CN105110296B - The method that phosphorus ore association chemical valence iodine high prepares iodine is reclaimed in Wet-process Phosphoric Acid Production - Google Patents
The method that phosphorus ore association chemical valence iodine high prepares iodine is reclaimed in Wet-process Phosphoric Acid Production Download PDFInfo
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- CN105110296B CN105110296B CN201510434732.6A CN201510434732A CN105110296B CN 105110296 B CN105110296 B CN 105110296B CN 201510434732 A CN201510434732 A CN 201510434732A CN 105110296 B CN105110296 B CN 105110296B
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Abstract
The invention discloses reclaiming the phosphorus ore association chemical valence iodine high method for preparing iodine in a kind of Wet-process Phosphoric Acid Production, in hydrolysis procedure, to continuous in phosphate ore pulp acidolysis groove or be passed through gas SO with gap2；In Phosphoric Acid Concentration operation, the free I entered in gas phase with sulfurous acid cleaning solution recycling elution2Molecule；Concentration cycles cleaning solution, adds hydrogen peroxide, filtering, obtains solid phase iodine.By to addition strong reducing property SO in phosphate ore pulp acidolysis groove2Gas, makes the chemical valence acid iodide double salt high in phosphorus ore be reduced into free I2Molecule, so as to chemical valence iodine high is recycled into utilization, can reduce the discharge and environmental pollution of chemical valence acid iodide double salt high；Do not change Wet Processes of Phosphoric Acid simultaneously, technological process is simple, and cost recovery is low, the value added height of products obtained therefrom Povidone-iodine.
Description
Technical field
The present invention relates to the recoverying and utilizing method of ore association iodine resource in phosphorus ore, in specifically a kind of Wet-process Phosphoric Acid Production
Reclaim the method that phosphorus ore association chemical valence iodine high prepares iodine.
Background technology
Iodine resource is one of world's scarce resource, is the grand strategy material of country.Ore association iodine is main with negative one in phosphorus ore
Valency iodine and chemical valence iodate form high are present.The main preservation of negative one valency iodine is in fluor-apatite Ca5[PO4]3F or carbon fluorine phosphorus ash Ca5
[PO4,CO3(OH)]3In (F, OH)；And it is H that chemical valence iodate high is then mostly+\Na+\K+\Ca2+Deng cation and [IO3 -] generation
Acid iodide Multiple salts forms exist.
It is reported that：Iodine in Cambrian marine deposit ore deposit phosphorus ore is main with NaIO3\KIO3\Ca(IO3)2And KH (IO3)2
Contour chemical valence iodate double salt form preservation is in collophane.Phosphorus ore association iodine content is very low, typically left in 16~35ppm
The right side, but reserves are huge.Therefore, raw iodine tool is of great significance during research is recovered in phosphorus ore.
At present, there is technical staff to study and reclaim ore association iodine in phosphorus ore from phosphoric acid production.Such as, Application No. 03135817.9
Patent document disclose it is a kind of from rock phosphate in powder containing iodine produce phosphorus product when the recirculated water, waste water, the waste gas that produce etc. it is discarded containing iodine
The method that iodine is extracted in thing.The patent document of Application No. 200510003058.2 disclose it is a kind of using Wet Processes of Phosphoric Acid from containing
The method that iodine is extracted in the phosphoric acid,diluted of iodine phosphorus ore production.
The studies above is only limitted to reclaim the negative one valency iodine in phosphoric acid.
Applicants have found that, in Wet-process Phosphoric Acid Production, during with sulfuric acid leaching phosphorus ore, the chemical valence acid iodide high in phosphorus ore
Salt can be directly entered in liquid phase phosphoric acid, in Strong oxdiative state.Therefore, the method for being provided with above-mentioned patent 200510003058.2,
Oxidation state iodine in phosphoric acid can not be reduced into free I2Molecule, so that this iodine during phosphorus ore can not be reclaimed.
The content of the invention
The purpose of the present invention is directed to the deficiencies in the prior art, there is provided phosphorus ore association is reclaimed in a kind of Wet-process Phosphoric Acid Production high
The method that chemical valence iodine prepares salt compounded of iodine, the unordered discharge of acid iodide double salt that can have both solved phosphorus ore association in phophatic fertilizer production process is caused
Environmental problem, can turn waste into wealth again, directly obtain corresponding iodine.
