CN104609381A - Method for purifying kiln phosphoric acid - Google Patents
Method for purifying kiln phosphoric acid Download PDFInfo
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Abstract
The invention relates to a method for purifying kiln phosphoric acid, and in particular relates to a method for deeply purifying and preparing food grade phosphoric acid of kiln phosphoric acid, the dechlorinating-deironing-sodium and metal cation removing-sulfate radical removing-lead arsenic removing-sulfuretted hydrogen removing-fluorine removing-diluting steps are adopted for preparing the food grade phosphoric acid; the technology is simple and easy to operate, the investment is saved, the yield of the food grade phosphoric acid is high, the purifying cost is low and the application field of the kiln phosphoric acid is broadened.
Description
Technical field
The present invention relates to a kind of kiln-process phosphoric acid purifying method, the deep purifying relating in particular to kiln-process phosphoric acid prepares the method for food grade phosphoric acid.
Technical background
Phosphoric acid production mainly contains wet method and Re Fa, and wet method is to the high (P of phosphorus ore grade requirement
2o
5>=25wt%), sulfuric acid consumption is large, poor product quality, and by-product phosphogypsum causes serious environmental pollution; Thermal phosphoric acid quality is good, but to the high (P of phosphorus ore grade requirement
2o
5>=25wt%), produce yellow phosphorus power consumption per ton up to more than 15000kWh, China's phosphate rock resource enriches, but more than 90% phosphorus ore is P
2o
5the mid low grade phosphate rock of≤20wt%, kiln-process phosphoric acid need not acid, few electricity consumption, directly can utilize mid low grade phosphate rock, meet China's phosphate rock resource feature, have a extensive future.
During kiln-process phosphoric acid is produced, some lower boiling species while phosphorus ore hot carbon reduction, the such as compound of lead, arsenic, iron, fluorine, chlorine and sulphur etc. be also reduced or (with) directly volatilization enter flue gas (partial impurities is also oxidized in flue gas further), for avoiding P in flue gas in existing kiln-process phosphoric acid technology
2o
5with water vapour with the condensation of metaphosphoric acid form, precipitation, blocking flue, require that the phosphorous flue gas of temperatures as high about 900 DEG C directly enters hydrated tower, carry out cooling, absorbing, above-mentioned impurity enters solution simultaneously, phosphoric acid is caused to pollute, therefore, although these foreign matter contents (usually often kind of foreign matter content < 1000ppm) at least reduce a more than order of magnitude than phosphoric acid by wet process in kiln-process phosphoric acid, but still fail to reach the quality index of PHOSPHORIC ACID TECH.GRADE, for improving kiln-process phosphoric acid quality, expanded application field, purification further of still needing.
To kiln-process phosphoric acid comprehensive decontamination there are no report, existing wet phosphoric acid purifying mainly adopts solvent extration, but extraction process is relatively good to the decontamination effect improving of metallic cation in phosphoric acid, and it is as poor in decontamination effect improvings such as sulfate radical, chlorion, fluorion, arsenates to negatively charged ion, therefore, also need to coordinate other purification process to remove; And the yield of PHOSPHORIC ACID TECH.GRADE only has about 60%, all the other can only produce fertilizer grade product, in addition, if obtain food grade phosphoric acid, also need to make further deep purifying to gained PHOSPHORIC ACID TECH.GRADE, therefore, the purification of kiln-process phosphoric acid needs to develop proprietary advanced purification process.
Existing wet phosphoric acid purifying and PHOSPHORIC ACID TECH.GRADE purification are prepared in food grade phosphoric acid technique, deep removal lead and arsenic mainly adopt sulphide precipitation (Chinese patent CN 200510048779.5), degree of depth sulfate radical mainly adopts the barium salt precipitator method, the degree of depth except fluorine mainly adopts concentrated or (with) add the method (Chinese patent CN 200510048779.5, CN 201010212175.0) of active silica, these methods can be used for reference in related impurities purification in kiln-process phosphoric acid.
Desolventize outside extraction process, in phosphoric acid, deironing can also adopt ion exchange method and the precipitator method etc., Zeo-karb has very strong avidity to iron, but the ion exchange resin regeneration of load iron difficulty, has that to adopt with Sodium Dimethyldithiocarbamate be the precipitation method of purification of precipitation agent, but Sodium Dimethyldithiocarbamate price is high, and the solid waste Karbam Black produced poisonous, be difficult to dispose, have the report adopting froth flotation cleaning deironing, but deironing rate is not high yet.
In solution, removing chloride ion mainly contains silver salt method, cuprous chloride method etc., and silver salt method is with Sulfuric acid disilver salt or Silver Nitrate for precipitation agent (Chinese patent CN200410039484.7), but cost of material is high, silver chloride regeneration rate is low, and therefore, cost is high; Cuprous chloride method reacts based on the chlorion in copper and cupric ion and solution the cuprous chloride forming indissoluble to precipitate, but long reaction time and dechlorination effect is not good.
