CN101007626A - Method for producing phosphate by wet method phosphoric acid purification and hydrochloric acid decomposition for phosphate ore - Google Patents

Method for producing phosphate by wet method phosphoric acid purification and hydrochloric acid decomposition for phosphate ore Download PDF

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CN101007626A
CN101007626A CN 200710048327 CN200710048327A CN101007626A CN 101007626 A CN101007626 A CN 101007626A CN 200710048327 CN200710048327 CN 200710048327 CN 200710048327 A CN200710048327 A CN 200710048327A CN 101007626 A CN101007626 A CN 101007626A
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phosphate
phosphoric acid
acid
carbonate
solution
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黄尚勋
黄明科
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Abstract

The invention discloses a wet method phosphor purifying and manufacturing method of phosphate, which is characterized by the following: decomposing impurity in kinds of fined phosphate through wet method; reacting carbonate and phosphate of ferric, aluminium, calcium and magnesium under certain condition; transmitting insoluble impurity phosphate into soluble phosphate with transmitting rate over 99%; transmitting entire phosphorus pentoxide into purified phosphate product; avoiding the loss of phosphor due to impurity sediment.

Description

A kind of wet phosphoric acid purifying and decomposing phosphate rock by chlorhydric acid are produced phosphatic method
Affiliated technical field
The present invention relates to a kind ofly use phosphoric acid by wet process and effectively separate the method that the impurity in the phosphoric acid by wet process is produced various fine phosphates, belong to the technical field of phosphate production.
The technology of the use Wet-process Phosphoric Acid Production phosphoric acid salt of indication of the present invention and effective separating impurity, refer to the phosphoric acid by wet process that uses the manufacturing of sulfuric acid decomposing phosphate rock or directly use hydrochloric acid (perhaps other acidic substance, the mixing solutions of the acid hydrolysate (as the muriate of iron, aluminium, calcium, magnesium or the like) that contains phosphoric acid and other impurity that nitric acid for example) decomposing phosphate rock obtains, phosphoric acid does not wherein need to separate in advance and purify.
Hydrochloric acid or nitric acid (comprising spent acid) that method provided by the invention is applicable to any concentration decompose the phosphorus ore of any grade, and the raw phosphoric acid that contains any concentration of impurities that obtains is used to make fine phosphate, and all impurity can access effective separation, all P 2O 5Can all transform into pure product.
Background technology
At present, known fine phosphate production technology is generally used thermal phosphoric acid, because contain various impurity, for example aluminium, iron, calcium, magnesium or the like in the phosphoric acid by wet process inevitably.These impurity making under the phosphatic operational condition, generate AlPO 4, FePO 4, CaHPO 4, MgHPO 4, MgNH 4PO 4, Ca 3(PO 4) 2, Mg 3(PO 4) 2Or the like throw out, cause a large amount of losses and the severe exacerbation quality product of Vanadium Pentoxide in FLAKES.The phosphorus ore of China generally contains many iron, aluminium, calcium, magnesium or the like impurity, and the situation of this phosphorus pentoxide losing is just more serious.These calcium phosphate precipitations generally have colloidal state character, are difficult to be used, and therefore, use impure many phosphoric acid by wet processes to make fine phosphate, are difficult to receive reasonable economic benefit.
Since a large amount of losses of the Vanadium Pentoxide in FLAKES that these impurity cause, the selected phosphorus ore of having to, and a large amount of low-grade phosphate ores can't utilize, and causes the serious waste of resource.
In addition, because the influence of above-mentioned phosphoric acid by wet process impurity when using phosphoric acid by wet process or wet phosphate to produce compound manure, can only obtain the water miscible product of part, this brings the problem of two aspects.Being that this fertilizer is not suitable for spraying on the one hand, having limited their result of use, is owing to contain a large amount of colloidal precipitate things on the other hand, give concentrate, the course of processing such as drying brings difficulty.Generally can only use slip to concentrate and spray granulating, not only equipment complexity, and increase energy consumption.
Owing to these reasons, use the technology of Wet-process Phosphoric Acid Production phosphoric acid salt and free from chloride sulphur based compound fertilizer and equipment to become complicated, product yield is low, and is of poor quality, hindered the development of phosphate industry and chemical fertilizer industry.
