CN101759166A - Method for pre-treating phosphorite by using acidic waste water in the production process of titanium pigment - Google Patents
Method for pre-treating phosphorite by using acidic waste water in the production process of titanium pigment Download PDFInfo
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- CN101759166A CN101759166A CN200910312895A CN200910312895A CN101759166A CN 101759166 A CN101759166 A CN 101759166A CN 200910312895 A CN200910312895 A CN 200910312895A CN 200910312895 A CN200910312895 A CN 200910312895A CN 101759166 A CN101759166 A CN 101759166A
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Abstract
The invention discloses a method for pre-treating phosphorite of wet process phosphoric acid by using acidic waste water in the production process of titanium pigment, which comprises the following steps: (1), collecting the acidic waste water into an acidic waste water storage groove, controlling the acid degree to be 2 to 5 percent and the total iron concentration to be 0.3 to 0.5 percent; (2), adding the acidic waste water and the milled phosphorite in a solid-to-liquid ratio of 2-5:1 into a reaction groove for reaction; and (3), performing solid-liquid separation on the slurry which is obtained in the step (2) to obtain a solid phase, namely the required phosphorite. The content of magnesium in the phosphorite which is treated by the method is reduced by over 70 percent, the loss ratio of the phosphorus is controlled to be within 1 percent; when the phosphorite which is treated by the process is used for producing the phosphoric acid by a wet method, the consumption of the sulfuric acid for mine per ton is reduced by about 10 percent; and the acidic waste water pretreats phosphorite and then is delivered to a sewage station for treatment, the consumption of lime or other alkaline substance is reduced by 60 percent compared with the mode of directly delivering the waste water to the sewage station, so the economical efficiency of the process is high.
Description
Technical field
The invention discloses and a kind ofly utilize the acid waste water in the sulfuric acid method titanium pigment production process that the phosphorus ore of phosphoric acid by wet process is carried out pretreated method, relate to that phosphorus ore purifies integrated technique in titanizing worker's waste water treatment and the phosphorous chemical industry, the useless secondary circulation comprehensive that belongs to titanizing worker and phosphorus chemical industry utilizes technical field.
Background technology
The production method of China titanium white enterprise overwhelming majority is a sulfuric acid process, in the sulfuric acid method titanium pigment production technique, its intermediate titanyl sulfate need be hydrolyzed into metatitanic acid and sulfuric acid, the sulfur waste acid that 1 ton of titanium dioxide of every production can produce 5-6 ton 20%-30% concentration, and in follow-up metatitanic acid washing procedure, can produce 16-25 ton left and right sides acid waste water (sulfur acid 2-5%, ferrous sulfate 0.3-0.5%).
The acid recovery of 20-30% sulfur waste handled a lot of patented technologies and relevant report, and for example patent CN1171777C and CN101049915 utilize the non-volatile solution condensing device of gas-liquid separation type and rotary kiln tail gas heat quantity that about 20% diluted acid is concentrated recycling respectively.And for acid waste water, because sulfuric acid concentration low (concentration 3%～5%, average 4%) and contain more impurity in the acid waste water, major part needs the vitriolic production technique directly to utilize, if by concentrating then can consume a large amount of energy, there is not economic benefit with reclaim(ed) sulfuric acid.Chinese patent CN1220970 discloses a kind of operational path that utilizes reactions such as this acid waste water and magnesium oxide to produce sal epsom, both solved environmental issue, realized economic benefit again, but sal epsom production is a little industry, a large amount of acid waste waters that at all can't the balance titanium white production bring.At present the sulfuric acid method titanium pigment corporate boss to use alkaline precipitating agent lime or carbide slag etc. to acid waste water neutralize, post precipitation, the clear liquid qualified discharge is stacked after the precipitated product press filtration, not only spent a large amount of in and cost but also consume a large amount of soils and stack waste residues.
