CN109795995A - A kind of method of hydrochloric acid method phosphoric acid by wet process efficient impurity removal - Google Patents
A kind of method of hydrochloric acid method phosphoric acid by wet process efficient impurity removal Download PDFInfo
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Abstract
The present invention relates to a kind of methods of hydrochloric acid method phosphoric acid by wet process efficient impurity removal, one or more of calcic inorganic matter, inorganic matter containing aluminium, siliceous inorganic matter, sulfur-bearing inorganic matter or fluorine-containing inorganic matter are added in hydrochloric acid method phosphoric acid by wet process, the molar ratio for adjusting Ca, Al, Si, S, F in hydrochloric acid method phosphoric acid by wet process is (20-50): (0.8-1.2): (1-1.20): (0.90-1.20): (12-15), it is reacted, makes Ca, Al, Si, S, F impurity element in hydrochloric acid method phosphoric acid by wet process with Ca4AlSiSO4F13·12H2The form of O is precipitated out, to reach purification purpose.Compared with prior art, the present invention once removes five kinds of impurity elements in phosphoric acid by wet process by changing phosphoric acid by wet process ingredient, makes the major impurity element in phosphoric acid by wet process with compound Ca4AlSiSO4F13·12H2The form of O is precipitated out, to realize the purpose of wet phosphoric acid purifying.
Description
Technical field
The invention belongs to phosphoric acid by wet process processing technology fields, more particularly, to a kind of hydrochloric acid method phosphoric acid by wet process efficient impurity removal
Method.
Background technique
The purification techniques of phosphoric acid by wet process mainly has ion-exchange, electroosmose process, crystallisation, membrane separation process, chemistry at present
The precipitation method, solvent precipitation, solvent extraction-chemical precipitation method group technology etc..But production it is upper it is most widely used, most pass through
Ji is chemical precipitation method, i.e. two sections of neutralisations.Calcium in phosphoric acid by wet process, fluorine, aluminium, magnesium, silicon and sulphur are its major impurity, using two
Section neutralisation can be purified effectively, and technique is also more mature, and quality is stablized, but shortcoming is the P in phosphoric acid2O5Utilization rate is simultaneously
It is not high, in one section and when sediment fraction P2O5For fertilizer grade monophosphate monophosphate product salt, product grade is reduced.
If patent CN106698372A proposes a kind of wet defluorination of phosphoric acid method, by the slurry after defluorination reaction
Sedimentation agent is added and achievees the purpose that wet defluorination of phosphoric acid convenient for the filtering of defluorinate slurry.It is wet that such method only reaches removing
Fluorine element in method phosphoric acid can not remove other impurities.Patent CN106185855A proposes a kind of a variety of nothings of utilization
Machine salt removes aluminium, magnesium addition in phosphoric acid by wet process, then removes fluorine impurity again, to realize that phosphoric acid by wet process be purification.It is such
Although method is not introduced into new foreign ion, but imurity-removal element species are limited and need multiple dedoping step.
Chinese patent CN103523764A discloses a kind of new method for reducing magnalium impurity in phosphoric acid by wet process, to wet process
Fluorine-containing ammonium class compound is added in phosphoric acid, fluorine-containing ammonium class compound additional amount is the 0.5%~5% of phosphoric acid by wet process quality, ageing
Temperature is 30~80 DEG C, and digestion time is 5~48 hours, and after natural subsidence, supernatant liquor is magnesium, purification with low aluminum content
Phosphoric acid by wet process.But the patent can only remove magnalium impurity, cannot remove other impurities.
It is described in United States Patent (USP) US4136199A with metal impurities ion (such as magnesium, aluminium) in sludge removal phosphoric acid by wet process
Method, sludge components are mainly calcirm-fluoride, it is obtained by lime or lime stone processing pond waste water.But acid obtained by the method
Magnesium, aluminium content are still very high in liquid, in addition, the technical process is difficult to control, because sludge changes at any time at branch.
A kind of complex compound sediment removal wet process phosphorus by forming Mg-Al-F-P is proposed in United States Patent (USP) US3642439A
Magnesium method in acid, it is 45%~53%P which, which requires concentration acid concentration,2O5, preferably 47%~51%P2O5, SiO in gelled acid2
Content keeps the hydrogen fluoride content in gelled acid for F/MgO (mass ratio) >=2.2 less than 0.2%, and preferably 3~12, it keeps dense
Dissolution aluminium content is Al in contracting acid2O3/ MgO (mass ratio) >=1.4, preferably 3~12, keep gelled acid at 50~100 DEG C at least
15~40 hours, in order to form a kind of a kind of complex precipitate being made of Mg-Al-F-P, if which precipitate component in ortho acid
The component should be added in deficiency into acid solution, and in order to reduce content of magnesium to greatest extent, excessive hydrogen fluoride and solvable is added into acid
Property aluminium salt, such as aluminum sulfate, aluminum nitrate.The complex compound sediment particle of Mg-Al-F-P obtained by the method is very tiny, need to be using centrifugation etc.
Mode is separated, and separating difficulty is larger, does not have industrialization meaning, while in order to generate Mg-Al-F-P complex compound, needing to introduce
Excessive hydrofluoric acid and aluminum soluble salt, processing cost is higher, in addition, the method is only limitted to removing magnesium, it is smaller to removing aluminium effect.
