CN105253869A - Method used for reducing fluorine content of by-products in wet phosphoric acid preparation processes - Google Patents
Method used for reducing fluorine content of by-products in wet phosphoric acid preparation processes Download PDFInfo
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Abstract
The invention discloses a method used for reducing fluorine content of by-products in wet phosphoric acid preparation processes, and belongs to the field of phosphoric acid preparation. The method comprises following steps: rock phosphate is smashed, and oxalic acid and succinic acid are added; preliminary removing of hydrofluoric acid is carried out via aeration and pressure reduction; a sodium salt and active SiO2 are added to obtained a precipitate, and an obtained solution is filtered; urea is added into obtained raw phosphoric acid so as to obtain a composite phosphate salt; and phosphoric acid is purified via crystallization so as to obtain a high purity phosphoric acid solution. Fluorine purity content of phosphoric acid products obtained via crystallization is low; purity is high; no pollution is caused; the method is simple; cost is low; and development and application value is high.
Description
Technical field
The invention discloses a kind of method that wet-layer preparation process phosphoric acid reduces Oil repellent in by product, belong to phosphoric acid production field.
Background technology
Phosphoric acid is one of the most basic chemical substance, be widely used in medical treatment, food, water treatment, chemistry and electron trade, therefore be in great demand, the phosphoric acid that above-mentioned industry needs impurity level few, the output of current phosphoric acid by wet process has accounted for 85% ~ 90% of phosphoric acid ultimate production.The overall throughput 2003 of China's phosphoric acid by wet process is large
Be about 7,400,000 tons of P
2o
5, output is 4,640,000 tons of P
2o
5.Phosphoric acid by wet process is the important intermediates of phosphorous chemical industry, always for the production of double superhosphate, ammonium phosphate, compound manure etc., but because raw material and process characteristic cause them impure many, mainly containing phosphoric acid salt such as aluminium, iron, magnesium, silicofluoride and free sulfuric acid etc.Because phosphoric acid by wet process needs separating impurity at a low viscosity, therefore product acid concentration is lower.For the phosphatic requirement making the quality of phosphoric acid meet manufacture level, feed grade, even food grade, must carry out purifying and concentrate.Along with the aggravation of energy dilemma, deep purifying is carried out to phosphoric acid by wet process and seems day by day urgent to replace thermal phosphoric acid.
Wet phosphoric acid purifying method presses its qualitative classification, mainly: solvent extraction purification method, ion-exchange-resin process and dialysis, the chemical precipitation method of purification and purging by crystallization method.In purging by crystallization, can be divided into two classes, a class is the method for purification of its melting temperature direct crystallization of high concentration phosphorus acid-utilising, and another kind of is generate complex salt crystal method.Crystallisation by cooling method refers to that phosphoric acid out, then isolates crystal to reach the method for purification of wet process phosphoric acid with form precipitating from solution of hemihydrate or phosphoric acid salt from solution.Crystallization process purifying phosphoric acid is adopted to have the advantages such as product purity is high, concentration is high, energy consumption is low, pollution-free.In crystallisation process, add additive change the proportioning of impurity in crystal and crystalline mother solution, can change the effect of purging by crystallization, therefore crystallization process purifying phosphoric acid obtains general application.
Summary of the invention
The technical problem that the present invention mainly solves: the phosphoric acid gone out for current wet-layer preparation is impure many, main based on Oil repellent, have a strong impact on the drawback of phosphoric acid application, provide a kind of method that wet-layer preparation process phosphoric acid reduces Oil repellent in by product, the present invention's Rock Phosphate (72Min BPL) adds oxalic acid and succsinic acid after pulverizing, utilize aeration and decompression technique first tentatively to remove hydrofluoric acid, then add sodium salt and active SiO
2produce sedimentation and filtration, in raw phosphoric acid, add urea production phosphoric acid composite salt afterwards utilize crystallization process purifying phosphoric acid, obtain the phosphoric acid solution that purity is high, the phosphoric acid product fluorine-containing impurity that the present invention's crystallization process purifies is few, purity is high, pollution-free, and production technique is simple, cost is low, has development and application values widely.
