CN106517124A - Method for green-producing high-quality calcium superphosphate co-generated magnesium chloride by low-level collophanite - Google Patents
Method for green-producing high-quality calcium superphosphate co-generated magnesium chloride by low-level collophanite Download PDFInfo
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- CN106517124A CN106517124A CN201610983043.5A CN201610983043A CN106517124A CN 106517124 A CN106517124 A CN 106517124A CN 201610983043 A CN201610983043 A CN 201610983043A CN 106517124 A CN106517124 A CN 106517124A
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- calcium
- magnesium chloride
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B1/00—Superphosphates, i.e. fertilisers produced by reacting rock or bone phosphates with sulfuric or phosphoric acid in such amounts and concentrations as to yield solid products directly
- C05B1/02—Superphosphates
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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
-
- 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
- C01B25/455—Phosphates containing halogen
-
- 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
-
- 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
- C01F5/00—Compounds of magnesium
- C01F5/26—Magnesium halides
- C01F5/30—Chlorides
Abstract
The invention relates to a method for green-producing high-quality calcium superphosphate co-generated magnesium chloride by low-level collophanite, comprising steps of a, performing acid splitting on carbonate in the phosphorite by hydrochloric acid and preparing phosphorus concentrate; b, preparing high-purity calcium sulfate; c, preparing magnesium chloride; after concentrating the filter fluid to a certain volume, preparing magnesium chloride. The invention has the advantages that the method is applicable to prepare high-efficient phosphatic fertilizer by directly producing high-quality low-magnesium phosphorite in hydrochloric acid decomposition, carbonate of low-level phosphorite and in particular to high-magnesium phosphorite; no waste discharges during the whole technical flow; by applying the invention, the phosphorus pentoxide content of phosphorite is promoted through one acidolysis while content of magnesium oxide in the phosphorite is also reduced; thus the problem of agglomeration and poor phosphatic fertilizer quality caused by high magnesium content during the ordinary calcium production can be solved; the phosphorite therefrom is directly reacted with sulfuric acid, thus high-quality phosphatic fertilizer of which available phosphorus is improved to 16-18% P2O5 can be obtained.
Description
Technical field
The present invention relates to a kind of method of low grade collophanite green production high-quality calcium superphosphate coproduction magnesium chloride.
Background technology
It is a kind of highly developed technique using phosphorus ore production calcium superphosphate (general calcium), during production general calcium, when
When the impurity content of raw ore ferrum, aluminum, magnesium etc. is high, the mobility of ore pulp is deteriorated, but also product physical property can be made to degenerate (bonding
With easy humidity), it is difficult the course of processing such as to cause to concentrate, be dried, and can only be concentrated using slip and slurry-spraying pelletizing, and equipment is complicated, energy
Consumption is high, typically add anticaking agent aborning for solving the above problems.As this production technology is not only existed and production
Industrial phosphoric acid and its salt fight for the problem of high-quality phosphate rock resource, and the addition of anticaking agent, reduce the content of available phosphoruss, subtract
The benefit that weak high-quality resource should be played, makes production cost high, and general grade is in 32%P2O5Phosphorus ore could produce effective percentage and exist
16-18%P2O5General calcium, product competitiveness is poor.Phosphorus ore de-magging is the key for solving the above problems.De-magging technique is mainly used
It is floatation and chemical method, wherein chemical method de-magging technique is simpler, easy to operate.Chemical de-magging includes high-temperature calcination, chemistry leaching
Lifting manipulation, as high-temperature calcination power consumption is big, high cost, chemical extraction method are the study hotspots in current phosphoric acid industry production.Using
Digestion agent have mineral acid (sulphuric acid, nitric acid, nitration mixture), organic acid and acid salt such as Magnesium hydrogen sulfate etc..
The content of the invention
The present invention is directed to above-mentioned prior art and proposes that the carbonate in a kind of utilization hydrochloric acid removing collophane produced phosphorus
The method of sour calcium coproduction magnesium chloride, solves directly using impurity interference problem during high magnesium low-grade Phosphate Rock fertilizer, with removing
The impurity such as magnesium in phosphorus ore, the carbonate of calcium and aluminum, ferrum are removed, and while improves phosphorus ore P2O5Content effect.