Summary of the invention
Object of the present invention aims to provide a kind of kiln-process phosphoric acid purifying method, for solvent extration purifying phosphoric acid technique Problems existing, provides the method for the kiln-process phosphoric acid purification production food grade phosphoric acid that a kind of technique is simple, food grade phosphoric acid yield is high, cost is low.
For achieving the above object, kiln-process phosphoric acid purifying method of the present invention, through dechlorination → deironing → except metallic cation → sulfate radical → deleading arsenic such as sodium → remove hydrogen sulfide → remove fluorine → dilution, obtained required food grade phosphoric acid, concrete steps are as follows:
1, dechlorination: take kiln-process phosphoric acid as raw material, kiln-process phosphoric acid is added in dechlorination reaction device, control solution temperature 40 ~ 80 DEG C, the chlorion blasted in the ozone and solution that concentration is 0.05 ~ 0.5g/L reacts, the intake of ozone is stoichiometric 3 ~ 10 times of chlorion in phosphoric acid, reaction times is 30 ~ 120min, and the chlorine that reaction generates is discharged;
2, deironing: remove the phosphoric acid after chlorine add to above-mentioned except in iron reactor, add the Fe in yellow prussiate of soda and phosphoric acid
3+reaction generates ferriferro cyanide precipitation, and the addition of yellow prussiate of soda is Fe in phosphoric acid
3+stoichiometric 0.98 ~ 1.02 times, temperature of reaction is 30 ~ 80 DEG C, and the reaction times is 60 ~ 180min, and reaction is finished, and filters;
3, except metallic cations such as sodium: the phosphoric acid after above-mentioned deironing is added cationic exchange coloum, cationic exchange is carried out with hydrogen type cation exchange resin, permutoid reaction temperature is 30 ~ 50 DEG C, in exchange column, the flow velocity of phosphoric acid solution is 3 ~ 10cm/min, the phosphoric acid for removing the metallic cations such as sodium flowed out bottom exchange column;
4, sulfate radical: by above-mentioned remove the metallic cations such as sodium after phosphoric acid add in sulfate radical reactor, the sulfate radical added in barium carbonate or hydrated barta and phosphoric acid reacts and generates barium sulfate precipitate, the add-on of barium is stoichiometric 0.98 ~ 1.0 times of sulfate radical in phosphoric acid, temperature of reaction is 30 ~ 60 DEG C, reaction times is 20 ~ 60min, reaction is finished, and filters;
5, deleading arsenic: the phosphoric acid after above-mentioned sulfate radical is added in deleading arsenic reactor, add the lead ion in thiophosphoric anhydride and phosphoric acid, arsonium ion reacts and generate sulfide precipitation, the add-on of thiophosphoric anhydride is plumbous in phosphoric acid and 3 ~ 10 times of arsenic stoichiometry summation, temperature of reaction is 20 ~ 50 DEG C, reaction times is 10 ~ 30min, reaction is finished, and filters;
6, hydrogen sulfide is removed: add in depriving hydrogen sulphide device by the phosphoric acid after above-mentioned deleading arsenic, blast warm air, sulfidion excessive in solution and hydrogen ion is made to form hydrogen sulfide also in gas overflowing, quantity of hot air is 1 ~ 5 kg of air per kg of water evaporated/kg of phosphoric acid, hot air temperature is 80 ~ 100 DEG C, solution temperature 80 ~ 100 DEG C;
7, fluorine is removed: add in defluorination reaction device by the above-mentioned phosphoric acid removing hydrogen sulfide, add active silica and vacuumize, active silica add-on is 2 ~ 5 times of fluorine chemistry metering in phosphoric acid, vacuum tightness is 85 ~ 95KPa, temperature of reaction 80 ~ 100 DEG C, reaction times 30 ~ 120min, the volatility silicon tetrafluoride that reaction generates and hydrogen fluoride gas overflow under vacuo, reaction is finished, and reaction mass is cooled to 30 ~ 50 DEG C, filters;
8, dilute: above-mentioned remove fluorine after phosphoric acid in add pure water or distilled water, by phosphoric acid quality concentration dilution to 75%, required food grade phosphoric acid can be obtained.
Adopt sodium hydroxide to absorb in step 1 ozone oxidation chlorion gained chlorine, gained absorption liquid through concentrated can by-product clorox product;
In the hydrogen sulfide that the blowout of step 6 warm air is superfluous, employing sodium hydroxide absorbs, and gained absorption liquid warp is concentrated, crystallization, by-product sodium sulphite product.
Kiln-process phosphoric acid purifying method of the present invention compared with prior art has following excellent effect.
