CN109795997A - A kind of improved method preparing high-purity phosphoric acid iron using the slag of phosphatization containing zinc - Google Patents
A kind of improved method preparing high-purity phosphoric acid iron using the slag of phosphatization containing zinc Download PDFInfo
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Abstract
The present invention discloses a kind of improved method for preparing high-purity phosphoric acid iron using phosphatization slag for raw material.The present invention first carries out alkali leaching to the slag of phosphatization containing zinc with strong base solution, removes most of trbasic zinc phosphate, complex Zn2Fe(PO4)2And other impurity metallic elements, obtain the sodium radio-phosphate,P-32 solution containing micro zinc ion；PH value of solution is adjusted with diluted acid again, is then extracted with dithizone, further removes zinc ion；Raffinate and ferric nitrate are finally added in the aqueous solution containing surfactant, with the pH monitoring charging terminal of reaction solution, after metathesis reaction is complete, filters drying to get high-purity phosphoric acid iron.The present invention can prepare high-purity phosphoric acid iron by the slag of phosphatization containing zinc by leaching, extraction, the operation of three step of metathesis reaction, not only simplification of flowsheet and reduction production cost and energy consumption, and the discharge and processing of pickling waste waters and adsorbent solids waste are avoided, make to produce more environmentally-friendly, economical.In addition, also improving the overall recovery of phosphate radical.
Description
Invention field
The invention belongs to chemical industry and environmental protection, and in particular to a kind of to prepare changing for high-purity phosphoric acid iron using the slag of phosphatization containing zinc
Into method.
Background technique
Since the steel corrosion accident of initiations such as get rusty occurs often, so phosphorization technology obtains in Iron and Steel Enterprises in China
It is widely applied.Metal forms one layer of phosphating coat on surface by parkerizing process, and phosphating coat has obstructed oxygen and water and gold
Belong to contact, effectively reduces corrosion of metal effect.In parkerizing process, except metal surface formed one layer of phosphating coat in addition to, together
When also generate a large amount of ferric phosphate and other metal ions (such as: zinc, nickel) insoluble phosphate precipitated in phosphating solution and
It is precipitated.Therefore, parkerizing process, which can generate, largely contains FePO4And Zn3(PO4) 2And Zn2Fe(PO4)2Etc. solid wastes phosphatization slag.Its
In, for Fe in phosphatization slag3+And PO4 3-Recycling become processing phosphatization slag main path.
Currently, utilizing the PO recycled from phosphatization slag4 3-The technique for preparing ferric phosphate is more, Chinese invention
CN107720715A discloses a kind of method for preparing battery ferric phosphate using phosphatization slag for raw material.The method uses dust technology pair
Phosphatization slag carries out pre- elution processing, to remove wherein a small amount of impurity metallic elements and part zinc ion, then is made with the leaching of NaOH alkali
Wherein Fe3+And with Zn2Fe(PO4)2Zn existing for form2+It is precipitated, filters to obtain Na3PO4Solution, then with activated carbon to molten
Liquid is adsorbed and is decolourized, then makes the Zn in solution with N235 or P204/P507 solvent extraction2+It is separated, adjusts raffinate pH
Source of iron solution reaction is added afterwards and obtains ferric phosphate.The method contains pickling, alkali leaching, adsorption bleaching, extraction and precipitation reaction etc. 5 steps
Suddenly, the preferable ferric phosphate of quality, but its insufficient major embodiment can be obtained are as follows: first is that process route is long, complicated for operation, material disappears
It consumes more, loss greatly, causes equipment investment and production cost higher；It gives up second is that the processes such as pickling, decoloration can generate more diluted acid
Water and adsorbent solids waste, production technology environment is unfriendly, three-protection design higher cost；Third is that in leaching liquid zinc impurities it is de-
Except in the process, extractant and solvent usage is big, extraction efficiency is low, single-stage extraction efficiency only has about 11%, causes solvent recovery mistake
Journey energy consumption is high, loss is big and the increase of production cost.Chinese invention CN106315535A discloses a kind of from the useless phosphatization of iron content zinc
The method of slag preparation pure ferric phosphate.The method first uses phosphoric acid,diluted washing to the Zn in phosphatization slag2+Impurity carries out partial removal, then
Using dilute hydrochloric acid make phosphatization slag dissolve, solution through ammonium hydroxide be complexed remove part zinc ion, then with phosphoric acid ester or it is amine extracted into
Micro iron ion and zinc ion in one-step removal solution, obtain raffinate and ferric chloride reaction generates phosphoric acid iron product.The method
Due to using phosphoric acid,diluted washing can only remove part in phosphatization slag containing zinc impurity, waste residue its solution after dissolving with hydrochloric acid again
In Zn content it is still higher, to considerably increase subsequent except Zn2+When extractant dosage；Simultaneously as P204/P507 is extracted
Zn2+When extractant and solvent usage is big, extraction efficiency is lower so that in product zinc ion content be still difficult to reach 50ppm hereinafter,
Product is not able to satisfy the quality criteria requirements of battery-grade iron phosphate；In addition, the technique is since step is more, production cost also compared with
It is high.