The technical solution adopted for the present invention to solve the technical problems is：A kind of low grade collophanite green production high-quality
The method of calcium superphosphate coproduction magnesium chloride, comprises the following steps：
Carbonate in a hydrochloric acidolysiss phosphorus ores prepares phosphorus concentrate
1 is slowly added in ore pulp obtained by the broken wet grindings of rock phosphate in powder Jing：1 hydrochloric acid, finishes, and continues stirring, reacted material
Slurry Jing is filtered, and obtains the phosphorus concentrate (P of grade raising2O5Improve 5-10%, MgO%<2) preparation high-quality general calcium, is directly used in,
Acidolysis filtrate retains；
The chemical equation being related to is：
Ca5F(PO4)3+ 10HCl=3H3PO4+5CaCl2+2HF
CaCO3+ 2HCl=CaCl2+CO2+H2O
MgCO3+ 2HCl=MgCl2+CO2+H2O
Fe2O3+ 3HCl=FeCl3+H2O
Al2O3+ 3HCl=AlCl3+H2O
Make in above-mentioned reaction, to be substantially carried out the decomposition of hydrochloric acid and carbonate by Controlled acidity, so as in the commensurability of de-magging,
Reduce the loss of phosphorus.React for exothermic reaction, temperature can be made to be warmed up to naturally 40-65 DEG C
B prepares high-purity sulfuric acid calcium
Acidolysis filtrate is placed in reactor, concentrated sulphuric acid is slowly added to, stirring is finished, is cooled down, be filtered to remove calcium sulfate, obtain
To former filtrate, acid reflux storage tank is proceeded to, merged with the washing liquid of first time washing calcium sulfate, for preparing 1：1 hydrochloric acid, used as next time point
The hydrochloric acid solution of solution rock phosphate in powder；Second wash filtrate retains, and the washing of the first time as next calcium sulfate is used；
The chemical equation being related to is：
In above-mentioned cyclic process, in acid reflux storage tank, superfluous filtrate is also handled as follows；
C prepares magnesium chloride
After concentrating the filtrate to certain volume, for preparing magnesium chloride.
By such scheme, described hydrochloric acid and rock phosphate in powder envelope-bulk to weight ratio are 0.8-1.3, Unit/mL:g.
By such scheme, the sulfate radical in the acidolysis filtrate described in step b in calcium oxide and the concentrated sulphuric acid for adding mole
Than for 0.5～1.0：1.0～1.5.
By such scheme, the phosphatase reaction in the filtrate after the concentration of step c in a small amount of calcium and solution, chlorine is separated out by standing
Calcium phosphate, is filtrated to get calcium chlorophosphate crude product, directly can be mixed with high-quality phosphate fertilizer with the phosphorus concentrate for preparing, or further pure
Change obtains the calcium chlorophosphate of purity raising.
CaCl2+H3PO4+H2O=CaClH2PO4·H2O+HCl
By such scheme, described prepares comprising the concrete steps that for magnesium chloride：After calcium in filtrate is with calcium chlorophosphate precipitating, filter
Also contain phosphoric acid and magnesium chloride in liquid, concentration can separate out ratio of evaporation, and filtrate is the mother solution of phosphoric acid, can return to acid reflux pond
Continue decomposing phosphate rock stone.
By such scheme, hydrochloric acid decomposes the calcium and magnesium being dissolved in filtrate and progressively can remove, due to during evaporation and concentration magnesium from
Sub- content is higher, in the case where evaporation capacity is little, you can magnesium chloride is separated out, reduces energy consumption.