In kiln-process phosphoric acid, iron ion can adopt simple chemical precipitation method deep removal, and deferrization process is simple, reduced investment; In kiln-process phosphoric acid, chlorion adopts ozone oxidation to remove, and overcomes traditional dechlorination process weak effect, defect that cost is high, chloride ion content≤5ppm (rolling over 85% phosphoric acid) in liquid after purification; Purification process can obtain food grade phosphoric acid, and the yield of food grade phosphoric acid is up to more than 95%, and far above the yield of gained PHOSPHORIC ACID TECH.GRADE during extraction process purification of wet process phosphoric acid, the purification cost that the present invention produces food grade phosphoric acid is low.
Embodiment
Below in conjunction with embodiment, kiln-process phosphoric acid purifying method of the present invention is described in further detail.
Kiln-process phosphoric acid purifying method of the present invention, through dechlorination → deironing → except metallic cation → sulfate radical → deleading arsenic such as sodium → remove hydrogen sulfide → remove fluorine → dilution, obtained required food grade phosphoric acid, concrete steps are as follows:
1, dechlorination: take kiln-process phosphoric acid as raw material, kiln-process phosphoric acid is added in dechlorination reaction device, control solution temperature 40 ~ 80 DEG C, the chlorion blasted in the ozone and solution that concentration is 0.05 ~ 0.5g/L reacts, the intake of ozone is stoichiometric 3 ~ 10 times of chlorion in phosphoric acid, reaction times is 30 ~ 120min, and the chlorine that reaction generates is discharged;
2, deironing: remove the phosphoric acid after chlorine add to above-mentioned except in iron reactor, add the Fe in yellow prussiate of soda and phosphoric acid
3+reaction generates ferriferro cyanide precipitation, and the addition of yellow prussiate of soda is Fe in phosphoric acid
3+stoichiometric 0.98 ~ 1.02 times, temperature of reaction is 30 ~ 80 DEG C, and the reaction times is 60 ~ 180min, and reaction is finished, and filters;
3, except metallic cations such as sodium: the phosphoric acid after above-mentioned deironing is added cationic exchange coloum, cationic exchange is carried out with hydrogen type cation exchange resin, permutoid reaction temperature is 30 ~ 50 DEG C, in exchange column, the flow velocity of phosphoric acid solution is 3 ~ 10cm/min, the phosphoric acid for removing the metallic cations such as sodium flowed out bottom exchange column;
4, sulfate radical: by above-mentioned remove the metallic cations such as sodium after phosphoric acid add in sulfate radical reactor, the sulfate radical added in barium carbonate or hydrated barta and phosphoric acid reacts and generates barium sulfate precipitate, the add-on of barium is stoichiometric 0.98 ~ 1.0 times of sulfate radical in phosphoric acid, temperature of reaction is 30 ~ 60 DEG C, reaction times is 20 ~ 60min, reaction is finished, and filters;
5, deleading arsenic: the phosphoric acid after above-mentioned sulfate radical is added in deleading arsenic reactor, add the lead ion in thiophosphoric anhydride and phosphoric acid, arsonium ion reacts and generate sulfide precipitation, the add-on of thiophosphoric anhydride is plumbous in phosphoric acid and 3 ~ 10 times of arsenic stoichiometry summation, temperature of reaction is 20 ~ 50 DEG C, reaction times is 10 ~ 30min, reaction is finished, and filters;
6, hydrogen sulfide is removed: add in depriving hydrogen sulphide device by the phosphoric acid after above-mentioned deleading arsenic, blast warm air, sulfidion excessive in solution and hydrogen ion is made to form hydrogen sulfide also in gas overflowing, quantity of hot air is 1 ~ 5 kg of air per kg of water evaporated/kg of phosphoric acid, hot air temperature is 80 ~ 100 DEG C, solution temperature 80 ~ 100 DEG C;
7, fluorine is removed: add in defluorination reaction device by the above-mentioned phosphoric acid removing hydrogen sulfide, add active silica and vacuumize, active silica add-on is 2 ~ 5 times of fluorine chemistry metering in phosphoric acid, vacuum tightness is 85 ~ 95KPa, temperature of reaction 80 ~ 100 DEG C, reaction times 30 ~ 120min, the volatility silicon tetrafluoride that reaction generates and hydrogen fluoride gas overflow under vacuo, reaction is finished, and reaction mass is cooled to 30 ~ 50 DEG C, filters;
8, dilute: above-mentioned remove fluorine after phosphoric acid in add pure water or distilled water, by phosphoric acid quality concentration dilution to 75%, required food grade phosphoric acid can be obtained.
Adopt sodium hydroxide to absorb in step 1 ozone oxidation chlorion gained chlorine, gained absorption liquid can by-product clorox product through concentrating.