In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is:
Wet-layer preparation process phosphoric acid reduces a method for Oil repellent in by product, it is characterized in that concrete preparation process is:
(1) Rock Phosphate (72Min BPL) of 2 ~ 3kg is first chosen, put into micronizer mill and be ground into the uniform small particles that particle diameter is 10 ~ 20 μm, Rock Phosphate (72Min BPL) particle after pulverizing is put into the beaker of 5L, by 0.2mol/L oxalic acid solution and massfraction 10% succinic acid solution, be added in the beaker of phosphorus-containing ore particle after 1:1 mixing by volume, and exceed Rock Phosphate (72Min BPL) particle surface 6 ~ 8cm, finally material in beaker is uniformly mixed;
(2) be filled with air at the below aeration blower of above-mentioned beaker, carry out aeration, aeration time is 30 ~ 60min, installs reliever of bleeding, be decompressed to-0.05 ~-0.07Mpa while aeration above beaker;
(3) first the mixing solutions in above-mentioned beaker is carried out centrifugation, obtain supernatant liquor, get the Na that mass ratio is 1:5
2cO
3with active SiO
2add respectively in clear liquid, after stirring 5 ~ 6min, the throw out produced is filtered and remove, get filtrate;
(4) the above-mentioned filtrate of getting 200 ~ 300mL puts into the there-necked flask of 500mL, be 9 ~ 10 by the pH value of the ammoniacal liquor regulates liquid of massfraction 20 ~ 30%, then there-necked flask is put into water bath with thermostatic control, the temperature in water-bath is kept to be at 40 ~ 50 DEG C, urea is added by urea and filtrate solid-liquid mass ratio 1:1, stir with magnetic stirring apparatus simultaneously, stirring velocity 400 ~ 500r/min, isothermal reaction 10 ~ 30min under stirring environment, backward solution in add the Sodium dodecylbenzene sulfonate of 3 ~ 4g, after stirring 5 ~ 10min, water bath with thermostatic control is reduced to 10 ~ 15 DEG C, and leave standstill solution 5 ~ 10min,
(5) solution after above-mentioned leaving standstill is carried out suction filtration with Bush's funnel, the crystal in funnel is taken out after suction filtration, and crystal dehydrated alcohol is cleaned 4 ~ 6 times repeatedly, then the crystal after abundant washing is added in the beaker of 500mL, then to the HNO adding mass concentration 65 ~ 70% in cup
3solution solid-liquid mass ratio is 1:1, and carries out stirring solid, liquid is fully mixed, and filters, obtain filtrate and be the high phosphoric acid solution of purity after stirring 20 ~ 30min.
Application method of the present invention: phosphoric acid the present invention prepared can be made phosphoric acid salt application food aspect or make water quality stabilizer and be applied in water treatment, survey by fluoride ion selective electrode method and prepare Oil repellent in phosphoric acid, survey 4 ~ 6 times, finally recording Oil repellent is 0.001 ~ 0.003%.
The invention has the beneficial effects as follows:
(1) the phosphoric acid product fluorine-containing impurity that purifies of the present invention's crystallization process is few, and purity is high and pollution-free;
(2) technique of wet-layer preparation phosphoric acid of the present invention is simple, and cost is low, has development and application values widely.
Embodiment
First the Rock Phosphate (72Min BPL) of 2 ~ 3kg is chosen, put into micronizer mill and be ground into the uniform small particles that particle diameter is 10 ~ 20 μm, Rock Phosphate (72Min BPL) particle after pulverizing is put into the beaker of 5L, by 0.2mol/L oxalic acid solution and massfraction 10% succinic acid solution, be added in the beaker of phosphorus-containing ore particle after 1:1 mixing by volume, and exceed Rock Phosphate (72Min BPL) particle surface 6 ~ 8cm, finally material in beaker is uniformly mixed, be filled with air at the below aeration blower of beaker, carry out aeration, aeration time is 30 ~ 60min, installs reliever of bleeding, be decompressed to-0.05 ~-0.07Mpa while aeration above beaker, first the mixing solutions in beaker is carried out centrifugation, obtain supernatant liquor, get the Na that mass ratio is 1:5
2cO
3with active SiO
2add respectively in clear liquid, after stirring 5 ~ 6min, the throw out produced is filtered and remove, get filtrate, the above-mentioned filtrate of getting 200 ~ 300mL puts into the there-necked flask of 500mL, be 9 ~ 10 by the pH value of the ammoniacal liquor regulates liquid of massfraction 20 ~ 30%, then there-necked flask is put into water bath with thermostatic control, the temperature in water-bath is kept to be at 40 ~ 50 DEG C, urea is added by urea and filtrate solid-liquid mass ratio 1:1, stir with magnetic stirring apparatus simultaneously, stirring velocity 400 ~ 500r/min, isothermal reaction 10 ~ 30min under stirring environment, backward solution in add the Sodium dodecylbenzene sulfonate of 3 ~ 4g, after stirring 5 ~ 10min, water bath with thermostatic control is reduced to 10 ~ 15 DEG C, and leave standstill solution 5 ~ 10min, solution after leaving standstill is carried out suction filtration with Bush's funnel, the crystal in funnel is taken out after suction filtration, and crystal dehydrated alcohol is cleaned 4 ~ 6 times repeatedly, then by fully washing after crystal add in the beaker of 500mL, again to being 1:1 with the HNO3 solution solid-liquid mass ratio adding mass concentration 65 ~ 70% in cup, and carry out stirring solid, liquid is fully mixed, filter after stirring 20 ~ 30min, obtain filtrate and be the high phosphoric acid solution of purity.
