CN105110296A - Method used for preparing iodine via recovery of phosphorus ore associated high valence iodine in wet phosphoric acid production - Google Patents
Method used for preparing iodine via recovery of phosphorus ore associated high valence iodine in wet phosphoric acid production Download PDFInfo
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- CN105110296A CN105110296A CN201510434732.6A CN201510434732A CN105110296A CN 105110296 A CN105110296 A CN 105110296A CN 201510434732 A CN201510434732 A CN 201510434732A CN 105110296 A CN105110296 A CN 105110296A
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- iodine
- phosphoric acid
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- phosphorus ore
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Abstract
The invention discloses a method used for preparing iodine via recovery of phosphorus ore associated high valence iodine in wet phosphoric acid production. According to the method, in the process of acidolysis, gas SO2 is delivered into a phosphoric ore pulp acidolysis tank continuously or intermittently; in the process of phosphoric acid concentration, recycling elution of free I2 molecules into a gas phase is carried out with sulphurous acid washing solution; an obtained recycling washing solution is subjected to concentration, hydrogen peroxide is added, and an obtained product is filtered so as to obtain solid phase iodine. According to the method, SO2 gas with strong reducing property is delivered into the phosphoric ore pulp acidolysis tank, so that salts of high valence iodine in phosphorus ore are reduced into free I2 molecules, and recovery of high valence iodine is realized, discharge of the salts of high valence iodine is reduced, and environmental pollution is avoided; at the same time, wet phosphoric acid production technology is not changed; the method is simple in processes; recovery cost is low; and additional value of obtained product iodine is high.
Description
Technical field
The present invention relates to the recoverying and utilizing method of association iodine resource in phosphorus ore, specifically in a kind of Wet-process Phosphoric Acid Production, reclaim the method that phosphorus ore association height valency iodine prepares iodine.
Background technology
Iodine resource is one of world's scarce resource, is the grand strategy material of country.In phosphorus ore, association iodine mainly exists with negative monovalence iodine and high valency iodate form.Negative monovalence iodine is mainly composed exists fluorapatite Ca
5[PO
4]
3f or carbon fluorine phosphorus ash Ca
5[PO
4, CO
3(OH)]
3in (F, OH); High valency iodate is then is mostly H
+na
+k
+ca
2+deng positively charged ion and [IO
3 -] the acid iodide Multiple salts forms that generates exists.
It is reported: the iodine in the phosphorus ore of marine deposit in cambrian period ore deposit is mainly with NaIO
3kIO
3ca (IO
3)
2and KH (IO
3)
2contour valency iodate double salt form is composed to be existed in collophanite.Phosphorus ore association iodine content is very low, and generally at about 16 ~ 35ppm, but reserves are huge.Therefore, research to be recovered in phosphorus ore raw iodine tool and to be of great significance.
At present, there is technician to study and reclaim association iodine phosphorus ore from phosphoric acid production.Such as, application number be 03135817.9 patent document discloses a kind of from the recirculated water, waste water, waste gas etc. that produce when producing phosphorus product containing iodine Rock Phosphate (72Min BPL) containing the method extracting iodine iodine waste.Application number is 200510003058.2 patent document discloses a kind of Wet Processes of Phosphoric Acid that utilizes extract the method for iodine from the dilute phosphoric acid produced containing iodine phosphorus ore.
Above-mentioned research is only limitted to reclaim the negative monovalence iodine in phosphoric acid.
Applicant studies discovery, and in Wet-process Phosphoric Acid Production, during with sulfuric acid leaching phosphorus ore, the high valency iodate in phosphorus ore can directly enter in liquid phase phosphoric acid, in Strong oxdiative state.Therefore, the method provided by above-mentioned patent 200510003058.2, can not be reduced into free I by the oxidation state iodine in phosphoric acid
2molecule, thus this iodine in phosphorus ore can not be reclaimed.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, the method reclaiming phosphorus ore association height valency iodine and prepare salt compounded of iodine is provided in a kind of Wet-process Phosphoric Acid Production, the environmental problem that the unordered discharge of acid iodide double salt that both can solve phosphorus ore association in phophatic fertilizer production process causes, can turn waste into wealth again, directly obtain corresponding iodine.