To sum up, there is also obvious deficiencies for prior art, it is therefore necessary to be improved above-mentioned technique.
Summary of the invention
To solve the deficiencies in the prior art, the present invention provides a kind of improvement that high-purity phosphoric acid iron is prepared using the slag of phosphatization containing zinc
Method.
The technical solution of the present invention is as follows:
A kind of improved method preparing high-purity phosphoric acid iron using the slag of phosphatization containing zinc, first soaks phosphatization slag using strong base solution
It takes, insoluble phosphate therein is made to carry out metathesis reaction with hydroxyl, generate hydroxide precipitating, filter to obtain its filtrate,
It is extracted with its pH of diluted acid tune to a certain range, then with dithizone, removes the trace zinc in solution further, is separated
Raffinate out is added source of iron solution reaction by certain ferrophosphorus ratio in raffinate and obtains high-purity phosphoric acid iron；Specifically include following step
It is rapid:
1. alkali soaks: strong base solution is added into phosphatization slag, carries out alkali leaching under agitation, then suspension is filtered,
Filtrate is collected in washing；
2. extraction: diluted acid is added dropwise into step 1. gained filtrate and adjusts its pH value, the organic solvent containing extractant is then added and stirs
It is extracted under the conditions of mixing, separates to obtain raffinate；
3. metathesis reaction: under stirring condition, raffinate and source of iron solution are added dropwise in the aqueous solution containing surfactant,
With the pH monitoring charging terminal of reaction solution, continues stirring and complete metathesis reaction, then filtered, washed, dried, obtained high-purity
Phosphoric acid iron product.
Further, step 1. in, strong base solution is NaOH solution；Mass concentration is 10 ~ 35%, preferably 20 ~ 30%；Highly basic
It is 1.0/(3.0 ~ 3.5 that the dosage of solution, which meets iron in phosphatization slag/alkali molar ratio).
Further, step 1. in, alkali soak the time be 60 ~ 180min, preferably 90 ~ 150min；It is 30 ~ 70 that alkali, which soaks temperature,
DEG C, preferably 45 ~ 55 DEG C.
Further, step 2. in, the diluted acid of dropwise addition is one kind or their mixed liquor of phosphoric acid,diluted or dust technology, diluted acid
Mass concentration be 0.5 ~ 5.0%, preferably 1. 0 ~ 2.5%；The pH for adjusting reaction solution is 6.0 ~ 8.0, preferably 6.8 ~ 7.5.
Further, step 2. in, extractant is dithizone；Extractant concentration be 0.2 ~ 2.0g/L, preferably 0.6 ~ 1.0
g/L；Solvent quantity is 1 ~ 4 times, preferably 2 ~ 3 times of zinc ion molar content in filtrate.
Further, step 2. in, one or both of the preferred chloroform of organic solvent or carbon tetrachloride, more preferably
For chloroform.
Further, step 2. in, extraction time be 5 ~ 60min, preferably 10 ~ 30min；Speed of agitator be 100 ~
500rpm, preferably 350 ~ 450rpm.
Further, step 3. in, the preferred neopelex of surfactant；The dosage of surfactant is multiple
The 0.02 ~ 0.20% of decomposition reaction solution quality, preferably 0.1 ~ 0.15%.
