid hydrolysis solution is carried out logical ammonia neutralization, control neutralization reaction terminal pH4.1, degree of neutralization 1.18;
(5) by step (4) neutralization reaction gained slip in temperature 70 C, under pressure 0.055MPa condition, carry out vacuum evaporation, removing free-water wherein;
(6) add Repone K toward step (5) evaporation concentration gained slip, the nitrogen in adjustment nutrient, phosphorus, potassium proportioning are 17-19-4;
(7) step (6) gained slip is carried out concentrate, granulation, final generation produces chloride NPK composite fertilizer.
embodiment 2
(1) by P
2o
5content is the ground phosphate rock that 21.57% Rock Phosphate (72Min BPL) is broken for globule size 5mm, washing lotion when being filtered with acidolysis section acid non-soluble substance by industrial by-product hydrochloric acid mixes, be mixed with the hydrochloric acid soln that weight fraction is 18%, above-mentioned hydrochloric acid soln is added acidolysis groove under agitation and ground phosphate rock carries out acidolysis reaction, hydrochloric acid consumption is 105% of theoretical amount, temperature of reaction is 45 DEG C, and the reaction times is 2.0h;
(2) under agitation, in step (1) acidolysis gained slip, add potassium sulfate carry out defluorination reaction, its consumption is 80% of theoretical amount, and temperature of reaction is 30 DEG C, and the reaction times is 1.0h, then filters slip, and filtrate is the acid hydrolysis solution through defluorinate process;
(3) under agitation, filter in gained filtrate toward step (2) and add ammonium sulfate partly decalcifying, ammonium sulfate consumption is sulfate radical and calcium ion mol ratio 0.80 in acid hydrolysis solution, temperature of reaction is 40 DEG C, reaction times is 3.0h, remove gypsum by solid-liquid separation, liquid phase is the acid hydrolysis solution after decalcification, gained gypsum 150g wash water/100g(gypsum) washing, under 90 DEG C of conditions drying can obtain gypsum product;
(4) step (3) gained acid hydrolysis solution is carried out logical ammonia neutralization, control neutralization reaction terminal pH4.0, degree of neutralization 1.10;
(5) by step (4) neutralization reaction gained slip in temperature 60 C, under pressure 0.07MPa condition, carry out vacuum evaporation, removing free-water wherein;
(6) add Repone K toward step (5) evaporation concentration gained slip, the nitrogen in adjustment nutrient, phosphorus, potassium proportioning are 18-17-5;
(7) step (6) gained slip is carried out concentrate, granulation, final generation produces chloride N-P-K composite fertilizer.
embodiment 3
(1) by P
2o
5content is the ground phosphate rock that 26.52% Rock Phosphate (72Min BPL) is broken for globule size 3mm, washing lotion when being filtered with acidolysis section acid non-soluble substance by industrial by-product hydrochloric acid mixes, be mixed with the hydrochloric acid soln that weight fraction is 20%, above-mentioned hydrochloric acid soln is added acidolysis groove under agitation and ground phosphate rock carries out acidolysis reaction, hydrochloric acid consumption is 103% of theoretical amount, temperature of reaction is 40 DEG C, and the reaction times is 0.5h;
(2) under agitation, in step (1) acidolysis gained slip, add sodium-chlor carry out defluorination reaction, its consumption is 70% of theoretical amount, and temperature of reaction is 40 DEG C, and the reaction times is 1.5h, then filters slip, and filtrate is the acid hydrolysis solution through defluorinate process;
(3) under agitation, filter in gained filtrate toward step (2) and add ammonium sulfate and potassium sulfate partly decalcifying, ammonium sulfate and potassium sulfate consumption are sulfate radical and calcium ion mol ratio 0.75 in acid hydrolysis solution, and ammonium sulfate: potassium sulfate mol ratio is 80:20, temperature of reaction is 60 DEG C, reaction times is 2.0h, gypsum is removed by solid-liquid separation, liquid phase is the acid hydrolysis solution after partly decalcifying, gained gypsum 120g wash water/100g(gypsum) washing, under 105 DEG C of conditions drying can obtain gypsum product;
(4) step (3) gained acid hydrolysis solution is carried out logical ammonia neutralization, control neutralization reaction terminal pH3.8, degree of neutralization 1.07;
(5) by step (4) neutralization reaction gained slip in temperature 80 DEG C, under pressure 0.045MPa condition, carry out vacuum evaporation, removing free-water wherein;
(6) add Repone K toward step (5) evaporation concentration gained slip, the nitrogen in adjustment nutrient, phosphorus, potassium proportioning are 19-17-6;
(7) step (6) gained slip is carried out concentrate, granulation, final generation produces chloride N-P-K composite fertilizer.