Phosphate fertilizer and phosphoric acid salt industry are produced phosphoric acid by wet process with phosphorus ore with sulfuric acid solution earlier usually, then phosphoric acid by wet process are processed into various products.Exist detrimental impurity such as iron, aluminium, magnesium in the phosphorus ore, vitriolic unit consumption when not only increasing acidolysis, and can increase the difficulty of following process and can influence the quality of the finished product.Particularly the magnesium in the phosphorus ore mainly exists with carbonate form, almost all enters in the phosphoric acid by wet process in the phosphorus ore acid hydrolysis process, makes the following process difficulty, and the quality of phosphate product is had a negative impact.Thereby need carry out pre-treatment to phosphorus ore, to remove these detrimental impurity.Usually adopt flotation and wet method demagging two class technologies both at home and abroad.The former exists facility investment big, and technical process is long, the drawback that unit cost is high.Therefore, various wet method demagging technology are arisen at the historic moment, as sulfur dioxide gas or treating with sulfurous acid phosphorus ore (CN88105674) de-magging, use de-magging collector (CN101011582) de-magging, 2005 the 5th phases of Sichuan chemical industry magazine " phosphorus ore purifies the research of de-magging " have been introduced use dilute sulphuric acid de-magging.This method is amounted to into the vitriol oil and is calculated each ton P
2O
5De-magging need consume 124 kilograms, consumes 97 kilograms of calculating of sulfuric acid less, one ton of P of every processing even if offset in the phosphoric acid production
2O
5Still need to consume 27 kilograms of vitriol oils.Above-mentioned various de-magging method ubiquity the shortcoming that cost is higher and the phosphorus loss is bigger, seldom is used in the actual production.
Except the vitriol oil cost that expends, directly use the technology of dilute sulphuric acid pre-treating phosphorite, exist also that the phosphorus rate of loss is big, the deficiency of the poor reproducibility of effect.Its reason is as the sulfuric acid of washing composition very strong, and local concentration difference phenomenon unavoidably occurs in washing process, all may cause phosphorus ore to be decomposed and react generation.Phosphate fertilizer was pointed out with multiple 1993 the 1st phases of fertile magazine " magnesium removal method for phosphorated ore ", in view of sulfuric acid is diprotic acid, two hydrionic dissociation constant difference are very big, if effectively use second hydrogen ion to participate in the washup reaction, can avoid phosphorus ore to be decomposed as far as possible and the P that brings
2O
5Loss.Chinese patent 90107689.9 has considered that the sulfate radical first stage ionization forms the phosphorus loss that local strong acid environment may bring, utilize the excessive mineral that contain the carbonic acid magnesium salts at first to generate magnesium hydrogen sulfate and carry out de-magnesium reaction as the acidifying washing composition with sulfuric acid reaction, because it has overcome the problem that sulfuric acid is crossed strong and local concentration difference phenomenon, in the de-magging process, the rate of loss of phosphorus decreases.But, because this technology is used the magnesium hydrogen sulfate de-magging, there is common-ion effcet, demagnesium rate decreases unavoidably.No matter use the dilute sulphuric acid de-magging still to use the magnesium hydrogen sulfate de-magging, all will consume sulfuric acid, can not solve the purpose of the acid consumption that reduces Wet-process Phosphoric Acid Production.Have only that to contain magnesium in the phosphorus ore too high, just be of practical significance when having a strong impact on the phosphoric acid by wet process operation, and in the operating process or the phosphorus loss is big, or demagnesium rate is low.
Summary of the invention
The objective of the invention is to overcome above-mentioned deficiency of the prior art, provide a kind of acid waste water that produces in the sulfuric acid method titanium pigment production process that utilizes that phosphorus ore is carried out pretreated method.Method provided by the invention in the acid waste water processing, is carried out pre-treatment to phosphorus ore in the phosphoric acid by wet process in effective solution sulfuric acid method titanium pigment production process, this pretreatment process demagnesium rate height, and the phosphorus rate of loss is low.
The present invention realizes that the technical scheme of foregoing invention purpose is:
A kind of method of utilizing the acid waste water pre-treating phosphorite in the sulfuric acid method titanium pigment production process comprises following processing step:
(1), the acid waste water in the sulfuric acid method titanium pigment Production Flow Chart is collected in the acid waste water storage tank, vitriolic quality percentage composition is 2～5% (if be not specifically noted in the control acid waste water, % of the present invention represents the quality percentage composition), the quality percentage composition of total iron is 0.3～0.5%;
(2), phosphorus ore is levigate, make the phosphorus ore more than 75% cross 100 mesh sieves, by liquid-solid ratio 2-5: 1 adds acid waste water and the good phosphorus ore of mill in the reactive tank and to react, and obtains reaction paste, and temperature of reaction is 30 ℃～50 ℃, and the reaction times is 0.5～2h;
(3), step (2) gained reaction paste is carried out solid-liquid separation, separating obtained solid phase is pretreated phosphorus ore, is used for producing of phosphoric acid by wet process; Separating obtained liquid phase is used to reclaim magnesium or send sewage works to handle.
