CN102674277B - Method for pre-treating phosphorus rock by mixture of titanium dioxide waste acid and fluorine-containing waste water - Google Patents
Method for pre-treating phosphorus rock by mixture of titanium dioxide waste acid and fluorine-containing waste water Download PDFInfo
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- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
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- C01B25/22—Preparation by reacting phosphate-containing material with an acid, e.g. wet process
- C01B25/222—Preparation by reacting phosphate-containing material with an acid, e.g. wet process with sulfuric acid, a mixture of acids mainly consisting of sulfuric acid or a mixture of compounds forming it in situ, e.g. a mixture of sulfur dioxide, water and oxygen
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Abstract
The invention discloses a method for pre-treating phosphorus rock by a mixture of titanium dioxide waste acid and fluorine-containing waste water. The method comprises the steps of collecting the titanium dioxide waste acid to a waste acid storage tank; controlling the concentration of sulfuric acid in the titanium dioxide waste acid to be 20-30%, and the concentration of ferrous sulfate to be 10-14%; mixing the fluorine-containing waste water and the titanium dioxide waste acid according to the mass ratio of (4-10):1 to obtain an acid solution; enabling the acid solution and the phosphorus rock to react to obtain a reaction slurry; and separating solid and liquid of the reaction slurry to obtain a solid phase, namely, pre-treated phosphorus rock. With the adoption of the method, post-treatment problem of the titanium dioxide waste acid and the fluorine-containing waste water is solved on the conditions of high magnesium removing rate and low phosphorus loss rate, so that the treatment cost is reduced; meanwhile, the problem that a pre-treatment pH value is influenced by the fluctuation of the acid concentration of the acid waste water in a process of pre-treating the phosphorus rock is solved; and the method is suitable for wet-process phosphoric acid production with different scales, is high in production efficiency and low in operation cost and is economic and practical.
Description
Technical field
The invention discloses a kind of titanium white waste acid in sulfuric acid method titanium pigment production process and by product fluoride waste of Wet-process Phosphoric Acid Production of utilizing the phosphorus ore of phosphoric acid by wet process is carried out to pretreated method, the fluoride waste that relates to spent acid processing, the phosphoric acid by wet process of titanizing work process and phosphorous chemical industry in phosphorus ore purify integrated technique, the useless circulation comprehensive of pair that belongs to titanizing work and phosphorus chemical industry utilizes technical field.
Background technology
The production method of titanium white enterprise of China overwhelming majority is sulfuric acid process, it is that ilmenite concentrate and the vitriol oil are carried out to acidolysis reaction generation intermediate titanyl sulfate, titanyl sulfate is hydrolyzed into metatitanic acid and sulfuric acid, and metatitanic acid obtains titanium dioxide product through techniques such as washing, calcining, pulverizing again.The Waste Sulfuric Acid that 1 ton of titanium dioxide of every production can produce 5-6 ton is titanium white waste acid (sulfur acid 20%-30%, ferrous sulfate 10-14%), and in follow-up washing metatitanic acid operation, can produce the acid waste water (sulfur acid 2-5%, ferrous sulfate 0.3-0.5%) of 16-25 ton.
To 20-30% titanium white waste acid, recycling has a lot of patented technologies and relevant report, and for example patent CN1966400A, by the mode of diffusion dialysis, obtains the dilute sulphuric acid of low sulfuric acid ferrous content, is used further to steel surface processing etc.; Patent CN1330562C is concentrated to after sulfuric acid 55-60% spent acid by flue gas and the concentrated mode of steam secondary, is back to titanium dioxide acid hydrolysis workshop section.Patent CN1171777C and CN101049915 utilize respectively gas-liquid separation type non-volatile solvent concentrating device and rotary kiln tail gas heat quantity to carry out concentration and recovery utilization to the diluted acid of 20% left and right.The utilization of titanium white waste acid is also useful on other industry, as produced ferrous sulfate, preparing the products such as artificial rutile, atlapulgite, manganese salt, ferromagnesium sulfate, zinc sulfate.Patent CN1274590C adopts titanium white waste acid except reacting and produce general calcium with ground phosphate rock after ferrous sulfate.Patent CN101871045B adopts titanium white waste acid production metallic zinc.But titanium white waste acid yet there are no relevant report for phosphorus ore purifying treatment.