Method provided by the invention can obtain the water-soluble chloride composite fertilizer of the middle and high concentration meeting CNS (GB15063-2001) (high density: total nutrient (N+P
2o
5+ K
2o) content>=40%, water-soluble phosphorus accounts for available phosphorus percentage>=70%; Middle concentration: total nutrient (N+P
2o
5+ K
2o) content>=30%, water-soluble phosphorus accounts for available phosphorus percentage>=50%), product can be used as avoids chlorine farm crop base fertilizer, and market potential is huge, and added value is high; Present method effluent discharge is few, with environmental friendliness; Phosphorus, nitrogen recovery are high, economically can utilize the hydrochloric acid of industrial by-product and domestic abundant Mid-and low-grade phosphate rock resources.
The hydrochloric acid of industrial production by-product is used for decomposing phosphate rock by the present invention, and the acid hydrolysis solution obtained is through defluorinate, partly decalcifying, and logical ammonia neutralization, adds potassium, chlorine-based compound fertilizer is produced in granulation.
Claims (8)
1. decomposing phosphate rock by chlorhydric acid partly decalcifying produces a method for high concentration cl base composite fertilizer, it is characterized in that, comprises the following steps:
A. adopt industrial by-product hydrochloric acid to be used for decomposing phosphate rock as acid hydrolysis solution, phosphorus ore raw material is mid low grade phosphate rock and phosphorus concentrate;
B. the phosphorus ore acid hydrolysis liquid obtained by step a adds defluorinating agent defluorinate, and separating acid insolubles obtains defluorinate acid hydrolysis solution;
C. the defluorinate acid hydrolysis solution obtained by step b adds calcium remover precipitated calcium ion, and filter the solid gypsum generated, filtrate is partly decalcifying acid hydrolysis solution;
D. the partly decalcifying acid hydrolysis solution obtained by step c leads in ammonia and ammonification, concentrated, adds potash fertilizer, granulation production chloro NPK composite fertilizer;
E. the solid gypsum obtained by step c obtains high purity gypsum product through washing, vacuum evaporation drying treatment.
2. a kind of decomposing phosphate rock by chlorhydric acid partly decalcifying according to claim 1 produces the method for high concentration cl base composite fertilizer, it is characterized in that: in step a, phosphorus ore globule size is 1 ~ 5mm, phosphorus ore P
2o
5content is 15% ~ 30%.
3. a kind of decomposing phosphate rock by chlorhydric acid partly decalcifying according to claim 1 produces the method for high concentration cl base composite fertilizer, it is characterized in that: in step a, the weight fraction of hydrochloric acid is 20 ~ 35%; Hydrochloric acid consumption is 100 ~ 105% of theoretical amount, temperature of reaction 25 ~ 50 DEG C, reaction times 0.5 ~ 2.0h.
4. a kind of decomposing phosphate rock by chlorhydric acid partly decalcifying according to claim 1 produces the method for high concentration cl base composite fertilizer, it is characterized in that: in step b, defluorinating agent is the one in sodium sulfate, sodium-chlor, potassium sulfate, Repone K; Consumption is 50 ~ 80% of theoretical amount; Temperature of reaction is 30 ~ 50 DEG C, and the reaction times is 1.0 ~ 2.5h.
5. a kind of decomposing phosphate rock by chlorhydric acid partly decalcifying according to claim 1 produces the method for high concentration cl base composite fertilizer, it is characterized in that: the calcium remover in step c is the mixture of a kind of or ammonium sulfate in ammonium sulfate, potassium sulfate and potassium sulfate, calcium remover consumption is sulfate radical and calcium ion mol ratio 0.6-0.85:1 in defluorinate acid hydrolysis solution, temperature of reaction is 30-60 DEG C, and the reaction times is 1.0-4.0h.