The phosphoric acid concentration of above-mentioned patent is very high, and above-mentioned patent forms a kind of a kind of composite precipitation being made of Mg-Al-F-P
Object is difficult to filter, is only used for de-magging.
It is proposed in United States Patent (USP) US4710366A and enough fluosilicic acid is added in wet dilute phosphoric acid, make F/ in phosphoric acid,diluted
MgO mass ratio is 2.5:1~10:1, then preferably 5:1 is concentrated into 45%~55%P2O5, at least to gelled acid crystallization treatment
8 hours or more, impurity magnesium, aluminium and fluorine is made to crystallize to form MgAlF5Precipitation, then the sediment is removed by modes such as centrifugations,
Make gelled acid solid content lower than 2%, then the acid is concentrated to as little as 56%P2O5, preferably in 56~63%P2O5, to obtain low magnalium
The gelled acid of impurity.But method gained sediment MgAlF5Crystallization is very tiny, need to be separated, be separated using modes such as centrifugations
Difficulty is big, does not have industrialization meaning.In addition, need to introduce a large amount of fluosilicic acid in order to reach more excellent F/MgO ratio, considerably increase
The concentration energy consumption of phosphoric acid by wet process influences driving rate, and should in addition, the introducing of a large amount of fluosilicic acid, increases the blocking of concentration systems
Technical process is complex, and economy is poor.
United States Patent (USP) US4692323A proposes a kind of by making magnesium, fluorine, aluminium impurity in phosphoric acid by wet process form composite junction
The process of brilliant object and precipitation and separation, the technique include by supplement fluorine compounds to adjust the F/Mg molar ratio in acid at least
To 4~20, aluminium compound is augmented to adjust the Al/Mg molar ratio in acid at least to 0.8~2, augments ammonium compounds to adjust acid
In NH4/ Mg molar ratio is allowed to generate insoluble compound crystal object (NH4) at least to 0.5~4x(Mg)y(Al)z(F,OH)6, then
It being separated using filtering or decantation, but fluorine compounds described in the method are hydrofluoric acid, the aluminium compound is aluminum nitrate,
The ammonium compounds is ammonium nitrate, and the dense acid is 25~35%P2O5Phosphoric acid,diluted, gained crystalline deposit object crystallization be it is micro-
Meter level crystallizes tiny, separation difficulty, and a large amount of hydrofluoric acid and nitric acid need to be added in order to generate above-mentioned compound crystal object in the method
Aluminium and ammonium nitrate, economy are poor.
Contamination precipitation is crystal (NH4) in above-mentioned patentx(Mg)y(Al)z(F,OH)6, impurity is tiny, and separation is difficult.
It refers to remove iron-based and aluminium base impurity using ammonium compounds in United States Patent (USP) US3328123A, but the method precipitating reagent
In do not contain fluorine.But the method fails to remove magnesium, still has higher magnesium ion in phosphoric acid.
Summary of the invention
The present invention provides one for the not high technical deficiency of wet defluorination of phosphoric acid higher cost, dust removal rate at this stage
The method of kind hydrochloric acid method phosphoric acid by wet process efficient impurity removal.
The present invention changes component ratio in phosphoric acid by wet process, before not consuming available phosphorus by the way that inexpensive compound is added
It puts, with compound Ca4AlSiSO4F13·12H2O form, while efficiently removing Ca, Al, Si, S, F impurity element.
The purpose of the present invention can be achieved through the following technical solutions:
Calcic inorganic matter is added in hydrochloric acid method phosphoric acid by wet process, contains aluminium for a kind of method of hydrochloric acid method phosphoric acid by wet process efficient impurity removal
One or more of inorganic matter, siliceous inorganic matter, sulfur-bearing inorganic matter or fluorine-containing inorganic matter adjust in hydrochloric acid method phosphoric acid by wet process
The molar ratio of Ca, Al, Si, S, F be (suggest supplement Ca, Al, Si, S, F molar ratio, can be value range, such as (a-b):
(c-d): form of presentation as (e-f) is exactly the value range with more preferable effect further, it is suggested that providing preferred range, with
And optimal proportionate relationship (such as 4:1:1:1:13), it is reacted, keeps Ca, Al, Si, S, F in hydrochloric acid method phosphoric acid by wet process miscellaneous
Prime element is with Ca4AlSiSO4F13·12H2The form of O is precipitated out, to reach purification purpose.
In an embodiment of the invention, calcic inorganic matter is added in hydrochloric acid method phosphoric acid by wet process, inorganic matter containing aluminium, contains
After silicon inorganic matter, sulfur-bearing inorganic matter or fluorine-containing inorganic matter, fluorine/aluminium molar ratio is controlled at (0.6-3): 1, control fluorine/calcium
Molar ratio at (0.03-0.11): 1, the rate of deposition of calcium ion is preferable when this range of concentration.
In an embodiment of the invention, calcic inorganic matter is added in hydrochloric acid method phosphoric acid by wet process, inorganic matter containing aluminium, contains
One or more of silicon inorganic matter, sulfur-bearing inorganic matter or fluorine-containing inorganic matter, adjust hydrochloric acid method phosphoric acid by wet process in Ca, Al, Si, S,
The molar ratio of F is 30:1:1:1:13.
