CN107128889A - 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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- CN107128889A CN107128889A CN201710334846.2A CN201710334846A CN107128889A CN 107128889 A CN107128889 A CN 107128889A CN 201710334846 A CN201710334846 A CN 201710334846A CN 107128889 A CN107128889 A CN 107128889A
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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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- Life Sciences & Earth Sciences (AREA)
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- Animal Husbandry (AREA)
- Zoology (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Processing Of Solid Wastes (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The present invention relates to the system and technique that a kind of decomposing phosphate rock by chlorhydric acid produces calcium hydrophosphate fodder.The system that a kind of decomposing phosphate rock by chlorhydric acid produces calcium hydrophosphate fodder, including extraction tank, the extraction tank is connected by pipeline with filter press I, the filter press I is connected by pipeline with defluorinate groove, the defluorinate groove is connected by pipeline with subsider I, the subsider I is connected by pipeline with filter press II, the filter press II is connected by pipeline with one section of neutralization chamber, one section of neutralization chamber is connected by pipeline with filter press III, the filter press III is connected by pipeline with two sections of neutralization chambers, two sections of neutralization chambers are connected by pipeline with filter press V, the filter press V is connected by pipeline with fluid bed.The present invention uses decomposing phosphate rock by chlorhydric acid, will not produce ardealite discarded object, produces pollution.
Description
Technical field
The present invention relates to calcium hydrophosphate fodder production field, 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 technology
Domestic feeding calcium production uses wet method phosphoric acid manufacture process, and because phosphorus ore raw material grade is low, processing technology is extensive,
Impurity content is more in product, and Oil repellent particularly therein is higher, has had a strong impact on product quality and purposes.Hydrochloric acid leaching phosphorus
Ore deposit method is similar with sulfuric acid process, does not simply generate calcium sulfate precipitation, therefore does not produce ardealite tailings, while passivation effect is also not present
Should.But hydrochloric acid method equally exists the problem of product impurity content is high.
The content of the invention
It is an object of the invention to provide the system and technique that a kind of decomposing phosphate rock by chlorhydric acid produces calcium hydrophosphate fodder, it is intended to
By adding sodium carbonate and adjusting the pH of filtrate after salt leaching-ore come removal of impurities, and utilize round-robin method raising calcium hydrophosphate fodder
Yield, while by-product precipitated calcium carbonate and ammonium chloride.
Technical solution of the present invention is：
The system that a kind of decomposing phosphate rock by chlorhydric acid produces calcium hydrophosphate fodder, including extraction tank, the extraction tank by pipeline with
Filter press I is connected, and the filter press I is connected by pipeline with defluorinate groove, and the defluorinate groove is connected by pipeline with subsider I,
The subsider I is connected by pipeline with filter press II, and the filter press II is connected by pipeline with one section of neutralization chamber, and described one
Section neutralization chamber is connected by pipeline with filter press III, and the filter press III is connected by pipeline with two sections of neutralization chambers, described two sections
Neutralization chamber is connected by pipeline with filter press V, and the filter press V is connected by pipeline with fluid bed；
The filter press II is also connected by pipeline with once neutralizing slurry groove, described once to neutralize slurry groove by pipeline with sinking
Drop groove II is connected, and the subsider II is connected by pipeline with filter press IV；
The filter press IV is also connected by pipeline with two sections of neutralization chambers.
Preferably, the defluorinate groove is also connected with screw(-type) feeder, and screw(-type) feeder is used to transport sodium carbonate to defluorinate groove.
Preferably, one section of neutralization chamber provided with ammonia access tube is neutralized for the first time, and two sections of neutralization chambers are provided with second
With ammonia access tube；
The filter press I is provided with slag discharge pipe, and defluorinate groove is connected with screw(-type) feeder, and the filter press machine III is provided with slag containing F
Discharge pipe；
The extraction tank enters to manage to enter with phosphorus ore provided with hydrochloric acid manages.
