CN107128889B - A kind of decomposing phosphate rock by chlorhydric acid produces the system and technique of calcium hydrophosphate fodder - Google Patents
A kind of decomposing phosphate rock by chlorhydric acid produces the system and technique of calcium hydrophosphate fodder Download PDFInfo
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- CN107128889B CN107128889B CN201710334846.2A CN201710334846A CN107128889B CN 107128889 B CN107128889 B CN 107128889B CN 201710334846 A CN201710334846 A CN 201710334846A CN 107128889 B CN107128889 B CN 107128889B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/20—Inorganic substances, e.g. oligoelements
- A23K20/26—Compounds containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
- C01B25/328—Defluorination during or after the preparation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/16—Halides of ammonium
- C01C1/164—Ammonium chloride
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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
- C01F11/18—Carbonates
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
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Abstract
The present invention relates to systems and technique that a kind of decomposing phosphate rock by chlorhydric acid produces calcium hydrophosphate fodder.A kind of system that decomposing phosphate rock by chlorhydric acid produces calcium hydrophosphate fodder, including extraction tank, the extraction tank is connect by pipeline with filter press I, the filter press I is connect by pipeline with defluorinate slot, the defluorinate slot is connect by pipeline with subsider I, the subsider I is connect by pipeline with filter press II, the filter press II is connect by pipeline with one section of neutralization chamber, one section of neutralization chamber is connect by pipeline with filter press III, the filter press III is connect by pipeline with two sections of neutralization chambers, two sections of neutralization chambers are connect by pipeline with filter press V, the filter press V is connect by pipeline with fluidized bed.The present invention uses decomposing phosphate rock by chlorhydric acid, will not generate ardealite waste, generates pollution.
Description
Technical field
The present invention relates to calcium hydrophosphate fodder production fields, and in particular to produces feed grade for a kind of decomposing phosphate rock by chlorhydric acid
The system and technique of calcium monohydrogen phosphate.
Background technique
Domestic feeding calcium production mostly uses wet method phosphoric acid manufacture process, and since phosphorus ore raw material grade is low, processing technology is extensive,
Impurity content is more in product, and fluorine content especially therein is higher, has seriously affected product quality and purposes.Hydrochloric acid leaching phosphorus
Mine method is similar with sulfuric acid process, does not generate calcium sulfate precipitation only, therefore does not generate ardealite tailings, while also there is no passivation effects
It answers.But hydrochloric acid method equally exists the high problem of product impurity content.
Summary of the invention
The object of the present invention is to provide systems and technique that a kind of decomposing phosphate rock by chlorhydric acid produces calcium hydrophosphate fodder, it is intended to
Calcium hydrophosphate fodder is improved to clean, and using round-robin method by the pH of filtrate after addition sodium carbonate and adjusting salt leaching-ore
Yield, while by-product precipitated calcium carbonate and ammonium chloride.
Technical solution of the present invention are as follows:
A kind of system that decomposing phosphate rock by chlorhydric acid produces calcium hydrophosphate fodder, including extraction tank, the extraction tank pass through pipe
Road is connect with filter press I, and the filter press I is connect by pipeline with defluorinate slot, and the defluorinate slot is connected by pipeline and subsider I
It connects, the subsider I is connect by pipeline with filter press II, and the filter press II is connect by pipeline with one section of neutralization chamber, institute
It states one section of neutralization chamber to connect by pipeline with filter press III, the filter press III is connect by pipeline with two sections of neutralization chambers, described
Two sections of neutralization chambers are connect by pipeline with filter press V, and the filter press V is connect by pipeline with fluidized bed；
The filter press II is also connect with the primary slurry slot that neutralizes by pipeline, and the primary neutralization slurry slot passes through pipeline
It is connect with subsider II, the subsider II is connect by pipeline with filter press IV；
The filter press IV is also connect with two sections of neutralization chambers by pipeline.