In an embodiment of the invention, the calcic inorganic matter is inorganic matter I, and the inorganic matter I is selected from chlorination
One of calcium, calcium carbonate, calcium oxide, calcium hydroxide, calcium nitrate, calcium bicarbonate or calcium sulfate are several；
In an embodiment of the invention, the inorganic matter containing aluminium is inorganic matter II, and the inorganic matter II is selected from chlorine
Change one or more of aluminium, aluminum sulfate, aluminium hydroxide, aluminium oxide, aluminum nitrate or aluminum phosphate；
In an embodiment of the invention, the siliceous inorganic matter is inorganic matter III, and the inorganic matter III is selected from silicon
One or more of sour sodium, potassium silicate, silica or fluosilicic acid；
In an embodiment of the invention, the sulfur-bearing inorganic matter is inorganic matter IV, and the inorganic matter III is selected from silicon
One or more of sour sodium, potassium silicate, silica or fluosilicic acid；
In an embodiment of the invention, the fluorine-containing inorganic matter is inorganic matter V, and the inorganic matter V is selected from fluorine
Change one or more of hydrogen, fluosilicic acid, potassium fluosilicate or prodan.
The above substance is the substance that can be dissolved in system, can reach same effect.
The preparation principle of hydrochloric acid method phosphoric acid by wet process is the hydrochloric acidolysis phosphorus ore preparing phosphoric acid for being better than phosphoric acid using acidity.It is described
Hydrochloric acid method phosphoric acid by wet process is the acid hydrolysis solution that 10%-30% concentration of hydrochloric acid extracts phosphorus ore.Wherein, P2O5Mass fraction is 5-10%, F
Mass fraction is 0.1-0.5%, Fe2O3Mass fraction is 0.1-0.5%, Al2O3Mass fraction is 0.1-0.3%, CaO mass
Score is 5-10%, SiO2Mass fraction is 0.1-0.3%, SO3Mass fraction is 0.1-0.5%.
In an embodiment of the invention, the calcic inorganic matter, inorganic matter containing aluminium, siliceous inorganic matter, sulfur-bearing without
The charging sequence of machine object or fluorine-containing inorganic matter are as follows: inorganic matter containing aluminium, siliceous inorganic matter, sulfur-bearing inorganic matter or fluorine-containing inorganic is first added
One or more of object is eventually adding calcic inorganic matter.If calcium salt is added in early period, the calcium salt of high concentration can not only improve phosphorus
The pH of acid, and calcium sulfate precipitation can be precipitated because of the excessive concentration of calcium, to influence Ca4AlSiSO4F13·12H2The generation of O.
In an embodiment of the invention, the condition reacted is that reaction temperature is 10-80 DEG C, and the reaction time is
0.5-24h。
In an embodiment of the invention, in reaction process, preferably control stirring rate is 10-160r/min.
In an embodiment of the invention, when reaction, first solution is heated, make calcic inorganic matter, containing aluminium without
The dissolution of one or more of machine object, siliceous inorganic matter, sulfur-bearing inorganic matter or fluorine-containing inorganic matter, then reduces the temperature of reaction system
Degree is to 20-40 DEG C.Temperature reduction is conducive to improve the degree of supersaturation of liquid phase and growing up for crystal, so that it is heavy to be conducive to impurity element
It forms sediment complete.
In an embodiment of the invention, reaction system is formed after precipitating, and precipitating is realized by the way of filtering
With the separation of liquid.
The present invention forms Ca, Al, Si, S, F element by adjusting impurity element concentration in phosphoric acid by wet process
Ca4AlSiSO4F13·12H2O precipitating, wherein Ca4AlSiSO4F13·12H2O is a kind of regular octahedron structure crystal, the chemical combination
Object solubility is small, and partial size can reach 10 μm, it is easy to filter.Five kinds of impurity elements of the method for the present invention energy primary sedimentation reduce wet
Method phosphoric acid major impurity content, especially defluorination effect are more excellent.
Through the invention research shows that:
(1) CaO concentration is to influence Ca in phosphoric acid by wet process4AlSiSO4F13·12H2O precipitates the key factor to be formed；To hydrochloric acid
For method phosphoric acid by wet process, CaO concentration is higher in liquid phase, F, Al in phosphoric acid by wet process2O3、SiO2And SO3Deposition removal rate it is higher.
(2) in phosphoric acid by wet process higher concentration F and Al2O3It can inhibit precipitate C a4AlSiSO4F13·12H2The generation of O,
Middle Al2O3Inhibiting effect be much larger than F, therefore the F and Al of higher concentration2O3Unfavorable clean-up effect.
(3) clean-up effect is preferable when the molar ratio of F/ (Al, Si, S) reaches or approaches 13 between element in phosphoric acid by wet process, salt
The highest rate of deposition of acid system phosphoric acid by wet process F is 71.35%, Al2O3Highest rate of deposition be 83.80%, SiO2Highest rate of deposition
It is 68.66%.