Summary of the invention
Impurity when overcoming above-mentioned use Wet-process Phosphoric Acid Production phosphoric acid salt disturbs and solves making full use of of low-grade phosphate ore or the like problem, and the present invention advises a kind of method of using phosphoric acid by wet process or directly using not separated phosphorus ore acid hydrolysis solution to produce various fine phosphates.This method not only can solve smoothly uses the phosphatic impurity interference problem of Wet-process Phosphoric Acid Production, can bring up to the rate of recovery of Vanadium Pentoxide in FLAKES near 100%, and can use the various spent acid of any concentration and the low-grade phosphate ore of any content, make full use of various resources, simplify technology simultaneously, reduce corrosion, simplified apparatus is received reasonable economical and technical benefit.
The technical solution adopted for the present invention to solve the technical problems is:
(1) technical scheme 1: technical scheme 1 solves various phosphoric acid by wet processes (perhaps phosphoric acid salt) and produces in the fine phosphate process, and problem is reclaimed in the conversion of the Vanadium Pentoxide in FLAKES of foreign matter of phosphor hydrochlorate throw out loss.Technical scheme is: use the mixing solutions of carbonate solution or carbonate and oxyhydroxide to handle the foreign matter of phosphor hydrochlorate throw out that produces in the various phosphoric acid by wet process courses of processing, make the Vanadium Pentoxide in FLAKES that wherein contains all be converted into purified Vanadium Pentoxide in FLAKES that can be water-soluble, all recycled, thoroughly solved the problem of impurity loss phosphorus.
Be example with the processing mode of using the bicarbonate of ammonia ammonification, the main chemical reactions of foundation is:
AlPO 4+2NH 3+3H 2O＝(NH 4) 2HPO 4+Al(OH) 3
FePO 4+2NH 3+3H 2O＝(NH 4) 2HPO 4+Fe(OH) 3
CaHPO 4+(NH4) 2CO 3＝(NH 4) 2HPO 4+CaCO 3
MgHPO 4+(NH4) 2CO 3＝(NH 4) 2HPO 4+MgCO 3
Ca 3(PO 4) 2+4NH 4HCO 3＝2(NH 4) 2HPO 4+3CaCO 3+CO 2+H 2O
Mg 3(PO 4) 2+4NH 4HCO 3＝2(NH 4) 2HPO 4+3MgCO 3+CO 2+H 2O
MgNH 4PO 4+NH 4HCO 3＝(NH 4) 2HPO 4+MgCO 3
The result of these reactions is:
All calcium phosphate precipitation things that are insoluble in water have changed into water-soluble phosphate, and all dirt has changed into oxyhydroxide and the carbonate that is insoluble in water simultaneously, thereby is effectively separated.
Here said carbonate and oxyhydroxide refer to following any material combination mode:
Carbonic acid gas+ammonia (ammonia, liquefied ammonia or ammoniacal liquor);
Carbonic acid gas+oxyhydroxide (for example sodium hydroxide, potassium hydroxide or the like, optionally the range of product of Sheng Chaning and decide);
Bicarbonate of ammonia+ammonia (ammonia, liquefied ammonia or ammoniacal liquor);
Sodium bicarbonate+sodium hydroxide;
Saleratus+potassium hydroxide;
Other carbonate+identical cationic oxyhydroxide.
Can pass through aforesaid method direct production phosphoric acid salt, also can use the phosphoric acid salt metathesis that obtains through aforesaid method to make other phosphoric acid salt.
For example: under the situation of using bicarbonate of ammonia+ammonia (ammonia, liquefied ammonia or ammoniacal liquor), obtain ammonium dibasic phosphate solution, can directly make the Secondary ammonium phosphate finished product, perhaps regulate pH value and separate out primary ammonium phosphate afterwards, perhaps further add the Repone K metathesis again and make potassium primary phosphate.
The condition that realizes above conversion reaction is:
CO in the reactive system 2: P 2O 5〉=0.6 (carbonate is according to CO 2Metering)
PH=6.0-10.0 (the composition content according to various impurity is selected best PH in this scope)
Range of reaction temperature :-20 to+100 ℃, wherein the optimum temps between the reaction period is 25-60 ℃, and reaction can improve temperature after finishing, and improves P 2O 5Dissolving and wash out efficient.
Filtration can be selected any suitable filter for use, and for example chamber-type press filter is carried out the circulated in countercurrent washing.Isolating lime carbonate can be used as the raw material of producing building materials and coating, perhaps is used for other purposes.
(2) technical scheme 2: technical scheme 2 solves the problem of directly using various lower concentration acid and low-grade phosphate ore to produce fine phosphate.Technical scheme is:
A, any its calcium salt of use are dissolved in acid (example hydrochloric acid, nitric acid or the like) decomposing phosphate rock of water.
