CN105110308A - Phosphorite comprehensive utilization method - Google Patents
Phosphorite comprehensive utilization method Download PDFInfo
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- CN105110308A CN105110308A CN201510503071.8A CN201510503071A CN105110308A CN 105110308 A CN105110308 A CN 105110308A CN 201510503071 A CN201510503071 A CN 201510503071A CN 105110308 A CN105110308 A CN 105110308A
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Abstract
The invention discloses a phosphorite comprehensive utilization method. The method is characterized by comprising the following steps: a. decomposing phosphorite by using acid; b. purifying an acidolysis solution; c. using raw materials containing ammonia compounds to gradually adjust the pH value of the acidolysis solution, and separating produced phosphate precipitate. d. storing the acidolysis solution containing water-soluble calcium; and e. adding a precipitating agent that generates calcium compound to the acidolysis solution containing water-soluble calcium so as to generate calcium compound precipitation. According to the phosphorite comprehensive utilization method disclosed by the invention, phosphorite can be completely, efficiently and comprehensively utilized, and the method is especially applicable to low grade phosphate and magnesium phosphate; acidolysis can be performed on the phosphorite to turn the phosphorite into phosphate, potassium dihydrogen phosphate, potassium nitrate, ammonium dihydrogen phosphate, feed-grade DCP, calcium dihydrogen phosphate fertilizers, high purity calcium carbonate, industrial calcium chloride, high purity calcium sulfate whisker. The process is simple and high in efficiency; phosphate products and calcium products are excellent in quality, and are free of waste water, exhaust gas and waste residue discharge, and the method can be completely compatible with current phosphorus product technology.
Description
Technical field
The present invention relates to the method for a kind of phosphorus ore comprehensive utilization, relate to the method for the raw material of phosphate rock-sulfuric acid being carried out to total integration utilization or rather, be particularly more applicable for and the total integration of low-grade phosphate ore and high-magnesium-phosphorus ore is utilized.
Background technology
The present inventor is the patent document of 200510067111.5 in the patent No., namely, in " the raw material comprehensive utilization of phosphate rock-sulfuric acid and the method for associated production of high purified microsphere nano calcium carbonate ", described technical scheme comprises 4 characterization step: 1, phosphorus ore and acid-respons prepare the acid hydrolysis solution of water-soluble calcium and phosphorus; 2, add the material regulating acid hydrolysis solution pH value, control pH value in 0-12 scopes; 3, acid hydrolysis solution is purified; 4, in acid hydrolysis solution, add the precipitation agent generating calcium cpd precipitation.
The method can reclaim pure calcium cpd and used acid group, but the phosphorus product obtained is impure: being containing Ca (H with what obtain during sulfuric acid decomposition phosphorus ore
2pO
4)
2h
2o, CaHPO
42H
2the mishmash of O and ground phosphate rock and acid non-soluble substance, what obtain in nitric acid phosphorus ammonium technique is phosphoric acid (or phosphoric acid salt) and the mixed solution of nitric acid (or nitrate).Have phosphorus ammonium technique or have phosphorus product Process ba-sis prerequisite under, unpurified phosphorus product can obtain to be processed and contributes to these complete processings further.The defect of this method is there is no independently pure phosphorus product.Though and in existing phosphorus product complete processing, have independent pure phosphorus product, fail to carry out high benefit recovery and utilization to calcium and spent acid root.
The present inventor is the patent document of 200610149043.1 in the patent No., and namely in " method of phosphate rock-sulfuric acid ", described technical scheme comprises 6 characterization step, that is:
A, use acid are reacted with phosphorus ore, generate the acid hydrolysis solution including water-soluble calcium and phosphoric acid;
B, isolate acid hydrolysis solution, with the phosphatase reaction in phosphorous compound and acid hydrolysis solution, generate and include Ca (H
2pO
4)
2h
2the solid substance of O xln;
C, isolate and include Ca (H
2pO
4)
2h
2the solid substance of O xln;
D, from acid hydrolysis solution, isolate fluorine cpd;
E, purification acid hydrolysis solution;
F, to purification after acid hydrolysis solution add precipitation agent, generate calcium cpd precipitation, isolate calcium cpd and filtrate.
Although this patented technology can obtain the calcium product of high purity and excellent Ca (H
2pO
4)
2h
2the solid substance of O xln, but because step b and step c is at generation and separation of C a (H
2pO
4)
2h
2when O xln, the Ca (H of separation
2pO
4)
2h
2o xln contains more circulation vector (chlorion Cl
-or nitrate ion NO
3 -); Also contain water miscible Ca (H in acid hydrolysis solution simultaneously
2pO
4)
2the acid hydrolysis solution leaving step c includes metal or the nonmetallic ions such as water-soluble phosphorus, magnesium, iron, manganese, zinc, metal ion particularly in phosphorus ore, is all the requisite element of crop growth, does not make good use of and cause reducing the farm crop practical function containing phosphatic manure due to these elements; Particularly circulation acid hydrolysis solution is in repeatedly circulating, and the accumulated concentrations of magnesium ion improves fast, causes the purity affecting calcium cpd in step f.
Summary of the invention
The object of the invention is to the defect overcoming above existing processing method, a kind of method that phosphorus ore fully utilizes is provided, whole raw materials in phosphate rock-sulfuric acid technique except acid non-soluble substance can be utilized, be particularly more applicable for and the total integration of low-grade phosphate ore and high-magnesium-phosphorus ore is utilized.
technical scheme
The method of a kind of phosphorus ore comprehensive utilization of the present invention,
A, use acid are reacted with phosphorus ore, generate the acid hydrolysis solution including water-soluble calcium and water-soluble phosphorus;
B, isolate acid hydrolysis solution, purification acid hydrolysis solution;
Characterized by further comprising following steps:
C, progressively regulate the pH value of acid hydrolysis solution with the raw material including ammoniate, and be separated the throw out produced, these throw outs comprise containing phosphoric acid salt;
D, be separated sedimentary acid hydrolysis solution and included water-soluble calcium, store the acid hydrolysis solution containing water-soluble calcium;
E, to add to the acid hydrolysis solution including water-soluble calcium and generate the precipitation agent of calcium cpd, generate calcium cpd precipitation, isolate calcium cpd precipitation and filtrate.
Acid described in step a is containing HCL or HNO
3, or H
3pO
4, acetic acid or four arbitrary proportions composition mixing acid.
Purification described in step b is by subsidence style, mechanical filter mode or adds purification medicament mode, and the acid hydrolysis solution obtained is the acid hydrolysis solution being separated solid substance.
The raw material including ammoniate described in step c, refers to and includes NH
4the raw material of the composition of OH; Progressively regulate the pH value of acid hydrolysis solution, refer to the pH value progressively improving acid hydrolysis solution; The throw out that the throw out being separated generation refers to producing under different pH condition is separated respectively.