Preferably, the defluorinate slot is also connect with screw(-type) feeder, and screw(-type) feeder is used to transport sodium carbonate to defluorinate slot.
Preferably, one section of neutralization chamber is equipped with and neutralizes ammonia access tube for the first time, and two sections of neutralization chambers are equipped in second
With ammonia access tube；
The filter press I is equipped with slag discharge pipe, and defluorinate slot is connect with screw(-type) feeder, and the filter press machine III, which is equipped with, to be contained
F slag discharge pipe；
The extraction tank enters pipe equipped with hydrochloric acid and phosphorus ore enters pipe.
The technique that decomposing phosphate rock by chlorhydric acid produces calcium hydrophosphate fodder is carried out using the system, the technique include with
Lower step:
1) hydrochloric acid feeds intake in mass ratio with phosphorus ore, stops into extraction tank, and overflow enters filter press I, isolate crude acid and
Slag；
2) crude acid after step 1) filter press I carries out filters pressing enters defluorinate slot, the carbon come with screw(-type) feeder conveying
After defluorination reaction occurs for sour sodium (additional amount calculates theoretical dosage according to the F- in crude acid), settled into subsider I, then pass through
It crosses II filters pressing of filter press and obtains defluorinate acid and slag containing F；
3) the defluorinate acid that step 2 obtains is divided into first segment defluorinate acid, second segment defluorinate acid two parts,
First segment defluorinate acid, which enters after one section of neutralization chamber is reacted with gas ammonia, obtains first segment into the progress filters pressing of filter press III
Defluorinate acid solution body and first segment defluorinate acid sludge, first segment defluorinate acid solution body enter two sections of neutralization chambers, and first segment defluorinate acid sludge enters
Slurry slot is neutralized, the consumption of phosphorus can be reduced in this way, the fluorine-containing calcium monohydrogen phosphate in the part of generation can be reacted with second segment defluorinate acid,
A part of phosphorus is recycled, the fluorine in one-step removal second segment defluorinate acid of going forward side by side；
First segment defluorinate acid sludge and second segment defluorinate acid enter it is primary neutralize slurry slot add water be mixed into subsider II into
It is entered back into after row sedimentation after filter press IV carries out filters pressing and obtains neutralizing slag and filtrate, entered by the filtrate after IV filters pressing of filter press
Two sections of neutralization chambers；
4) it first segment defluorinate acid solution and carries out in two sections after entering two sections of neutralization chambers by the liquid after IV filters pressing of filter press
The filtering of filter press V is entered back into after, fluidized bed drying obtains calcium hydrophosphate fodder；
Complete the production of feed grade phosphoric acid hydrogen.
Preferably, the mass ratio of the step 1) hydrochloric acid and phosphorus ore is (according to hydrochloric acid and fluorapatite Response calculation theory matter
Amount) it is 1.05:1, it is 1h in the extraction tank residence time, the hydrochloric acid mass percent is 30%-35%, P in phosphorus ore2O5Quality
Percentage composition 27%-30%.Phosphrus reagent is 99% in obtained crude acid after reaction.
Preferably, the defluorinate temperature of the step 2 defluorination reaction is 70-90 DEG C, and it is heavy to be settled into subsider I
The drop time is 12h.It the use of the defluorinate rate of sodium carbonate defluorinate is at this time 60%-68%.
Preferably, the step 3) first segment defluorinate acid, second segment defluorinate acid mass ratio are 1:1；
It is 40-60 DEG C that the step 3) first segment defluorinate acid, which enters the temperature that one section of neutralization chamber is reacted, pH=1.2-
2.0；
Preferably, the step 3) first segment defluorinate acid sludge and second segment defluorinate acid enter primary neutralization slurry slot and water is mixed
Closing the time settled into subsider II is 12h；
It is 1:1 that the step 3), which once neutralizes the addition mass ratio of second segment defluorinate acid and water in slurry slot,.
Preferably, two sections of neutralization temperature controls of the step 4) are 50-70 DEG C, pH=4.5-5.0.