In the processing method of the present invention, can increase pretreating effect by the fineness that improves ground phosphate rock, the described phosphorus ore of step (2) has more than 90% can reach pretreating effect preferably can be by 100 mesh sieves the time.
In the reaction process of described acid waste water of step (2) and phosphorus ore, by adding the pH value of phosphorus ore or acid waste water control reaction mixture, initial pH value is controlled at 2～3, and the pH value was controlled at 2.8～4 before reaction finished.
The gained solid phase is used further to producing of phosphoric acid by wet process after step (3) solid-liquid separation after washing, with the content of impurity in the further reduction solid phase.
The liquid phase that step (3) solid-liquid separation goes out is sent neutralization precipitations such as sewage works milk of lime, sodium hydroxide, ammoniacal liquor, and endpoint pH is controlled at 7～9.
The present invention utilizes sulfate process titanium dioxide to produce dilute sulphuric acid pre-treating phosphorite remaining in the acid waste water of route output, and detrimental impurity such as calcium in the phosphorus ore, magnesium are removed as far as possible, and the quality of phosphorus ore is improved.In the operational path of the present invention in the employed acid waste water vitriolic content be 2～5% and contain total concentration of iron that the waste water that acidity is low excessively should directly send waste water station or reach the concentration that meets above-mentioned requirements with the allotment of higher concentration acid waste water at 0.3～5% ferrous sulfate; The phosphorus ore of participating in reaction needs levigate to there being the phosphorus ore more than 75% to cross 100 mesh sieves, if phosphorus ore is to add with the form of ore pulp, the moisture that ore pulp is brought into causes liquid-solid ratio to increase and liquid phase acidity reduce should be to reduce the acid waste water dosage and the used acid waste water concentration of raising remedy; Being reflected under 30～50 ℃ the temperature of acid waste water and phosphorus ore carried out.Because the acid waste water typical temperature between 30-50 ℃, adds reaction meeting generation little heat itself, so, generally do not need extra heating.Under above-mentioned reaction conditions, diluted acid in the acid waste water and the carbonate in the phosphorus ore (are mainly CaCO
3MgCO
3) reaction, main reaction formula is as follows:
CaCO
3MgCO
3+2H
2SO
4＝CaSO
4+MgSO
4+2H2O+2CO
2↑
Do not participate in reaction directly though the thin acid in the acid waste water is ferrous, a large amount of iron ions promotes to dredge acid and mainly exists with the forms of dredging sour hydrogen salt, avoids dredging acid directly and phosphorus reaction, causes the phosphorus loss; In addition, the existence of a large amount of ferrous ions makes the pH value of solution be easier to be stabilized in the 2-4 interval, and this pH value scope required optimum range of de-magnesium reaction exactly.Reaction is carried out solid-liquid separation, MgSO after finishing
4Discharge with liquid phase separation Deng soluble impurity.Isolated liquid phase is sent sewage plant or is used to produce magnesium compound or sends into neutralization precipitations such as sewage works milk of lime, sodium hydroxide, ammoniacal liquor.Because the acidity of acid waste water is very low, adds that the temperature of reaction of control is also lower, the effective constituent Ca in the phosphorus ore
5F (PO
4)
3Can not be decomposed and the CaSO of one of reaction product
4Together stayed solid phase, this part of sulfuric acid calcium can be discharged system in the extraction slurry filtration stage as phosphorus slag with newly-generated calcium sulfate in the follow-up phosphorus ore extractive reaction.When solid phase is used to produce phosphoric acid by wet process,, can suitably reduces and dredge sour consumption, save cost because easy acidolysis impurity is decomposed by the diluted acid in the acid waste water when pre-treatment in the phosphorus ore.
Acid waste water is through after the above-mentioned technology, its acidity has bigger decline, thereby reduce greatly sewage disposal in and cost, carbonate in the phosphorus ore etc. easily acidolysis impurity major part decompose in preprocessing process, thereby the consumption of dredging acid in follow-up extraction process will reduce, most magnesium in the phosphorus ore and a spot of thin acid are ferrous discharges with liquid phase, and phosphorus ore quality is improved, and demagnesium rate of the present invention is more than 70%.Though this process can cause the phosphorus loss below 1%, compares with other ore dressing forms or compares with sparse sour de-magging, demagnesium rate height and its phosphorus rate of loss and comprehensive cost are minimum.