In the hydrogen sulfide that the blowout of step 6 warm air is superfluous, employing sodium hydroxide absorbs, and gained absorption liquid warp is concentrated, crystallization, by-product sodium sulphite product.
Embodiment 1
Kiln-process phosphoric acid raw material (wt.%) composed as follows:
1, dechlorination: the kiln-process phosphoric acid of above-mentioned composition is added in dechlorination reaction device, control solution temperature 80 DEG C, the chlorion blasted in the ozone and solution that concentration is 0.05g/L reacts, the intake of ozone is stoichiometric 10 times of chlorion in phosphoric acid, reaction times is 120min, and the chlorine that reaction generates is discharged;
2, deironing: remove the phosphoric acid after chlorine add to above-mentioned except in iron reactor, add the Fe in yellow prussiate of soda and phosphoric acid
3+reaction generates ferriferro cyanide precipitation, and the addition of yellow prussiate of soda is Fe in phosphoric acid
3+stoichiometric 1.02 times, temperature of reaction is 80 DEG C, and the reaction times is 60min, and reaction is finished, and filters;
3, except metallic cations such as sodium: the phosphoric acid after above-mentioned deironing is added cationic exchange coloum, cationic exchange is carried out with hydrogen type cation exchange resin, permutoid reaction temperature is 50 DEG C, in exchange column, the flow velocity of phosphoric acid solution is 10cm/min, the phosphoric acid for removing the metallic cations such as sodium flowed out bottom exchange column;
4, sulfate radical: by above-mentioned remove the metallic cations such as sodium after phosphoric acid add in sulfate radical reactor, the sulfate radical added in barium carbonate and phosphoric acid reacts and generates barium sulfate precipitate, the add-on of barium is stoichiometric 1.0 times of sulfate radical in phosphoric acid, temperature of reaction is 60 DEG C, reaction times is 20min, reaction is finished, and filters;
5, deleading arsenic: the phosphoric acid after above-mentioned sulfate radical is added in deleading arsenic reactor, add the lead ion in thiophosphoric anhydride and phosphoric acid, arsonium ion reacts and generate sulfide precipitation, the add-on of thiophosphoric anhydride is plumbous in phosphoric acid and 5 times of arsenic stoichiometry summation, temperature of reaction is 50 DEG C, reaction times is 10min, reaction is finished, and filters;
6, hydrogen sulfide is removed: add in depriving hydrogen sulphide device by the phosphoric acid after above-mentioned deleading arsenic, blast warm air, sulfidion excessive in solution and hydrogen ion is made to form hydrogen sulfide also in gas overflowing, quantity of hot air is 1 kg of air per kg of water evaporated/kg of phosphoric acid, hot air temperature is 100 DEG C, solution temperature 100 DEG C;
7, fluorine is removed: add in defluorination reaction device by the above-mentioned phosphoric acid removing hydrogen sulfide, add active silica and vacuumize, active silica add-on is 2 times of fluorine chemistry metering in phosphoric acid, vacuum tightness is 95KPa, temperature of reaction 90 DEG C, reaction times 60min, the volatility silicon tetrafluoride that reaction generates and hydrogen fluoride gas overflow under vacuo, reaction is finished, and reaction mass is cooled to 50 DEG C, filters;
8, dilute: above-mentioned remove fluorine after phosphoric acid in add pure water, by phosphoric acid quality concentration dilution to 75%, can food grade phosphoric acid be obtained.
The food grade phosphoric acid yield of above embodiment 1 is 95.5%, and gained food grade phosphoric acid chemical constitution (wt.%) is as follows:
Embodiment 2
Kiln-process phosphoric acid raw material composition is with embodiment 1.