Preferably, the step 4) fluidized bed drying temperature is 100-110 DEG C.
The invention has the advantages that:
1, using decomposing phosphate rock by chlorhydric acid, ardealite waste will not be generated, generates pollution.
2, after using sodium carbonate defluorinate, the F in crude acid-Content is lower, is conducive to subsequent workshop section's removal of impurities, available to contain F
Calcium hydrophosphate fodder lower than 0.1%.
3, using round-robin method recovery section phosphorus and using the further defluorinate of filter residue, phosphrus reagent is improved, again using defluorinate acid
Dissolution is primary to neutralize slag, can effectively improve the yield of calcium hydrophosphate fodder (with P2O5Meter) it can achieve 80% or more, finished product
P content >=16%, F≤0.18%, Ca >=14% in calcium hydrophosphate fodder.
Detailed description of the invention
Fig. 1 is present system schematic diagram；
In figure: extraction tank 1, filter press I 2, defluorinate slot 3, subsider I 4, filter press II 5, one section of neutralization chamber 6, filter press III
7, primary neutralization slurry slot 8, subsider II 9, filter press IV 10, two sections of neutralization chambers 11, filter press V 12, fluidized bed 13, first
Secondary neutralization ammonia access tube 14, second of neutralization ammonia access tube 15, slag discharge pipe 16, screw(-type) feeder 17, the discharge of slag containing F
Pipe 18, hydrochloric acid enter pipe 19, and phosphorus ore enters pipe 20.
Specific embodiment
The present invention is further illustrated below with reference to embodiment, but the scope of protection of present invention is not limited to implement
The range of example statement.
Embodiment 1
A kind of system that decomposing phosphate rock by chlorhydric acid produces calcium hydrophosphate fodder, including extraction tank 1, the extraction tank 1 pass through
Pipeline is connect with filter press I 2, and the filter press I 2 is connect by pipeline with defluorinate slot 3, and the defluorinate slot 3 is by pipeline and sinks
It drops slot I 4 to connect, the subsider I 4 is connect by pipeline with filter press II 5, and the filter press II 5 passes through in pipeline and one section
It is connected with slot 6, one section of neutralization chamber 6 is connect by pipeline with filter press III 7, and the filter press III 7 passes through pipeline and two sections
Neutralization chamber 11 connects, and two sections of neutralization chambers 11 are connect by pipeline with filter press V 12, and the filter press V 12 passes through pipeline
It is connect with fluidized bed 13；
The filter press II 5 is also connect with the primary slurry slot 8 that neutralizes by pipeline, and the primary neutralization slurry slot 8 passes through
Pipeline is connect with subsider II 9, and the subsider II 9 is connect by pipeline with filter press IV 10；
The filter press IV 10 is also connect with two sections of neutralization chambers 11 by pipeline.
Preferably, the defluorinate slot 3 is also connect with screw(-type) feeder, and screw(-type) feeder is used to transport carbonic acid to defluorinate slot 3
Sodium.
Preferably, one section of neutralization chamber 6 is equipped with and neutralizes ammonia access tube 14 for the first time, and two sections of neutralization chambers 11 are equipped with second
Secondary neutralization ammonia access tube 15；
The filter press I 2 is equipped with slag discharge pipe 16, and defluorinate slot 3 is connect with screw(-type) feeder 17, the filter press machine III
7 are equipped with the discharge pipe of slag containing F 18；
The extraction tank 1 enters pipe 19 equipped with hydrochloric acid and phosphorus ore enters pipe 20.