The present invention can promote Ca by adjusting part constituent content in phosphoric acid by wet process4AlSiSO4F13·12H2The generation of O, this
When phosphoric acid by wet process in F impurity be significantly reduced, other than F, also there is different degrees of drop in Ca, Al, Si, S impurity content
It is low.Ca4AlSiSO4F13·12H2O contains five kinds of impurity elements in phosphoric acid by wet process and the fluorine content in compound is higher, is one
Kind can efficiently defluorinate and removal of impurities compound.The present invention is by adjusting CaO, Al in phosphoric acid by wet process2O3、SiO2、SO3With F's
Content proportion, so that impurity element is more with compound Ca4AlSiSO4F13·12H2The form of O is precipitated out, to reach
The purpose of purification of wet process phosphoric acid.
Detailed description of the invention
Fig. 1: 3 gained Ca of embodiment4AlSiSO4F13·12H2The electron microscope of O precipitating；
Fig. 2: embodiment 5-10 product X RD analyzes result；
Fig. 3: 10 gained Ca of embodiment4AlSiSO4F13·12H2The electron microscope of O precipitating；
Fig. 4: the electron microscope of precipitating obtained by embodiment 12.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Hydrochloric acid method phosphoric acid by wet process used in following embodiment is obtained by 15% (wt) hydrochloric acidolysis de-magging phosphorus ore, phosphoric acid by wet process at
Point with the molar ratio of each element in phosphoric acid by wet process respectively as table 1 with shown in table 2.
1 phosphoric acid by wet process ingredient of table (concentration is mass fraction)
The molar ratio of each element in 2 phosphoric acid by wet process of table
Analyze data from table 2: the molar ratio 6.26 of F/Al in phosphoric acid by wet process, the molar ratio 6.91 of F/Si, F/S's rubs
You are than being 4.21, according to Ca4AlSiSO4F13·12H2The element proportion relation of O, F content is insufficient, and CaO contains in phosphoric acid by wet process
Amount is but significantly excessive.Therefore, following embodiment changes constituent content, meets element relation or close to above-mentionedization
The molar relationship for closing object, thus to probe into the clean-up effect of phosphoric acid by wet process under different condition.
The operating method of embodiment 1-4 are as follows:
Reactor with stirring keeps its temperature in setting value with water bath with thermostatic control, temperature fluctuation range ± 0.5 DEG C, to anti-
Answer and quantitative hydrochloric acid method phosphoric acid by wet process be added in device, be then added in the reactor through measuring soluble compound (calcic without
One or more of machine object, inorganic matter containing aluminium, siliceous inorganic matter, sulfur-bearing inorganic matter or fluorine-containing inorganic matter), adjust its element group
Cheng Hou first passes through heating water bath to 60-70 DEG C, so that soluble compound dissolves, then continuously stirs under the conditions of 20-30 DEG C
12h is reacted, is filtered, after washing, is chemically analyzed the content of filtrate and phosphorus, fluorine and silicon in solid respectively, inhaled with atom
Receive the aluminium element content in spectrophotometry measurement filtrate and solid.
Embodiment 1
500mL beaker is taken, 85% phosphoric acid 21.11g, inorganic matter V (40%HF1.84g), II (18 water of inorganic matter are weighed
Aluminum sulfate 2.66g), inorganic matter III (silica 0.32g), inorganic matter IV (98% concentrated sulfuric acid 0.88g), which is placed in, fills 166.19g
It in the beaker of distilled water, after its dissolution, is added inorganic matter I (calcium oxide 7.0g), control reaction temperature is 30 DEG C, stirring rate
For 160r/min, the reaction time be 12h after be filtered, washed, it is drying precipitated, obtain white precipitate 0.33g, the wet process phosphorus after reaction
F, CaO, Al in acid2O3And SiO2Removal efficiency be respectively 14.99%, 8.28%, 13.62%, 6.87%.
Embodiment 2
500mL beaker is taken, 85% phosphoric acid 21.11g, inorganic matter V (40%HF1.84g), II (18 water of inorganic matter are weighed
Aluminum sulfate 2.66g), inorganic matter III (silica 0.32g), inorganic matter IV (98% concentrated sulfuric acid 0.88g), which is placed in, fills 163.19g
It in the beaker of distilled water, after its dissolution, is added inorganic matter I (calcium oxide 10.0g), control reaction temperature is 30 DEG C, stirring speed
Rate is 160r/min, the reaction time be 12h after be filtered, washed, it is drying precipitated, obtain white precipitate 0.68g, the wet process after reaction
F, CaO, Al in phosphoric acid2O3And SiO2Removal efficiency be respectively 29.98%, 11.82%, 19.45%, 9.81%.
Embodiment 3
500mL beaker is taken, 85% phosphoric acid 21.11g, inorganic matter V (40%HF1.84g), II (18 water of inorganic matter are weighed
Aluminum sulfate 2.66g), inorganic matter III (silica 0.32g), inorganic matter IV (98% concentrated sulfuric acid 0.88g), which is placed in, fills 155.51g
It in the beaker of distilled water, after its dissolution, is added inorganic matter I (calcium oxide 17.68g), control reaction temperature is 30 DEG C, stirring speed
Rate is 160r/min, the reaction time be 12h after be filtered, washed, it is drying precipitated, obtain white precipitate 1.35g, the wet process after reaction
F, CaO, Al in phosphoric acid2O3And SiO2Removal efficiency be respectively 61.64%, 4.16%, 55.79%, 28.13%.