The present invention realizes producing according to sequence described above, compared with prior art, the advantage and feature of the present invention：
(1) using the present invention, while phosphorus ore phosphorus pentoxide content being lifted by an acidolysis, reduce oxygen in phosphorus ore
Change the content of magnesium, it is the problems such as the caking caused due to content of magnesium height in solving general calcium production and phosphate fertilizer poor quality, thus obtained
Phosphorus ore is directly obtained available phosphoruss with sulfuric acid reaction and brings up to 16-18%P2O5High-quality phosphate fertilizer.Solve using current de-magging agent
When due to after de-magging phosphorus ore grade can not improve, and can only using high-grade phosphorus ore produce general calcium problem.The present invention adopts salt
Sour decomposing phosphate rock concentrate after filtering, not scrubbed its index just can reach and directly produce high-quality general calcium with sulfuric acid reaction
Raw material standard, eliminates washing process, though the phosphorus ore of generation is stained with a small amount of chloride ion, and can during with strong sulfuric acid response
Become gas and hydrogen chloride is escaped together, and fluohydric acid gas is absorbed by absorption cell together；
(2) reported in literature using sulphuric acid or Magnesium hydrogen sulfate as de-magging agent when, can simultaneously with the life of difficulty soluble salt calcium sulfate
Into, phosphorus ore surface is wrapped in, causes de-magging effect undesirable, and the deposition of calcium sulfate, the grade of phosphorus ore can be also reduced, it is uncomfortable
The production requirement of high-quality phosphate fertilizer is produced in the de-magging of mid low grade phosphate rock.And de-magging agent is done using nitric acid, due to the valency of nitric acid
Lattice are expensive, and research application is not extensive.The reasons why during decomposing phosphate rock of the present invention using hydrochloric acid is：1) hydrochloric acid low price, and in control
The impurity such as calcium in phosphorus ore, magnesium carbonate and aluminum, ferrum can be effectively removed during salt manufacturing acid addition, by an acidolysis and centrifugation be
Phosphorus ore phosphorus pentoxide grade can be improved 5-10%, index of the content of magnesia less than 2%；2) process the filtrate after phosphorus ore again
With strong sulfuric acid response, generate hydrochloric acid and obtain high-quality Gypsum Fibrosum simultaneously, the Gypsum Fibrosum impurity content can be directly used for preparing Gypsum Fibrosum crystalline substance less
Palpus or high-quality Gypsum Fibrosum powder；3) hydrochloric acid that reaction is generated can continue decomposing phosphate rock as acid reflux, reduce cost of material, arrange without waste liquid
Put；4) in cyclic process, the accumulation of impurity is separated out with crystallization mode by evaporating its near saturated solution, can be divided by stage evaporation
Calcium chlorophosphate and magnesium chloride are not obtained.
(3) suitable for hydrochloric acid decomposition, that the carbonate of low-grade phosphate ore, particularly high-magnesium-phosphorus ore are directly produced high-grade is low
Magnesium phosphorus ore is used for the preparation of efficient phosphorous fertilizer, without waste discharge in whole technological process.
(4) present invention from decomposing phosphate rock by chlorhydric acid when it is different from carbonate and apatite reactivity, by control institute salt adding
The amount of acid, reaches reservation apatite, decomposes and remove calcium, magnesium carbonate, so as to reduce content of magnesium in phosphorus ore, and while lifts phosphorus
The purpose of ore deposit phosphorus pentoxide content, the impurity being harmful to calcium superphosphate product quality in can making low-grade phosphate ore is most of to be separated
Out, the problems such as solving its caking.For in, the utilization of low-grade phosphate ore provides new way, is the added value for improving phosphor resource
There is provided new method, with good social benefit.
Description of the drawings
Fig. 1 is the process flow diagram of the present invention.
Specific embodiment
Flow process as shown in Figure 1, the method for the present invention include acidolysis, centrifugation, precipitation, concentration, crystallization, centrifugation step.It is described
In acidolysis, centrifugation, first most of carbonate in phosphorus ore is made to be converted into solubility calcium chloride phosphate ore pulp and a certain amount of hydrochloric acid reaction
And magnesium chloride, in centrifuged phosphorus ore, the content of phosphorus pentoxide lifts 5-10% compared with raw ore, and magnesium oxide is down to by 5-8%
Less than 2%.
Dominant response formula：
CaCO3+ 2HCl=CaCl2+CO2+H2O
MgCO3+ 2HCl=MgCl2+CO2+H2O
Calcium ion in centrifugal liquid is allowed to Precipitation by adding concentrated sulphuric acid.It is centrifuged again, can obtains after washing 2 times
Calcium sulfate of the purity more than 95%.The precipitation can generate hydrochloric acid while making calcium chloride transformation be calcium sulfate precipitation,
Filter the acidity in the filtrate after calcium sulfate and can reach the 50-60% of hydrochloric acid content needed for decomposing phosphate rock in terms of hydrochloric acid, as returning
Original volume about 40-50% hydrochloric acid need to be only added when sour.If the hydrogen chloride gas that will be generated in the reactor for adding concentrated sulphuric acid
Body imports acid reflux pond, then 30-40% of the required concentrated hydrochloric acid for original volume hydrochloric acid.