The technique that decomposing phosphate rock by chlorhydric acid produces calcium hydrophosphate fodder is carried out using the system, the technique include with
Lower step:
1) hydrochloric acid feeds intake in mass ratio with phosphorus ore, stops into extraction tank 1, and overflow enters filter press I 2, isolates crude acid
And slag；
2) crude acid after step 1) filter press I carries out filters pressing enters defluorinate slot 3, the carbon come with screw(-type) feeder conveying
After defluorination reaction occurs for sour sodium (additional amount calculates theoretical dosage according to the F- in crude acid), settled into subsider I 4, then
Defluorinate acid and the slag of filter residue containing F are obtained by II 5 filters pressing of filter press；
3) the defluorinate acid that step 2 obtains is divided into first segment defluorinate acid, second segment defluorinate acid two parts,
First segment defluorinate acid, which enters after one section of neutralization chamber 6 is reacted with gas ammonia, obtains first into the progress filters pressing of filter press III 7
Section defluorinate acid solution body and first segment defluorinate acid sludge, first segment defluorinate acid solution body enter two sections of neutralization chambers 11, first segment defluorinate acid sludge
Into slurry slot 8 is neutralized, the consumption of phosphorus can be reduced in this way, and the fluorine-containing calcium monohydrogen phosphate in the part of generation can be with second segment defluorinate acid
Reaction, recycles a part of phosphorus, the fluorine in one-step removal second segment defluorinate acid of going forward side by side；
First segment defluorinate acid sludge and second segment defluorinate acid enter the primary slurry slot 8 that neutralizes and water are added to be mixed into subsider II 9
It is entered back into after being settled after filter press IV 10 carries out filters pressing and obtains neutralizing slag and filtrate, pass through the liquid after IV 10 filters pressing of filter press
Body enters two sections of neutralization chambers 11；Primarily to carrying out secondary defluorinate.
4) first segment defluorinate acid solution and by the liquid after IV 10 filters pressing of filter press enter two sections of neutralization chambers 11 after carry out two
The filtering of filter press V 12 is entered back into after Duan Zhonghe, fluidized bed 13 is dried to obtain calcium hydrophosphate fodder；
Complete the production of feed grade phosphoric acid hydrogen.
Preferably, the mass ratio of the step 1) hydrochloric acid and phosphorus ore is (according to hydrochloric acid and fluorapatite Response calculation theory matter
Amount) it is 1.05:1, it is 1h in 1 residence time of extraction tank, the hydrochloric acid mass percent is 30%-35%, P in phosphorus ore2O5Quality
Percentage composition 27%-30%.
Preferably, the defluorinate temperature of the step 2 defluorination reaction is 70-90 DEG C, and it is heavy to be settled into subsider I 4
The drop time is 12h.
Preferably, the step 3) first segment defluorinate acid, second segment defluorinate acid mass ratio are 1:1；
It is 40-60 DEG C that the step 3) first segment defluorinate acid, which enters the temperature that one section of neutralization chamber 6 is reacted, pH=1.2-
2.0；
Preferably, the step 3) first segment defluorinate acid sludge and second segment defluorinate acid enter primary neutralization slurry slot 8 and water
Being mixed into the time that subsider II 9 is settled is 12h；
It is 1:1 that the step 3), which once neutralizes the addition mass ratio of second segment defluorinate acid and water in slurry slot,.
Preferably, two sections of neutralization temperature controls of the step 4) are 50-70 DEG C, pH=4.5-5.0.
Preferably, the step 4) fluidized bed drying temperature is 100-110 DEG C.
Embodiment 2
A kind of decomposing phosphate rock by chlorhydric acid produces the technique of calcium hydrophosphate fodder, including extraction tank, filter press, defluorinate slot, heavy
Slot, one section of neutralization chamber, primary neutralization slurry slot, two sections of neutralization chambers, fluidized beds drop, and process flow chart is as shown in Figure 1.