Embodiment 4
500mL beaker is taken, 85% phosphoric acid 21.11g, inorganic matter V (40%HF1.84g), II (18 water of inorganic matter are weighed
Aluminum sulfate 2.66g), inorganic matter III (silica 0.32g), inorganic matter IV (98% concentrated sulfuric acid 0.88g), which is placed in, fills 153.31g
It in the beaker of distilled water, after its dissolution, is added inorganic matter I (calcium oxide 20.00g), control reaction temperature is 30 DEG C, stirring speed
Rate is 160r/min, the reaction time be 12h after be filtered, washed, it is drying precipitated, obtain white precipitate 1.42g, the wet process after reaction
F, CaO, Al in phosphoric acid2O3And SiO2Removal efficiency be respectively 61.95%, 4.18%, 56.07%, 28.37%.
The quality of liquid phase is as shown in table 3 after embodiment 1-4 reaction.
The quality of liquid phase after 3 embodiment 1-4 of table reaction
| Number | F/% | CaO/% | Al2O3/ % | SiO2/ % |
| Embodiment 1 | 0.31 | 3.21 | 0.13 | 0.15 |
| Embodiment 2 | 0.25 | 4.41 | 0.12 | 0.14 |
| Embodiment 3 | 0.13 | 8.47 | 0.07 | 0.11 |
| Embodiment 4 | 0.12 | 9.58 | 0.06 | 0.11 |
Impurity element rate of deposition, experimental result are as shown in table 4 under different calcium ion concentrations in investigation embodiment 1-4.
Impurity element rate of deposition under the different calcium ion concentrations of table 4
As shown in Table 4, F, SiO in phosphoric acid by wet process2、Al2O3Rate of deposition with solution calcium ion concentration increase and gradually increase
Add, the phosphorus fluorine ratio in phosphoric acid by wet process also gradually increases at this time.When the concentration of CaO reaches 8.84% in phosphoric acid by wet process, it is further added by calcium
The rate of deposition of ion concentration, impurity element almost no longer increases, at this time the utilization rate of CaO only 4.20% in solution.Therefore, wet process
Other compositions are constant in phosphoric acid only changes CaO content, and the phosphorus fluorine ratio of phosphoric acid by wet process is (with P in embodiment2O5/ F mass ratio calculates) most
High energy reaches 48.81；The highest rate of deposition that the highest rate of deposition of F is 61.95%, CaO is 11.82%, Al2O3Highest precipitating
Rate is 56.82%, SiO2Highest rate of deposition be 28.30%, a large amount of CaO residual is in the liquid phase.
3 gained Ca of embodiment4AlSiSO4F13·12H2The electron microscope of O precipitating is as shown in Figure 1.
In order to find the limit range of each impurity element precipitating in phosphoric acid by wet process, following example 5-11 considers to increase liquid phase
The concentration of middle F makes in liquid phase initial F/Al, F/Si, F/S molar ratio close to 13, then consider to change major influence factors (F,
CaO, Al2O3) probe into each element rate of deposition.
The operating method of embodiment 5-11 are as follows:
Reactor with stirring keeps its temperature in setting value with water bath with thermostatic control, temperature fluctuation range ± 0.5 DEG C, to anti-
Answer and quantitative hydrochloric acid method phosphoric acid by wet process be added in device, be then added in the reactor through measuring soluble compound (calcic without
One or more of machine object, inorganic matter containing aluminium, siliceous inorganic matter, sulfur-bearing inorganic matter or fluorine-containing inorganic matter), adjust its element group
Cheng Hou first passes through heating water bath to 60-70 DEG C, so that soluble compound dissolves, then continuously stirs under the conditions of 20-30 DEG C
12h is reacted, is filtered, after washing, is chemically analyzed the content of filtrate and phosphorus, fluorine and silicon in solid respectively, inhaled with atom
Receive the aluminium element content in spectrophotometry measurement filtrate and solid.
Embodiment 5
500mL beaker is taken, 85% phosphoric acid 21.11g, inorganic matter V (40%HF 3.68g), II (18 water of inorganic matter are weighed
Aluminum sulfate 2.66g), inorganic matter III (silica 0.32g), inorganic matter IV (98% concentrated sulfuric acid 0.88g), which is placed in, fills 161.35g
It in the beaker of distilled water, after its dissolution, is added inorganic matter I (calcium oxide 10.00g), control reaction temperature is 30 DEG C, stirring speed
Rate is 160r/min, the reaction time be 12h after be filtered, washed, it is drying precipitated, obtain white precipitate 2.54g, the wet process after reaction
F, CaO, Al in phosphoric acid2O3And SiO2Removal efficiency be respectively 57.89%, 26.90%, 58.24%, 59.52%.
Embodiment 6
500mL beaker is taken, 85% phosphoric acid 21.11g, inorganic matter V (40%HF 3.68g), II (18 water of inorganic matter are weighed
Aluminum sulfate 2.66g), inorganic matter III (silica 0.32g), inorganic matter IV (98% concentrated sulfuric acid 0.88g), which is placed in, fills 153.67g
It in the beaker of distilled water, after its dissolution, is added inorganic matter I (calcium oxide 17.68g), control reaction temperature is 30 DEG C, stirring speed
Rate is 160r/min, the reaction time be 12h after be filtered, washed, it is drying precipitated, obtain white precipitate 3.12g, the wet process after reaction
F, CaO, Al in phosphoric acid2O3And SiO2Removal efficiency be respectively 70.64%, 11.37%, 82.97%, 67.98%.