1, dechlorination: the kiln-process phosphoric acid of above-mentioned composition is added in dechlorination reaction device, control solution temperature 60 DEG C, the chlorion blasted in the ozone and solution that concentration is 0.5g/L reacts, the intake of ozone is stoichiometric 3 times of chlorion in phosphoric acid, reaction times is 30min, and the chlorine that reaction generates is discharged;
2, deironing: remove the phosphoric acid after chlorine add to above-mentioned except in iron reactor, add the Fe in yellow prussiate of soda and phosphoric acid
3+reaction generates ferriferro cyanide precipitation, and the addition of yellow prussiate of soda is Fe in phosphoric acid
3+stoichiometric 1.0 times, temperature of reaction is 60 DEG C, and the reaction times is 180min, and reaction is finished, and filters;
3, except metallic cations such as sodium: the phosphoric acid after above-mentioned deironing is added cationic exchange coloum, cationic exchange is carried out with hydrogen type cation exchange resin, permutoid reaction temperature is 30 DEG C, in exchange column, the flow velocity of phosphoric acid solution is 3cm/min, the phosphoric acid for removing the metallic cations such as sodium flowed out bottom exchange column;
4, sulfate radical: by above-mentioned remove the metallic cations such as sodium after phosphoric acid add in sulfate radical reactor, the sulfate radical added in barium carbonate and phosphoric acid reacts and generates barium sulfate precipitate, the add-on of barium is stoichiometric 0.98 times of sulfate radical in phosphoric acid, temperature of reaction is 30 DEG C, reaction times is 60min, reaction is finished, and filters;
5, deleading arsenic: the phosphoric acid after above-mentioned sulfate radical is added in deleading arsenic reactor, add the lead ion in thiophosphoric anhydride and phosphoric acid, arsonium ion reacts and generate sulfide precipitation, the add-on of thiophosphoric anhydride is plumbous in phosphoric acid and 3 times of arsenic stoichiometry summation, temperature of reaction is 20 DEG C, reaction times is 30min, reaction is finished, and filters;
6, remove hydrogen sulfide: added in depriving hydrogen sulphide device by the phosphoric acid after above-mentioned deleading arsenic, blast warm air, hot air temperature is 80 DEG C, phosphoric acid Temperature 80 DEG C, and controlling to blast quantity of hot air is 5 kg of air per kg of water evaporated/kg of phosphoric acid;
7, fluorine is removed: add in defluorination reaction device by the above-mentioned phosphoric acid removing hydrogen sulfide, add active silica and vacuumize, active silica add-on is 5 times of fluorine chemistry metering in phosphoric acid, vacuum tightness is 85KPa, temperature of reaction 80 DEG C, reaction times 120min, the volatility silicon tetrafluoride that reaction generates and hydrogen fluoride gas overflow under vacuo, reaction is finished, and reaction mass is cooled to 30 DEG C, filters;
8, dilute: above-mentioned remove fluorine after phosphoric acid in add distilled water, by phosphoric acid quality concentration dilution to 75%, can food grade phosphoric acid be obtained.
The food grade phosphoric acid yield of above embodiment 2 is 96.1%, and gained food grade phosphoric acid chemical constitution (wt.%) is as follows:
Embodiment 3
Kiln-process phosphoric acid raw material composition is with embodiment 1.
1, dechlorination: the kiln-process phosphoric acid of above-mentioned composition is added in dechlorination reaction device, control solution temperature 40 DEG C, the chlorion blasted in the ozone and solution that concentration is 0.2g/L reacts, the intake of ozone is stoichiometric 5 times of chlorion in phosphoric acid, reaction times is 90min, and the chlorine that reaction generates is discharged;
2, deironing: remove the phosphoric acid after chlorine add to above-mentioned except in iron reactor, add the Fe in yellow prussiate of soda and phosphoric acid
3+reaction generates ferriferro cyanide precipitation, and the addition of yellow prussiate of soda is Fe in phosphoric acid
3+stoichiometric 0.98 times, temperature of reaction is 30 DEG C, and the reaction times is 120min, and reaction is finished, and filters;
3, except metallic cations such as sodium: the phosphoric acid after above-mentioned deironing is added cationic exchange coloum, cationic exchange is carried out with hydrogen type cation exchange resin, permutoid reaction temperature is 40 DEG C, in exchange column, the flow velocity of phosphoric acid solution is 6cm/min, the phosphoric acid for removing the metallic cations such as sodium flowed out bottom exchange column;
4, sulfate radical: by above-mentioned remove the metallic cations such as sodium after phosphoric acid add in sulfate radical reactor, the sulfate radical added in hydrated barta and phosphoric acid reacts and generates barium sulfate precipitate, the add-on of barium is stoichiometric 0.99 times of sulfate radical in phosphoric acid, temperature of reaction is 45 DEG C, reaction times is 40min, reaction is finished, and filters;
5, deleading arsenic: the phosphoric acid after above-mentioned sulfate radical is added in deleading arsenic reactor, add the lead ion in thiophosphoric anhydride and phosphoric acid, arsonium ion reacts and generate sulfide precipitation, the add-on of thiophosphoric anhydride is plumbous in phosphoric acid and 10 times of arsenic stoichiometry summation, temperature of reaction is 40 DEG C, reaction times is 20min, reaction is finished, and filters;
6, hydrogen sulfide is removed: add in depriving hydrogen sulphide device by the phosphoric acid after above-mentioned deleading arsenic, blast warm air, sulfidion excessive in solution and hydrogen ion is made to form hydrogen sulfide also in gas overflowing, quantity of hot air is 3 kg of air per kg of water evaporated/kg of phosphoric acid, hot air temperature is 90 DEG C, solution temperature 90 DEG C;
7, fluorine is removed: add in defluorination reaction device by the above-mentioned phosphoric acid removing hydrogen sulfide, add active silica and vacuumize, active silica add-on is 4 times of fluorine chemistry metering in phosphoric acid, vacuum tightness is 90KPa, temperature of reaction 100 DEG C, reaction times 30min, the volatility silicon tetrafluoride that reaction generates and hydrogen fluoride gas overflow under vacuo, reaction is finished, and reaction mass is cooled to 40 DEG C, filters;
8, dilute: above-mentioned remove fluorine after phosphoric acid in add pure water, by phosphoric acid quality concentration dilution to 75%, can food grade phosphoric acid be obtained.