Applicants have found that, in phosphorus ore leaching process, using reducing leaching phosphorus ore technique, the height in phosphorus ore can be made
Chemical valence acid iodide double salt is reduced into free I2Molecule, recycles Phosphoric Acid Concentration technique in existing phosphoric acid production technique from phosphoric acid
It is middle to separate free I2Molecule, makes free I2Molecule is reclaimed after entering gas phase, is directly produced iodine.
According to the studies above, the technical solution adopted by the present invention is comprised the following steps：
(1) in hydrolysis procedure, to continuous in phosphate ore pulp acidolysis groove or be passed through gas SO with gap2, with phosphate ore pulp volume ratio
Calculate, per 1M330~300mg gases SO is passed through in phosphate ore pulp2；
In Phosphoric Acid Concentration operation, entered in gas phase with the sulfurous acid cleaning solution recycling elution that concentration is 0.1~7.0g/l
Free I2Molecule, obtains circulating cleaning solution containing iodine；
(3) concentration of circulating cleaning solution containing iodine for obtaining step (2), until in concentrate concentration of hydrogen iodide rise to 20~
150g/l；
(4) supernatant of above-mentioned steps (3) concentrate is taken, to excessive commercially available hydrogen peroxide is added in supernatant, is filtered, obtained
To solid phase iodine.
The main chemical reactions of above steps have：
NaIO3+SO2→I2+Na2SO4
I2+SO2+H2O→HI+H2SO4
HI+H2O2→I2+H2O
Further, per 1M in step (1)3100~150mg gases SO is passed through in phosphate ore pulp2。
Further, sulfurous acid cleaning solution concentration used by rapid (2) is 3~3.5g/l.
Further, concentration of hydrogen iodide is contained in 50~100g/l in step (3) gained concentrate.
The beneficial effects of the present invention are：One is by addition strong reducing property SO in acidolysis groove2Gas, in making phosphorus ore
Chemical valence acid iodide double salt high is reduced into free I2Molecule, so as to chemical valence iodine high is recycled into utilization, can reduce chemical valence high
The discharge and environmental pollution of acid iodide double salt；Two is not change Wet Processes of Phosphoric Acid, with containing H2SO3Cleaning solution recycling elution phosphoric acid
The water vapour of concentration technology evaporation, can be absorbed into the free I of gas phase2Molecule, realization is separated with phosphoric acid, is reclaimed with other phosphorus ores
The technique of iodine is compared, and technological process is simple, and energy consumption is low, and iodine cost recovery is low.
Specific embodiment
The technical scheme in the embodiment of the present invention is clearly and completely described below.
The useful phosphorus ore of institute of the invention is Cambrian marine deposit phosphorus ore, and the iodine in phosphorus ore is main with NaIO3\KIO3\Ca
(IO3)2And KH (IO3)2Contour chemical valence iodate double salt is present, and amount of iodine is in 15~40ppm or so.
Embodiment 1：
(1) in hydrolysis procedure, to continuous in phosphate ore pulp acidolysis groove or be passed through gas SO with gap2, with phosphate ore pulp volume ratio
Calculate, per 1M330mg gases SO is passed through in phosphate ore pulp2；
(2) in Phosphoric Acid Concentration operation, the trip entered in gas phase with the sulfurous acid cleaning solution recycling elution that concentration is 0.1g/l
From I2Molecule, obtains circulating cleaning solution containing iodine；
(3) above-mentioned circulating cleaning fluid containing iodine is concentrated with the method for evaporation, until concentration of hydrogen iodide reaches 20g/ in concentrate
l；
(4) supernatant of above-mentioned concentrate is taken, to the dioxygen that dropwise addition commercial gravimetric percent concentration in supernatant is 27%
The aqueous solution, untill no longer producing precipitation in solution, filtering obtains solid phase iodine.
Embodiment 2：
(1) in hydrolysis procedure, to continuous in phosphate ore pulp acidolysis groove or be passed through gas SO with gap2, with phosphate ore pulp volume ratio
Calculate, per 1M3300mg gases SO is passed through in phosphate ore pulp2；
(2) in Phosphoric Acid Concentration operation, the trip entered in gas phase with the sulfurous acid cleaning solution recycling elution that concentration is 7.0g/l
From I2Molecule, obtains circulating cleaning solution containing iodine；
(3) above-mentioned circulating cleaning fluid containing iodine is concentrated with the method for evaporation, until concentration of hydrogen iodide reaches 150g/ in concentrate
l；
(4) supernatant of above-mentioned concentrate is taken, to the dioxygen that dropwise addition commercial gravimetric percent concentration in supernatant is 27%
The aqueous solution, untill no longer producing precipitation in solution, filtering obtains solid phase iodine.