Reaction conditions:
Phosphorus ore P 2O 5%: do not limit;
Breeze granularity: 40-60 order
Acid concentration %: do not limit;
Proportion scale: according to the Theoretical Calculation amount of chemical reaction, excessive acid 5-10%;
Temperature of reaction: 25-60 ℃
Stirring reaction is complete to acidolysis reaction.
Add 0.3-0.6% polyacrylamide solution flocculation sediment:
Polyacrylamide usage quantity: 200-600g/t breeze
After separating phosphoric acid solution, use clear water countercurrent washing breeze slag 2-3 time, once wash out water and incorporate phosphoric acid solution into, secondary washes out water and is used for secondary response complex acid down.
The principal reaction equation: with the hydrochloric acid reaction is example.
Ca 5F(PO4) 2+10HCl＝5CaCl 2+3H 3PO 4+HF
6HF+SiO 2＝H 2SiF 6+2H 2O
Fe 2O 3+6HCl＝2FeCl 3+3H 2O
Al 2O 3+6HCl＝2AlCl 3+3H 2O
CaCO 3+2HCl＝CaCl 2+H 2O+CO 2
MgCO 3+2HCl＝MgCl 2+H 2O+CO 2
Reaction is finished and is mainly contained following composition in the solution:
H 3PO 4+CaCl 2+FeCl 3+AlCl 3+MgCl 2+H 2SiF 6
B, defluorinate:, can reclaim Sodium Silicofluoride according to common known technology defluorinate if recovery value is arranged:
H 2SiF 6+2NaCl＝Na 2SiF 6+2HCl
C, precipitate phosphoric acid salt: add alkaline matter in above-mentioned mixing solutions, for example lime carbonate or calcium oxide neutralize the Vanadium Pentoxide in FLAKES precipitation fully, filter.
P in the solution 2O 5All be precipitated as following material (therefore obtaining enrichment) so can use any low-grade phosphate ore:
AlPO 4+ FePO 4+ CaHPO 4+ MgHPO 4+ Ca 3(PO 4) 2(on a small quantity)+Mg 3(PO 4) 2(on a small quantity)+MgNH 4PO 4(not existing when having ammonia)
Solution after the filtration is quite purified calcium chloride solution, can be used to make the calcium chloride product, perhaps makes purified ammonium chloride (by-product light calcium carbonate), perhaps makes hydrochloric acid and recycles (known technology).
D, manufacturing phosphoric acid salt finished product: the calcium phosphate precipitation that obtains among the C (wherein mainly is CaHPO 4) transform into the fine phosphate that needs according to the method for narration in the technical scheme 1.
For example: use salt of wormwood and potassium hydroxide to transform and obtain dipotassium hydrogen phosphate:
AlPO 4+K 2CO 3+2H 2O＝K 2HPO 4+CO 2+Al(OH) 3
FePO 4+K 2CO 3+2H 2O＝K 2HPO 4+CO 2+Fe(OH) 3
CaHPO 4+K 2CO 3＝K 2HPO 4+CaCO 3
MgHPO 4+K 2CO 3＝K 2HPO 4+MgCO 3
The use pressure filter filters, and obtains dipotassium hydrogen phosphate solution, concentrates the postcooling crystallization, obtains the dipotassium hydrogen phosphate finished product.
After the above-mentioned solution concentration, regulate the scope of pH value to 3.5-4.5 with hydrochloric acid, crystallisation by cooling, centrifugation then obtains the potassium primary phosphate finished product.
Also can be according to the method in the technical scheme 1, use bicarbonate of ammonia and ammonia to make Secondary ammonium phosphate, obtain the biphosphate ammonium product after perhaps using hydrochloric acid to regulate PH.Perhaps directly in ammonium dibasic phosphate solution, add Repone K, regulate PH then and obtain the potassium primary phosphate finished product.
Use similar method can obtain other phosphate product.
The invention has the beneficial effects as follows:
(1) use many phosphoric acid by wet processes of impurity or wet phosphate to produce fine phosphate product (for example potassium primary phosphate), quality product can reach the same level of product that thermal phosphoric acid is produced, the Vanadium Pentoxide in FLAKES of contamination precipitation can all obtain reclaiming, and realizes the phosphorus yield near 100%.
