A kind of ultralow grade phosphorus mine stone de-magging the method for producing magnesium hydroxide
Technical field
A kind of method that the present invention relates to ultralow grade phosphorus mine stone de-magging and produce magnesium hydroxide.
Background technology
Rich ore in China's phosphate rock resource only accounts for 8% left and right, 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 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, international commodity phosphorus ore also there are certain requirements magnesium phosphorus ratio.Many technological problemses that current domestic Wet-process Phosphoric Acid Production enterprise generally brings in the face of Rock Phosphate (72Min BPL) dilution, for example: in Wet-process Phosphoric Acid Production, reactive behavior is poor, gypsum crystallization is difficult, slurry filtration poor performance, finished product phosphoric acid foreign matter content be up to the requirement less than fertilizer industry level.Phosphorus ore de-magging method of the prior art is mainly the physical methods such as flotation, reverse flotation, but is difficult to MgO content to drop to below 1%, and phosphorus is lost in more than 5%, and facility investment in early stage is huge.In China's phosphate rock resource, the marine deposit phosphorite of difficult choosing is that collophanite accounts for more than 75%.Because collophanite contains rhombspar and both flotabilities are close more, therefore use method for floating could not solve well rhombspar separation problem in collophanite always.
Application number is that the patent application document of 88105674.X discloses a kind of Rock Phosphate (72Min BPL) de-magging technique, with 100 object iron content ground phosphate rock and water, to be made into the slurries of certain solid-to-liquid ratio, pass into sulfurous gas, make slip keep pH=2.0~5.0, under normal temperature and pressure, react after 8~24 hours, with sedimentation and filtration method or pen, analyse method etc., the liquid phase containing magnesium is separated with phosphorus concentrate, and waste water discharges or is used as him after processing with proper method.CN102115819A discloses the method that reclaims magnesium in low-grade high-magnesium-phosphorus ore therefrom, first with the low-grade high-magnesium-phosphorus ore of mixture centering of de-magging agent magnesium hydrogen sulfate or the vitriol oil and magnesium sulfate, carry out chemical method de-magging, make the most of magnesium stripping from phosphate ore pulp in phosphorus ore, gained solid filter cake is 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 by compound de-magging agent with containing magnesium phosphorus ore powder, to add water and carry out hybrid reaction, this compound de-magging agent contains sulfuric acid and is at least selected from a kind of component in disodium ethylene diamine tetraacetate and nitric acid, after solid-liquid separation, solid phase is 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) to obtain magnesium hydrate precipitate.
Summary of the invention
A kind of method that the object of the present invention is to provide ultralow grade phosphorus mine stone de-magging and produce magnesium hydroxide, solves the problems of the prior art.
The object of the invention is to be achieved through the following technical solutions.
Ultralow grade phosphorus mine stone de-magging a method of producing magnesium hydroxide, be by ground phosphate rock with after de-magging agent mixing de-magnesium reaction, carry out solid-liquid separation, solid is phosphorus concentrate, adds neutralization precipitation agent to obtain containing magnesium by product in liquid; It is characterized in that: the ultralow grade phosphorus mine stone of take is raw material, using the mixing acid of sulfurous acid, sulfuric acid and silicofluoric acid as de-magging agent, the washing water that wash solid phase after solid-liquid separation are mixed and carry out neutralization-precipitation reaction with separating obtained solution, described Production Flow Chart is:
(1) Rock Phosphate (72Min BPL) is milled to obtain fineness be 60~100 object ground phosphate rock; The sulfuric acid that is 1~20% by the sulfurous acid of concentration >=5% and concentration joins in the silicate fluoride solution of concentration >=17%, and the mass ratio 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, has reacted to reaction solution pH=3~6 o'clock;
(5) after having reacted, adopt while hot filter type that solution is separated with solid phase, solution is the solution containing magnesium salts;
(4) with distilled water, solid phase is washed to washing water and is neutral, gained solid is dried, and is phosphorus ore concentrate;
(5) solution containing magnesium salts is mixed with washing water, add precipitation agent caustic soda, solution is adjusted to pH=9~12, at 30~60 ℃, react 30~80min, through solid-liquid separation, obtain magnesium hydroxide solid and waste liquid;
(6) gained magnesium hydroxide solid drying, pulverizing are obtained to powdered form magnesium hydroxide.
In described step (1), the fineness of ground phosphate rock is 80~90 orders.
PH=1~2 of mix acid liquor in described step (1).
In described step (2), be warming up to 40~50 ℃.
In described step (2), stir speed (S.S.) is 300r/min.
In described step (2), the reaction times is 30min.
In described step (2), has reacted reaction solution pH=4~5 o'clock.
Described step is adjusted to pH=10~11 by solution in (5).
Waste liquid in described step (6) is delivered to Sodium Silicofluoride workshop for the production of Sodium Silicofluoride
Natural Rock Phosphate (72Min BPL) is divided into phosphatic rock and the large class of phosphorite two, and their main component is all calcium monofluorophosphate [Ca
5(PO
4)
3f], the magnesium major part in phosphorus ore is with rhombspar (CaCO
3mgCO
3) form exist.In reaction process of the present invention, the equation of the main chemical reaction occurring is as follows:
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 the rhombspar in Rock Phosphate (72Min BPL), just must select the de-magging agent of a kind of acidity between carbonic acid and phosphoric acid, otherwise will cause larger phosphorus loss.With sulfuric acid under condition, be better than phosphoric acid, but silicofluoric acid acidity is weaker than phosphoric acid slightly, both mix existence, and the ionic equation in 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, the reaction in mix acid liquor has been played to certain shock absorption, reduced to a certain extent sulfuric acid, make acid solution can not decompose calcium monofluorophosphate [Ca
5(PO
4)
3f], just can not cause phosphorus loss yet.Add sulfurous acid can further reduce H in reaction solution
+activity, but because sulfurous acid is volatile, oxidizable and must control usage quantity, in the present invention, sulfurous acid and other two kinds sour proportionings are scientific and reasonable, are conducive to the carrying out of chemical reaction and effective utilization of resource.