The food grade phosphoric acid yield of above embodiment 3 is 96.5%, and gained food grade phosphoric acid chemical constitution (wt.%) is as follows:
Claims (4)
1. a kiln-process phosphoric acid purifying method, through dechlorination → deironing → except metallic cation → sulfate radical → deleading arsenic such as sodium → remove hydrogen sulfide → remove fluorine → dilution, obtained required food grade phosphoric acid, is characterized in that concrete steps are as follows:
(1) dechlorination: take kiln-process phosphoric acid as raw material, kiln-process phosphoric acid is added in dechlorination reaction device, control solution temperature 40 ~ 80 DEG C, the chlorion blasted in the ozone and solution that concentration is 0.05 ~ 0.5g/L reacts, the intake of ozone is stoichiometric 3 ~ 10 times of chlorion in phosphoric acid, reaction times is 30 ~ 120min, and the chlorine that reaction generates is discharged;
(2) deironing: remove the phosphoric acid after chlorine add to above-mentioned except in iron reactor, add the Fe in yellow prussiate of soda and phosphoric acid
3+reaction generates ferriferro cyanide precipitation, and the addition of yellow prussiate of soda is Fe in phosphoric acid
3+stoichiometric 0.98 ~ 1.02 times, temperature of reaction is 30 ~ 80 DEG C, and the reaction times is 60 ~ 180min, and reaction is finished, and filters;
(3) except metallic cations such as sodium: the phosphoric acid after above-mentioned deironing is added cationic exchange coloum, cationic exchange is carried out with hydrogen type cation exchange resin, permutoid reaction temperature is 30 ~ 50 DEG C, in exchange column, the flow velocity of phosphoric acid solution is 3 ~ 10cm/min, the phosphoric acid for removing the metallic cations such as sodium flowed out bottom exchange column;
(4) sulfate radical: by above-mentioned remove the metallic cations such as sodium after phosphoric acid add in sulfate radical reactor, the sulfate radical added in barium carbonate or hydrated barta and phosphoric acid reacts and generates barium sulfate precipitate, the add-on of barium is stoichiometric 0.98 ~ 1.0 times of sulfate radical in phosphoric acid, temperature of reaction is 30 ~ 60 DEG C, reaction times is 20 ~ 60min, reaction is finished, and filters;
(5) deleading arsenic: the phosphoric acid after above-mentioned sulfate radical is added in deleading arsenic reactor, add the lead ion in thiophosphoric anhydride and phosphoric acid, arsonium ion reacts and generate sulfide precipitation, the add-on of thiophosphoric anhydride is plumbous in phosphoric acid and 3 ~ 10 times of arsenic stoichiometry summation, temperature of reaction is 20 ~ 50 DEG C, reaction times is 10 ~ 30min, reaction is finished, and filters;
(6) hydrogen sulfide is removed: add in depriving hydrogen sulphide device by the phosphoric acid after above-mentioned deleading arsenic, blast warm air, sulfidion excessive in solution and hydrogen ion is made to form hydrogen sulfide also in gas overflowing, quantity of hot air is 1 ~ 5 kg of air per kg of water evaporated/kg of phosphoric acid, hot air temperature is 80 ~ 100 DEG C, solution temperature 80 ~ 100 DEG C;
(7) fluorine is removed: add in defluorination reaction device by the above-mentioned phosphoric acid removing hydrogen sulfide, add active silica and vacuumize, active silica add-on is 2 ~ 5 times of fluorine chemistry metering in phosphoric acid, vacuum tightness is 85 ~ 95KPa, temperature of reaction 80 ~ 100 DEG C, reaction times 30 ~ 120min, the volatility silicon tetrafluoride that reaction generates and hydrogen fluoride gas overflow under vacuo, reaction is finished, and reaction mass is cooled to 30 ~ 50 DEG C, filters;
(8) dilute: above-mentioned remove fluorine after phosphoric acid in add pure water or distilled water, by phosphoric acid quality concentration dilution to 75%, required food grade phosphoric acid can be obtained.