(2) under the situation of using hydrochloric acid, nitric acid or the like decomposing phosphate rock, owing to leach the P that 2O 5Separate P in this process with mother liquor through coprecipitation mode 2O 5Obtain enrichment simultaneously, therefore can use the diluted acid (comprising spent acid) of any concentration and use the low-grade phosphate ore of any content to process the fine phosphate product, can realize the resource utilization and the maximum economic benefit of fullest.
(3) well-known, using any mineral acid and phosphorus ore to react the purification of the phosphoric acid by wet process that makes and concentrating is the very thing of difficulty, not only a P 2O 5Loss is serious, and equipment corrosion is serious.The present invention has avoided the course of processing of phosphoric acid by wet process, the various phosphoric acid salt of direct production, and process is simple, and equipment corrosion no longer becomes problem.
(4) be used for decomposing phosphate rock if use the sulfuric acid circulation to make hydrochloric acid, then all calcium becomes the high-quality lime carbonate that building material industry needs in a large number, and the headachy phosphogypsum of regeneration does not help environment protection.
Total effect of all these usefulness can produce very high economic benefit and social benefit.
Description of drawings
Accompanying drawing is the process flow diagram of the present invention when using decomposing phosphate rock by chlorhydric acid to make Secondary ammonium phosphate
In the accompanying drawings, hydrochloric acid and ground phosphate rock (40-60 order) are according to all Fe in the phosphorus ore 2O 3+ Al 2O 3The metering of the ratio of the 105-110% of the Theoretical Calculation amount of the needed HCl of+CaO+MgO complete reaction is in acidolysis reaction groove 1, in 25-60 ℃ of stirring reaction 1 hour.
Then, whole slips are transferred in the slag separation groove 2, added polyacrylamide solution (0.3-0.6%) flocculation, staticly settle after stirring, settled solution is transferred to neutralization reaction groove 3.Pump into neutralization reaction groove 3 last time washing out water, the back clarification that stirs, clear liquor pumps into neutralization reaction groove 3.Re-use clear water washing slag once, after the clarification wash out under water secondary response the time as the first time washing soln use.
Then, in neutralization reaction groove 3, add the milk of lime stirring reaction, make calcium phosphate precipitation complete to PH=4.3-4.8.Total overall reaction completely slip pump into chamber-type press filter 4 and filter, wash Cl-≤0.3% to the filter cake.Filtrate is sent to calcium chloride workshop section.All filter cake is transported in the conversion reaction groove 5 that adds circulating mother liquor, stirs, and keeping temperature is 30-40 ℃, and the bicarbonate of ammonia that adds calculated amount is (according to CO 2: P 2O 5=0.6 ratio), feed ammonia and keep PH=7.5-8.0, stirring reaction 1 hour, elevated temperature continues to stir 30 minutes to 50-60 ℃ then.
The total overall reaction slip is transported to chamber-type press filter 6 and filters, and washs P in the filter cake 2O 5≤ 0.3%, packing is sold (lime carbonate) behind the filtration cakes torrefaction.
Then, filtering solution is transported to vaporizer 7, is concentrated to proportion and reaches 1.35-1.40, put into crystallizer tank 8 crystallisation by cooling, separate and dry the back through whizzer 9 and pack, obtain the Secondary ammonium phosphate finished product.The isolating mother liquor of whizzer returns conversion reaction groove 5 batchings.
Embodiment
Embodiment: present embodiment is the phosphorus-containing waste slag that conversion processing produces in the production process when using agricultural primary ammonium phosphate and Repone K as the raw material production potassium primary phosphate, reclaims P 2O 5Experimental result.At 3m 3The stirring reaction container in, add the round-robin phosphorus bearing slag and transform washing soln 2m 3(P 2O 5=65.140g/l), add agricultural monoammonium phosphate and Repone K solubilizing reaction and filter the phosphorus-containing waste slag 1000kg (P that obtains 2O 5=21.31%), adds bicarbonate of ammonia 230kg,, and feed the PH=7.5-8.0 that ammonia keeps reaction mass 30-40 ℃ of stirring reaction 1 hour.After-filtration, washing leaching cake are finished in reaction.Obtain 2.60 cubic metres of filtrates (adding a wash water), P 2O 5=131.53g/l, Fe in the solution 2O 3+ Al 2O 3+ CaO+MgO≤0.00015g/l.P in the lime carbonate that filtration obtains 2O 5=0.28% (butt calculating).Reclaim solution and send the potassium primary phosphate production plant, P205 total yield=99.34%.

