A kind of ultralow grade phosphorus mine stone de-magging and the method for producing magnesium hydroxide
Technical field
The method that the present invention relates to a kind of ultralow grade phosphorus mine stone de-magging and produce magnesium hydroxide.
Background technology
Rich ore in China's phosphate rock resource only accounts for about 8%, and former phosphorus ore mostly is mid-low grade collophanite ore, and the foreign matter contents such as its Mg, Al, Fe are higher.In the Wet-process Phosphoric Acid Production process, the existence of impurity Mg not only affects the production of phosphoric acid by wet process, also phosphoric acid deep processing economic and technical norms is had a significant effect.In addition, the international commodity phosphorus ore also has certain requirement to magnesium phosphorus ratio.Many technological problemses that present domestic Wet-process Phosphoric Acid Production enterprise generally brings in the face of the Rock Phosphate (72Min BPL) dilution, for example: reactive behavior is poor in the Wet-process Phosphoric Acid Production, gypsum crystallization is difficult, slurry filtration poor performance, finished product phosphoric acid foreign matter content be up to the requirement less than the fertilizer industry level.Phosphorus ore de-magging method of the prior art mainly is the physical methods such as flotation, reverse flotation, but is difficult to MgO content is dropped to below 1%, and phosphorus is lost in more than 5%, and the facility investment in early stage is huge.The marine deposit phosphorite of difficult choosing is that collophanite accounts for more than 75% in China's phosphate rock resource.Because collophanite contains rhombspar more and both flotabilities are close, therefore use method for floating to fail to solve well rhombspar separation problem in the collophanite always.
Application number is that the patent application document of 88105674.X discloses a kind of Rock Phosphate (72Min BPL) de-magging technique, the slurries that are made into certain solid-to-liquid ratio with 100 purpose iron content ground phosphate rock and water, pass into sulfurous gas, make slip keep pH=2.0~5.0, after reacting 8~24 hours under the normal temperature and pressure, analyse method etc. with sedimentation and filtration method or pen, the liquid phase that will contain magnesium is separated with the phosphorus concentrate, discharges after waste water is processed with proper method or is used as him.CN102115819A discloses the method that reclaims magnesium in the low-grade high-magnesium-phosphorus ore therefrom, the low-grade high-magnesium-phosphorus ore of mixture centering with de-magging agent magnesium hydrogen sulfate or the vitriol oil and sal epsom carries out the chemical method de-magging first, make the most of magnesium stripping from phosphate ore pulp in the phosphorus ore, the gained solid filter cake is the de-magging concentrate, liquid further add neutralization precipitation agent monoammonium phosphate or monoammonium phosphate and bicarbonate of ammonia or with ammoniacal liquor or with liquefied ammonia in any mixture, obtain magnesium ammonium phosphate sediment, as slow release fertilizer.CN100392124C discloses the processing method that reclaims magnesium from high-magnesium-phosphorus ore stone, first with compound de-magging agent with contain magnesium phosphorus ore powder and add water and carry out hybrid reaction, this compound de-magging agent contains sulfuric acid and is selected from least a kind of component in disodium ethylene diamine tetraacetate and the nitric acid, after the solid-liquid separation, solid phase is the phosphorus concentrate, liquid phase is for containing magnesium solution, and solution adds neutralization precipitation agent (being selected from milk of lime, sodium hydroxide solution and ammoniacal liquor) and obtains magnesium hydrate precipitate.
Summary of the invention
The method that the object of the present invention is to provide a kind of ultralow grade phosphorus mine stone de-magging and produce magnesium hydroxide solves the problems of the prior art.
The objective of the invention is to be achieved through the following technical solutions.
A kind of ultralow grade phosphorus mine stone de-magging and the method for producing magnesium hydroxide are with behind ground phosphate rock and the de-magging agent mixing de-magnesium reaction, carry out solid-liquid separation, and solid is the phosphorus concentrate, add the neutralization precipitation agent in the liquid and obtain containing the magnesium by product; It is characterized in that: take ultralow grade phosphorus mine stone as raw material, as the de-magging agent, the washing water that will wash solid phase after solid-liquid separation mix with separating obtained solution and carry out neutralization-precipitation reaction with the mixing acid of sulfurous acid, sulfuric acid and silicofluoric acid, and described Production Flow Chart is:
(1) Rock Phosphate (72Min BPL) is milled to obtain fineness be 60~100 purpose ground phosphate rock; Be that 1~20% sulfuric acid joins in the silicate fluoride solution of concentration 〉=17% with the sulfurous acid of concentration 〉=5% and concentration, the mass ratio of adding is sulfurous acid: sulfuric acid: silicofluoric acid=1:1.2:1.3, stir, and obtain the agent of mixing acid de-magging;
(4) ground phosphate rock is joined in the agent of mixing acid de-magging, be warming up to 30~60 ℃, stir speed (S.S.) 300~350r/min, reaction times 10~60min, a some reaction is finished to reaction solution pH=3~6;
(5) after reaction is finished, adopt while hot filter type that solution is separated with solid phase, solution is the solution that contains magnesium salts;
(4) with distilled water solid phase is washed to washing water and be neutral, the oven dry of gained solid is the phosphorus ore concentrate;
The solution that (5) will contain magnesium salts mixes with washing water, adds the precipitation agent caustic soda, and solution is transferred to pH=9~12, at 30~60 ℃ of lower reaction 30~80min, obtains magnesium hydroxide solid and waste liquid through solid-liquid separation;
(6) gained magnesium hydroxide solid drying, pulverizing are obtained the powdered form magnesium hydroxide.