For the processing of titanium white waste acid, conventional is to be back to titanium dioxide acid hydrolysis workshop section at present, and it need be concentrated to the reuse problem that to a certain degree could solve spent acid completely, and the concentrated expense of titanium white waste acid is higher in addition, basic suitable with the fresh vitriol oil.When titanium white waste acid reuse ratio is high, the impurity in titanyl sulfate is as vanadium, and the enrichments gradually in titanium liquid such as chromium, manganese, cause certain influence to the quality of finished product titanium dioxide, are unfavorable for producing high-grade titanium dioxide product.
Phosphate fertilizer and phosphoric acid salt industry are first produced phosphoric acid by wet process (device is commonly called as extraction tank) by phosphorus ore with sulfuric acid solution conventionally, then phosphoric acid by wet process are processed into various products.Phosphorus ore generates calcium sulfate, phosphoric acid and hydrofluoric acid in acidolysis process and sulfuric acid reaction.
The HF part that reaction generates generates SiF with the pasc reaction in phosphorus ore
4overflow, after the exhaust system water spray by phosphorous chemical industry extraction tank, become HF and SiF
4the aqueous solution.This aqueous solution is referred to as fluoride waste, fluorine content 1-5g/l in fluoride waste.
For the processing of fluoride waste generally, be in adopting two sections and press filtration mode is processed, and add the auxiliary agent such as quantitative iron, aluminium salt, it can make fluorine content reach 10mg/l.About the processing of phosphorous chemical industry fluoride waste, under existing Wet Processes of Phosphoric Acid condition, be generally to turn back to the filtering system of extraction slip as bath water.1. fluoride waste is directly as the technique of wash water, and K, Na, Ca plasma in itself and phosphoric acid generate tiny silicofluoride and Calcium Fluoride (Fluorspan) precipitation, stop up filter cloth, cause filtration capacity to decline, filter cloth fouling aggravation, and the cleaning interval shortens.2. fluoride waste neutralizes separately, and clear liquid returns to phosphorous chemical industry technique.Can avoid the impact on filtering system, but need newly-increased neutralization and filter-pressing device, fluoride waste adopts in the alkaline calcareous materials such as milk of lime and fluoride waste, generate Calcium Fluoride (Fluorspan) or calcium silicofluoride precipitation, its body refuse settling velocity is slow, and after filtering separation, filter cake liquid holdup is high, severe operational environment.3. not individual curing of fluoride waste, neutralization after fluoride waste is directly mixed with quantitative titanium dioxide acid waste water, because of fluoride waste fluorine content higher, once and press filtration, can not effectively guarantee the qualified discharge of fluorine, neutralization after fluoride waste is mixed in 1:10 ratio with acid waste water, can not make the fluorine content in discharge water reach below 10mg/l.