Claims (4)

1, a kind of wet phosphoric acid purifying and decomposing phosphate rock by chlorhydric acid are produced phosphatic method, can make the calcium phosphate precipitation that is insoluble in water of iron, aluminium, calcium, magnesium (also comprising manganese, zinc, copper, nickel or the like) impurity be converted into water-soluble phosphate fully.It is characterized in that: make these calcium phosphate precipitation things and carbonate solution or the carbonate mixing solutions stirring reaction with oxyhydroxide, proportion scale is CO 2: P 2O 5〉=0.6, temperature of reaction is-20 to+100 ℃, and the pH value of reaction mass is controlled at (according to the best pH value of the one-tenth component selections of impurity in the material) within the scope of 6-10, filters P after stirring reaction time 0.5-2 hours 2 reacts completely 2O 5Water-soluble transformation efficiency can reach more than 99%.
2, method according to claim 1 is characterized in that: the mixture of employed carbonate or carbonate and oxyhydroxide can be following enumerate any:
(1) carbonic acid gas and alkaline hydrated oxide (ammonium hydroxide or other alkaline hydrated oxides);
(2) supercarbonate (bicarbonate of ammonia, sodium bicarbonate, saleratus or the like) and alkaline hydrated oxide (ammonium hydroxide, sodium hydroxide, potassium hydroxide or other alkaline hydrated oxides);
(3) carbonate (yellow soda ash, salt of wormwood or the like) and alkaline hydrated oxide (sodium hydroxide, potassium hydroxide or other alkaline hydrated oxides);
(4) carbonate (yellow soda ash, salt of wormwood or the like).
3, method according to claim 1 is characterized in that: the calcium phosphate precipitation thing that is insoluble in water that is transformed is the foreign matter of phosphor hydrochlorate throw out that produces in the process of processing by the phosphoric acid by wet process of various acid (for example sulfuric acid, hydrochloric acid and nitric acid or the like) decomposing phosphate rock manufacturing or is processing isolated foreign matter of phosphor hydrochlorate throw out in the phosphatic process of being made by phosphoric acid by wet process.
4, method according to claim 1, it is characterized in that: use the phosphorus ore of any grade of acidic solution (example hydrochloric acid, nitric acid or the like) decomposition of any concentration to make the solution that contains phosphoric acid, use alkaline matter (for example ammonia or bicarbonate of ammonia, lime carbonate or lime, magnesiumcarbonate or magnesium oxide, sodium bicarbonate or yellow soda ash, saleratus or salt of wormwood, sodium hydroxide or potassium hydroxide or the like) this solution precipitation that neutralizes to go out to contain P then 2O 5Throw out, make itself and solution separating, then according to method described in the claim 1 and condition, use the various raw materials of enumerating in the claim 2, the P in these throw outs 2O 5Transform into various water-soluble phosphoric acid salts solutions, and then create various purified phosphate product.
CN 200710048327 2007-01-25 2007-01-25 Method for producing phosphate by wet method phosphoric acid purification and hydrochloric acid decomposition for phosphate ore Pending CN101007626A (en)

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102502550A (en) * 2011-10-27 2012-06-20 黄继曦 Method for preparing water-soluble fertilizer and fine phosphate by converting water-insoluble phosphorus
CN102649657A (en) * 2012-05-18 2012-08-29 成都市新都化工股份有限公司 Production method for macroelement fully water-soluble fertilizer
CN103523764A (en) * 2013-06-27 2014-01-22 云南云天化国际化工股份有限公司 Method for reducing magnesium and aluminum impurities in wet-process phosphoric acid
CN103641574A (en) * 2013-12-25 2014-03-19 黄明科 Method for producing chemically synthesized water soluble fertilizer
CN105253869A (en) * 2015-09-27 2016-01-20 常州市奥普泰科光电有限公司 Method used for reducing fluorine content of by-products in wet phosphoric acid preparation processes
CN105819452A (en) * 2016-04-01 2016-08-03 龚家竹 Method for recovering fluorine resource from fluorination residues of feed phosphate
CN106187327A (en) * 2016-07-12 2016-12-07 贵州芭田生态工程有限公司 Mid low grade phosphate rock prepares method and the compound fertilizer product of high contents of calcium and magnesium compound fertilizer