The present invention is owing to use the acid waste water pre-treating phosphorite, as long as contain the impurity of easy acidolysis in the phosphorus ore, as lime carbonate, magnesiumcarbonate etc., can use, reach and reduce the purpose that sulfuric acid consumption alleviates cost for wastewater treatment, simultaneously, there is a large amount of ferrous irons in the acid waste water, effectively controlled the sulfuric acid intensity in the waste water, avoided because acidity causes the excessive problem of phosphorus loss in the phosphorus ore excessively by force, and acid waste water is mainly with iron ion control sulfuric acid intensity, do not have the common-ion effcet that exists in the patent 90107689.9, can guarantee higher demagnesium rate.Phosphorus ore Mg content through the inventive method pre-treatment gained descends more than 70%, and the phosphorus rate of loss is controlled in 1%, and through the pretreated phosphorus ore of this technology, when being used for Wet-process Phosphoric Acid Production, the sulfuric acid that ore deposit per ton consumes descends about 10%.Send sewage plant to handle behind the acid waste water pre-treating phosphorite again, consume 60% lime or other alkaline matter than directly sending sewage plant to lack, therefore, this technology has very high economy.
Description of drawings:
Fig. 1 is a process flow diagram of the present invention.
Embodiment
The present invention is described in further detail below in conjunction with embodiment.But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment, allly all belong to scope of the present invention based on the technology that content of the present invention realized.
The method of utilizing the acid waste water pre-treating phosphorite in the sulfuric acid method titanium pigment production process that the present invention enumerates mainly comprises following processing step:
(1), the acid waste water in the sulfuric acid method titanium pigment Production Flow Chart is collected in the acid waste water storage tank, control its acidity at 2～5% (mass ratioes), total concentration of iron is at 0.3～0.5% (mass ratio);
(2), phosphorus ore is levigate, make the phosphorus ore more than 75% cross 100 mesh sieves, by liquid-solid ratio 2-5: 1 adds acid waste water and the good phosphorus ore of mill in the reactive tank and to react, and obtains reaction paste, and temperature of reaction is 30 ℃～50 ℃, and the reaction times is 0.5～2h;
(3), step (2) gained reaction paste is carried out solid-liquid separation, separating obtained solid phase is pretreated phosphorus ore, is used for producing of phosphoric acid by wet process; Separating obtained liquid phase is used to reclaim magnesium or send sewage works to handle.
Embodiment 1
With 1000 kilograms of solid contents 75% phosphorus ore (P
2O
5Content is 26%, Mg content is 2.4%, breeze 100 mesh screen residues 15%) (sulfuric acid concentration is 3%, and temperature is 45 ℃ for ore pulp and acid waste water, titanium content is 0.15%, iron level is 0.26%) 3000 liters import 10 cubical pretreatment reaction grooves by pipeline, phosphorus ore and acid waste water are under agitation reacted, stirring velocity is 100rpm, the initial pH value of control reaction mixture is 2, initial reaction temperature is 40 ℃, reacts that the final pH value is 2.8 after 2 hours, and temperature is 37 ℃.The reaction paste that goes out reactive tank carries out solid-liquid separation by press filtration, P in the filter cake butt
2O
5Content is 27.1%, and Mg content is 0.65%, and titanium content is 0.09%, and iron level is 0.07%.Sulfuric acid content is 0.4% in the filtrate, and Mg content is 0.41%, and titanium content is 0.17%, and iron level is 0.23%, and phosphorus content is 87ppm.
The demagnesium rate of present embodiment is 74.05%, and the phosphorus rate of loss is 0.51%.
Embodiment 2
Ore pulp among the embodiment 1 and acid waste water are imported 10 cubical successive reaction grooves with 10 liters/minute and 30 liters of/minute inlet amounies by pipeline respectively, keep liquid level stabilizing in the reactive tank with 40 liters/minute load, stirring velocity is 100rpm, reactive tank opening for feed pH value stabilization is in the 2-2.2 interval, temperature is at 41 ℃, reactive tank discharge port pH value stabilization is in the 2.7-3.0 interval, and temperature maintenance is at 36-37 ℃.Filter cake butt P after the discharging press filtration
2O
5Content is 27.5%, and Mg content is 0.58%, and titanium content is 0.09%, and iron level is 0.08%.Acid content is 0.39% in the filtrate, and Mg content is 0.43%, and titanium content is 0.14%, and iron level is 0.23%, and phosphorus content is 75ppm.