Sichuan Lomon Titanium Industry Co., Ltd. is in the patent CN101759166B of application on December 31st, 2009, a kind of method of utilizing the acid waste water pre-treating phosphorite in Producing Titanium Dioxide process is disclosed, it is that (controlling sulfuric acid quality percentage composition is 2-5% by acid waste water, total weight of iron percentage composition is 0.3-0.5%) be that more than 75% ground phosphate rock reacts and obtains reaction slurry in reactive tank with solid content, reaction slurry is carried out to solid-liquid separation, separating obtained solid phase is pretreated phosphorus ore, use the method to process phosphorus ore phosphorus rate of loss extremely low, demagnesium rate is high, phosphorus ore Mg content can be solved effectively high, affect the problem of Wet-process Phosphoric Acid Production, and reduced acid waste water in and expense.But acid waste water derives from the wash water in hydrolyzation material plasm scouring process, early stage, acid concentration and iron level were higher, and the later stage is lower, in whole process, the fluctuation of concentration of acid waste water is larger, from initial nearly 20% sulfuric acid concentration, during to end 0.4%, sulfuric acid concentration fluctuation greatly.In phosphorus ore preprocessing process, acid concentration fluctuation can cause the pH value in preprocessing process that larger variation occurs, and in the time that acid concentration raises suddenly, can cause the phosphorus in phosphorus ore to decompose, and affects phosphorus yield, increases the environmental protection pressure of sewage plant water treatment.Want to stablize the pH value of phosphorus ore preprocessing process, generally have two kinds of methods: one is to carry out buffered acid waste water with great storage tank, generally, need the storage tank of the flow of 6-8 hour could effectively regulate and control the water quality of acid waste water.1 ton of titanium dioxide, the amount that produces acid waste water is 40m
3, titanium dioxide hourly output, by 20 tons of calculating, needs 4800m
3storage tank, its construction costs is higher.Another kind is online operating device, by monitoring at any time the PH changing conditions in preprocessing process, carrys out the flow of adjustment of acidity waste water.Due to online PH, count the automatic control equipment price that work-ing life is shorter and relevant in pre-treatment slip higher, therefore generally use seldom in industrial application.
Titanium dioxide for certain production capacity simultaneously, the sulfuric acid amount in titanium white waste acid and the acid waste water of discharge is certain.Acid waste water pre-treating phosphorite, when quality and one timing of acid waste water concentration of phosphorus ore, treatable phosphorus ore amount has just been determined.In the time that the industrial scale of phosphoric acid by wet process is larger, acid waste water quantity not sufficient is when meeting phosphorus ore pre-treatment requirement, and the Mg content after processing in phosphorus ore is higher, and demagnesium rate is lower, and the demagnesium rate of phosphorus ore does not reach re-set target, brings negative impact to the production of phosphoric acid by wet process.
Summary of the invention
Object of the present invention is just for the deficiencies in the prior art, providing a kind of utilizes the fluoride waste in titanium white waste acid and the phosphoric acid by wet process producing in sulfuric acid method titanium pigment production process to carry out pretreated method to phosphorus ore, this pretreatment process is to reach demagnesium rate high, under the low condition of phosphorus rate of loss, solve the post-processed problem of titanium white waste acid and fluoride waste, reduce the processing cost of titanium white waste acid and fluoride waste, also solved the acid waste water impact that acid concentration fluctuates on pre-treatment pH value in pre-treating phosphorite process simultaneously, it is applicable to the Wet-process Phosphoric Acid Production of different scales, production efficiency is high, running cost is low, economical and practical.
To achieve these goals, the technical solution used in the present invention is such: a kind of method of the mixture pre-treating phosphorite that utilizes titanium white waste acid and fluoride waste, comprise by acidic solution and solid content being that more than 75% ground phosphate rock reacts and obtains reaction slurry in reactive tank, the processing step that reaction slurry is carried out to solid-liquid separation, is characterized in that: described acidic solution is made by following processing step:
(1) titanium white waste acid in sulfuric acid method titanium pigment production process is collected in spent acid storage tank, the sulfuric acid quality percentage composition of controlling titanium white waste acid is 20-30%, and the quality percentage composition of ferrous sulfate is 10-14%;
(2) fluoride waste and titanium white waste acid are mixed to get to acidic solution by the mass ratio of 4-10:1.
Wherein, the by product that the described fluoride waste of step (2) is phosphoric acid by wet process, fluorine content is 1-5g/l
The present invention utilizes the titanium white waste acid of sulfate process titanium dioxide production line output and the fluoride waste of phosphorous chemical industry to mix pre-treating phosphorite, the detrimental impurity such as calcium, magnesium in phosphorus ore is removed as far as possible, reduced the acid of sulfuric acid and consume and improve the quality of phosphoric acid by wet process after phosphorus ore acid hydrolysis.After mixing with titanium white waste acid by fluoride waste, phosphorus ore is carried out to pre-treatment, effectively reduced the content of fluorine in liquid phase, under the further neutrality condition of de-magging filtrate, the fluorine content in liquid phase can reach emission standard easily.It is equivalent to phosphorus ore pre-treatment is in a section of fluoride waste and technique, and the filtrate after de-magging is treated in two sections of fluoride waste and technique.A water part up to standard after processing is directly discharged, and a part is returned to phosphate system water as a supplement.