Further, step 3. in, the preferred iron nitrate solution of source of iron solution, mass concentration be 10 ~ 30%, preferably 15 ~
25%；The dosage of ferric nitrate is PO in raffinate4 3-0.60 ~ 1.0 times of molal quantity, preferably 0.75 ~ 0.85 times.
Further, step 3. in, the pH value of the terminal that feeds is 2.0 ~ 3.0；Continuing the temperature being stirred to react is 30 ~ 80
DEG C, preferably 40 ~ 50 DEG C；Time is 90 ~ 180min, preferably 100 ~ 120min；Speed of agitator be 60 ~ 150rpm, preferably 90 ~
120rpm。
Further, step 3. in, raffinate and source of iron solution are added dropwise simultaneously.
Using phosphoric acid iron product obtained by the above method, quality can reach " battery ferric phosphate (HG/T 4701-
2014) " standard requirements, and the overall recovery of phosphate radical can be up to 90% or more in phosphatization slag.
The beneficial effects of the present invention are:
The present invention improves technique on the basis of CN107720715A, generation pickling waste waters longer for original process process
The five-step approaches such as the pickling of original process, alkali leaching, adsorption bleaching, extraction and precipitation reaction are prepared ferric phosphate and improved by the problems such as more
For leaching, extraction, metathesis reaction three-step approach, process flow is shortened, reduces equipment investment and material consumption, energy consumption；By suitable
The suitable control of condition and the selection of Suitable agents, realize the cancellation of pickling and adsorption bleaching craft unit, not only eliminate acid
The generation and emission treatment for washing waste water and adsorbent solids waste, make to produce more environmentally-friendly, economical, and improve phosphatization slag
The overall recovery of middle phosphate radical can be up to 90% or more, while zinc can be almost substantially completely removed.
The present invention has done biggish improvement to technique, technique is optimized by the reasonable disposition of technique, especially in phosphoric acid
Sodium solution removes Zn2+In purification process, Zn will be removed in original process2+Extractant is changed to dithizone by P204/P507, extracts molten
Agent replaces with chloroform or carbon tetrachloride by kerosene equal solvent, significantly improves it to Zn2+Effect of extracting, Zn2+Single-stage
Extraction efficiency reaches 25% or more, while guaranteeing product quality, significantly reduces the dosage of organic solvent, hence it is evident that saves
Production cost and energy consumption；The agent of dithizone solid phase extraction is used simultaneously, and use is safer than primary liquid extractant, solvent
Recycle simpler convenience.
In short, improved method of the invention has, process flow is simple, equipment investment is few, product quality is high, production cost
The features such as low, production process safety and environmental protection, the recycling of phosphate radical is high-efficient in phosphatization slag, be the utilization being worthy to be popularized
The slag of phosphatization containing zinc prepares the new technology path of high-purity phosphoric acid iron.
Specific embodiment
The present invention is described in detail by following embodiment, but the present invention is not limited thereto.
Embodiment 1
It takes 10.0 g phosphatization slags to be placed in a beaker, a small amount of water wetting is added thereto, in 80rpm speed of agitator and 50 DEG C of temperature
Under, the NaOH solution that 20mL mass fraction is 20%, heating stirring and the reaction was continued 180min is added dropwise, suspension through being filtered by vacuum,
Filtrate is obtained, with phosphoric acid tune filtrate pH to 7.0.Dithizone-chloroform organic liquor that mass concentration is 0.6g/L is prepared, is taken
In the clear filtrate that it is 7.0 to pH that the 20mL organic liquor, which is added, 15min is stirred under 350rpm revolving speed, is stood 6min separation, is obtained
To extract liquor and raffinate, the dilute sulfuric acid that resulting extract liquor mass concentration is 10% is stripped, the extractant of recycling repeats to use
In extraction process.Claim the Fe(NO3)39H2O [Fe (NO of 14.5g3) 3·9H2O] it is configured to the iron nitrate solution of 95 mL, it weighs
The dissolution of 20mL water is added in the neopelex of 0.06g, at 100rpm stirring and 50 DEG C, in neopelex
Iron nitrate solution and raffinate is added dropwise simultaneously in aqueous solution, drops to charging when reacting liquid pH value is 3.0 and finishes, continue to be stirred to react
Suspension is filtered, washing, obtains filter residue by 120min, dry the 8.2g high-purity phosphoric acid iron at 120 DEG C.Sample analysis is taken, is calculated
The overall recovery for obtaining phosphate radical in phosphatization slag is 87.8%, and Zn content is 32.02ppm in product.Zinc is total entire technical process
Removal efficiency reaches 99.48%, and zinc reaches 31.44% in the single-stage removal efficiency of extraction process.