The demagnesium rate 77.2% of present embodiment, phosphorus rate of loss 0.04%.
Embodiment 3
The filter cake after pressure filtration water content is 20% among the embodiment 1, adopt the washing of 150 liters of recirculated waters after, filter cake butt P after the press filtration
2O
5Content is 27.2%, and Mg content is 0.42%, and titanium content is 0.08%, and iron level is 0.03%.Mg content is 0.21% in the washings, and titanium content is 0.1%, and iron level is 0.22%, and phosphorus content is 12ppm.
Embodiment 4
Use lime to be neutralized to the pH value filtrate after the process press filtration among the embodiment 1 and be 9, consume lime (CaO content is 50%) 38 kilograms,, directly use the lime neutralization, will consume 123 kilograms in lime if the acid waste water among the embodiment 1 does not remove pre-treating phosphorite.
Embodiment 5
With being neutralized to pH through the filtrate behind the de-magging with liming in the example 1 is 5-6, through press filtration, gets clear liquid and continues to use sodium hydroxide to be neutralized to pH value to be 10, after its sedimentation and filtration is washed with water, to dry, receive 32 kilograms of magnesium hydroxides.
Embodiment 6
Among the embodiment 3,, carried out extractive reaction 3-4 hour with 91% concentration sulfuric acid down, consume 845 kilograms in 91% sulfuric acid, make 220g/L phosphoric acid (P behind the filtration gypsum at 90 ℃ through the filter cake behind the washing and filtering
2O
5) 873 liters, F content is 14g/L, Mg content is 0.31%.
Claims (5)
1. method of utilizing the acid waste water pre-treating phosphorite in the production process of titanium pigment is characterized in that comprising following processing step:
(1), the acid waste water in the sulfuric acid method titanium pigment Production Flow Chart is collected in the acid waste water storage tank, vitriolic quality percentage composition is 2～5% in the control acid waste water, and the quality percentage composition of total iron is 0.3～0.5%;
(2), phosphorus ore is levigate, make the ground phosphate rock more than 75% cross 100 mesh sieves, by liquid-solid ratio 2-5: 1 adds acid waste water and the good phosphorus ore of mill in the reactive tank and to react, and obtains reaction paste, and temperature of reaction is 30 ℃～50 ℃, and the reaction times is 0.5～2h;
(3), step (2) gained reaction paste is carried out solid-liquid separation, separating obtained solid phase is pretreated phosphorus ore, is used for producing of phosphoric acid by wet process; Separating obtained liquid phase is used to reclaim magnesium or send sewage works to handle.
2. the method for utilizing the acid waste water pre-treating phosphorite in the production process of titanium pigment according to claim 1 is characterized in that: the described phosphorus ore of step (2) is can be by the ground phosphate rock of 100 mesh sieves more than 90%.
3. the method for utilizing the acid waste water pre-treating phosphorite in the production process of titanium pigment according to claim 1, it is characterized in that: in the reaction process of described acid waste water of step (2) and phosphorus ore, by adding the pH value of phosphorus ore or acid waste water control reaction mixture, initial pH value is controlled at 2～3, and the pH value was controlled at 2.8～4 before reaction finished.
4. the method for utilizing the acid waste water pre-treating phosphorite in the production process of titanium pigment according to claim 1 is characterized in that: the gained solid phase is used further to producing of phosphoric acid by wet process after step (3) solid-liquid separation after washing.
5. the method for utilizing the acid waste water pre-treating phosphorite in the production process of titanium pigment according to claim 1, it is characterized in that: the liquid phase that step (3) solid-liquid separation goes out is sent neutralization precipitations such as sewage works milk of lime, sodium hydroxide, ammoniacal liquor, and endpoint pH is controlled at 7～9.
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| CN100528743C (en) * | 2005-12-29 | 2009-08-19 | 叶树滋 | Process for preparing high purity phosphoric acid-ammonium by titanium dioxide waste acid |
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