Embodiment 7
500mL beaker is taken, 85% phosphoric acid 21.11g, inorganic matter V (40%HF 3.68g), II (18 water of inorganic matter are weighed
Aluminum sulfate 1.33g), inorganic matter III (silica 0.32g), inorganic matter IV (98% concentrated sulfuric acid 0.88g), which is placed in, fills 152.34g
It in the beaker of distilled water, after its dissolution, is added inorganic matter I (calcium oxide 17.68g), control reaction temperature is 30 DEG C, stirring speed
Rate is 160r/min, the reaction time be 12h after be filtered, washed, it is drying precipitated, obtain white precipitate 2.63g, the wet process after reaction
F, CaO, Al in phosphoric acid2O3And SiO2Removal efficiency be respectively 60.04%, 9.66%, 70.52%, 57.78%.
Embodiment 8
500mL beaker is taken, 85% phosphoric acid 21.11g, inorganic matter V (40%HF 3.68g), II (18 water of inorganic matter are weighed
Aluminum sulfate 2.66g), inorganic matter III (silica 0.32g), inorganic matter IV (98% concentrated sulfuric acid 0.88g), which is placed in, fills 152.34g
It in the beaker of distilled water, after its dissolution, is added inorganic matter I (calcium oxide 20.00g), control reaction temperature is 30 DEG C, stirring speed
Rate is 160r/min, the reaction time be 12h after be filtered, washed, it is drying precipitated, obtain white precipitate 3.13g, the wet process after reaction
F, CaO, Al in phosphoric acid2O3And SiO2Removal efficiency be respectively 71.35%, 11.48%, 83.80%, 68.66%.
Embodiment 9
500mL beaker is taken, 85% phosphoric acid 21.11g, inorganic matter V (40%HF 3.68g), II (18 water of inorganic matter are weighed
Aluminum sulfate 5.32g), inorganic matter III (silica 0.32g), inorganic matter IV (98% concentrated sulfuric acid 0.88g), which is placed in, fills 151.01g
It in the beaker of distilled water, after its dissolution, is added inorganic matter I (calcium oxide 17.68g), control reaction temperature is 30 DEG C, stirring speed
Rate is 160r/min, the reaction time be 12h after be filtered, washed, it is drying precipitated, obtain white precipitate 6.29g, the wet process after reaction
F, CaO, Al in phosphoric acid2O3And SiO2Removal efficiency be respectively 0.00%, 1.84%, 0.00%, 0.00%.
Embodiment 10
500mL beaker is taken, 85% phosphoric acid 21.11g, inorganic matter V (40%HF 7.36g), II (18 water of inorganic matter are weighed
Aluminum sulfate 2.66g), inorganic matter III (silica 0.32g), inorganic matter IV (98% concentrated sulfuric acid 0.88g), which is placed in, fills 149.99g
It in the beaker of distilled water, after its dissolution, is added inorganic matter I (calcium oxide 17.68g), control reaction temperature is 30 DEG C, stirring speed
Rate is 160r/min, the reaction time be 12h after be filtered, washed, it is drying precipitated, obtain white precipitate 0.89g, the wet process after reaction
F, CaO, Al in phosphoric acid2O3And SiO2Removal efficiency be respectively 10.20%, 19.67%, 26.25%, 28.92%.
Embodiment 11
500mL beaker is taken, 85% phosphoric acid 21.11g, inorganic matter V (40%HF 3.68g), II (18 water of inorganic matter are weighed
Aluminum sulfate 2.66g), inorganic matter III (silica 0.64g), inorganic matter IV (98% concentrated sulfuric acid 0.88g), which is placed in, fills 153.35g
It in the beaker of distilled water, after its dissolution, is added inorganic matter I (calcium oxide 17.68g), control reaction temperature is 30 DEG C, stirring speed
Rate is 160r/min, the reaction time be 12h after be filtered, washed, it is drying precipitated, obtain white precipitate 0.89g, the wet process after reaction
F, CaO, Al in phosphoric acid2O3And SiO2Removal efficiency be respectively 70.70%, 11.45%, 83.02%, 34.12%.
The quality of liquid phase is as shown in table 5 after embodiment 5-11 reaction.
The quality of liquid phase after table 5 reacts
| Number | F/% | CaO/% | Al2O3/ % | SiO2/ % |
| 5 | 0.29 | 3.66 | 0.06 | 0.06 |
| 6 | 0.21 | 7.83 | 0.03 | 0.05 |
| 7 | 0.28 | 8.01 | 0.02 | 0.07 |
| 8 | 0.20 | 8.85 | 0.02 | 0.05 |
| 9 | 0.70 | 8.68 | 0.30 | 0.16 |
| 10 | 1.25 | 7.10 | 0.07 | 0.11 |
| 11 | 0.21 | 7.88 | 0.03 | 0.21 |
The experimental result of embodiment 5-11 is as shown in table 6.