The technique that decomposing phosphate rock by chlorhydric acid produces calcium hydrophosphate fodder is carried out using described system, the technique include with
Lower step：
1）Hydrochloric acid feeds intake in mass ratio with phosphorus ore, is stopped into extraction tank, and overflow enters filter press I, isolates thick acid and slag；
2）By step 1）Filter press I carries out the thick acid after press filtration and enters defluorinate groove, the sodium carbonate come with screw(-type) feeder conveying
（F- of the addition in thick acid calculates theoretical consumption）After generation defluorination reaction, settled into subsider I, then through overvoltage
The press filtration of filter II obtains defluorinate acid and slag containing F；
3）Step 2）Obtained defluorinate acid is divided into first paragraph defluorinate acid, the sour two parts of second segment defluorinate,
First paragraph defluorinate acid enters one section of neutralization chamber and obtains first paragraph defluorinate with carrying out press filtration into filter press III after gas ammonia reaction
Acid solution body and first paragraph defluorinate acid sludge, first paragraph defluorinate acid solution body enter two sections of neutralization chambers, and first paragraph defluorinate acid sludge, which enters, to be neutralized
Slurry groove, can so reduce the consumption of phosphorus, and the calcium monohydrogen phosphate that the part of generation is fluorine-containing can be reclaimed with second segment defluorinate acid reaction
Fluorine in a part of phosphorus, one-step removal second segment defluorinate acid of going forward side by side；
First paragraph defluorinate acid sludge and second segment defluorinate acid, which enter once to neutralize slurry groove and add water, to be mixed into subsider II and is sunk
Filter press IV is entered back into after drop to carry out obtaining neutralizing slag and filtrate after press filtration, enters two sections by the filtrate after the press filtration of filter press IV
Neutralization chamber；
4）First paragraph defluorinate acid solution and being entered by the liquid after the press filtration of filter press IV after two sections of neutralization chambers carry out two sections neutralize after
Enter back into that filter press V is filtered, fluidized bed drying obtains calcium hydrophosphate fodder；
Complete the production of feed grade phosphoric acid hydrogen.
Preferably, the step 1）The mass ratio of hydrochloric acid and phosphorus ore（According to hydrochloric acid and the theoretical matter of fluorapatite Response calculation
Amount）For 1.05:1, it is 1h in the extraction tank residence time, the hydrochloric acid mass percent is P in 30%-35%, phosphorus ore2O5Quality
Percentage composition 27%-30%.Phosphrus reagent is 99% in thick acid obtained by after reaction.
Preferably, the step 2）The defluorinate temperature of defluorination reaction is 70-90 DEG C, into sinking that subsider I is settled
The drop time is 12h.The use of the defluorinate rate of sodium carbonate defluorinate is now 60%-68%.
Preferably, the step 3）First paragraph defluorinate acid, the sour mass ratio of second segment defluorinate are 1:1；
The step 3）The temperature that first paragraph defluorinate acid is reacted into one section of neutralization chamber is 40-60 DEG C, pH=1.2-2.0；
Preferably, the step 3）First paragraph defluorinate acid sludge and second segment defluorinate acid enter once neutralization slurry groove and water and are mixed into
It is 12h to enter the time that subsider II settled；
The step 3）The addition mass ratio for once neutralizing second segment defluorinate acid and water in slurry groove is 1:1.
Preferably, the step 4）Two sections of neutral temperature controls are 50-70 DEG C, pH=4.5-5.0.
Preferably, the step 4）Fluid bed drying temperature is 100-110 DEG C.
Beneficial effect of the present invention：
1st, using decomposing phosphate rock by chlorhydric acid, ardealite discarded object will not be produced, pollution is produced.
2nd, after using sodium carbonate defluorinate, the F in thick acid-Content is lower, is conducive to follow-up workshop section's removal of impurities, can obtain containing F
Calcium hydrophosphate fodder less than 0.1%.
3rd, using round-robin method recovery section phosphorus and using the further defluorinate of filter residue, phosphrus reagent is improved, using defluorinate acid again
Dissolving once neutralizes slag, can effectively improve the yield of calcium hydrophosphate fodder（With P2O5Meter）More than 80%, finished product can be reached
P content >=16%, F≤0.18%, Ca >=14% in calcium hydrophosphate fodder.
Brief description of the drawings
Fig. 1 is present system schematic diagram；
In figure：Extraction tank 1, filter press I 2, defluorinate groove 3, subsider I 4, filter press II 5, one section of neutralization chamber 6, filter press III 7, one
Secondary neutralization slurry groove 8, subsider II 9, filter press IV 10, two sections of neutralization chambers 11, filter press V 12, fluid bed 13, in first time
With ammonia access tube 14, second of neutralization ammonia access tube 15, slag discharge pipe 16, screw(-type) feeder 17, the discharge pipe of slag containing F
18, hydrochloric acid enters pipe 19, and phosphorus ore enters pipe 20.