Embodiment 2
It takes 10.0 g phosphatization slags to be placed in a beaker, a small amount of water wetting is added thereto, in 80rpm speed of agitator and 50 DEG C of temperature
Under, the NaOH solution that 20mL mass fraction is 20% is added dropwise, heating stirring reacts 180min, and suspension must be filtered through being filtered by vacuum
Liquid, with phosphoric acid tune filtrate pH to 7.0.Dithizone-carbon tetrachloride organic liquor that mass concentration is 0.6g/L is prepared, takes 10mL should
In the clear filtrate that it is 7.0 to pH that organic liquor, which is added, 15min is stirred under 450rpm revolving speed, is stood 6min separation, is extracted
The dilute sulfuric acid that resulting extract liquor mass concentration is 10% is stripped by liquid and raffinate, and the extractant of recycling is recycled and reused for extracting
Process.Claim the Fe(NO3)39H2O [Fe (NO of 15.0g3) 3·9H2O] it is configured to the iron nitrate solution of 100mL, weigh 0.1g's
Neopelex adds 30mL water to dissolve, at 150rpm stirring and 50 DEG C, in sodium dodecyl benzene sulfonate aqueous solution
Iron nitrate solution and raffinate is added dropwise simultaneously, drops to charging when reacting liquid pH value is 2.0 and finishes, continue to be stirred to react 120min,
Suspension is filtered, washing, obtains filter residue dry 8.5g high-purity phosphoric acid iron at 120 DEG C.Calculate to obtain phosphate radical in phosphatization slag
Overall recovery is 89.3%, Zn content 20.75ppm in product.Zinc reaches 99.47% in total removal efficiency of entire technical process, zinc
Reach 25.77% in the single-stage removal efficiency of extraction process.
Embodiment 3
It takes 25 g phosphatization slags to be placed in a beaker, a small amount of water wetting is added thereto, at a temperature of 120rpm speed of agitator and 60 DEG C,
The NaOH solution that 50mL mass fraction is 23% is added dropwise, heating stirring reacts 210min, and suspension is filtered by vacuum, and obtains filtrate, uses
Phosphoric acid tune filtrate pH to 7.25 prepares dithizone-chloroform organic liquor that mass concentration is 0.8g/L, and taking 20mL, this is organic
In the clear filtrate that it is 7.25 to pH that liquid, which is added, 20min is stirred under 550rpm revolving speed, is stood 10min separation, is obtained extract liquor
And raffinate, it repeats the extraction process one time.The dilute sulfuric acid that resulting extract liquor mass concentration is 10% is stripped, recycling
Extractant is recycled and reused for extraction process.Claim the Fe(NO3)39H2O [Fe (NO of 35.5g3) 3·9H2O] it is configured to the nitre of 180 mL
Sour ferrous solution, the neopelex for weighing 0.3g add 50mL water to dissolve, at 200rpm stirring and 40 DEG C, in dodecane
Iron nitrate solution and raffinate is added dropwise simultaneously in base benzene sulfonate aqueous solution, drops to charging when reacting liquid pH value is 2.5 and finishes, after
It is continuous to be stirred to react 150min, suspension is filtered, washing, obtains filter residue dry 21.5g high-purity phosphoric acid iron at 120 DEG C.It calculates
The overall recovery for obtaining phosphate radical in phosphatization slag is 91.21%, and Zn content is 24.46ppm in product.Zinc is in entire technical process
Total removal efficiency reaches 99.49%, and zinc reaches 44.17% in the single-stage removal efficiency of extraction process.