The precipitation analysis of 6 different conditions of mixture ratios each element of table
As known from Table 6, when F/Al, F/Si, F/S molar ratio are close to 13 in phosphoric acid by wet process, CaO content, phosphorus fluorine ratio are improved
32.41 can be reached；The highest rate of deposition that the highest rate of deposition of F is 71.35%, CaO is 11.48%, Al2O3Highest it is heavy
Shallow lake rate is 83.80%, SiO2Highest rate of deposition be 68.66%, improve CaO content in phosphoric acid by wet process, contamination precipitation again at this time
Rate almost no longer increases.Fluorine content increases and Al2O3When content reduces by one times, the rate of deposition of F, Al, Si and Ca have apparent drop
It is low；The content of other elements is constant at this time, Al2O3When content doubles, precipitated product is changed into CaSO4·2H2O, F,
Al2O3, Al2O3Rate of deposition be all 0.It is above-mentioned the experimental results showed that, the Al of excessive concentrations in solution2O3It is unfavorable for precipitating
Ca4AlSiSO4F13·12H2The generation of O.Phosphoric acid by wet process matches under the conditions of more excellent, and fluorine content increases to 1.40%, and precipitating is main
For Ca4AlSiSO4F13·12H2O and CaF2, the rate of deposition of each element reduces instead under this condition, so hydrochloric acid method phosphoric acid by wet process
The F of middle excessive concentrations is beneficial to CaF2Generation.When test 2 on the basis of increase SiO2When content, F, Al2O3With the precipitating of CaO
Rate almost no longer changes, and value is almost the same with 2 results of experiment.Therefore hydrochloric acid method wet phosphoric acid purifying more preferably condition are as follows: F:
0.70%, CaO:8.84%, Al2O3: 0.15%, SiO2: 0.16%.
XRD analysis is carried out to the product of embodiment 5-10, as a result as shown in Figure 2.
From the XRD diagram spectrum analysis of Fig. 2: the solid precipitating that embodiment 5-8 is generated is all CaSO4·2H2O(PDF
) and Ca file:33-3114AlSiSO4F13·12H2The mixture of O (PDF file:49-1054), the precipitating that embodiment 9 generates
For CaSO4·2H2O (PDF file:33-311), what embodiment 10 generated is precipitated as Ca4AlSiSO4F13·12H2O(PDF
) and CaF file:49-10542The mixture of (PDF file:35-0816).
It is analyzed by above embodiments, it can be seen that impurity can make impurity by adjusting its liquid phase ingredient in phosphoric acid by wet process
Cycling of elements is Ca4AlSiSO4F13·12H2O achievees the purpose that purification to reduce impurity content in phosphoric acid by wet process.It is this net
Change method is a kind of completely new phosphoric acid by wet process impurity removal process, due to compound Ca4AlSiSO4F13·12H2O includes five kinds of impurity members
Element, the purification process are F, CaO, Al in a kind of efficient removal phosphoric acid by wet process2O3、SiO2And SO3The mode of five kinds of impurity changes
The method of a certain impurity element is individually removed when wet phosphoric acid purifying in the past.Above-mentioned wet phosphoric acid purifying technical process phosphorus
Loss late is lower and phosphoric acid by wet process in F, CaO, Al2O3、SiO2And SO3Removal efficiency be also able to maintain in higher level, be conducive to change
Into phosphoric acid by wet process impurity removal process, the quality of phosphoric acid by wet process is sufficiently improved, there is good application prospect in Wet Processes of Phosphoric Acid.
Fig. 3 is 10 gained Ca of embodiment4AlSiSO4F13·12H2The electron microscope of O, it is seen that Ca4AlSiSO4F13·12H2O is
A kind of regular octahedron structure crystal, the compound solubility is small, and partial size can reach 10 μm, it is easy to filter.
Embodiment 12
500mL beaker is taken, 85% phosphoric acid 21.11g, inorganic matter V (40%HF 3.68g), II (18 water of inorganic matter are weighed
Aluminum sulfate 2.66g), addition inorganic matter I (calcium oxide 17.68g) inorganic matter IV (98% concentrated sulfuric acid 0.88g), which is placed in, to be filled
In the beaker of 152.34g distilled water, after its dissolution, inorganic matter III (silica 0.32g), control reaction temperature is 30 DEG C,
Stirring rate is 160r/min, the reaction time be 12h after be filtered, washed, it is drying precipitated, white precipitate 3.98g is obtained, after reaction
Phosphoric acid by wet process in F, CaO, Al2O3And SiO2Removal efficiency be respectively 35.01%, 32.95%, 16.68%, 31.79%.
The electron microscope that precipitates obtained by the present embodiment as shown in figure 4, as can be seen from Figure 4 its partial size very little, in addition to
Ca4AlSiSO4F13·12H2Other than O, there are also other precipitatings such as calcium sulfate, and therefore, calcium salt is added in the phase before the reaction, high concentration
Calcium salt can not only improve the pH of phosphoric acid, but also calcium sulfate precipitation can be precipitated because of the excessive concentration of calcium, to influence
Ca4AlSiSO4F13·12H2The generation of O.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (9)
1. a kind of method of hydrochloric acid method phosphoric acid by wet process efficient impurity removal, which is characterized in that in hydrochloric acid method phosphoric acid by wet process be added calcic without
One or more of machine object, inorganic matter containing aluminium, siliceous inorganic matter, sulfur-bearing inorganic matter or fluorine-containing inorganic matter, adjustment hydrochloric acid method are wet
The molar ratio of Ca, Al, Si, S, F are (20-50): (0.8-1.2): (1-1.20): (0.90-1.20): (12-15) in method phosphoric acid,
It is reacted, makes Ca, Al, Si, S, F impurity element in hydrochloric acid method phosphoric acid by wet process with Ca4AlSiSO4F13·12H2The form of O is heavy
Shallow lake comes out, to reach purification purpose.