Described includes NH
4the raw material of the composition of OH, refers to containing NH
4oH and calcium, magnesium, zinc, manganese, iron, aluminium and be of value to the mixing solutions of compound of farm crop.
The throw out separated described in step c, comprise the calcium salt containing phosphoric acid, these throw outs react with the water-soluble cpds containing sulfate radical further, generate the solids including calcium sulfate composition, be separated the solids including calcium sulfate composition, liquid includes water soluble phosphorous compounds.
The described calcium salt comprised containing phosphoric acid, further with sylvite, the ammonium salt of sulfuric acid, the sulfuric acid reaction of sulfuric acid, generate the solids including calcium sulfate composition, be separated the solids including calcium sulfate composition, liquid comprises sylvite, the ammonium salt of phosphoric acid, phosphoric acid containing water-soluble phosphoric acid.
Described generation includes the solids of calcium sulfate composition, refers to the calcium sulfate crystal whiskers that length-to-diameter ratio is greater than 5.
NH described in step c
4oH refers to NH
3with H
2the NH that O reaction generates
4oH.
Described NH
4the mixing solutions of the compound of OH and calcium, magnesium, refers to ammonium salt and the compound containing calcium and react the solution, ammonium salt and the compound that contains magnesium that generate and react the solution generated.
The described compound containing calcium comprises the calcium salt of calcium oxide containing calcium oxide, calcium hydroxide, dolomite calcination and magnesium oxide, phosphoric acid.
Storage described in steps d contains the acid hydrolysis solution of water-soluble calcium, comprises from what store and distributes liquid product, as the liquid starting material of other explained hereafter calcium cpd containing the acid hydrolysis solution of water-soluble calcium.
The precipitation agent adding generation calcium cpd to the acid hydrolysis solution including water-soluble calcium described in step e, adds the precipitation agent generating calcium cpd and refers to the water-soluble cpds comprised containing carbonate or the water-soluble cpds containing sulfate radical; The calcium cpd generated includes the throw out of ingredients calcium carbonate accordingly or includes the throw out of calcium sulfate composition.
Described adds to the acid hydrolysis solution including water-soluble calcium the precipitation agent generating calcium cpd, adds the precipitation agent generating calcium cpd and refers to containing sulfate radical and hydrogen ion H
+water-soluble cpds; The calcium cpd generated is the throw out including calcium sulfate composition, and isolated filtrate includes hydrogen ion H
+return step a and phosphorus ore reacts.
Adding containing sulfate radical and hydrogen ion H to the acid hydrolysis solution including water-soluble calcium described in step e
+the precipitation agent of water-soluble cpds, comprise and add sulfate radical and hydrogen ion H
+water-soluble cpds precipitation agent before first add acid, alkali, salt, organism as generating the control agent of calcium sulfate precipitation, the calcium sulfate crystal whiskers making the calcium sulfate precipitation of generation become length-to-diameter ratio to be greater than 5.
Described acid, alkali, salt, organism comprise and containing: mineral acid is HCl, HNO
3or H
3pO
4; Organic acid is formic acid, acetic acid, lipid acid, polyprotonic acid or alcohols; Inorganic salt comprise containing K
+, Na
+, NH4
+, Mg
2+, Al
3+, Mn
2+the water-soluble phosphate of ion, muriate or nitrate; Organic salt comprises the various tensio-active agents containing water soluble allcylbenzene soap, alkylbenzene sulfonate; Alkali is Mg (OH)
2.
detailed Description Of The Invention
Below technological principle of the present invention is described in detail.
The operation that the present invention includes, step are as follows:
A, use acid are reacted with phosphorus ore, generate the acid hydrolysis solution including water-soluble calcium and water-soluble phosphorus:
The present invention selects the strong acid that can generate water-soluble calcium as HCl, HNO
3, H
3pO
4or the mixing acid of three's arbitrary proportion composition carrys out decomposing phosphate rock, in order to some trace element being of value to farm crop in phosphate rock-sulfuric acid to greatest extent, add part acetic acid, therefore the trace element that obtains of acid hydrolysis solution of the present invention is more.Due to degradation production mainly water miscible calcium and phosphoric acid, this just reduces the requirement to phosphorus ore granularity from reaction principle, from practical standpoint, granularity can be selected at the mineral aggregate of below 300mm, as long as phosphorus ore is immersed in acid hydrolysis solution, in 1 hour, just acid hemolysis process can be completed.As long as and the capacity in acidolysis pond is more than or equal to 2 times of acid hydrolysis solution volume, just can save ball milling operation, reduce phosphorus ore granularity and pond internal recycle is taked to acid hydrolysis solution, can fast response be added.
B, isolate acid hydrolysis solution, purification acid hydrolysis solution:
For the acid hydrolysis solution after phosphate rock-sulfuric acid, preferably isolate solid substance with subsidence style, after 1-2 hours natural subsidence just separable go out more than 99% solid substance.If add flocculation agent, settling process can be completed fast.Due to the mainly yellow sand (silicate) of the acid non-soluble substance in phosphorus ore, step b is being separated yellow sand as topmost separation task.
C, progressively regulate the pH value of acid hydrolysis solution with the raw material including ammoniate, and be separated the throw out produced, these throw outs comprise containing phosphoric acid salt:
To be separated in the acid hydrolysis solution of solid substance main containing water-soluble calcium and water-soluble phosphate, also containing many water miscible elements being of value to crop growth, such as: magnesium, zinc, manganese, iron, aluminium and be of value to the water-soluble cpds of farm crop.The present invention is the pH value progressively regulating acid hydrolysis solution with the raw material including ammoniate, and these elements being of value to crop growth are reclaimed becomes calcium phosphate precipitation thing, and is separated these throw outs produced.During ammonification acid hydrolysis solution, along with the rising of pH value during ammonification, phosphoric acid by wet process ammonification mainly contains to throw out during different pH:
pH1.0—1.6（Fe,Al)
3NH
4H
8(PO
4)
6 ·6H
2O
pH1.6—2.2（Fe,Al)NH
4(HPO
4)
2 ·H
2O
pH2.3（Fe,Al)NH
4(HPO
4)
2 ·0.5H
2O
pH>2.3（Fe,Al)NH
4HPO
4F
2
pH3.5（Fe,Al)
3NH
4H
8(PO
4)
6 ·6H
2O
（Fe,Al)NH
4(HPO
4)
2 ·0.5H
2O
（Fe,Al)Mg(NH
4)
2(HPO
4)
2 ·F
3
pH4.3（Fe,Al)NH
4(HPO
4)
2 ·0.5H
2O
（Fe,Al)Mg(NH
4)
2(HPO
4)
2 ·F
3
pH5.6（Fe,Al)NH
4(HPO
4)
2 ·0.5H
2O
（Fe,Al)Mg(NH
4)
2(HPO
4)
2 ·F
3
pH>6（Fe,Al)NH
4(PO
4)
2OH
·2H
2O
（Fe,Al)(NH
4)
2H
2(PO
4)
2F
·n2H
2O
(to throw out during different pH, select from " production technique of phosphoric acid phosphorus ammonium ", chemical fertilizer department of Ministry of Chemical Industry, China Phosphate Industry Association (CPIA) writes group and writes in these phosphoric acid by wet process ammonifications)
Due to the mixing solutions that acid hydrolysis solution is containing water-soluble calcium and water-soluble phosphorus, as use NH
4during OH adjust ph, secondary calcium phosphate also will produce throw out.Because pH=4 secondary calcium phosphate starts to produce precipitation, pH=8 secondary calcium phosphate precipitation completely.