CaCl2+H2SO4=CaSO4+2HCl
The condensing crystallizing is divided into two steps, due to the increase of cycle-index in the filtrate after calcium sulfate precipitation centrifugation,
Magnesium ion content increase in circulation fluid, when in acid solution is circulated, density of magnesium chloride is close to its saturated concentration half, evaporation and concentration is first
Calcium chlorophosphate is separated out first, the supernatant continues concentration and separates out magnesium chloride, and filtrate enters acid reflux pond.
Phosphatase reaction in filtrate after present invention concentration in a small amount of calcium and solution, separates out calcium chlorophosphate, mistake by standing
Filter obtains calcium chlorophosphate crude product, directly can be mixed with high-quality phosphate fertilizer with the phosphorus concentrate for preparing, or be further purified and obtain pure
The calcium chlorophosphate that degree is improved.After calcium in filtrate is with calcium chlorophosphate precipitating, in filtrate, also contain phosphoric acid and magnesium chloride, concentration can be analysed
Go out ratio of evaporation, mother solution of the filtrate for phosphoric acid can return to acid reflux pond and continue decomposing phosphate rock stone.
Embodiment 1
P in dry ore deposit2O5, each content of CaO, MgO is 22.74%, 40.64%, 4.96%, with mechanical agitation, is added containing 210
The phosphate ore pulp of gram dry ore deposit, takes 105mL concentrated hydrochloric acid and adds 105mL tap waters, be added in constant pressure funnel after mix homogeneously, and reaction exists
Carry out under room temperature condition, the fast drop 1 in flowsheet of slurry agitation：1 hydrochloric acid, after dripping off, stops after being further continued for reaction 15 minutes, takes out
Filter, solid drying are weighed, 155.4 grams of weight.P in the solid phosphorus concentrate2O529.04% and 1.32% is respectively with content of MgO,
Be directly used in preparation high-quality general calcium, in gained acidolysis filtrate, add the concentrated sulphuric acid 18mL suitable with calcium ion amount of substance, Jing from
The heart is washed, is dried to obtain calcium sulfate, adds 40-50 milliliter concentrated hydrochloric acid, be configured to 1 in removing the filtrate of calcium：After 1 hydrochloric acid, 210 are taken
Milliliter decomposes new phosphate ore pulp as acid reflux, and second wash filtrate retains, and the washing of the first time as next calcium sulfate is used；It is surplus
Extraction raffinate body retains, and six times loop test result shows, decomposes dry 1260 grams of ore deposit, can produce about 918 grams of concentrate, P in concentrate2O5,
MgO, CaO content respectively may be about 28.6%, 1.71%, 38.2%, isolate and obtain 330g calcium sulfate, wherein P2O5,CaO,MgO
Each content is 0.54%, 29.14%, 0.92%, produces phosphoric acid, hydrochloric acid, magnesium, calcium, ferrum and aluminum ions pending liquid about
740mL, produces 76.3 grams of 9.2 grams of calcium chlorophosphate and magnesium chloride Jing after evaporation, concentration, and the condensing crystallizing is divided into two steps, sulphuric acid
Due to the increase of cycle-index in filtrate after calcium deposit centrifugation, magnesium ion content increase in circulation fluid, when circulation acid solution
When middle density of magnesium chloride is close to its saturated concentration half, evaporation and concentration separates out calcium chlorophosphate first, and the supernatant continues concentration analysis
Go out magnesium chloride, filtrate enters acid reflux pond.