Pre-treating phosphorite after adopting titanium white waste acid and fluoride waste to mix, take full advantage of existing phosphorous chemical industry and titanium chemical plant installations, can effectively reduce the processing costs of titanium white waste acid and fluoride waste, pretreated phosphorus ore demagnesium rate is high, phosphorus loss is extremely low, and the sulfuric acid unit consumption of phosphorous chemical industry reduces greatly.
Sulfuric acid content 20-30% in the titanium white waste acid using in operational path of the present invention, ferrous sulfate content 10-14%; The fluoride waste of phosphorous chemical industry, fluorine content 1-5g/l.The mixed acid solution of titanium white waste acid and fluoride waste carries out with reacting at the temperature of 30-50 ℃ of phosphorus ore.Because spent acid typical temperature is between 30-50 ℃, the temperature of fluoride waste, between 40-50 ℃, adds that the spent acid heat of dilution and pretreatment reaction itself can produce a small amount of heat, so do not need extra heating.
Hydrofluoric acid in fluoride waste reacts raw Calcium Fluoride (Fluorspan) and calcium silicofluoride precipitation with the carbonate salt in silicofluoric acid (aqueous solution of silicon tetrafluoride) and phosphorus ore, effectively avoid fluoride waste processing costs and the facility investment of neutralization separately, taken full advantage of existing resource.After fluoric acid solution in phosphorus ore, enter phosphoric acid system, then remove by technology of dicalcium phosphate by wet method, all enter fertilizer grade phosphate product, can not impact follow-up phosphate product.Adopt this method, the Mg content of phosphorus ore reduces greatly on the one hand, and extraction tank vitriol oil unit consumption reduces; Avoided on the other hand fluoride waste separately in and processing and the facility investment expense of press filtration, while also having avoided filtration washing, directly adopt fluoride waste washing, the impact bringing to filtration.After fluoride waste and spent acid pre-treating phosphorite, fluorine content in fluoride waste is reduced to 80mg/l, in further de-magging filtrate neutralizing treatment process, the ferrous hydroxide that ferrous sulfate in itself and titanium white waste acid generates and ironic hydroxide produce absorption, can effectively fluorine content be reduced to below 10mg/l, thus qualified discharge and reuse.
Although the ferrous sulfate in titanium white waste acid is not participated in reaction directly, a large amount of iron ions, has promoted that sulfuric acid mainly exists with the form of hydrosulfate, avoids sulfuric acid directly to react with phosphorus ore, causes phosphorus loss.After reaction finishes, carry out liquid-solid separation, MgSO
4discharge with liquid phase Deng soluble impurity.Isolate that liquid phase is sent sewage plant or for producing magnesium compound or sending into the neutralization precipitations such as milk of lime for sewage plant, sodium hydroxide, ammoniacal liquor.Because titanium white waste acid mixes with phosphorous chemical industry fluoride waste, acidity is lower afterwards, adds that the temperature of reaction of control is also lower, the effective constituent Ca in phosphorus ore
5f (PO
4)
3can not be decomposed, therefore phosphorus loss is extremely low.
Phosphorus ore is after above-mentioned technique pre-treatment, carbonate in phosphorus ore etc. easily acidolysis impurity major part decompose in preprocessing process, in follow-up extraction tank acidolysis process, the consumption of the vitriol oil reduces, most of magnesium in preprocessing process in phosphorus ore is discharged with liquid phase, the quality of phosphorus ore is improved, and demagnesium rate of the present invention is more than 70%.Although this process can cause the phosphorus loss below 1%, compares with other phosphorus ore de-magging technique, demagnesium rate is high, phosphorus loss is low, and has effectively processed phosphorous chemical industry fluoride waste, and comprehensive cost is minimum.