Again because of (Fe, Al) during pH3.5
3nH
4h
8(PO
4)
6 .6H
2o, (Fe, Al) NH
4(HPO
4)
2 .0.5H
2o, (Fe, Al) Mg (NH
4)
2(HPO
4)
2 .f
3these calcium phosphate precipitation things are all citric soluble slow-release fertilizers, it is all available phosphorus, and substantially can magnesium, zinc, manganese, iron, aluminium and the water-soluble cpds being of value to farm crop be all enriched in this pH value range, because pH value is less than 4, do not reach the pH value that secondary calcium phosphate starts to produce precipitation, secondary calcium phosphate also can not form throw out, at this moment phosphoric acid is dissolved in acid hydrolysis solution with the form of monocalcium phosphate, during saturation ratio under only having the content when monocalcium phosphate to exceed this temperature, Ca (H will be generated
2pO
4)
2h
2the solid substance of O xln, is also blended in these citric soluble calcium phosphate precipitations.Exactly because magnesium, zinc, manganese, iron, aluminium and fluorochemical all form calcium phosphate precipitation thing, thus purify acid hydrolysis solution more up hill and dale.
Particularly fluorine-containing calcium phosphate salt, as fluorine-containing monocalcium phosphate, secondary calcium phosphate, also can enter step c together with ammoniate, use the suitable adjust ph of acid hydrolysis solution after step b purification, make pH value carry out ammonification between 1-3, fluorine-containing monocalcium phosphate, secondary calcium phosphate are generated
(Fe, Al) Mg (NH 4 ) 2 (HPO 4 ) 2 f 3 throw out, thus realize phosphatic defluorinate.This uses in ammonia compound and the advantage of acid hydrolysis solution.
After being separated these throw outs, the composition of acid hydrolysis solution only has water-soluble calcium and water-soluble phosphorus substantially, that is:
Ca (H
2pO
4)
2+ 4CaCl
2+ 2NH
4cl(is with hydrochloric acidolysis phosphorus ore) formula (1)
Or Ca (H
2pO
4)
2+ 4Ca(NO
3)
2+ 2NH
4nO
3(with nitric acid solution phosphorus ore) formula (2)
Ammonium salt in its Chinese style (1), formula (2) uses NH exactly
4formed after the muriate (or nitrate) such as magnesium, zinc, manganese, iron, aluminium in OH and in acid hydrolysis solution.
Acid hydrolysis solution after particularly removing fluorochemical, if continue ammonification, as long as pH value is greater than 4, the secondary calcium phosphate that will generate not containing fluorochemical precipitates, the namely secondary calcium phosphate of feed grade.For hydrochloric acidolysis phosphorus ore, be shown below:
Ca (H
2pO
4)
2+ 4CaCl
2+ 2NH
4cl+2NH
4oH==2CaHPO
4 .2H
2o
↓+ 4NH
4cl+3CaCl
2formula (3)
Because formula (3) can isolate the CaHPO of high purity
4 .2H
2o
↓, this pure phosphoric acid salt both can as calcium hydrophosphate fodder product, also can as the phosphorus product raw material of secondary processing, that is:
2CaHPO
4 .2H
2o
↓+ 2H
2sO
4===2H
3pO
4+
2CaSO 4 . 2H 2 o ↓ formula (4)
2CaHPO
4 .2H
2o
↓+ 2KHSO
4===2KH
2pO
4+
2CaSO 4 . 2H 2 o ↓ formula (5)
2CaHPO
4 .2H
2o
↓+ (NH
4)
2sO
4+ H
2sO
4===2NH
4h
2pO
4+
2CaSO 4 . 2H 2 o ↓ formula (6)
The reaction conditions of control formula (4), formula (5), formula (6), can generate the crystal of calcium sulfate of crystal whisker-shaped.
D, be separated sedimentary acid hydrolysis solution and included water-soluble calcium, store the acid hydrolysis solution containing water-soluble calcium;
Be separated the acid hydrolysis solution containing water-soluble calcium that phosphoric acid salt is later, store the acid hydrolysis solution of this water-soluble calcium, the raw material that water-soluble calcium is provided to other technique can be separated at any time, this raw material both also contained water-soluble calcium containing ammonium, time with hydrochloric acid (or nitric acid) phosphate rock-sulfuric acid, as long as the concentration of acid is improved, the water-soluble calcium solution of high density just can be provided.
This acid hydrolysis solution containing water-soluble calcium being separated various impurity and water-soluble phosphate, can directly enter next step of the present invention.
E, to add to the acid hydrolysis solution including water-soluble calcium and generate the precipitation agent of calcium cpd, generate calcium cpd precipitation.
The precipitation agent that the present invention adds comprises the water-soluble cpds containing carbonate or the water-soluble cpds containing sulfate radical; The calcium cpd generated includes the throw out of ingredients calcium carbonate accordingly or includes the throw out of calcium sulfate composition.For hydrochloric acidolysis phosphorus ore, be shown below:
4NH
4cl+3CaCl
2+ 3 (NH
4)
2cO
3==4NH
4cl+
3CaCO 3 ↓ + 6NH 4 clformula (7)
4NH
4cl+3CaCl
2+ 3 (NH
4)
2sO
4+ 2H
2o===4NH
4cl+
6NH 4 cl+3CaSO 4 . 2H 2 o ↓formula (8)
4NH
4cl+3CaCl
2+ 3H
2sO
4+ 2H
2o===4NH
4cl+
3CaSO 4 . 2H 2 o ↓ + 6HClformula (9)
Wherein, the filtrate in formula (9) contains 4NH
4the hydrochloric acid of Cl+6HCl regeneration, can return step a for next phosphate rock-sulfuric acid that circulates.
In order to make the resultant of formula (8), formula (9)
3CaSO 4 . 2H 2 o ↓ generate the shape of calcium sulfate crystal whiskers, the present invention before reactions, first adds the control agent of calcium sulfate crystal whiskers to acid hydrolysis solution, the control agent of these calcium sulfate crystal whiskers comprises and containing: acid, alkali, salt, organism.Wherein mineral acid is HCl, HNO
3or H
3pO
4; Organic acid is formic acid, acetic acid, lipid acid, polyprotonic acid or alcohols; Inorganic salt are containing K
+, Na
+, NH4
+, Mg
2+, Al
3+, Mn
2+the water-soluble phosphate of ion, muriate or nitrate; Organic salt comprises the various tensio-active agents containing water soluble allcylbenzene soap, alkylbenzene sulfonate; Alkali is Mg (OH)
2.