Embodiment 2
P in dry ore deposit2O5, each content of CaO, MgO is 22.65%, 32.5%, 7.8%, with mechanical agitation, is added containing 417.3
The phosphate ore pulp of gram dry ore deposit, takes 220mL concentrated hydrochloric acid and adds 220mL tap waters, be added in constant pressure funnel after mix homogeneously, and reaction exists
Carry out under room temperature condition, the fast drop 1 in flowsheet of slurry agitation：1 hydrochloric acid, after dripping off, stops after being further continued for reaction 25 minutes, takes out
Filter, solid drying are weighed, 315.1 grams of weight.P in the solid phosphorus concentrate2O5, each contents of MgO are 30.02%, 1.32%, filtrate
It is middle to add the concentrated sulphuric acid 37.5mL suitable with calcium ion amount of substance, Jing centrifuge washings, calcium sulfate is dried to obtain, the filtrate of removing calcium
Middle addition 90-100 milliliter concentrated hydrochloric acid, is configured to 1：After 1 hydrochloric acid, take 440 milliliters and decompose new phosphate ore pulp as acid reflux.Raffinate
Body retains, and six times loop test result shows, decomposes dry 2502 grams of ore deposit, can produce about 1843 grams of concentrate, P in concentrate2O5,MgO,
CaO content respectively may be about 29.5%, 1.56%, 35.8%, isolates and obtains purity>94% 443g calcium sulfate, produces phosphorous
Acid, hydrochloric acid, magnesium, calcium, ferrum and aluminum ions pending liquid about 1510mL, Jing evaporation, concentration after produce 16.2 grams of calcium chlorophosphate and
231.6 grams of magnesium chloride, the condensing crystallizing are divided into two steps, due to cycle-index in the filtrate after calcium sulfate precipitation centrifugation
Increase, magnesium ion content increase in circulation fluid, when in acid solution is circulated, density of magnesium chloride is close to its saturated concentration half, is evaporated dense
Contracting, separates out calcium chlorophosphate first, and the supernatant continues concentration and separates out magnesium chloride, and filtrate enters acid reflux pond.
To sum up：The present invention uses middle-low grade high-magnesium-phosphorus ore, using the carbonate in a certain amount of decomposing phosphate rock by chlorhydric acid, has
There is the impurity such as magnesium, the carbonate of calcium and aluminum, ferrum in removing phosphorus ore, and while improve phosphorus ore P2O5Content effect.The technology can make to take off
Magnesium phosphorus ore P2O5Content improve 5～10 percentage points so as to can reach as production calcium superphosphate phosphorus ore content country mark
Standard, due in technical process without waste discharge, the response rate of phosphorus pentoxide bringing up to be close to 100%, production it is general
Calcium product is prevented from caking, and impurity content is low, can significantly save production cost.Receive good technical economic benefit.
Claims (5)
1. a kind of method of low grade collophanite green production high-quality calcium superphosphate coproduction magnesium chloride, comprises the following steps：
Carbonate in a hydrochloric acidolysiss phosphorus ores prepares phosphorus concentrate
1 is slowly added in ore pulp obtained by the broken wet grindings of rock phosphate in powder Jing：1 hydrochloric acid, finishes, and continues stirring, reacted slip Jing
Filter, obtain the phosphorus concentrate of grade raising, be directly used in preparation high-quality general calcium, acidolysis filtrate retains；
B prepares high-purity sulfuric acid calcium
Acidolysis filtrate is placed in reactor, concentrated sulphuric acid is slowly added to, stirring is finished, is cooled down, be filtered to remove calcium sulfate, obtain original
Filtrate, proceeds to acid reflux storage tank, for preparing 1：1 hydrochloric acid, used as the hydrochloric acid solution of next decomposing phosphate rock stone；Second wash filtrate is protected
Stay, the washing of the first time as next calcium sulfate is used；
In above-mentioned cyclic process, in acid reflux storage tank, superfluous filtrate is also handled as follows；
C prepares magnesium chloride
After concentrating the filtrate to certain volume, for preparing magnesium chloride.
2. the method for the low grade collophanite green production high-quality calcium superphosphate coproduction magnesium chloride as described in claim 1, its
Described hydrochloric acid and rock phosphate in powder envelope-bulk to weight ratio are characterised by for 0.8-1.3, Unit/mL:g.
3. the method for the low grade collophanite green production high-quality calcium superphosphate coproduction magnesium chloride as described in claim 1, its
The mol ratio of the sulfate radical being characterised by calcium ion in the acidolysis filtrate described in step b and the concentrated sulphuric acid for adding is 0.5～
1.0：1.0～1.5.