Embodiment
The present invention is further illustrated with reference to embodiment, but the scope of protection of present invention is not limited to implement
The scope of example statement.
Embodiment 1
The system that a kind of decomposing phosphate rock by chlorhydric acid produces calcium hydrophosphate fodder, including extraction tank 1, the extraction tank 1 pass through pipeline
It is connected with filter press I 2, the filter press I 2 is connected by pipeline with defluorinate groove 3, the defluorinate groove 3 passes through pipeline and subsider I
4 connections, the subsider I 4 is connected by pipeline with filter press II 5, and the filter press II 5 passes through pipeline and one section of neutralization chamber 6
Connection, one section of neutralization chamber 6 is connected by pipeline with filter press III 7, and the filter press III 7 passes through pipeline and two sections of neutralization chambers
11 connections, two sections of neutralization chambers 11 are connected by pipeline with filter press V 12, and the filter press V 12 passes through pipeline and fluidisation
Bed 13 is connected；
The filter press II 5 is also connected by pipeline with once neutralizing slurry groove 8, and the slurry groove 8 that once neutralizes passes through pipeline
It is connected with subsider II 9, the subsider II 9 is connected by pipeline with filter press IV 10；
The filter press IV 10 is also connected by pipeline with two sections of neutralization chambers 11.
Preferably, the defluorinate groove 3 is also connected with screw(-type) feeder, and screw(-type) feeder is used to transport carbonic acid to defluorinate groove 3
Sodium.
Preferably, one section of neutralization chamber 6 is provided with second provided with ammonia access tube 14, two sections of neutralization chambers 11 are neutralized for the first time
Secondary neutralization ammonia access tube 15；
The filter press I 2 is provided with slag discharge pipe 16, and defluorinate groove 3 is connected with screw(-type) feeder 17, and the filter press machine III 7 is set
There is the discharge pipe of slag containing F 18；
The extraction tank 1 enters pipe 19 provided 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 described system, the technique include with
Lower step：
1）Hydrochloric acid feeds intake in mass ratio with phosphorus ore, is stopped into extraction tank 1, and overflow enters filter press I 2, isolates thick acid and ore deposit
Slag；
2）By step 1）Filter press I carries out the thick acid after press filtration and enters defluorinate groove 3, the sodium carbonate come with screw(-type) feeder conveying
（F- of the addition in thick acid calculates theoretical consumption）After generation defluorination reaction, settled into subsider I 4, then pass through
The press filtration of filter press II 5 obtains defluorinate acid and the slag of filter residue containing F；
3）Step 2）Obtained defluorinate acid is divided into first paragraph defluorinate acid, the sour two parts of second segment defluorinate,
First paragraph defluorinate is sour de- with obtaining first paragraph into the progress press filtration of filter press III 7 after gas ammonia reaction into one section of neutralization chamber 6
Fluoric acid liquid and first paragraph defluorinate acid sludge, first paragraph defluorinate acid solution body enter two sections of neutralization chambers 11, and first paragraph defluorinate acid sludge enters
Slurry groove 8 is neutralized, the consumption of phosphorus can be so reduced, the calcium monohydrogen phosphate that the part of generation is fluorine-containing can be anti-with second segment defluorinate acid
Should, a part of phosphorus is reclaimed, the fluorine in one-step removal second segment defluorinate acid of going forward side by side；
First paragraph defluorinate acid sludge and second segment defluorinate acid add water into once neutralization slurry groove 8 is mixed into the progress of subsider II 9
Filter press IV 10 is entered back into after sedimentation to carry out obtaining neutralizing slag and filtrate after press filtration, is entered by the liquid after the press filtration of filter press IV 10
Enter two sections of neutralization chambers 11；Primarily to carrying out secondary defluorinate.
4）First paragraph defluorinate acid solution and by the liquid after the press filtration of filter press IV 10 enter two sections of neutralization chambers 11 after carry out two
The filtering of filter press V 12, fluid bed 13 are entered back into after Duan Zhonghe and is dried to obtain calcium hydrophosphate fodder；
Complete the making of feed grade phosphoric acid hydrogen.