In " a kind of novel method of scale operation calcium sulfate crystal whiskers " (patent No. 200710148664.2) patented technology that the present inventor authorizes, disclose the method for producing high-purity high-quality calcium sulfate crystal whiskers, particularly before synthesis calcium sulfate crystal whiskers, add the crystal controlling agent that calcium sulfate crystal whiskers made by various tensio-active agent, not only be conducive to the quick generation of calcium sulfate crystal whiskers, high-quality is simple and easy more more can to make secondary processing calcium sulfate crystal whiskers, very easily can change purposes and the shape of calcium sulfate crystal whiskers.
Due to the acidolysis phosphorus ore that often circulates, all want an acidolysis part magnesium, zinc, manganese, iron, aluminium plasma, use NH
4generate a part of ammonium salt always with during acid hydrolysis solution during OH carries out, repeatedly circulate phosphate rock-sulfuric acid, and ammonium salt concentration constantly increases, and is separated these ammonium salts NH
4 +ion, can use multiple existing mode, the preferred milk of lime regeneration of the present invention: (ammonium salt is expressed with ammonium chloride)
2NH
4cl+Ca (OH)
2=CaCl
2+ 2NH
4oH formula (10)
Steam volatile ammonia, solution becomes calcium chloride water, that is:
CaCl
2+ 2NH
4oH==CaCl
2+ 2NH
3↑+2H
2o formula (11)
The resultant CaCl of formula (10)
2+ 2NH
4oH can be directly used in formula (3); The resultant 2NH of formula (11)
3↑ also may be used for formula (3), CaCl
2+ 2H
2o solution can be directly used in manufacture solid calcium chloride.
beneficial effect:
1, dominant ideas of the present invention are the advantages making full use of the chemical energy that has of acid and existing phosphide complete processing, no matter use HCl, HNO
3, H
3pO
4, H
2sO
4or phosphorite stope can be become purer the phosphoric acid salt solids, potassium primary phosphate, primary ammonium phosphate and the phosphoric acid solution that have very high value added and use value by mixing acid, calcium becomes the industrial filler calcium sulfate crystal whiskers CaSO of high-purity
4or CaCO
3, fluorine and phosphoric acid salt form double salt and enter phosphorus compound fertilizer, and phosphate rock-sulfuric acid spent acid is recycled completely, become the various potassium, sodium, the ammonium salt that there are high benefit, realize the theoretical utilization ratio 100% of raw material, define independently phosphate rock-sulfuric acid novel process.
2, the present invention also has the characteristic with existing phosphorus ammonium and phosphorus product complete processing compatibility and coproduction simultaneously, when particularly the present invention is applied to feed one calcium and dicalcium, the theoretical transformation rate of phosphorus is high, and without efflux wastewater and phosphogypsum, this is that current art far cannot realize.
3, the present invention can be compatible with existing kinds of processes in a variety of manners, and its technique and product have wide DEVELOPMENT PROSPECT.As used low-concentration hcl and by-product hydrochloric acid technique, phosphogypsum thiamine process, synthesis ammonium handicraft product etc., the present invention not only receives the advantage of these techniques and product, also these techniques are offered help, and all can realize raw materials used 100% utilization ratio under high benefit prerequisite, fully show the present invention and be based upon novelty under high benefit prerequisite and practicality.
4, the method for a kind of phosphorus ore comprehensive utilization of the present invention, energy consumption is low, cost is low, high efficiency, technique are simply arranged outward without waste water.
5, high to the processing benefit of low-grade phosphate ore, cost is low, opened up a series of high-quality phosphoric acid salt or phosphoric acid processing new way.
Accompanying drawing explanation
Accompanying drawing is technological principle schematic flow sheet of the present invention.
Embodiment
Below in conjunction with accompanying drawing, the present invention is further illustrated.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.The method of unreceipted actual conditions in the following example, usually conveniently condition.
embodiment 1: the present invention's application of sulfuric acid solution phosphorus ore
With sulfuric acid decomposition Phosphate Rock ammonium and phosphoric acid salt, the raw materials used basis of current technology increases circulatory mediator HCl, HNO
3, H
3pO
4, acetic acid or its arbitrary proportion mixing acid, just can promote the present invention and realize utilizing the total integration of raw material.Its novelty and practicality are embodied in no matter phosphorus ore grade height, and foreign matter content is how many, does not all affect quality and the phosphorus product quality of high-purity calcium cpd.Combine with existing phosphorus ammonium technique, the present invention not only can obtain the calcium product of high purity, can also provide strong phosphoric acid without the need to evaporation concentration or phosphoric acid salt to it.
Implementation step illustrates:
A, use acid are reacted with phosphorus ore, generate the acid hydrolysis solution including water-soluble calcium and water-soluble phosphorus;
HCl, HNO are selected in the acid of the present embodiment
3, H
3pO
4, acetic acid or its arbitrary proportion mixing acid.
In step a, raw ore particle diameter being less than 300mm puts into acidolysis pond and acid-respons 1--4 hour, H
+ionic concn is 3-12mol/l preferably;
B, isolate acid hydrolysis solution, purification acid hydrolysis solution;
In step b, release the acid hydrolysis solution in acidolysis pond, be separated the acid non-soluble substances such as yellow sand through natural subsidence, again through mechanical filter purification acid hydrolysis solution, the acid hydrolysis solution including water-soluble phosphorus and water-soluble calcium being separated solid substance put into calcic clean solution tank stand-by.
C, progressively regulate the pH value of acid hydrolysis solution with the raw material including ammoniate, and be separated the throw out produced, these throw outs comprise containing phosphoric acid salt;
NH is included in described raw material
4the composition of OH, refers to containing NH
4oH and calcium, magnesium, zinc, manganese, iron, aluminium and be of value to the mixing solutions of compound of farm crop;
The compound of the described calcium contained, comprises monocalcium phosphate and secondary calcium phosphate that Oil repellent exceeds standard;
In step c, use the acid hydrolysis solution including water-soluble phosphorus and water-soluble calcium after purification, with including NH
4the raw material adjust ph of the composition of OH, controls the pH value of acid hydrolysis solution between 1-4, makes the fluorine in acid hydrolysis solution, magnesium, zinc, manganese, iron, aluminium plasma, generates this (Fe, Al) NH
4(HPO
4)
2 .0.5H
2o and (Fe, Al) Mg (NH
4)
2(HPO
4)
2 .f
3solubility in citric acid calcium phosphate precipitation, thus acid hydrolysis solution is become be stripped of fluorine, magnesium, zinc, manganese, iron, the isoionic acid hydrolysis solution of aluminium.This fluorine-containing citric acid soluble phosphorus hydrochlorate, containing N: about 7.5%, P
2o
5: about 40%;
The monocalcium phosphate exceeded standard for Oil repellent and secondary calcium phosphate, also can utilize the phosphoric acid salt that the acid hydrolysis solution of step b (because containing phosphoric acid) acidolysis is fluorine-containing, fluorion acidolysis out, then use and include NH
4the raw material adjust ph of the composition of OH, makes fluorion and phosphoric acid salt generate (Fe, Al) Mg (NH
4)
2(HPO
4)
2 .f
3double salt and defluorinate;
In order to obtain the acid hydrolysis solution of defluorinate, can the pH value of acid hydrolysis solution be controlled 4 when defluorinate, now just having reached the pH value generating secondary calcium phosphate.