CN106586990A (en) * 2016-11-09 2017-04-26 中化重庆涪陵化工有限公司 Method of using phosphoric acid by wet process to produce monopotassium phosphate
CN107121351A (en) * 2017-03-28 2017-09-01 华南理工大学 A kind of method for decomposing of acid solution
CN107151026A (en) * 2017-06-08 2017-09-12 四川理工学院 A kind of method of low concentration fluorine-containing hydrochloric acid comprehensive utilization
CN107954406A (en) * 2017-11-03 2018-04-24 菏泽金正大生态工程有限公司 A kind of method of complex salt purification of wet process phosphoric acid production high-quality industrial phosphoric acid diammonium
CN108328592A (en) * 2018-03-16 2018-07-27 成都理工大学 A kind of technique for using phosphoric acid by wet process to produce magnesium monohydrogen phosphate for raw material
CN108383552A (en) * 2018-03-19 2018-08-10 成都理工大学 A kind of production method of potassium acid phosphate
CN110548317A (en) * 2019-09-20 2019-12-10 瓮福达州化工有限责任公司 Flocculating agent and impurity sedimentation system suitable for wet-process phosphoric acid production
CN112321348A (en) * 2020-11-17 2021-02-05 李东峰 Nitrogen-phosphorus-potassium water-soluble fertilizer and preparation method thereof

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102502550A (en) * 2011-10-27 2012-06-20 黄继曦 Method for preparing water-soluble fertilizer and fine phosphate by converting water-insoluble phosphorus
CN102649657A (en) * 2012-05-18 2012-08-29 成都市新都化工股份有限公司 Production method for macroelement fully water-soluble fertilizer
CN103523764A (en) * 2013-06-27 2014-01-22 云南云天化国际化工股份有限公司 Method for reducing magnesium and aluminum impurities in wet-process phosphoric acid
CN103523764B (en) * 2013-06-27 2016-08-17 云南云天化国际化工股份有限公司 A kind of reduce the method for magnalium impurity in phosphoric acid by wet process
CN103641574A (en) * 2013-12-25 2014-03-19 黄明科 Method for producing chemically synthesized water soluble fertilizer
CN103641574B (en) * 2013-12-25 2016-03-30 黄明科 A kind of production method of chemosynthesis water-soluble fertilizer
CN105253869A (en) * 2015-09-27 2016-01-20 常州市奥普泰科光电有限公司 Method used for reducing fluorine content of by-products in wet phosphoric acid preparation processes
CN105253869B (en) * 2015-09-27 2017-12-05 海南医学院 A kind of wet method prepares the method that process phosphoric acid reduces Oil repellent in accessory substance
CN105819452A (en) * 2016-04-01 2016-08-03 龚家竹 Method for recovering fluorine resource from fluorination residues of feed phosphate
CN105819452B (en) * 2016-04-01 2018-01-30 龚家竹 A kind of method that fluorine resource is reclaimed in the defluorination residues from feed phosphate
CN106187327A (en) * 2016-07-12 2016-12-07 贵州芭田生态工程有限公司 Mid low grade phosphate rock prepares method and the compound fertilizer product of high contents of calcium and magnesium compound fertilizer
CN106586990A (en) * 2016-11-09 2017-04-26 中化重庆涪陵化工有限公司 Method of using phosphoric acid by wet process to produce monopotassium phosphate
CN106586990B (en) * 2016-11-09 2019-03-19 长江师范学院 With the method for Wet-process Phosphoric Acid Production potassium dihydrogen phosphate
CN107121351A (en) * 2017-03-28 2017-09-01 华南理工大学 A kind of method for decomposing of acid solution
CN107121351B (en) * 2017-03-28 2020-02-18 华南理工大学 Acidic solution analysis method
CN107151026A (en) * 2017-06-08 2017-09-12 四川理工学院 A kind of method of low concentration fluorine-containing hydrochloric acid comprehensive utilization
CN107954406A (en) * 2017-11-03 2018-04-24 菏泽金正大生态工程有限公司 A kind of method of complex salt purification of wet process phosphoric acid production high-quality industrial phosphoric acid diammonium
CN108328592A (en) * 2018-03-16 2018-07-27 成都理工大学 A kind of technique for using phosphoric acid by wet process to produce magnesium monohydrogen phosphate for raw material
CN108383552A (en) * 2018-03-19 2018-08-10 成都理工大学 A kind of production method of potassium acid phosphate
CN110548317A (en) * 2019-09-20 2019-12-10 瓮福达州化工有限责任公司 Flocculating agent and impurity sedimentation system suitable for wet-process phosphoric acid production
CN112321348A (en) * 2020-11-17 2021-02-05 李东峰 Nitrogen-phosphorus-potassium water-soluble fertilizer and preparation method thereof

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