The fineness of ground phosphate rock is 80~90 orders in the described step (1).
The pH=1 of mix acid liquor~2 in the described step (1).
Be warming up to 40~50 ℃ in the described step (2).
Stir speed (S.S.) is 300r/min in the described step (2).
The reaction times is 30min in the described step (2).
Reaction solution pH=4 in the described step (2)~reaction in 5 o'clock is finished.
Described step transfers to pH=10~11 with solution in (5).
Waste liquid in the described step (6) is delivered to the Sodium Silicofluoride workshop for the production of Sodium Silicofluoride
Natural Rock Phosphate (72Min BPL) is divided into phosphatic rock and phosphorite two large classes, and their main component all is calcium monofluorophosphate [Ca
5(PO
4)
3F], the magnesium major part in the phosphorus ore is with rhombspar (CaCO
3MgCO
3) form exist.The equation of the main chemical reaction that occurs is as follows in the reaction process of the present invention:
4H
++CaCO
3·MgCO
3→Ca
2++Mg
2++2CO
2+2H
2O
Because this reaction is the reaction of strong acid weak acid processed, therefore if remove rhombspar in the Rock Phosphate (72Min BPL), just must selects the de-magging agent of a kind of acidity between carbonic acid and phosphoric acid, otherwise will cause the loss of larger phosphorus.Be better than phosphoric acid with sulfuric acid under the condition, but silicofluoric acid acidity is weaker than phosphoric acid slightly, both mix existence, and then the ionic equation in the mix acid liquor is:
H
2SiF
6≈H
++HSiF6
-≈2H
++SiF
6 2-
H
2SO
4=2H
++SO
4 2-
Because there is middle strong acid silicofluoric acid partial ionization to exist, certain shock absorption has been played in the reaction in the mix acid liquor, reduced to a certain extent sulfuric acid, so that acid solution can not decomposed calcium monofluorophosphate [Ca
5(PO
4)
3F], just can not cause the phosphorus loss yet.Add sulfurous acid and can further reduce H in the reaction solution
+Activity, but since volatile, the easy oxidation of sulfurous acid and must control usage quantity, the proportioning of sulfurous acid and other two kinds of acid is scientific and reasonable among the present invention, is conducive to carrying out and the efficient utilization of resource of chemical reaction.
Beneficial effect of the present invention: adopt silicofluoric acid, sulfuric acid and sulfurous acid three mix acid liquor as the de-magging agent, reduced P
2O
5Loss; Production process route is short, and is simple to operate, and the one-time investment cost is low; De-magging is effective, and the magnesium decreasing ratio can reach more than 80%, and Mg content is lower than 1% in the gained concentrate; Gained phosphorus ore concentrate quality better, grade has improved 5~10%, P
2O
5Yield is high, can reach under the optimum process condition more than 99%, generally promotes P
2O
5Content 3~5%.Reaction is finished terminal point and is easy to judge, assaying reaction liquid pH=3~6 can be judged to react and finish.The product liquid phase can be processed fully, and the production magnesium hydroxide is powdered form, and waste liquid can supply Sodium Silicofluoride production, does not produce any slag and effluent etc.Adopt sulfuric acid, the mixing acid that silicofluoric acid and additive mix is as the de-magging agent, sulfuric acid can improve the rhombspar reactive behavior on the one hand, first hydrogen ion ionization constant of silicofluoric acid and first hydrogen ion ionization constant of phosphoric acid approach, can reduce the phosphorus loss, under optimum process condition, the phosphorus loss is less than 1%, the magnesium decreasing ratio is greater than 80%, gained solution can obtain magnesium hydrate precipitate through processing, waste liquid after the processing can supply the Sodium Silicofluoride production and application, can not produce any waste, the magnesium hydrate precipitate after the processing can also be as good inorganic fire-retarded agent addition agent.
Description of drawings
Fig. 1 is process flow diagram of the present invention.
Embodiment
In order to deepen the understanding of the present invention, the present invention is described in further detail below in conjunction with drawings and Examples, but do not consist of the restriction to protection domain of the present invention.