4. the method for the low grade collophanite green production high-quality calcium superphosphate coproduction magnesium chloride as described in claim 1, its
The phosphatase reaction in a small amount of calcium and solution in the filtrate after the concentration of step c is characterised by, calcium chlorophosphate is separated out by standing, is filtered
Calcium chlorophosphate crude product is obtained, and directly high-quality phosphate fertilizer can be mixed with the phosphorus concentrate for preparing, or is further purified and obtain purity
The calcium chlorophosphate of raising.
5. the method for the low grade collophanite green production high-quality calcium superphosphate coproduction magnesium chloride as described in claim 4, its
It is characterised by described and prepares comprising the concrete steps that for magnesium chloride：After calcium in filtrate is with calcium chlorophosphate precipitating, also contain in filtrate
Phosphoric acid and magnesium chloride, concentration can separate out ratio of evaporation, and mother solution of the filtrate for phosphoric acid can return to acid reflux pond and continue to decompose phosphorus
Ore.
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| CN201610983043.5A CN106517124B (en) | 2016-11-09 | 2016-11-09 | A kind of method of low grade collophanite green production high-quality calcium superphosphate coproduction magnesium chloride |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109384210A (en) * | 2017-08-08 | 2019-02-26 | 川恒生态科技有限公司 | A method of utilizing hydrochloric acid and Phosphate Rock acid calcium salt and calcium sulfate |
| CN110790594A (en) * | 2019-10-16 | 2020-02-14 | 铜仁学院 | Method for producing secondary element water-soluble fertilizer from manganese slag |
| CN113149053A (en) * | 2021-02-23 | 2021-07-23 | 湖北省长江资源循环利用及装备创新中心有限公司 | New chemical demagging method for collophanite |
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| JPS5175696A (en) * | 1974-12-27 | 1976-06-30 | Onoda Chem Ind Co Ltd | RINKOSEKINO BUNKAIHO |
| CN102534801A (en) * | 2012-02-23 | 2012-07-04 | 云南民族大学 | Method for improving quality of calcium sulfate whiskers |
| CN102874779A (en) * | 2012-08-18 | 2013-01-16 | 湖北沃裕化工有限公司 | New method for producing monoammonium phosphate by using middle and low-grade phosphate ore without discharging of solid waste |
| CN104593867A (en) * | 2014-12-25 | 2015-05-06 | 武汉工程大学 | Method for preparing in-situ modified nano-magnesium hydroxide whiskers by taking phosphate tailings as raw materials |
| CN104773716A (en) * | 2014-01-09 | 2015-07-15 | 姚鼎文 | Method used for decomposing middle and low-grade phosphorus ore with hydrochloric acid to prepare feed sodium phosphate calcium |
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2016
- 2016-11-09 CN CN201610983043.5A patent/CN106517124B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5175696A (en) * | 1974-12-27 | 1976-06-30 | Onoda Chem Ind Co Ltd | RINKOSEKINO BUNKAIHO |
| CN102534801A (en) * | 2012-02-23 | 2012-07-04 | 云南民族大学 | Method for improving quality of calcium sulfate whiskers |
| CN102874779A (en) * | 2012-08-18 | 2013-01-16 | 湖北沃裕化工有限公司 | New method for producing monoammonium phosphate by using middle and low-grade phosphate ore without discharging of solid waste |
| CN104773716A (en) * | 2014-01-09 | 2015-07-15 | 姚鼎文 | Method used for decomposing middle and low-grade phosphorus ore with hydrochloric acid to prepare feed sodium phosphate calcium |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109384210A (en) * | 2017-08-08 | 2019-02-26 | 川恒生态科技有限公司 | A method of utilizing hydrochloric acid and Phosphate Rock acid calcium salt and calcium sulfate |
| CN110790594A (en) * | 2019-10-16 | 2020-02-14 | 铜仁学院 | Method for producing secondary element water-soluble fertilizer from manganese slag |
| CN113149053A (en) * | 2021-02-23 | 2021-07-23 | 湖北省长江资源循环利用及装备创新中心有限公司 | New chemical demagging method for collophanite |
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