6. decomposing phosphate rock by chlorhydric acid partly decalcifying according to claim 1 produces the method for high concentration cl base composite fertilizer, it is characterized in that: ammonia used with ammonification in steps d is liquefied ammonia, and potash fertilizer raw material is Repone K.
7. decomposing phosphate rock by chlorhydric acid partly decalcifying according to claim 1 produces the method for high concentration cl base composite fertilizer, it is characterized in that: the neutralization reaction terminal pH of steps d is 3.8 ~ 4.2, degree of neutralization 1.0-1.2.
8. decomposing phosphate rock by chlorhydric acid partly decalcifying according to claim 1 produces the method for high concentration cl base composite fertilizer, it is characterized in that: in step e, the condition of vacuum evaporation is temperature 60-80 DEG C, pressure 0.04 ~ 0.08MPa.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104925772A (en) * | 2015-05-06 | 2015-09-23 | 贵州省化工研究院 | Process for preparing phosphate concentrate and byproduct magnesium-containing calcium carbonate from medium-low-grade phosphorite |
| CN105272441A (en) * | 2015-09-23 | 2016-01-27 | 四川泸天化股份有限公司 | Process for production of liquid compound fertilizer by combination of decomposition of phosphate ore by use of nitric acid and removal of calcium by use of potassium salt |
| CN108046864A (en) * | 2017-11-13 | 2018-05-18 | 兰小春 | Hydrochloric acid decomposes the method and device of low-grade phosphate ore production water soluble composite fertilizer |
| CN108946689A (en) * | 2017-05-27 | 2018-12-07 | 山东红日化工股份有限公司 | A kind of production method of potassium dihydrogen phosphate |
| CN108975975A (en) * | 2017-05-31 | 2018-12-11 | 山东红日化工股份有限公司 | A kind of production method of decomposing phosphate rock by chlorhydric acid production amino compound fertilizer |
| CN112745160A (en) * | 2021-01-21 | 2021-05-04 | 瓮福（集团）有限责任公司 | Novel process for preparing NPK compound fertilizer by using phosphogypsum and potassium feldspar |
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| CN102126742A (en) * | 2011-01-20 | 2011-07-20 | 山东金正大生态工程股份有限公司 | Method for producing chloride-based compound fertilizer and co-producing gypsum through decomposing phosphorite with hydrochloric acid |
| CN102417169A (en) * | 2011-08-15 | 2012-04-18 | 武善东 | Acidolysis method of magnesium-containing phosphate rock |
| CN102583290A (en) * | 2012-02-18 | 2012-07-18 | 张黔生 | Low-grade phosphorite mineral dressing technology and method for producing by-product high-purity gypsum powder |
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| CN102126742A (en) * | 2011-01-20 | 2011-07-20 | 山东金正大生态工程股份有限公司 | Method for producing chloride-based compound fertilizer and co-producing gypsum through decomposing phosphorite with hydrochloric acid |
| CN102417169A (en) * | 2011-08-15 | 2012-04-18 | 武善东 | Acidolysis method of magnesium-containing phosphate rock |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104925772A (en) * | 2015-05-06 | 2015-09-23 | 贵州省化工研究院 | Process for preparing phosphate concentrate and byproduct magnesium-containing calcium carbonate from medium-low-grade phosphorite |
| CN105272441A (en) * | 2015-09-23 | 2016-01-27 | 四川泸天化股份有限公司 | Process for production of liquid compound fertilizer by combination of decomposition of phosphate ore by use of nitric acid and removal of calcium by use of potassium salt |
| CN108946689A (en) * | 2017-05-27 | 2018-12-07 | 山东红日化工股份有限公司 | A kind of production method of potassium dihydrogen phosphate |
| CN108975975A (en) * | 2017-05-31 | 2018-12-11 | 山东红日化工股份有限公司 | A kind of production method of decomposing phosphate rock by chlorhydric acid production amino compound fertilizer |
| CN108046864A (en) * | 2017-11-13 | 2018-05-18 | 兰小春 | Hydrochloric acid decomposes the method and device of low-grade phosphate ore production water soluble composite fertilizer |
| CN112745160A (en) * | 2021-01-21 | 2021-05-04 | 瓮福（集团）有限责任公司 | Novel process for preparing NPK compound fertilizer by using phosphogypsum and potassium feldspar |
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Application publication date: 20150128 |