Throw out before pH4 is fluorine-containing citric acid soluble phosphorus hydrochlorate and the mixed phosphate of water-soluble phosphoric acid calcium dihydrogen, the phosphoric acid salt of defluorinate that what pH value was greater than 4 generations is, the phosphoric acid salt of the high purity of this defluorinate, may be used for processing feed-grade phosphate, potassium primary phosphate, ammonium phosphate and phosphoric acid.
In order to make acid hydrolysis solution neutralize pH4 before sedimentary nutrient keep roughly a scope as far as possible, when the magnesium of acid hydrolysis solution, zinc, manganese, iron plasma content reduce, the content of these ions can be increased artificially, to guarantee the nutrient content of this citric acid soluble phosphorus product; Particularly high-magnesium-phosphorus ore, will obtain very good comprehensive utilization in the present invention, obtains the phosphorus compound fertilizer of the very excellent nitrogen of quality, phosphorus, magnesium.
D, be separated sedimentary acid hydrolysis solution and included water-soluble calcium, store the acid hydrolysis solution containing water-soluble calcium.
The present invention stores the acid hydrolysis solution containing water-soluble calcium, mainly makes three kinds of purposes: one is at any time for providing the raw material of manufacture solid calcium chloride (or nitrocalcite); Two is at any time for the production of the calcium carbonate of high purity; Three is for the production of calcium sulfate crystal whiskers.
E, to add to the acid hydrolysis solution including water-soluble calcium and generate the precipitation agent of calcium cpd, generate calcium cpd precipitation, isolate calcium cpd precipitation and filtrate.
The present embodiment mainly uses the acid hydrolysis solution of steps d to produce calcium sulfate crystal whiskers, and in order to obtain superior in quality calcium sulfate crystal whiskers, first we will prepare sulphuric acid soln.
When preparing sulphuric acid soln, control the concentration of sulphuric acid soln 1-20%, and add calcium sulfate crystal whiskers control agent, the control agent of these calcium sulfate crystal whiskers comprises and containing: acid, alkali, salt, organism.Wherein mineral acid is HCl, HNO
3, or H
3pO
4; Organic acid is formic acid, acetic acid, lipid acid, polyprotonic acid or alcohols; Inorganic salt are containing K
+, Na
+, NH4
+, Mg
2+, Al
3+, Mn
2+the water-soluble phosphate of ion, muriate or nitrate; Organic salt comprises the various tensio-active agents containing water soluble allcylbenzene soap, alkylbenzene sulfonate; Alkali is Mg (OH)
2.
Next is the pH value that adjustment kit contains the acid hydrolysis solution of water-soluble calcium, and the present embodiment uses the mixing acid of hydrochloric acid, nitric acid, acetic acid or three's arbitrary proportion.
After the acid hydrolysis solution including water-soluble calcium mixes with sulphuric acid soln, generate the circulation acid hydrolysis solution of calcium sulfate crystal whiskers and regeneration, isolate and include hydrogen ion H
+filtrate return step a and phosphorus ore reacts.
Repeatedly circulating in phosphate rock-sulfuric acid, the ammonium ion in acid hydrolysis solution increases gradually, in order to the ammonium ion NH of controlled circulation acid hydrolysis solution
4 +, what the present invention stored from steps d separate part reacts containing the acid hydrolysis solution of water-soluble calcium and milk of lime, makes it generate containing NH
4the mixing solutions of OH and calcium, magnesium ion, for step c, progressively regulates the pH value of the acid hydrolysis solution from step b.
embodiment 2: the present invention is applied to production calcium hydrophosphate fodder
In the present embodiment, novelty of the present invention and practicality are embodied in under sulfuric acid and the phosphorus ore condition that is main raw material, go out the secondary calcium phosphate of feed grade with the acidolysis of closed loop acid hydrolysis method, and make raw material obtain total integration to utilize.With existing calcium hydrogen phosphate fodder technics comparing, because use ammoniacal liquor with acid hydrolysis solution in the present invention, what remove that fluorine cpd obtain is the compound nitrogen phosphate fertilizer of the slow-releasing of high density.
Implementation step illustrates:
A, use acid are reacted with phosphorus ore, generate the acid hydrolysis solution including water-soluble calcium and water-soluble phosphorus;
HCl, HNO are selected in the acid of the present embodiment
3, H
3pO
4, acetic acid or its arbitrary proportion mixing acid;
In step a, raw ore particle diameter being less than 300mm puts into acidolysis pond and acid-respons 1--4 hour, H
+ionic concn is 3-12mol/l preferably.
B, isolate acid hydrolysis solution, purification acid hydrolysis solution;
In step b, release the acid hydrolysis solution in acidolysis pond, be separated the acid non-soluble substances such as yellow sand through natural subsidence, again through mechanical filter purification acid hydrolysis solution, the acid hydrolysis solution including water-soluble phosphorus and water-soluble calcium being separated solid substance put into calcic clean solution tank stand-by.
C, progressively regulate the pH value of acid hydrolysis solution with the raw material including ammoniate, and be separated the throw out produced, these throw outs comprise containing phosphoric acid salt;
NH is included in described raw material
4the composition of OH, refers to containing NH
4oH and calcium, magnesium, zinc, manganese, iron, aluminium and be of value to the mixing solutions of compound of farm crop.
In step c, use the acid hydrolysis solution including water-soluble phosphorus and water-soluble calcium after purification, with including NH
4the raw material adjust ph of the composition of OH, controls the pH value of acid hydrolysis solution between 1-4, makes the fluorine in acid hydrolysis solution, magnesium, zinc, manganese, iron, aluminium plasma, generates this (Fe, Al) NH
4(HPO
4)
2 .0.5H
2o and (Fe, Al) Mg (NH
4)
2(HPO
4)
2 .f
3solubility in citric acid calcium phosphate precipitation, thus acid hydrolysis solution is become be stripped of fluorine, magnesium, zinc, manganese, iron, the isoionic acid hydrolysis solution of aluminium.