Beneficial effect of the present invention: adopt silicofluoric acid, sulfuric acid and sulfurous acid three mix acid liquor as de-magging agent, reduced P
2o
5loss; Production process route is short, simple to operate, and one-time investment cost is low; De-magging is effective, and magnesium decreasing ratio can reach more than 80%, and in gained concentrate, Mg content is lower than 1%; Gained phosphorus ore concentrate quality better, grade has improved 5~10%, P
2o
5yield is high, can reach more than 99% under optimum process condition, generally promotes P
2o
5content 3~5%.Reacted terminal and be easy to judge, assaying reaction liquid pH=3~6, can judge and react.Product liquid phase can be processed completely, and production magnesium hydroxide is powdered form, and waste liquid can be produced for Sodium Silicofluoride, does not produce any slag and effluent etc.Adopt sulfuric acid, the mixing acid that silicofluoric acid and additive mix is as de-magging agent, sulfuric acid can improve 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 phosphorus loss, under optimum process condition, phosphorus loss is less than 1%, magnesium decreasing ratio is greater than 80%, gained solution can obtain magnesium hydrate precipitate through processing, waste liquid after processing can supply Sodium Silicofluoride production and application, can not produce any waste, magnesium hydrate precipitate after processing can also be as good inorganic fire-retarded agent addition agent.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention.
Embodiment
In order to deepen the understanding of the present invention, below in conjunction with drawings and Examples, the present invention is described in further detail, but do not form limiting the scope 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 by Rock Phosphate (72Min BPL); After being mixed, sulfuric acid, sulfurous acid and silicofluoric acid obtain mixing acid; Then make ground phosphate rock and mixing acid react under intensification, agitation condition; Filter after completion of the reaction the phosphorus ore concentrate of the solid phase that separation obtains after distilled water wash obtains de-magging; The liquid phase that separation obtains is the solution containing magnesium salts, it is mixed with the washing water after washing solid phase, and add caustic soda to regulate pH, and reaction gains carry out after solid-liquid separation obtaining magnesium hydroxide solid and waste liquid; After magnesium hydroxide solid drying, pulverizing, obtain powdered form magnesium hydroxide.
Embodiment 1
Get ultralow grade phosphorus mine stone (P
2o
5≤ 28%, MgO>=3%, MgO/P
2o
5>=10%).Rock Phosphate (72Min BPL) is milled, and to obtain fineness be 60 object ground phosphate rock; The sulfurous acid that is 5% by concentration and concentration are that 5% sulfuric acid joins in the silicate fluoride solution of concentration 17%, and the mass ratio 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, has reacted during to reaction solution pH=3; After having reacted, adopt while hot filter type that solution is separated with solid phase, solution is the solution containing magnesium salts; With distilled water, solid phase is washed to washing water and is neutral, gained solid is dried, and is phosphorus ore concentrate; Solution containing magnesium salts is mixed with washing water, add precipitation agent caustic soda, solution is adjusted to pH=9, at 30 ℃, react 80min, through solid-liquid separation, obtain magnesium hydroxide solid and waste liquid; Gained magnesium hydroxide solid drying, pulverizing are obtained to 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) is milled, and to obtain fineness be 80 object ground phosphate rock; The sulfurous acid that is 10% by concentration and concentration are that 10% sulfuric acid joins in the silicate fluoride solution of concentration 34%, and the mass ratio 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, has reacted during to reaction solution pH=4; After having reacted, adopt while hot filter type that solution is separated with solid phase, solution is the solution containing magnesium salts; With distilled water, solid phase is washed to washing water and is neutral, gained solid is dried, and is phosphorus ore concentrate; Solution containing magnesium salts is mixed with washing water, add precipitation agent caustic soda, solution is adjusted to pH=10, at 45 ℃, react 60min, through solid-liquid separation, obtain magnesium hydroxide solid and waste liquid; Gained magnesium hydroxide solid drying, pulverizing are obtained to 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) is milled, and to obtain fineness be 100 object ground phosphate rock; The sulfurous acid that is 20% by concentration and concentration are that 20% sulfuric acid joins in the silicate fluoride solution of concentration 51%, and the mass ratio 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, has reacted during to reaction solution pH=6; After having reacted, adopt while hot filter type that solution is separated with solid phase, solution is the solution containing magnesium salts; With distilled water, solid phase is washed to washing water and is neutral, gained solid is dried, and is phosphorus ore concentrate; Solution containing magnesium salts is mixed with washing water, add precipitation agent caustic soda, solution is adjusted to pH=12, at 60 ℃, react 30min, through solid-liquid separation, obtain magnesium hydroxide solid and waste liquid; Gained magnesium hydroxide solid drying, pulverizing are obtained to powdered form magnesium hydroxide.