The present invention, owing to using titanium white waste acid and phosphorous chemical industry fluoride waste pre-treating phosphorite, has reached the consumption of the reduction vitriol oil, improves phosphorus ore quality, reduces the object of the processing costs of titanium white waste acid and fluoride waste.Meanwhile, take full advantage of existing apparatus, saved facility investment.Technical process is simple, and useless secondary recycle, has reduced the impact on environment.Through the pretreated phosphorus ore of this technique, during for Wet-process Phosphoric Acid Production, the vitriol oil that ore deposit per ton consumes 10% left and right that declines.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.But this should be interpreted as to the scope of the above-mentioned theme of the present invention only limits to following embodiment, all technology realizing based on content of the present invention all belong to scope of the present invention.
What the present invention enumerated utilizes titanium white waste acid and fluoride waste to process the method for phosphorus ore, mainly comprises following processing step:
1) spent acid in sulfuric acid method titanium pigment production process is collected in spent acid storage tank, the sulfuric acid quality percentage composition of controlling spent acid is 20-30%, and the quality percentage composition of ferrous sulfate is 10-14%;
2) the by product fluoride waste of phosphoric acid by wet process (fluorine content 1-5g/l) is mixed by 4-6:1 mass ratio with titanium white waste acid;
3) phosphorus ore is levigate, make more than 75% ground phosphate rock cross 100 mesh sieves, in pretreatment tank, react with the phosphorus ore of milled by liquid-solid ratio 2-5:1.Temperature of reaction 30-50 ℃, the reaction times is 0.5-2h, ph value of reaction 2-4;
4) by step 3) reaction paste carry out solid-liquid separation, separating obtained solid phase is pretreated phosphorus ore, for the production of phosphoric acid by wet process, separating obtained liquid phase is used for reclaiming magnesium or send sewage plant processing.
Embodiment 1
899.59Kg fluoride waste (fluorine content 3.3g/l) and 249.89Kg titanium white waste acid (sulfuric acid concentration is 20%, ferrous sulfate content 10%) are by the phosphorus ore (P that is 65% with 1000kg solid content after tube mixer short mix
2o
5content is that 28.54%, MgO content is 2.63%, breeze 100 mesh screen residues 11%) ore pulp, input 5m by pipeline respectively
3pretreatment reaction groove, makes phosphorus ore under agitation react with titanium white waste acid, and stirring intensity is 100rpm, and the pH value of controlling reaction slurry is 2.5,44 ℃ of temperature, and material is 2h in the residence time of pretreatment tank.The slip that goes out pretreatment tank carries out solid-liquid separation and washing by pressure filter, P in filter cake butt
2o
5content 29.08%, MgO content is 0.15%.Filtrate pH value 3.0, MgO content is 0.47%, P content 51.3mg/l, F content 85mg/l.
The demagnesium rate of the present embodiment is 94.40%, and phosphorus rate of loss is 0.002%.After filtrate after de-magging and washing lotion are mixed, adopt lime slurry neutralization, discharge water P content 0.03mg/l, F content 2.87mg/l.
Embodiment 2
2024.39Kg fluoride waste (fluorine content 4.2g/l) and 303.66Kg titanium white waste acid (sulfuric acid concentration is 30%, ferrous sulfate content 14%) are by the phosphorus ore (P that is 65% with 1000kg solid content after tube mixer short mix
2o
5content is that 28.54%, MgO content is 2.63%, breeze 100 mesh screen residues 11%) ore pulp, input 5m by pipeline respectively
3pretreatment reaction groove, makes phosphorus ore under agitation react with titanium white waste acid, and stirring intensity is 100rpm, and the pH value of controlling reaction slurry is 3.0,42 ℃ of temperature, and material is 2h in the residence time of pretreatment tank.The slip that goes out pretreatment tank carries out solid-liquid separation and washing by pressure filter, P in filter cake butt
2o
5content 28.76%, MgO content is 0.47%.Filtrate pH value 3.5, MgO content is 0.45%, P content 1.1mg/l, F content 68mg/l.
The demagnesium rate of the present embodiment is 79.38%, and phosphorus rate of loss is 0.003%.After filtrate after de-magging and washing lotion are mixed, adopt lime slurry neutralization, discharge water P content 0.02mg/l, F content 2.49mg/l.