This fluorine-containing citric acid soluble phosphorus hydrochlorate, containing N: about 7.5%, P
2o
5: about 40%;
The monocalcium phosphate exceeded standard for Oil repellent and secondary calcium phosphate, also can utilize the phosphoric acid salt that the acid hydrolysis solution of step b (because containing phosphoric acid) acidolysis is fluorine-containing, fluorion acidolysis out, then use and include NH
4the raw material adjust ph of the composition of OH, makes fluorion and phosphoric acid salt generate (Fe, Al) Mg (NH
4)
2(HPO
4)
2 .f
3double salt and defluorinate;
In order to obtain the acid hydrolysis solution of defluorinate, can the pH value of acid hydrolysis solution be controlled 4 when defluorinate, now just having reached the pH value generating secondary calcium phosphate;
Throw out before pH4 is fluorine-containing citric acid soluble phosphorus hydrochlorate and the mixed phosphate of water-soluble phosphoric acid calcium dihydrogen, the calcium phosphate salt of defluorinate that what pH value was greater than 4 generations is, the calcium phosphate salt of the high purity of this defluorinate, mainly phosphoric acid defluorination hydrogen calcium, because containing a small amount of monocalcium phosphate solid, its butt P
2o
5content is generally between 52--56%.
Due to including NH
4the raw material of the composition of OH regulates the pH value of acid hydrolysis solution, and the calcium hydrophosphate fodder separated wets product, and containing ammonium ion, the present embodiment first washs with the liming containing calcium ion, then is washed till without ammonia taste with clear water.
D, be separated sedimentary acid hydrolysis solution and included water-soluble calcium, store the acid hydrolysis solution containing water-soluble calcium, for the production of calcium sulfate crystal whiskers.
E, to add to the acid hydrolysis solution including water-soluble calcium and generate the precipitation agent of calcium cpd, generate calcium cpd precipitation, isolate calcium cpd precipitation and filtrate.
The present embodiment mainly uses the acid hydrolysis solution of steps d to produce calcium sulfate crystal whiskers, and in order to obtain superior in quality calcium sulfate crystal whiskers, first we will prepare sulphuric acid soln.
When preparing sulphuric acid soln, control the concentration of sulphuric acid soln 1-20%, and add calcium sulfate crystal whiskers control agent, the control agent of these calcium sulfate crystal whiskers comprises and containing: acid, alkali, salt, organism.Wherein mineral acid is HCl, HNO
3, or H
3pO
4; Organic acid is formic acid, acetic acid, lipid acid, polyprotonic acid or alcohols; Inorganic salt are containing K
+, Na
+, NH4
+, Mg
2+, Al
3+, Mn
2+the water-soluble phosphate of ion, muriate or nitrate; Organic salt comprises the various tensio-active agents containing water soluble allcylbenzene soap, alkylbenzene sulfonate; Alkali is Mg (OH)
2.
Next is the pH value that adjustment kit contains the acid hydrolysis solution of water-soluble calcium, and the present embodiment uses the mixing acid of the arbitrary proportion of hydrochloric acid, nitric acid, acetic acid.
After the acid hydrolysis solution including water-soluble calcium mixes with sulphuric acid soln, generate the circulation acid hydrolysis solution of calcium sulfate crystal whiskers and regeneration, isolate and include hydrogen ion H
+filtrate return step a and phosphorus ore reacts.
Repeatedly circulating in phosphate rock-sulfuric acid, the ammonium ion in acid hydrolysis solution increases gradually, in order to the ammonium ion NH of controlled circulation acid hydrolysis solution
4 +, what the present invention stored from steps d separate part reacts containing the acid hydrolysis solution of water-soluble calcium and milk of lime, makes it generate containing NH
4the mixing solutions of OH and calcium, magnesium ion, for step c, as the pH value of the acid hydrolysis solution progressively regulated from step b.
Real
execute example 3: the present invention HCl is the phosphate rock-sulfuric acid technique of raw material
Implement object:
Rely at without phosphorus Product Process and use HNO
3, HCl is when being raw material phosphate rock-sulfuric acid, the present embodiment stresses to receive variously has high economic benefit, less energy-consumption, the technique of Low investment and product, forms a high benefit and fully utilizes novel process.
With HCl decomposing phosphate rock mainly in order to receive by-product HCl(gas) or dilute hydrochloric acid, a large amount of by-product hydrochloric acids is used for acidolysis low-grade phosphate ore, obtains phosphorus product and technical grade calcium product;
By acid concentration: carry out acidolysis with HCl to phosphorus ore, be a kind of open loop acid hydrolysis method, acid concentration is 6-12mol/l preferably, with concentration height as well.
Implementation step illustrates:
A, use acid are reacted with phosphorus ore, generate the acid hydrolysis solution including water-soluble calcium and water-soluble phosphorus;
HCl is selected in the acid of the present embodiment;
In step a, the raw ore that particle diameter is less than 300mm is put into acidolysis pond and reacts 1--4 hour, H with hydrochloric acid soln
+ionic concn is 6-12mol/l preferably.
B, isolate acid hydrolysis solution, purification acid hydrolysis solution;
In step b, release the acid hydrolysis solution in acidolysis pond, be separated the acid non-soluble substances such as yellow sand through natural subsidence, again through mechanical filter purification acid hydrolysis solution, the acid hydrolysis solution including water-soluble phosphorus and water-soluble calcium chloride being separated solid substance put into calcic clean solution tank stand-by.
C, progressively regulate the pH value of acid hydrolysis solution with the raw material including ammoniate, and be separated the throw out produced, these throw outs comprise containing phosphoric acid salt;
In step c, use the acid hydrolysis solution including water-soluble phosphorus and water-soluble calcium after purification, with including NH
4the raw material adjust ph of the composition of OH, controls the pH value of acid hydrolysis solution between 1-4, makes the fluorine in acid hydrolysis solution, magnesium, zinc, manganese, iron, aluminium plasma, generates this (Fe, Al) NH
4(HPO
4)
2 .0.5H
2o and (Fe, Al) Mg (NH
4)
2(HPO
4)
2 .f
3solubility in citric acid calcium phosphate precipitation, thus acid hydrolysis solution is become be stripped of fluorine, magnesium, zinc, manganese, iron, the isoionic acid hydrolysis solution of aluminium.
This fluorine-containing citric acid soluble phosphorus hydrochlorate, containing N: about 7.5%, P
2o
5: about 40%;
In order to obtain the acid hydrolysis solution of defluorinate, can the pH value of acid hydrolysis solution be controlled 4 when defluorinate, now just having reached the pH value generating secondary calcium phosphate;
Throw out before pH4 is fluorine-containing citric acid soluble phosphorus hydrochlorate and the mixed phosphate of water-soluble phosphoric acid calcium dihydrogen, the calcium phosphate salt of defluorinate that what pH value was greater than 4 generations is, the calcium phosphate salt of the high purity of this defluorinate, mainly phosphoric acid defluorination hydrogen calcium, because containing a small amount of monocalcium phosphate solid, its butt P
2o
5content is generally between 52--56%, and this is that the secondary calcium phosphate of feed grade wets product, and the calcium hydrophosphate fodder separated wets product, and containing ammonium ion, the present embodiment first washs with the liming containing calcium ion, then is washed till without ammonia taste with clear water.