Application method of the present invention: phosphoric acid the present invention prepared can be widely applied in chemistry and electron trade, and survey Oil repellent in its phosphoric acid by fluoride ion selective electrode method, survey 4 ~ 6 times, finally recording Oil repellent is 0.001 ~ 0.003%.
Example 1
First the Rock Phosphate (72Min BPL) of 2kg is chosen, put into micronizer mill and be ground into the uniform small particles that particle diameter is 10 μm, Rock Phosphate (72Min BPL) particle after pulverizing is put into the beaker of 5L, by 0.2mol/L oxalic acid solution and massfraction 10% succinic acid solution, be added in the beaker of phosphorus-containing ore particle after 1:1 mixing by volume, and exceed Rock Phosphate (72Min BPL) particle surface 6cm, finally material in beaker is uniformly mixed; Be filled with air at the below aeration blower of beaker, carry out aeration, aeration time is 30min, installs reliever of bleeding, be decompressed to-0.05Mpa while aeration above beaker; First the mixing solutions in beaker is carried out centrifugation, obtain supernatant liquor, get the Na that mass ratio is 1:5
2cO
3with active SiO
2add respectively in clear liquid, after stirring 5min, the throw out produced is filtered and remove, get filtrate; The above-mentioned filtrate of getting 200mL puts into the there-necked flask of 500mL, be 9 by the pH value of the ammoniacal liquor regulates liquid of massfraction 20%, then there-necked flask is put into water bath with thermostatic control, the temperature in water-bath is kept to be at 40 DEG C, urea is added by urea and filtrate solid-liquid mass ratio 1:1, stir with magnetic stirring apparatus simultaneously, stirring velocity 400r/min, isothermal reaction 10min under stirring environment, backward solution in add the Sodium dodecylbenzene sulfonate of 3g, after stirring 5min, water bath with thermostatic control is reduced to 10 DEG C, and leaves standstill solution 5min; Solution after leaving standstill is carried out suction filtration with Bush's funnel, takes out the crystal in funnel after suction filtration, and crystal dehydrated alcohol is cleaned 4 times repeatedly, then the crystal after abundant washing is added in the beaker of 500mL, then to the HNO adding mass concentration 65% in cup
3solution solid-liquid mass ratio is 1:1, and carries out stirring solid, liquid is fully mixed, and filters, obtain filtrate and be the high phosphoric acid solution of purity after stirring 20min.
The phosphoric acid product fluorine-containing impurity that the present invention's crystallization process purifies is few, purity is high and pollution-free, phosphoric acid the present invention prepared is made phosphoric acid salt application food aspect or is made water quality stabilizer and is applied in water treatment, Oil repellent in its phosphoric acid is surveyed by fluoride ion selective electrode method, survey 4 times, finally recording Oil repellent is 0.001%.