2. kiln-process phosphoric acid purifying method according to claim 1, is characterized in that concrete steps are as follows:
(1) dechlorination: kiln-process phosphoric acid is added in dechlorination reaction device, control solution temperature 80 DEG C, the chlorion blasted in the ozone and solution that concentration is 0.05g/L reacts, the intake of ozone is stoichiometric 10 times of chlorion in phosphoric acid, reaction times is 120min, and the chlorine that reaction generates is discharged;
(2) deironing: remove the phosphoric acid after chlorine add to above-mentioned except in iron reactor, add the Fe in yellow prussiate of soda and phosphoric acid
3+reaction generates ferriferro cyanide precipitation, and the addition of yellow prussiate of soda is Fe in phosphoric acid
3+stoichiometric 1.02 times, temperature of reaction is 80 DEG C, and the reaction times is 60min, and reaction is finished, and filters;
(3) except metallic cations such as sodium: the phosphoric acid after above-mentioned deironing is added cationic exchange coloum, cationic exchange is carried out with hydrogen type cation exchange resin, permutoid reaction temperature is 50 DEG C, in exchange column, the flow velocity of phosphoric acid solution is 10cm/min, the phosphoric acid for removing the metallic cations such as sodium flowed out bottom exchange column;
(4) sulfate radical: by above-mentioned remove the metallic cations such as sodium after phosphoric acid add in sulfate radical reactor, the sulfate radical added in barium carbonate and phosphoric acid reacts and generates barium sulfate precipitate, the add-on of barium is stoichiometric 1.0 times of sulfate radical in phosphoric acid, temperature of reaction is 60 DEG C, reaction times is 20min, reaction is finished, and filters;
(5) deleading arsenic: the phosphoric acid after above-mentioned sulfate radical is added in deleading arsenic reactor, add the lead ion in thiophosphoric anhydride and phosphoric acid, arsonium ion reacts and generate sulfide precipitation, the add-on of thiophosphoric anhydride is plumbous in phosphoric acid and 5 times of arsenic stoichiometry summation, temperature of reaction is 50 DEG C, reaction times is 10min, reaction is finished, and filters;
(6) hydrogen sulfide is removed: add in depriving hydrogen sulphide device by the phosphoric acid after above-mentioned deleading arsenic, blast warm air, sulfidion excessive in solution and hydrogen ion is made to form hydrogen sulfide also in gas overflowing, quantity of hot air is 1 kg of air per kg of water evaporated/kg of phosphoric acid, hot air temperature is 100 DEG C, solution temperature 100 DEG C;
(7) fluorine is removed: add in defluorination reaction device by the above-mentioned phosphoric acid removing hydrogen sulfide, add active silica and vacuumize, active silica add-on is 2 times of fluorine chemistry metering in phosphoric acid, vacuum tightness is 95KPa, temperature of reaction 90 DEG C, reaction times 60min, the volatility silicon tetrafluoride that reaction generates and hydrogen fluoride gas overflow under vacuo, reaction is finished, and reaction mass is cooled to 50 DEG C, filters;
(8) dilute: above-mentioned remove fluorine after phosphoric acid in add pure water, by phosphoric acid quality concentration dilution to 75%, can food grade phosphoric acid be obtained.
3. kiln-process phosphoric acid purifying method according to claim 1, is characterized in that concrete steps are as follows:
(1) dechlorination: kiln-process phosphoric acid is added in dechlorination reaction device, control solution temperature 60 DEG C, the chlorion blasted in the ozone and solution that concentration is 0.5g/L reacts, the intake of ozone is stoichiometric 3 times of chlorion in phosphoric acid, reaction times is 30min, and the chlorine that reaction generates is discharged;
(2) deironing: remove the phosphoric acid after chlorine add to above-mentioned except in iron reactor, add the Fe in yellow prussiate of soda and phosphoric acid
3+reaction generates ferriferro cyanide precipitation, and the addition of yellow prussiate of soda is Fe in phosphoric acid
3+stoichiometric 1.0 times, temperature of reaction is 60 DEG C, and the reaction times is 180min, and reaction is finished, and filters;
(3) except metallic cations such as sodium: the phosphoric acid after above-mentioned deironing is added cationic exchange coloum, cationic exchange is carried out with hydrogen type cation exchange resin, permutoid reaction temperature is 30 DEG C, in exchange column, the flow velocity of phosphoric acid solution is 3cm/min, the phosphoric acid for removing the metallic cations such as sodium flowed out bottom exchange column;
(4) sulfate radical: by above-mentioned remove the metallic cations such as sodium after phosphoric acid add in sulfate radical reactor, the sulfate radical added in barium carbonate and phosphoric acid reacts and generates barium sulfate precipitate, the add-on of barium is stoichiometric 0.98 times of sulfate radical in phosphoric acid, temperature of reaction is 30 DEG C, reaction times is 60min, reaction is finished, and filters;
(5) deleading arsenic: the phosphoric acid after above-mentioned sulfate radical is added in deleading arsenic reactor, add the lead ion in thiophosphoric anhydride and phosphoric acid, arsonium ion reacts and generate sulfide precipitation, the add-on of thiophosphoric anhydride is plumbous in phosphoric acid and 3 times of arsenic stoichiometry summation, temperature of reaction is 20 DEG C, reaction times is 30min, reaction is finished, and filters;
(6) remove hydrogen sulfide: added in depriving hydrogen sulphide device by the phosphoric acid after above-mentioned deleading arsenic, blast warm air, hot air temperature is 80 DEG C, phosphoric acid Temperature 80 DEG C, and controlling to blast quantity of hot air is 5 kg of air per kg of water evaporated/kg of phosphoric acid;
(7) fluorine is removed: add in defluorination reaction device by the above-mentioned phosphoric acid removing hydrogen sulfide, add active silica and vacuumize, active silica add-on is 5 times of fluorine chemistry metering in phosphoric acid, vacuum tightness is 85KPa, temperature of reaction 80 DEG C, reaction times 120min, the volatility silicon tetrafluoride that reaction generates and hydrogen fluoride gas overflow under vacuo, reaction is finished, and reaction mass is cooled to 30 DEG C, filters;
(8) dilute: above-mentioned remove fluorine after phosphoric acid in add distilled water, by phosphoric acid quality concentration dilution to 75%, can food grade phosphoric acid be obtained.