Fig. 1 is process flow diagram of the present invention, and as shown in Figure 1, the present invention is milled into ground phosphate rock with Rock Phosphate (72Min BPL); To obtain mixing acid after sulfuric acid, sulfurous acid and the silicofluoric acid mixing; Ground phosphate rock and mixing acid are reacted under intensification, agitation condition; React and filter after complete, separate the phosphorus ore concentrate of solid phase after distilled water wash obtains de-magging that obtains; Separating the liquid phase obtain is the solution that contains magnesium salts, it is mixed with washing water after the washing solid phase, and add caustic soda adjusting pH, reacts gains and carries out obtaining magnesium hydroxide solid and waste liquid after the solid-liquid separation; Obtain the powdered form magnesium hydroxide after magnesium hydroxide solid drying, the pulverizing.
Embodiment 1
Get ultralow grade phosphorus mine stone (P
2O
5≤ 28%, MgO 〉=3%, MgO/P
2O
5〉=10%).Rock Phosphate (72Min BPL) milled, and to obtain fineness be 60 purpose ground phosphate rock; Be that 5% sulfurous acid and concentration are that 5% sulfuric acid joins in the silicate fluoride solution of concentration 17% with concentration, the mass ratio of adding is sulfurous acid: sulfuric acid: silicofluoric acid=1:1.2:1.3, stir, and obtain the agent of mixing acid de-magging; Ground phosphate rock is joined in the agent of mixing acid de-magging, be warming up to 30 ℃, stir speed (S.S.) 300r/min, reaction times 10min, reaction is finished during to reaction solution pH=3; After reaction is finished, adopt while hot filter type that solution is separated with solid phase, solution is the solution that contains magnesium salts; With distilled water solid phase is washed to washing water and to be neutral, the oven dry of gained solid is the phosphorus ore concentrate; The solution that will contain magnesium salts mixes with washing water, adds the precipitation agent caustic soda, and solution is transferred to pH=9, at 30 ℃ of lower reaction 80min, obtains magnesium hydroxide solid and waste liquid through solid-liquid separation; Gained magnesium hydroxide solid drying, pulverizing are obtained the powdered form magnesium hydroxide.
Embodiment 2
Get ultralow grade phosphorus mine stone (P
2O
5≤ 28%, MgO 〉=3%, MgO/P
2O
5〉=10%).Rock Phosphate (72Min BPL) milled, and to obtain fineness be 80 purpose ground phosphate rock; Be that 10% sulfurous acid and concentration are that 10% sulfuric acid joins in the silicate fluoride solution of concentration 34% with concentration, the mass ratio of adding is sulfurous acid: sulfuric acid: silicofluoric acid=1:1.2:1.3, stir, and obtain the agent of mixing acid de-magging; Ground phosphate rock is joined in the agent of mixing acid de-magging, be warming up to 45 ℃, stir speed (S.S.) 325r/min, reaction times 30min, reaction is finished during to reaction solution pH=4; After reaction is finished, adopt while hot filter type that solution is separated with solid phase, solution is the solution that contains magnesium salts; With distilled water solid phase is washed to washing water and to be neutral, the oven dry of gained solid is the phosphorus ore concentrate; The solution that will contain magnesium salts mixes with washing water, adds the precipitation agent caustic soda, and solution is transferred to pH=10, at 45 ℃ of lower reaction 60min, obtains magnesium hydroxide solid and waste liquid through solid-liquid separation; Gained magnesium hydroxide solid drying, pulverizing are obtained the powdered form magnesium hydroxide.
Embodiment 3
Get ultralow grade phosphorus mine stone (P
2O
5≤ 28%, MgO 〉=3%, MgO/P
2O
5〉=10%).Rock Phosphate (72Min BPL) milled, and to obtain fineness be 100 purpose ground phosphate rock; Be that 20% sulfurous acid and concentration are that 20% sulfuric acid joins in the silicate fluoride solution of concentration 51% with concentration, the mass ratio of adding is sulfurous acid: sulfuric acid: silicofluoric acid=1:1.2:1.3, stir, and obtain the agent of mixing acid de-magging; Ground phosphate rock is joined in the agent of mixing acid de-magging, be warming up to 60 ℃, stir speed (S.S.) 350r/min, reaction times 60min, reaction is finished during to reaction solution pH=6; After reaction is finished, adopt while hot filter type that solution is separated with solid phase, solution is the solution that contains magnesium salts; With distilled water solid phase is washed to washing water and to be neutral, the oven dry of gained solid is the phosphorus ore concentrate; The solution that will contain magnesium salts mixes with washing water, adds the precipitation agent caustic soda, and solution is transferred to pH=12, at 60 ℃ of lower reaction 30min, obtains magnesium hydroxide solid and waste liquid through solid-liquid separation; Gained magnesium hydroxide solid drying, pulverizing are obtained the powdered form magnesium hydroxide.