Preferably, the step 1）The mass ratio of hydrochloric acid and phosphorus ore（According to hydrochloric acid and the theoretical matter of fluorapatite Response calculation
Amount）For 1.05:1, it is 1h in the residence time of extraction tank 1, the hydrochloric acid mass percent is P in 30%-35%, phosphorus ore2O5Quality
Percentage composition 27%-30%.
Preferably, the step 2）The defluorinate temperature of defluorination reaction is 70-90 DEG C, into sinking that subsider I 4 is settled
The drop time is 12h.
Preferably, the step 3）First paragraph defluorinate acid, the sour mass ratio of second segment defluorinate are 1:1；
The step 3）The temperature that first paragraph defluorinate acid is reacted into one section of neutralization chamber 6 is 40-60 DEG C, pH=1.2-2.0；
Preferably, the step 3）First paragraph defluorinate acid sludge and second segment defluorinate acid, which enter, once neutralizes slurry groove 8 and water mixing
It is 12h into the time that subsider II 9 is settled；
The step 3）The addition mass ratio for once neutralizing second segment defluorinate acid and water in slurry groove is 1:1.
Preferably, the step 4）Two sections of neutral temperature controls are 50-70 DEG C, pH=4.5-5.0.
Preferably, the step 4）Fluid 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 groove, subsider,
One section of neutralization chamber, slurry groove, two sections of neutralization chambers, fluid beds are once neutralized, process chart is as shown in Figure 1.
34%（HCl）Hydrochloric acid and 27% (P2O5) phosphorus ore in mass ratio 1.05:1 feeds intake, into extraction tank, and the residence time is 1h,
Overflow enters filter press, isolates thick acid and slag, and the thick acid after press filtration enters defluorinate groove, comes with screw(-type) feeder conveying
Sodium carbonate（F- of the addition in thick acid calculates theoretical consumption）Generation defluorination reaction, 12h, upper strata are settled into subsider
Clear liquid enters filter press, the defluorinate acid in mass ratio 1 after press filtration:1, one section of neutralization chamber is partly into, is partly into once
Neutralize slurry groove；Be passed through ammonia into one section of neutralization chamber, control 40-60 DEG C of temperature, ph=1.2-2.0, be filtrated to get filtrate 1. with
Slag is once neutralized, slag is once neutralized and squeezes into once neutralization slurry groove, by the mass ratio 1 with defluorinate acid:1 to once neutralize slurry groove
In add water, be well mixed after enter subsider, sedimentation 12h after, into filter press press filtration, clear liquid and one section of neutralization chamber pass through press filtration
Clear liquid mixing afterwards, into two sections of neutralization chambers；Ammonia is passed through into two sections of neutralization chambers, 50-70 DEG C of temperature, ph=4.5- is controlled
5.0, the yield to calcium hydrophosphate fodder, wherein calcium monohydrogen phosphate of filtering drying（With P2O5Meter）Can reach 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 the limitation for the present invention, this Shen
Please in embodiment and feature in embodiment in the case where not conflicting, can mutually be combined.The protection model of the present invention
Enclose the equivalent substitution side of technical characteristic in the technical scheme that should be recorded with claim, including the technical scheme of claim record
Case is protection domain.Equivalent substitution i.e. within this range is improved, also within protection scope of the present invention.
Claims (10)
1. the system that a kind of decomposing phosphate rock by chlorhydric acid produces calcium hydrophosphate fodder, including extraction tank（1）, it is characterised in that：It is described
Extraction tank（1）Pass through pipeline and filter press I（2）Connection, the filter press I（2）Pass through pipeline and defluorinate groove（3）Connection, it is described
Defluorinate groove（3）Pass through pipeline and subsider I（4）Connection, the subsider I（4）Pass through pipeline and filter press II（5）Connection, institute
State filter press II（5）Pass through pipeline and one section of neutralization chamber（6）Connection, one section of neutralization chamber（6）Pass through pipeline and filter press III
（7）Connection, the filter press III（7）Pass through pipeline and two sections of neutralization chambers（11）Connection, two sections of neutralization chambers（11）Pass through pipe
Road and filter press V（12）Connection, the filter press V（12）Pass through pipeline and fluid bed（13）Connection；
The filter press II（5）By pipeline also with once neutralizing slurry groove（8）Connection, it is described once to neutralize slurry groove（8）It is logical
Piping and subsider II（9）Connection, the subsider II（9）Pass through pipeline and filter press IV（10）Connection；
The filter press IV（10）By pipeline also with two sections of neutralization chambers（11）Connection.