34%(HCl) hydrochloric acid and 27% (P2O5) phosphorus ore 1.05:1 in mass ratio feeds intake, into extraction tank, residence time 1h,
Overflow enters filter press, isolates crude acid and slag, and the crude acid after filters pressing enters defluorinate slot, comes with screw(-type) feeder conveying
Sodium carbonate (additional amount calculates theoretical dosage according to the F- in crude acid) defluorination reaction occurs, settle 12h, upper layer into subsider
Clear liquid enters filter press, the defluorinate acid 1:1 in mass ratio after filters pressing, and a part enters one section of neutralization chamber, and a part enters primary
Neutralize slurry slot；Be passed through ammonia into one section of neutralization chamber, control 40-60 DEG C of temperature, ph=1.2-2.0, be obtained by filtration filtrate 1. with
Primary to neutralize slag, primary neutralization slag, which is squeezed into, once neutralizes slurry slot, neutralizes slurry slot to primary by the mass ratio 1:1 with defluorinate acid
In plus water, enter subsider after mixing, after settling 12h, into filter press filters pressing, clear liquid is with one section of neutralization chamber by filters pressing
Clear liquid mixing afterwards, into two sections of neutralization chambers；It is passed through ammonia into two sections of neutralization chambers, controls 50-70 DEG C of temperature, ph=4.5-
5.0, filtering drying arrives calcium hydrophosphate fodder, and wherein the yield of calcium monohydrogen phosphate is (with P2O5Meter) can achieve 80% with
On, P content >=16%, F≤0.18%, Ca >=14% in finished product feedstuff calcium hydrophosphate.
The above embodiments are only the preferred technical solution of the present invention, and are not construed as limitation of the invention, this Shen
Please in embodiment and embodiment in feature in the absence of conflict, can mutual any combination.Protection model of the invention
The technical solution that should be recorded with claim is enclosed, the equivalent replacement side of technical characteristic in the technical solution recorded including claim
Case is protection scope.Equivalent replacement i.e. within this range is improved, also within protection scope of the present invention.
Claims (2)
1. a kind of decomposing phosphate rock by chlorhydric acid produces the technique of calcium hydrophosphate fodder, the system that the technique uses includes extraction tank
(1), it is characterised in that: the extraction tank (1) connect by pipeline with filter press I (2), the filter press I (2) pass through pipeline and
Defluorinate slot (3) connection, the defluorinate slot (3) connects by pipeline with subsider I (4), the subsider I (4) pass through pipeline and
Filter press II (5) connection, the filter press II (5) are connect by pipeline with one section of neutralization chamber (6), one section of neutralization chamber (6)
It being connect by pipeline with filter press III (7), the filter press III (7) is connect by pipeline with two sections of neutralization chambers (11), and described two
Section neutralization chamber (11) is connect by pipeline with filter press V (12), and the filter press V (12) is connected by pipeline and fluidized bed (13)
It connects；
The filter press II (5) is also connect with primary neutralize slurry slot (8) by pipeline, and the primary neutralization slurry slot (8) is logical
Piping is connect with subsider II (9), and the subsider II (9) is connect by pipeline with filter press IV (10)；
The filter press IV (10) is also connect with two sections of neutralization chambers (11) by pipeline；The defluorinate slot (3) is gone back and screw feeder
Machine connection, screw(-type) feeder are used to transport sodium carbonate to defluorinate slot (3)；
One section of neutralization chamber (6), which is equipped with, neutralizes ammonia access tube (14) for the first time, and two sections of neutralization chambers (11) are equipped in second
With ammonia access tube (15)；
The filter press I (2) is equipped with slag discharge pipe (16), and defluorinate slot (3) is connect with screw(-type) feeder (17), the filter press
III (7) are equipped with the discharge pipe of slag containing F (18)；
The extraction tank (1) enters pipe (19) equipped with hydrochloric acid and phosphorus ore enters pipe (20)；
The technique the following steps are included:
1) hydrochloric acid feeds intake in mass ratio with phosphorus ore, stops into extraction tank (1), and overflow enters filter press I (2), isolates crude acid
And slag；
2) crude acid after step 1) filter press I carries out filters pressing enters defluorinate slot (3), the carbonic acid come with screw(-type) feeder conveying
It after defluorination reaction occurs for sodium, is settled into subsider I (4), obtains defluorinate acid using filter press II (5) filters pressing and containing F
Slag；
3) the defluorinate acid that step 2 obtains is divided into first segment defluorinate acid, second segment defluorinate acid two parts,
First segment defluorinate acid, which enters after one section of neutralization chamber (6) is reacted, obtains first segment into filter press III (7) progress filters pressing
Defluorinate acid solution body and first segment defluorinate acid sludge, first segment defluorinate acid solution body enter two sections of neutralization chambers (11), first segment defluorinate acid sludge
Into neutralization slurry slot (8)；
First segment defluorinate acid sludge and second segment defluorinate acid enter primary neutralize after slurry slot (8) add water mixing and enter subsider II
(9) it is entered back into after being settled after filter press IV (10) carries out filters pressing and obtains neutralizing slag and liquid, pressed by filter press IV (10)
Liquid after filter enters two sections of neutralization chambers (11)；
4) it first segment defluorinate acid solution and two sections of neutralization chambers (11) is entered by the liquid after filter press IV (10) filters pressing carries out two afterwards
Filter press V (12) filtering is entered back into after Duan Zhonghe, fluidized bed (13) is dried to obtain calcium hydrophosphate fodder；
Complete the production of calcium hydrophosphate fodder；
The step 3) first segment defluorinate acid, second segment defluorinate acid mass ratio are 1:1；The step 3) first segment defluorinate acid enters
The temperature that one section of neutralization chamber (6) is reacted is 40-60 DEG C, pH=1.2-2.0；
The optimum quality ratio of the step 1) hydrochloric acid and phosphorus ore is 1.05:1, is 1h, the hydrochloric acid in extraction tank (1) residence time
Mass percent is 30-35%, P in phosphorus ore2O5Mass percentage 27%-30%；
The defluorinate temperature of the step 2 defluorination reaction is 70-90 DEG C, and the sedimentation time settled into subsider I (4) is
12h；It the use of the defluorinate rate of sodium carbonate defluorinate is at this time 60%-68%；
It is heavy that the step 3) first segment defluorinate acid sludge and second segment defluorinate acid are mixed into primary neutralization slurry slot (8) plus water
The time that drop slot II (9) is settled is 12h；The step 3) once neutralizes the addition of second segment defluorinate acid and water in slurry slot
Mass ratio is 1:1；
Two sections of neutralization temperature controls of the step 4) are 50-70 DEG C, pH=4.5-5.0.
2. technique according to claim 1, it is characterised in that: the step 4) fluidized bed drying temperature is 100-110 DEG C.
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| CN108706991A (en) * | 2018-06-13 | 2018-10-26 | 贵阳开磷化肥有限公司 | A kind of method of phosphoric acid byproduct hydrogen ammonium in high-quality double superphosphate preparation process |
| CN111099568A (en) * | 2019-12-30 | 2020-05-05 | 龙蟒大地农业有限公司 | Production method of feed-grade calcium hydrophosphate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5322675A (en) * | 1990-11-09 | 1994-06-21 | Director-General Of Agency Of Industrial Science And Technology | Method of preparing calcium phosphate |
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|---|---|---|---|---|
| CN1108055A (en) * | 1994-12-30 | 1995-09-13 | 吴隽 | Feed-stuff grade calcium hydrophosphate prodn. defluorination method circulating |
| CN1183378A (en) * | 1995-10-20 | 1998-06-03 | 四川联合大学 | Method for producing feed calcium hydrogen phosphate |
| CN103754854A (en) * | 2013-12-17 | 2014-04-30 | 柳州东风化工股份有限公司 | Preparation method for feed and calcium hydrogen phosphate by using hydrochloric acid process |
| CN104555965A (en) * | 2015-02-11 | 2015-04-29 | 铜陵化学工业集团有限公司 | Method of combined production of multiple phosphates and phosphate fertilizer from low grade phosphate ore |
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