The secondary calcium phosphate of this feed grade, because purity is very high, can process various industrial phosphoric acid salt.
D, be separated sedimentary acid hydrolysis solution and included water-soluble calcium chloride, stored this acid hydrolysis solution containing water-soluble calcium, for the production of high-purity calcium carbonate and ammonium chloride or manufacture calcium chloride.
Real
execute example 4: the present invention HNO 3 for the phosphate rock-sulfuric acid technique of raw material
Implement object:
Use HNO
3decomposing phosphate rock is mainly in order to obtain phosphorus product and technical grade calcium sulfate crystal whiskers and low cost nitric acid NaNO
3, KNO
3.
By acid concentration:
Use HNO
3carry out acidolysis to phosphorus ore, be a kind of open loop acid hydrolysis method, acid concentration is 6-12mol/l preferably, with concentration height as well.
Implementation step illustrates:
A, use acid are reacted with phosphorus ore, generate the acid hydrolysis solution including water-soluble calcium and water-soluble phosphorus;
HNO is selected in the acid of the present embodiment
3;
In step a, the raw ore that particle diameter is less than 300mm is put into acidolysis pond and reacts 1--4 hour, H with salpeter solution
+ionic concn is 6-12mol/l preferably.
B, isolate acid hydrolysis solution, purification acid hydrolysis solution;
In step b, release the acid hydrolysis solution in acidolysis pond, be separated the acid non-soluble substances such as yellow sand through natural subsidence, again through mechanical filter purification acid hydrolysis solution, the acid hydrolysis solution including water-soluble phosphorus and water-soluble nitrocalcite being separated solid substance put into calcic clean solution tank stand-by.
C, progressively regulate the pH value of acid hydrolysis solution with the raw material including ammoniate, and be separated the throw out produced, these throw outs comprise containing phosphoric acid salt;
In step c, use the acid hydrolysis solution including water-soluble phosphorus and water-soluble calcium after purification, with including NH
4the raw material adjust ph of the composition of OH, controls the pH value of acid hydrolysis solution between 1-4, makes the fluorine in acid hydrolysis solution, magnesium, zinc, manganese, iron, aluminium plasma, generates this (Fe, Al) NH
4(HPO
4)
2 .0.5H
2o and (Fe, Al) Mg (NH
4)
2(HPO
4)
2 .f
3solubility in citric acid calcium phosphate precipitation, thus acid hydrolysis solution is become be stripped of fluorine, magnesium, zinc, manganese, iron, the isoionic acid hydrolysis solution of aluminium.
This fluorine-containing citric acid soluble phosphorus hydrochlorate, containing N: about 7.5%, P
2o
5: about 40%;
In order to obtain the acid hydrolysis solution of defluorinate, can the pH value of acid hydrolysis solution be controlled 4 when defluorinate, now just having reached the pH value generating secondary calcium phosphate;
Throw out before pH4 is fluorine-containing citric acid soluble phosphorus hydrochlorate and the mixed phosphate of water-soluble phosphoric acid calcium dihydrogen, the calcium phosphate salt of defluorinate that what pH value was greater than 4 generations is, the calcium phosphate salt of the high purity of this defluorinate, mainly phosphoric acid defluorination hydrogen calcium, because containing a small amount of monocalcium phosphate solid, its butt P
2o
5content is generally between 52--56%, and this is that the secondary calcium phosphate of feed grade wets product, and the calcium hydrophosphate fodder separated wets product, and containing ammonium ion, the present embodiment first washs with the liming containing calcium ion, then is washed till without ammonia taste with clear water.
The secondary calcium phosphate of this feed grade, because purity is very high, can process various industrial phosphoric acid salt.
D, be separated sedimentary acid hydrolysis solution and included water-soluble nitrocalcite, stored the acid hydrolysis solution containing water-soluble calcium, for the production of high-purity calcium carbonate and ammonium nitrate or manufacture calcium sulfate crystal whiskers and saltpetre.The preferred manufacture calcium sulfate crystal whiskers of the present invention and saltpetre.
E, to add to the acid hydrolysis solution including water-soluble calcium and generate the precipitation agent of calcium cpd, generate calcium cpd precipitation, isolate calcium cpd precipitation and filtrate.
The present embodiment mainly uses the ca nitrate soln of steps d to produce calcium sulfate crystal whiskers and saltpetre, and in order to obtain superior in quality calcium sulfate crystal whiskers, first we will prepare potassium sulfate solution.
When preparing potassium sulfate solution, control potassium nitrate solution and dissolve potassium sulfate, concentration controls 1-20%, because we require the potassium nitrate solution obtaining high cleanliness, the potassium nitrate solution of high density selected by the control agent producing calcium sulfate crystal whiskers, at the present embodiment, potassium nitrate solution becomes the solvent dissolving potassium sulfate and the control agent generating calcium sulfate crystal whiskers.
Next is the pH value that adjustment kit contains the acid hydrolysis solution of water-soluble nitrocalcite, and the present embodiment uses nitric acid to regulate, and the pH value of nitrocalcite acid hydrolysis solution controls 2-5, to obtaining superior in quality calcium sulfate crystal whiskers.
After the acid hydrolysis solution including water-soluble nitrocalcite mixes with sulphuric acid soln, generate calcium sulfate crystal whiskers and potassium nitrate solution, isolate calcium sulfate crystal whiskers, potassium nitrate solution send evaporization process to produce saltpetre solid.
Claims (10)
1. a method for phosphorus ore comprehensive utilization,
A, use acid are reacted with phosphorus ore, generate the acid hydrolysis solution including water-soluble calcium and water-soluble phosphorus;
B, isolate acid hydrolysis solution, purification acid hydrolysis solution;
Characterized by further comprising following steps:
C, progressively regulate the pH value of acid hydrolysis solution with the raw material including ammoniate, and be separated the throw out produced, these throw outs comprise containing phosphoric acid salt;
D, be separated sedimentary acid hydrolysis solution and included water-soluble calcium, store the acid hydrolysis solution containing water-soluble calcium;
E, to add to the acid hydrolysis solution including water-soluble calcium and generate the precipitation agent of calcium cpd, generate calcium cpd precipitation, isolate calcium cpd precipitation and filtrate.