Example 2
First the Rock Phosphate (72Min BPL) of 2.5kg is chosen, put into micronizer mill and be ground into the uniform small particles that particle diameter is 15 μm, Rock Phosphate (72Min BPL) particle after pulverizing is put into the beaker of 5L, by 0.2mol/L oxalic acid solution and massfraction 10% succinic acid solution, be added in the beaker of phosphorus-containing ore particle after 1:1 mixing by volume, and exceed Rock Phosphate (72Min BPL) particle surface 7cm, finally material in beaker is uniformly mixed; Be filled with air at the below aeration blower of beaker, carry out aeration, aeration time is 45min, installs reliever of bleeding, be decompressed to-0.06Mpa while aeration above beaker; First the mixing solutions in beaker is carried out centrifugation, obtain supernatant liquor, get the Na that mass ratio is 1:5
2cO
3with active SiO
2add respectively in clear liquid, after stirring min, the throw out produced is filtered and remove, get filtrate; The above-mentioned filtrate of getting 250mL puts into the there-necked flask of 500mL, be 9 by the pH value of the ammoniacal liquor regulates liquid of massfraction 25%, then there-necked flask is put into water bath with thermostatic control, the temperature in water-bath is kept to be at 45 DEG C, urea is added by urea and filtrate solid-liquid mass ratio 1:1, stir with magnetic stirring apparatus simultaneously, stirring velocity 450r/min, isothermal reaction 20min under stirring environment, backward solution in add the Sodium dodecylbenzene sulfonate of 3.5g, after stirring 8min, water bath with thermostatic control is reduced to 13 DEG C, and leaves standstill solution 8min; Solution after leaving standstill is carried out suction filtration with Bush's funnel, takes out the crystal in funnel after suction filtration, and crystal dehydrated alcohol is cleaned 5 times repeatedly, then the crystal after abundant washing is added in the beaker of 500mL, then to the HNO adding mass concentration 68% in cup
3solution solid-liquid mass ratio is 1:1, and carries out stirring solid, liquid is fully mixed, and filters, obtain filtrate and be the high phosphoric acid solution of purity after stirring 25min.
The phosphoric acid product fluorine-containing impurity that the present invention's crystallization process purifies is few, purity is high and pollution-free, phosphoric acid the present invention prepared is made phosphoric acid salt application food aspect or is made water quality stabilizer and is applied in water treatment, Oil repellent in its phosphoric acid is surveyed by fluoride ion selective electrode method, survey 5 times, finally recording Oil repellent is 0.002%.
Example 3
First the Rock Phosphate (72Min BPL) of 3kg is chosen, put into micronizer mill and be ground into the uniform small particles that particle diameter is 20 μm, Rock Phosphate (72Min BPL) particle after pulverizing is put into the beaker of 5L, by 0.2mol/L oxalic acid solution and massfraction 10% succinic acid solution, be added in the beaker of phosphorus-containing ore particle after 1:1 mixing by volume, and exceed Rock Phosphate (72Min BPL) particle surface 8cm, finally material in beaker is uniformly mixed; Be filled with air at the below aeration blower of beaker, carry out aeration, aeration time is 60min, installs reliever of bleeding, be decompressed to-0.07Mpa while aeration above beaker; First the mixing solutions in beaker is carried out centrifugation, obtain supernatant liquor, get the Na that mass ratio is 1:5
2cO
3with active SiO
2add respectively in clear liquid, after stirring 6min, the throw out produced is filtered and remove, get filtrate; The above-mentioned filtrate of getting 300mL puts into the there-necked flask of 500mL, be 10 by the pH value of the ammoniacal liquor regulates liquid of massfraction 30%, then there-necked flask is put into water bath with thermostatic control, the temperature in water-bath is kept to be at 50 DEG C, urea is added by urea and filtrate solid-liquid mass ratio 1:1, stir with magnetic stirring apparatus simultaneously, stirring velocity 500r/min, isothermal reaction 30min under stirring environment, backward solution in add the Sodium dodecylbenzene sulfonate of 4g, after stirring 10min, water bath with thermostatic control is reduced to 15 DEG C, and leaves standstill solution 10min; Solution after leaving standstill is carried out suction filtration with Bush's funnel, takes out the crystal in funnel after suction filtration, and crystal dehydrated alcohol is cleaned 6 times repeatedly, then the crystal after abundant washing is added in the beaker of 500mL, then to the HNO adding mass concentration 70% in cup
3solution solid-liquid mass ratio is 1:1, and carries out stirring solid, liquid is fully mixed, and filters, obtain filtrate and be the high phosphoric acid solution of purity after stirring 30min.
The phosphoric acid product fluorine-containing impurity that the present invention's crystallization process purifies is few, purity is high and pollution-free, phosphoric acid the present invention prepared is made phosphoric acid salt application food aspect or is made water quality stabilizer and is applied in water treatment, Oil repellent in its phosphoric acid is surveyed by fluoride ion selective electrode method, survey 6 times, finally recording Oil repellent is 0.003%.