2. a kind of method of hydrochloric acid method phosphoric acid by wet process efficient impurity removal according to claim 1, which is characterized in that hydrochloric acid method is wet
It is added after calcic inorganic matter, inorganic matter containing aluminium, siliceous inorganic matter, sulfur-bearing inorganic matter or fluorine-containing inorganic matter in method phosphoric acid, control
Fluorine/aluminium molar ratio is at (0.6-3): 1, fluorine/calcium molar ratio is controlled at (0.03-0.11): 1.
3. a kind of method of hydrochloric acid method phosphoric acid by wet process efficient impurity removal according to claim 1, which is characterized in that hydrochloric acid method is wet
Be added in method phosphoric acid one of calcic inorganic matter, inorganic matter containing aluminium, siliceous inorganic matter, sulfur-bearing inorganic matter or fluorine-containing inorganic matter or
Several, the molar ratio for adjusting Ca, Al, Si, S, F in hydrochloric acid method phosphoric acid by wet process is 30:1:1:1:13.
4. a kind of method of hydrochloric acid method phosphoric acid by wet process efficient impurity removal according to claim 1, which is characterized in that the calcic
Inorganic matter is inorganic matter I, and the inorganic matter I is selected from calcium chloride, calcium carbonate, calcium oxide, calcium hydroxide, calcium nitrate, calcium bicarbonate
Or one of calcium sulfate or several；
The inorganic matter containing aluminium is inorganic matter II, and the inorganic matter II is selected from aluminium chloride, aluminum sulfate, aluminium hydroxide, aluminium oxide, nitre
One or more of sour aluminium or aluminum phosphate；
The siliceous inorganic matter is inorganic matter III, and the inorganic matter III is in sodium metasilicate, potassium silicate, silica or fluosilicic acid
One or more；
The sulfur-bearing inorganic matter is inorganic matter IV, and the inorganic matter III is in sodium metasilicate, potassium silicate, silica or fluosilicic acid
One or more；
The fluorine-containing inorganic matter is inorganic matter V, and the inorganic matter V is selected from hydrogen fluoride, fluosilicic acid, potassium fluosilicate or prodan
One or more of.
5. a kind of method of hydrochloric acid method phosphoric acid by wet process efficient impurity removal according to claim 1, which is characterized in that the hydrochloric acid
Method phosphoric acid by wet process is the acid hydrolysis solution that 10%-30% concentration of hydrochloric acid extracts phosphorus ore, wherein P2O5Mass fraction is 5-10%, F mass
Score is 0.1-0.5%, Fe2O3Mass fraction is 0.1-0.5%, Al2O3Mass fraction is 0.1-0.3%, CaO mass fraction
For 5-10%, SiO2Mass fraction is 0.1-0.3%, SO3Mass fraction is 0.1-0.5%.
6. a kind of method of hydrochloric acid method phosphoric acid by wet process efficient impurity removal according to claim 1, which is characterized in that the calcic
The charging sequence of inorganic matter, inorganic matter containing aluminium, siliceous inorganic matter, sulfur-bearing inorganic matter or fluorine-containing inorganic matter are as follows: first be added containing aluminium without
One or more of machine object, siliceous inorganic matter, sulfur-bearing inorganic matter or fluorine-containing inorganic matter, are eventually adding calcic inorganic matter.
7. a kind of method of hydrochloric acid method phosphoric acid by wet process efficient impurity removal according to claim 1, which is characterized in that reacted
Condition be reaction temperature be 10-80 DEG C, reaction time 0.5-24h.
8. a kind of method of hydrochloric acid method phosphoric acid by wet process efficient impurity removal according to claim 1, which is characterized in that when reaction,
First solution is heated, is made in calcic inorganic matter, inorganic matter containing aluminium, siliceous inorganic matter, sulfur-bearing inorganic matter or fluorine-containing inorganic matter
One or more of dissolutions, then reduce the temperature of reaction system to 20-40 DEG C.
9. a kind of method of hydrochloric acid method phosphoric acid by wet process efficient impurity removal according to claim 1, which is characterized in that reaction system
It is formed after precipitating, the separation of precipitating and liquid is realized by the way of filtering.
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| CN112176185A (en) * | 2020-09-28 | 2021-01-05 | 江西永兴特钢新能源科技有限公司 | Method for removing fluorine from lepidolite roasting leaching solution |
| CN114014287A (en) * | 2021-11-08 | 2022-02-08 | 宜都兴发化工有限公司 | Wet-process phosphoric acid purification method |
| CN115594158A (en) * | 2022-12-01 | 2023-01-13 | 云南布兰特化工有限公司（Cn） | Method for preparing yellow phosphorus from phosphate by using silicothermic reduction and application |
| CN115838183A (en) * | 2023-02-15 | 2023-03-24 | 中南大学 | Method for separating silicon and magnesium from black talc |
| CN115838183B (en) * | 2023-02-15 | 2023-05-26 | 中南大学 | Method for separating silicon magnesium from black talc |
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