Claims (10)
1. a kind of improved method for preparing high-purity phosphoric acid iron using phosphatization slag for raw material, which is characterized in that soak, extract including alkali,
Metathesis reaction specifically comprises the following steps:
1. alkali soaks: strong base solution is added into phosphatization slag, carries out alkali leaching under agitation, then suspension is filtered,
Filtrate is collected in washing；
2. extraction: diluted acid is added dropwise into step 1. gained filtrate and adjusts its pH value, the organic solvent containing extractant is then added and stirs
It is extracted under the conditions of mixing, separates to obtain raffinate；
3. metathesis reaction: under stirring condition, raffinate and source of iron solution are added dropwise in the aqueous solution containing surfactant,
With the pH monitoring charging terminal of reaction solution, continues stirring and complete metathesis reaction, then filtered, washed, dried, obtained high-purity
Phosphoric acid iron product.
2. the improved method according to claim 1 for preparing high-purity phosphoric acid iron using phosphatization slag for raw material, which is characterized in that
Step 1. in, strong base solution is NaOH solution, and mass concentration is 10 ~ 35%, and dosage meets iron in phosphatization slag/alkali molar ratio
For 1.0/(3.0 ~ 3.5).
3. the improved method according to claim 1 for preparing high-purity phosphoric acid iron using phosphatization slag for raw material, which is characterized in that
Step 1. in, alkali soak the time be 60 ~ 180min；It is 30 ~ 70 DEG C that alkali, which soaks temperature,.
4. the improved method according to claim 1 for preparing high-purity phosphoric acid iron using phosphatization slag for raw material, which is characterized in that
Step 2. in, the diluted acid of dropwise addition is one kind or their mixed liquor of phosphoric acid,diluted or dust technology, the mass concentration of diluted acid is 0.5 ~
5.0%；The pH for adjusting reaction solution is 6.0 ~ 8.0.
5. the improved method according to claim 1 for preparing high-purity phosphoric acid iron using phosphatization slag for raw material, which is characterized in that
Step 2. in, the extractant be dithizone, extractant concentration be 0.2 ~ 2.0g/L, Solvent quantity be filtrate in zinc from
1 ~ 4 times of sub- molar content.
6. the improved method according to claim 1 for preparing high-purity phosphoric acid iron using phosphatization slag for raw material, which is characterized in that
Step 2. in, organic solvent be one or both of chloroform or carbon tetrachloride.
7. the improved method according to claim 1 for preparing high-purity phosphoric acid iron using phosphatization slag for raw material, which is characterized in that
Step 2. in, extraction time be 5 ~ 60min；Speed of agitator is 100 ~ 500rpm.
8. the improved method according to claim 1 for preparing high-purity phosphoric acid iron using phosphatization slag for raw material, which is characterized in that
Step 3. in, surfactant is neopelex；The dosage of surfactant is metathesis reaction solution quality
0.02~0.20%。
9. the improved method according to claim 1 for preparing high-purity phosphoric acid iron using phosphatization slag for raw material, which is characterized in that
Step 3. in, source of iron solution be iron nitrate solution, mass concentration be 10 ~ 30%；The dosage of ferric nitrate is PO in raffinate4 3-It rubs
0.60 ~ 1.0 times of that number；Raffinate and source of iron solution are added dropwise simultaneously.
10. the improved method according to claim 1 for preparing high-purity phosphoric acid iron using phosphatization slag for raw material, feature exist
In, step 3. in, the pH value for the terminal that feeds is 2.0 ~ 3.0；Continue the temperature being stirred to react be 30 ~ 80 DEG C, the time be 90 ~
180min；Speed of agitator is 60 ~ 150rpm.
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Cited By (2)
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| CN112938920A (en) * | 2021-03-30 | 2021-06-11 | 生态环境部南京环境科学研究所 | Method and device for preparing industrial zinc phosphate and iron phosphate by using zinc-containing waste hydrochloric acid |
| CN117427618A (en) * | 2023-12-20 | 2024-01-23 | 中国农业大学 | Chitosan modified yellow phosphorus slag-bentonite composite material and preparation method and application thereof |
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Application publication date: 20190524 |