2. system according to claim 1, it is characterised in that：The defluorinate groove（3）Also it is connected with screw(-type) feeder, spiral
Batcher is used to give defluorinate groove（3）Transport sodium carbonate.
3. system according to claim 1, it is characterised in that：One section of neutralization chamber（6）Ammonia is neutralized provided with first time
Access tube（14）, two sections of neutralization chambers（11）Ammonia access tube is neutralized provided with second（15）；
The filter press I（2）Provided with slag discharge pipe（16）, defluorinate groove（3）With screw(-type) feeder（17）Connection, the filter press
Machine III（7）Provided with the discharge pipe of slag containing F（18）；
The extraction tank（1）Enter provided with hydrochloric acid and manage（19）Enter with phosphorus ore and manage（20）.
4. the technique that decomposing phosphate rock by chlorhydric acid produces calcium hydrophosphate fodder, its feature are carried out using the system described in claim 3
It is：The technique comprises the following steps：
1）Hydrochloric acid feeds intake in mass ratio with phosphorus ore, into extraction tank（1）Stop, overflow enters filter press I（2）, isolate thick acid
And slag；
2）By step 1）Filter press I carries out the thick acid after press filtration and enters defluorinate groove（3）, the carbonic acid come with screw(-type) feeder conveying
Sodium（F- of the addition in thick acid calculates theoretical consumption）After generation defluorination reaction, into subsider I（4）Settled, then
By filter press II（5）Press filtration obtains defluorinate acid and slag containing F；
3）Step 2）Obtained defluorinate acid is divided into first paragraph defluorinate acid, the sour two parts of second segment defluorinate,
First paragraph defluorinate acid enters one section of neutralization chamber（6）Enter filter press III after being reacted（7）Carry out press filtration and obtain first paragraph
Defluorinate acid solution body and first paragraph defluorinate acid sludge, first paragraph defluorinate acid solution body enter two sections of neutralization chambers（11）, first paragraph defluorinate acid sludge
Into neutralization slurry groove（8）；
First paragraph defluorinate acid sludge and second segment defluorinate acid, which enter, once neutralizes slurry groove（8）Add water and enter subsider II after mixing
（9）Filter press IV is entered back into after being settled（10）Carry out obtaining neutralizing slag and liquid after press filtration, pass through filter press IV（10）Pressure
Liquid after filter enters two sections of neutralization chambers（11）；
4）First paragraph defluorinate acid solution and pass through filter press IV（10）Liquid after press filtration enters two sections of neutralization chambers（11）After carry out two
Filter press V is entered back into after Duan Zhonghe（12）Filtering, fluid bed（13）It is dried to obtain calcium hydrophosphate fodder；
Complete the production of calcium hydrophosphate fodder.
5. technique according to claim 4, it is characterised in that：
The step 1）The optimum quality ratio of hydrochloric acid and phosphorus ore is 1.05:1, in extraction tank（1）Residence time is 1h, the hydrochloric acid
Mass percent is P in 30-35%, phosphorus ore2O5Weight/mass percentage composition 27%-30%.
6. technique according to claim 4, it is characterised in that：
The step 2）The defluorinate temperature of defluorination reaction is 70-90 DEG C, into subsider I（4）The sedimentation time settled is
12h；The use of the defluorinate rate of sodium carbonate defluorinate is now 60%-68%.
7. technique according to claim 4, it is characterised in that：
The step 3）First paragraph defluorinate acid, the sour mass ratio of second segment defluorinate are 1:1；
The step 3）First paragraph defluorinate acid enters one section of neutralization chamber（6）The temperature reacted is 40-60 DEG C, pH=1.2-
2.0。
8. technique according to claim 4, it is characterised in that：
The step 3）First paragraph defluorinate acid sludge and second segment defluorinate acid, which enter, once neutralizes slurry groove（8）Adding water, it is heavy to be mixed into
Groove II drops（9）The time settled is 12h；
The step 3）The addition mass ratio for once neutralizing second segment defluorinate acid and water in slurry groove is 1:1.
9. technique according to claim 4, it is characterised in that：
The step 4）Two sections of neutral temperature controls are 50-70 DEG C, pH=4.5-5.0.
10. technique according to claim 4, it is characterised in that：
The step 4）Fluid bed drying temperature is 100-110 DEG C.
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| 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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| 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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