Claims (1)
1. one kind is utilized the method for the mixture pre-treating phosphorite of titanium white waste acid and fluoride waste, comprise by acidic solution and solid content being that more than 75% ground phosphate rock reacts and obtains reaction slurry in reactive tank, the processing step that reaction slurry is carried out to solid-liquid separation, is characterized in that: described acidic solution is made by following processing step:
(1) titanium white waste acid in sulfuric acid method titanium pigment production process is collected in spent acid storage tank, the sulfuric acid quality percentage composition of controlling titanium white waste acid is 20-30%, and the quality percentage composition of ferrous sulfate is 10-14%;
(2) fluoride waste and titanium white waste acid are mixed to get to acidic solution by the mass ratio of 4-10:1;
The by product that described in step (2), fluoride waste is phosphoric acid by wet process, fluorine content is 1-5g/l.
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| CN201210165209.4A CN102674277B (en) | 2012-05-25 | 2012-05-25 | Method for pre-treating phosphorus rock by mixture of titanium dioxide waste acid and fluorine-containing waste water |
| PCT/CN2012/078206 WO2013174062A1 (en) | 2012-05-25 | 2012-07-05 | Method for pre-treating phosphorus rock by mixture of titanium dioxide waste acid and fluorine-containing waste water |
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| CN104108814B (en) * | 2014-07-22 | 2016-03-30 | 四川龙蟒钛业股份有限公司 | A kind of method processing Rutile type Titanium Dioxide waste water |
| CN104129816B (en) * | 2014-07-31 | 2016-03-30 | 襄阳龙蟒钛业有限公司 | The method of a kind of titanium white gelled acid deironing |
| CN104876198B (en) * | 2015-05-12 | 2016-10-05 | 贵州开磷集团股份有限公司 | A kind of prodan produces and phosphorus ore de-magging combination treatment method |
| CN105536492B (en) * | 2015-12-25 | 2019-03-08 | 昆明尔康科技有限公司 | A kind of method that ammonium fluoride waste water prepares phosphate ore pulp desulfurizing agent |
| CN107021466B (en) * | 2017-04-24 | 2019-08-02 | 四川龙蟒钛业股份有限公司 | Sulfuric acid method titanium pigment acid waste water is used for the pretreated closed circulation process of phosphorus ore |
| CN107128890B (en) * | 2017-06-20 | 2019-08-27 | 四川龙蟒磷化工有限公司 | Titanium white waste acid is used for the closed circulation process of phosphorus ore de-magging |
| CN109573972B (en) * | 2019-01-23 | 2021-05-28 | 山东鲁北企业集团总公司 | Method for producing phosphoric acid and low-silicon gypsum from medium-low grade phosphorite |
| CN115283422B (en) * | 2022-07-21 | 2023-10-31 | 上海市政工程设计研究总院（集团）有限公司 | Treatment method of glass etching waste residues |
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| CN101759166A (en) * | 2009-12-31 | 2010-06-30 | 四川龙蟒钛业股份有限公司 | Method for pre-treating phosphorite by using acidic waste water in the production process of titanium pigment |
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| US4178347A (en) * | 1978-05-17 | 1979-12-11 | Olin Corporation | Process for the simultaneous production of wet process phosphoric acid and sodium silicofluoride |
| US4402923A (en) * | 1980-10-20 | 1983-09-06 | Davy Mckee Corporation | Process for making phosphoric acid |
| CN1376635A (en) * | 2002-05-09 | 2002-10-30 | 四川龙蟒集团有限责任公司 | Process for preparing phosphoric acid from waste sulfuric acid as by-product of titanium oxide powder by wet method |
| CN100528743C (en) * | 2005-12-29 | 2009-08-19 | 叶树滋 | Process for preparing high purity phosphoric acid-ammonium by titanium dioxide waste acid |
| CN101774557A (en) * | 2010-02-21 | 2010-07-14 | 安徽安纳达钛业股份有限公司 | Method for producing phosphoric acid with titanium white waste |
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