Applicant studies discovery, in phosphorus ore leaching process, adopts reducing leaching phosphorus ore technique, the high valency acid iodide double salt in phosphorus ore can be made to be reduced into free I
2molecule, recycles the Phosphoric Acid Concentration technique separated free I from phosphoric acid in existing phosphoric acid production technique
2molecule, makes free I
2molecule reclaims after entering gas phase, direct production iodine.
According to above-mentioned research, the technical solution used in the present invention comprises the following steps:
(1) at hydrolysis procedure, in phosphate ore pulp acidolysis groove, gas SO is passed into continuously or with gap
2, calculate with phosphate ore pulp volume ratio, every 1M
330 ~ 300mg gas SO is passed in phosphate ore pulp
2;
In Phosphoric Acid Concentration operation, enter the free I in gas phase with the sulfurous acid washings recycling elution that concentration is 0.1 ~ 7.0g/l
2molecule, obtains containing iodine circulating cleaning solution;
(3) what step (2) obtained concentrates, until concentration of hydrogen iodide rises to 20 ~ 150g/l in concentrated solution containing iodine circulating cleaning solution;
(4) get the supernatant liquor of above-mentioned steps (3) concentrated solution, in supernatant liquor, add excessive commercially available hydrogen peroxide, filter, obtain solid phase iodine.
The main chemical reactions of above steps has:
NaIO
3+SO
2→I
2+Na
2SO
4
I
2+SO
2+H
2O→HI+H
2SO
4
HI+H
2O
2→I
2+H
2O
Further, every 1M in step (1)
3100 ~ 150mg gas SO is passed in phosphate ore pulp
2.
Further, rapid (2) sulfurous acid washings used concentration is 3 ~ 3.5g/l.
Further, concentration of hydrogen iodide is contained in step (3) gained concentrated solution at 50 ~ 100g/l.
Beneficial effect of the present invention is: one is by adding strong reducing property SO in acidolysis groove
2gas, makes the high valency acid iodide double salt in phosphorus ore be reduced into free I
2molecule, thus high valency iodine is recycled utilization, discharge and the environmental pollution of high valency acid iodide double salt can be reduced; Two is do not change Wet Processes of Phosphoric Acid, with containing H
2sO
3the water vapor of washings recycling elution Phosphoric Acid Concentration technique evaporation, can absorb and enter gas phase and to dissociate I
2molecule, realizes being separated with phosphoric acid, and compared with the technique reclaiming iodine with other phosphorus ore, technical process is simple, and energy consumption is low, and iodine cost recovery is low.
Embodiment
Below the technical scheme in the embodiment of the present invention is clearly and completely described.
The useful phosphorus ore of the present invention is marine deposit in cambrian period phosphorus ore, and the iodine in phosphorus ore is mainly with NaIO
3kIO
3ca (IO
3)
2and KH (IO
3)
2contour valency iodate double salt exists, and amount of iodine is at about 15 ~ 40ppm.
Embodiment 1:
(1) at hydrolysis procedure, in phosphate ore pulp acidolysis groove, gas SO is passed into continuously or with gap
2, calculate with phosphate ore pulp volume ratio, every 1M
330mg gas SO is passed in phosphate ore pulp
2;
(2) in Phosphoric Acid Concentration operation, the free I in gas phase is entered with the sulfurous acid washings recycling elution that concentration is 0.1g/l
2molecule, obtains containing iodine circulating cleaning solution;
(3) concentrate by the method for evaporation above-mentioned containing iodine circulating cleaning fluid, until concentration of hydrogen iodide reaches 20g/l in concentrated solution;
(4) get the supernatant liquor of above-mentioned concentrated solution, in supernatant liquor, drip the hydrogen peroxide solution that commercial gravimetric percentage concentration is 27%, until no longer produce precipitation in solution, filter, obtain solid phase iodine.