Claims (1)
1. wet-layer preparation process phosphoric acid reduces a method for Oil repellent in by product, it is characterized in that concrete preparation process is:
(1) Rock Phosphate (72Min BPL) of 2 ~ 3kg is first chosen, put into micronizer mill and be ground into the uniform small particles that particle diameter is 10 ~ 20 μm, Rock Phosphate (72Min BPL) particle after pulverizing is put into the beaker of 5L, by 0.2mol/L oxalic acid solution and massfraction 10% succinic acid solution, be added in the beaker of phosphorus-containing ore particle after 1:1 mixing by volume, and exceed Rock Phosphate (72Min BPL) particle surface 6 ~ 8cm, finally material in beaker is uniformly mixed;
(2) be filled with air at the below aeration blower of above-mentioned beaker, carry out aeration, aeration time is 30 ~ 60min, installs reliever of bleeding, be decompressed to-0.05 ~-0.07Mpa while aeration above beaker;
(3) first the mixing solutions in above-mentioned beaker is carried out centrifugation, obtain supernatant liquor, get the Na that mass ratio is 1:5
2cO
3with active SiO
2add respectively in clear liquid, after leaving standstill 30 ~ 40min after stirring 5 ~ 6min, the throw out produced is filtered and remove, get filtrate;
(4) the above-mentioned filtrate of getting 200 ~ 300mL puts into the there-necked flask of 500mL, be 9 ~ 10 by the pH value of the ammoniacal liquor regulates liquid of massfraction 20 ~ 30%, then there-necked flask is put into water bath with thermostatic control, the temperature in water-bath is kept to be at 40 ~ 50 DEG C, urea is added by urea and filtrate solid-liquid mass ratio 1:1, stir with magnetic stirring apparatus simultaneously, stirring velocity 400 ~ 500r/min, isothermal reaction 10 ~ 30min under stirring environment, backward solution in add the Sodium dodecylbenzene sulfonate of 3 ~ 4g, after stirring 5 ~ 10min, water bath with thermostatic control is reduced to 10 ~ 15 DEG C, and leave standstill solution 5 ~ 10min,
(5) solution after above-mentioned leaving standstill is carried out suction filtration with Bush's funnel, the crystal in funnel is taken out after suction filtration, and crystal dehydrated alcohol is cleaned 4 ~ 6 times repeatedly, then the crystal after abundant washing is added in the beaker of 500mL, then to the HNO adding mass concentration 65 ~ 70% in cup
3solution solid-liquid mass ratio is 1:1, and carries out stirring solid, liquid is fully mixed, and filters, obtain filtrate and be the high phosphoric acid solution of purity after stirring 20 ~ 30min.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108083244A (en) * | 2018-01-12 | 2018-05-29 | 武汉工程大学 | Using method of the neopelex as cleaner purification of wet process phosphoric acid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1730385A (en) * | 2005-06-09 | 2006-02-08 | 北京泓远迪绿色技术有限公司 | Method for purifying wet-process phosphoric acid by crystallization |
| CN101007626A (en) * | 2007-01-25 | 2007-08-01 | 黄尚勋 | Method for producing phosphate by wet method phosphoric acid purification and hydrochloric acid decomposition for phosphate ore |
| CN101219781A (en) * | 2007-12-07 | 2008-07-16 | 苏兆祥 | Clean production of phosphate and phosphoric acid with low ore grade phosphorus ore hydrochloric acid circulation |
| CN101824536A (en) * | 2009-03-03 | 2010-09-08 | 北京有色金属研究总院 | Process for extracting rare-earth from sulfuric acid treating phosphorite process |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1730385A (en) * | 2005-06-09 | 2006-02-08 | 北京泓远迪绿色技术有限公司 | Method for purifying wet-process phosphoric acid by crystallization |
| CN101007626A (en) * | 2007-01-25 | 2007-08-01 | 黄尚勋 | Method for producing phosphate by wet method phosphoric acid purification and hydrochloric acid decomposition for phosphate ore |
| CN101219781A (en) * | 2007-12-07 | 2008-07-16 | 苏兆祥 | Clean production of phosphate and phosphoric acid with low ore grade phosphorus ore hydrochloric acid circulation |
| CN101824536A (en) * | 2009-03-03 | 2010-09-08 | 北京有色金属研究总院 | Process for extracting rare-earth from sulfuric acid treating phosphorite process |
Non-Patent Citations (1)
| Title |
|---|
| 段利中等: "湿法磷酸精制技术的研究及其工业化进展", 《IM&P化工矿物与加工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108083244A (en) * | 2018-01-12 | 2018-05-29 | 武汉工程大学 | Using method of the neopelex as cleaner purification of wet process phosphoric acid |
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