Embodiment 3：
(1) in hydrolysis procedure, to continuous in phosphate ore pulp acidolysis groove or be passed through gas SO with gap2, with phosphate ore pulp volume ratio
Calculate, per 1M3150mg gases SO is passed through in phosphate ore pulp2；
(2) in Phosphoric Acid Concentration operation, the trip entered in gas phase with the sulfurous acid cleaning solution recycling elution that concentration is 3.5g/l
From I2Molecule, obtains circulating cleaning solution containing iodine；
(3) above-mentioned circulating cleaning fluid containing iodine is concentrated with the method for evaporation, until concentration of hydrogen iodide reaches 50g/ in concentrate
l；
(4) supernatant of above-mentioned concentrate is taken, to the dioxygen that dropwise addition commercial gravimetric percent concentration in supernatant is 27%
The aqueous solution, untill no longer producing precipitation in solution, filtering obtains solid phase iodine.
Embodiment 4：
(1) in hydrolysis procedure, to continuous in phosphate ore pulp acidolysis groove or be passed through gas SO with gap2, with phosphate ore pulp volume ratio
Calculate, per 1M3100mg gases SO is passed through in phosphate ore pulp2；
(2) in Phosphoric Acid Concentration operation, with dissociating that the sulfurous acid cleaning solution recycling elution that concentration is 3g/l enters in gas phase
I2Molecule, obtains circulating cleaning solution containing iodine；
(3) above-mentioned circulating cleaning fluid containing iodine is concentrated with the method for evaporation, until concentration of hydrogen iodide reaches 100g/ in concentrate
l；
(4) supernatant of above-mentioned concentrate is taken, to the dioxygen that dropwise addition commercial gravimetric percent concentration in supernatant is 27%
The aqueous solution, untill no longer producing precipitation in solution, filtering obtains solid phase iodine.
Claims (4)
1. the method that phosphorus ore association chemical valence iodine high prepares iodine is reclaimed in Wet-process Phosphoric Acid Production, is comprised the following steps：
(1) in hydrolysis procedure, to continuous in phosphate ore pulp acidolysis groove or be passed through gas SO with gap2, calculated with phosphate ore pulp volume ratio,
Per 1M330~300mg gases SO is passed through in phosphate ore pulp2；
(2) in Phosphoric Acid Concentration operation, the trip entered in gas phase with the sulfurous acid cleaning solution recycling elution that concentration is 0.1~7.0g/l
From I2Molecule, obtains circulating cleaning solution containing iodine；
(3) concentration of circulating cleaning solution containing iodine for obtaining step (2), until concentration of hydrogen iodide rises to 20~150g/ in concentrate
l；
(4) supernatant of step (3) gained concentrate is taken, to excessive commercially available hydrogen peroxide is added in supernatant, is filtered, consolidate
Phase iodine.
2. the method that phosphorus ore association high price iodine prepares iodine, its feature are reclaimed in Wet-process Phosphoric Acid Production according to claim 1
It is：Per 1M in step (1)3100~150mg gases SO is passed through in phosphate ore pulp2。
3. the method that phosphorus ore association high price iodine prepares iodine is reclaimed in Wet-process Phosphoric Acid Production according to claim 1：Step (2)
Sulfurous acid cleaning solution concentration used is 3~3.5g/l.
4. the method that phosphorus ore association chemical valence iodine high prepares iodine is reclaimed in Wet-process Phosphoric Acid Production according to claim 1, its
It is characterized in：Containing concentration of hydrogen iodide in 50~100g/l in step (3) gained concentrate.
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| CN1284723C (en) * | 2003-09-10 | 2006-11-15 | 陈肖虎 | Method for extracting iodine from rejected material generated during production of phosphor product from iodine-containing phosphorus ore |
| CN101323434A (en) * | 2008-06-26 | 2008-12-17 | 瓮福（集团）有限责任公司 | Method for reclaiming iodine from concentrated phosphoric acid from wet method phosphoric acid production |
| CN101318625B (en) * | 2008-07-10 | 2010-06-09 | 贵州大学 | Method for recycling iodine from diluted phosphoric acid for phosphoric acid manufacture with wet-process |
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