2.
according to claimthe method of a kind of phosphorus ore comprehensive utilization described in 1, is characterized in that:
Acid described in step a is containing HCL or HNO
3, or H
3pO
4, acetic acid or four arbitrary proportions composition mixing acid;
Purification described in step b is by subsidence style, mechanical filter mode or adds purification medicament mode, and the acid hydrolysis solution obtained is the acid hydrolysis solution being separated solid substance;
The raw material including ammoniate described in step c, refers to and includes NH
4the raw material of the composition of OH; Progressively regulate the pH value of acid hydrolysis solution, refer to the pH value progressively improving acid hydrolysis solution; The throw out that the throw out being separated generation refers to producing under different pH condition is separated respectively;
Storage described in steps d contains the acid hydrolysis solution of water-soluble calcium, comprises from what store and distributes liquid product, as the liquid starting material of other explained hereafter calcium cpd containing the acid hydrolysis solution of water-soluble calcium;
The precipitation agent adding generation calcium cpd to the acid hydrolysis solution including water-soluble calcium described in step e, the precipitation agent added comprises the water-soluble cpds containing carbonate or the water-soluble cpds containing sulfate radical; The calcium cpd generated includes the throw out of ingredients calcium carbonate accordingly or includes the throw out of calcium sulfate composition.
3.
according to claimthe method of a kind of phosphorus ore comprehensive utilization described in 2, is characterized in that:
NH is included described in step c
4the raw material of the composition of OH, refers to containing NH
4oH and calcium, magnesium, zinc, manganese, iron, aluminium and be of value to the mixing solutions of compound of farm crop.
4.
according to claimthe method of a kind of phosphorus ore comprehensive utilization described in 2, is characterized in that:
NH described in step c
4the mixing solutions of the compound of OH and calcium, magnesium, refers to ammonium salt and the compound containing calcium and react the solution, ammonium salt and the compound that contains magnesium that generate and react the solution generated;
The precipitation agent adding generation calcium cpd to the acid hydrolysis solution including water-soluble calcium described in step e, the precipitation agent added refers to containing sulfate radical and hydrogen ion H
+water-soluble cpds; The calcium cpd generated is the throw out including calcium sulfate composition, and isolated filtrate includes hydrogen ion H
+return step a and phosphorus ore reacts.
5.
according to claimthe method of a kind of phosphorus ore comprehensive utilization described in 4, is characterized in that:
Adding containing sulfate radical and hydrogen ion H to the acid hydrolysis solution including water-soluble calcium described in step e
+the precipitation agent of water-soluble cpds, comprise and add sulfate radical and hydrogen ion H
+water-soluble cpds precipitation agent before first add acid, alkali, salt, organism as generating the control agent of calcium sulfate precipitation, the calcium sulfate crystal whiskers making the calcium sulfate precipitation of generation become length-to-diameter ratio to be greater than 5;
Described acid, alkali, salt, organism comprise and containing: mineral acid is HCl, HNO
3, or H
3pO
4; Organic acid is formic acid, acetic acid, lipid acid, polyprotonic acid or alcohols; Inorganic salt are containing K
+, Na
+, NH4
+, Mg
2+, Al
3+, Mn
2+the water-soluble phosphate of ion, muriate or nitrate; Organic salt comprises the various tensio-active agents containing water soluble allcylbenzene soap, alkylbenzene sulfonate; Alkali is Mg (OH)
2.
6.
according to claimthe method of a kind of phosphorus ore comprehensive utilization described in 1, is characterized in that:
The throw out separated described in step c, comprise the calcium salt containing phosphoric acid, these throw outs react with the water-soluble cpds containing sulfate radical further, generate the solids including calcium sulfate composition, be separated the solids including calcium sulfate composition, liquid includes water soluble phosphorous compounds.
7.
according to claimthe method of a kind of phosphorus ore comprehensive utilization described in 6, is characterized in that:
The calcium salt comprised containing phosphoric acid described in step c, further with sylvite, the ammonium salt of sulfuric acid, the sulfuric acid reaction of sulfuric acid, generate the solids including calcium sulfate composition, separating calcium sulphate solids, liquid comprises sylvite, the ammonium salt of phosphoric acid, phosphoric acid containing water-soluble phosphoric acid.
8.
according to claimthe method of a kind of phosphorus ore comprehensive utilization described in 7, is characterized in that:
Generation described in step c includes the solids of calcium sulfate composition, refers to the calcium sulfate crystal whiskers that length-to-diameter ratio is greater than 5.
9.
according to claimthe method of a kind of phosphorus ore comprehensive utilization described in 3, is characterized in that:
NH described in step c
4oH refers to NH
3with H
2the NH that O reaction generates
4oH.
10.
according to claimthe method of a kind of phosphorus ore comprehensive utilization described in 4, is characterized in that:
Compound containing calcium comprises the calcium salt of calcium oxide containing calcium oxide, calcium hydroxide, dolomite calcination and magnesium oxide, phosphoric acid.
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| CN106564925A (en) * | 2016-11-01 | 2017-04-19 | 昆明理工大学 | Method for preparing calcium sulfate whisker and phosphate compound fertilizer by coupling inorganic acid and sulfate and decomposing phosphate rock |
| CN107188145A (en) * | 2016-03-14 | 2017-09-22 | 姚鼎文 | The method that one kind makes industrial potassium dihydrogen phosphate with hydrochloric acid decomposing medium and low grade, melamine complex salt crystal legal system |
| CN108557791A (en) * | 2018-06-08 | 2018-09-21 | 武汉工程大学 | The method for preparing calcium dihydrogen phosphate using low-grade phosphate ore |
| CN109399594A (en) * | 2018-11-08 | 2019-03-01 | 昆明理工大学 | A kind of cleaning method of mid low grade phosphate rock powder |
| CN111438002A (en) * | 2020-04-20 | 2020-07-24 | 武汉工程大学 | Method for treating silicon-calcium collophanite by 'floating-chemical' coupling |
| CN112047348A (en) * | 2020-09-17 | 2020-12-08 | 云南磷化集团有限公司 | Method for full resource utilization of high-silicon low-magnesium low-grade phosphate ore |
| CN112938917A (en) * | 2021-01-28 | 2021-06-11 | 北京大学 | Preparation method of efficient nano-phosphate fertilizer and nano-phosphate fertilizer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107188145A (en) * | 2016-03-14 | 2017-09-22 | 姚鼎文 | The method that one kind makes industrial potassium dihydrogen phosphate with hydrochloric acid decomposing medium and low grade, melamine complex salt crystal legal system |
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| CN108557791A (en) * | 2018-06-08 | 2018-09-21 | 武汉工程大学 | The method for preparing calcium dihydrogen phosphate using low-grade phosphate ore |
| CN109399594A (en) * | 2018-11-08 | 2019-03-01 | 昆明理工大学 | A kind of cleaning method of mid low grade phosphate rock powder |
| CN111438002A (en) * | 2020-04-20 | 2020-07-24 | 武汉工程大学 | Method for treating silicon-calcium collophanite by 'floating-chemical' coupling |
| CN112047348A (en) * | 2020-09-17 | 2020-12-08 | 云南磷化集团有限公司 | Method for full resource utilization of high-silicon low-magnesium low-grade phosphate ore |
| CN112938917A (en) * | 2021-01-28 | 2021-06-11 | 北京大学 | Preparation method of efficient nano-phosphate fertilizer and nano-phosphate fertilizer |
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Application publication date: 20151202 |