4. kiln-process phosphoric acid purifying method according to claim 1, is characterized in that concrete steps are as follows:
(1) dechlorination: kiln-process phosphoric acid is added in dechlorination reaction device, control solution temperature 40 DEG C, the chlorion blasted in the ozone and solution that concentration is 0.2g/L reacts, the intake of ozone is stoichiometric 5 times of chlorion in phosphoric acid, reaction times is 90min, and the chlorine that reaction generates is discharged;
(2) deironing: remove the phosphoric acid after chlorine add to above-mentioned except in iron reactor, add the Fe in yellow prussiate of soda and phosphoric acid
3+reaction generates ferriferro cyanide precipitation, and the addition of yellow prussiate of soda is Fe in phosphoric acid
3+stoichiometric 0.98 times, temperature of reaction is 30 DEG C, and the reaction times is 120min, and reaction is finished, and filters;
(3) except metallic cations such as sodium: the phosphoric acid after above-mentioned deironing is added cationic exchange coloum, cationic exchange is carried out with hydrogen type cation exchange resin, permutoid reaction temperature is 40 DEG C, in exchange column, the flow velocity of phosphoric acid solution is 6cm/min, the phosphoric acid for removing the metallic cations such as sodium flowed out bottom exchange column;
(4) sulfate radical: by above-mentioned remove the metallic cations such as sodium after phosphoric acid add in sulfate radical reactor, the sulfate radical added in hydrated barta and phosphoric acid reacts and generates barium sulfate precipitate, the add-on of barium is stoichiometric 0.99 times of sulfate radical in phosphoric acid, temperature of reaction is 45 DEG C, reaction times is 40min, reaction is finished, and filters;
(5) deleading arsenic: the phosphoric acid after above-mentioned sulfate radical is added in deleading arsenic reactor, add the lead ion in thiophosphoric anhydride and phosphoric acid, arsonium ion reacts and generate sulfide precipitation, the add-on of thiophosphoric anhydride is plumbous in phosphoric acid and 10 times of arsenic stoichiometry summation, temperature of reaction is 40 DEG C, reaction times is 20min, reaction is finished, and filters;
(6) hydrogen sulfide is removed: add in depriving hydrogen sulphide device by the phosphoric acid after above-mentioned deleading arsenic, blast warm air, sulfidion excessive in solution and hydrogen ion is made to form hydrogen sulfide also in gas overflowing, quantity of hot air is 3 kg of air per kg of water evaporated/kg of phosphoric acid, hot air temperature is 90 DEG C, solution temperature 90 DEG C;
(7) fluorine is removed: add in defluorination reaction device by the above-mentioned phosphoric acid removing hydrogen sulfide, add active silica and vacuumize, active silica add-on is 4 times of fluorine chemistry metering in phosphoric acid, vacuum tightness is 90KPa, temperature of reaction 100 DEG C, reaction times 30min, the volatility silicon tetrafluoride that reaction generates and hydrogen fluoride gas overflow under vacuo, reaction is finished, and reaction mass is cooled to 40 DEG C, filters;
(8) dilute: above-mentioned remove fluorine after phosphoric acid in add pure water, by phosphoric acid quality concentration dilution to 75%, can food grade phosphoric acid be obtained.
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| CN111268660A (en) * | 2020-03-20 | 2020-06-12 | 贵州川恒化工股份有限公司 | Method for preparing food-grade phosphoric acid from wet-process phosphoric acid |
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