Embodiment 2:
(1) at hydrolysis procedure, in phosphate ore pulp acidolysis groove, gas SO is passed into continuously or with gap
2, calculate with phosphate ore pulp volume ratio, every 1M
3300mg gas SO is passed in phosphate ore pulp
2;
(2) in Phosphoric Acid Concentration operation, the free I in gas phase is entered with the sulfurous acid washings recycling elution that concentration is 7.0g/l
2molecule, obtains containing iodine circulating cleaning solution;
(3) concentrate by the method for evaporation above-mentioned containing iodine circulating cleaning fluid, until concentration of hydrogen iodide reaches 150g/l in concentrated solution;
(4) get the supernatant liquor of above-mentioned concentrated solution, in supernatant liquor, drip the hydrogen peroxide solution that commercial gravimetric percentage concentration is 27%, until no longer produce precipitation in solution, filter, obtain solid phase iodine.
Embodiment 3:
(1) at hydrolysis procedure, in phosphate ore pulp acidolysis groove, gas SO is passed into continuously or with gap
2, calculate with phosphate ore pulp volume ratio, every 1M
3150mg gas SO is passed in phosphate ore pulp
2;
(2) in Phosphoric Acid Concentration operation, the free I in gas phase is entered with the sulfurous acid washings recycling elution that concentration is 3.5g/l
2molecule, obtains containing iodine circulating cleaning solution;
(3) concentrate by the method for evaporation above-mentioned containing iodine circulating cleaning fluid, until concentration of hydrogen iodide reaches 50g/l in concentrated solution;
(4) get the supernatant liquor of above-mentioned concentrated solution, in supernatant liquor, drip the hydrogen peroxide solution that commercial gravimetric percentage concentration is 27%, until no longer produce precipitation in solution, filter, obtain solid phase iodine.
Embodiment 4:
(1) at hydrolysis procedure, in phosphate ore pulp acidolysis groove, gas SO is passed into continuously or with gap
2, calculate with phosphate ore pulp volume ratio, every 1M
3100mg gas SO is passed in phosphate ore pulp
2;
(2) in Phosphoric Acid Concentration operation, the free I in gas phase is entered with the sulfurous acid washings recycling elution that concentration is 3g/l
2molecule, obtains containing iodine circulating cleaning solution;
(3) concentrate by the method for evaporation above-mentioned containing iodine circulating cleaning fluid, until concentration of hydrogen iodide reaches 100g/l in concentrated solution;
(4) get the supernatant liquor of above-mentioned concentrated solution, in supernatant liquor, drip the hydrogen peroxide solution that commercial gravimetric percentage concentration is 27%, until no longer produce precipitation in solution, filter, obtain solid phase iodine.
Claims (4)
1. reclaim the method that phosphorus ore association height valency iodine prepares iodine in Wet-process Phosphoric Acid Production, comprise the following steps:
(1) at hydrolysis procedure, in phosphate ore pulp acidolysis groove, gas SO is passed into continuously or with gap
2, calculate with phosphate ore pulp volume ratio, every 1M
330 ~ 300mg gas SO is passed in phosphate ore pulp
2;
(2) in Phosphoric Acid Concentration operation, the free I in gas phase is entered with the sulfurous acid washings recycling elution that concentration is 0.1 ~ 7.0g/l
2molecule, obtains containing iodine circulating cleaning solution;
(3) what step (2) obtained concentrates, until concentration of hydrogen iodide rises to 20 ~ 150g/l in concentrated solution containing iodine circulating cleaning solution;
(4) get the supernatant liquor of step (3) gained concentrated solution, in supernatant liquor, add excessive commercially available hydrogen peroxide, filter, obtain solid phase iodine.
2. reclaim the method that phosphorus ore association high price iodine prepares iodine in Wet-process Phosphoric Acid Production according to claim 1, it is characterized in that: every 1M in step (1)
3100 ~ 150mg gas SO is passed in phosphate ore pulp
2.
3. reclaim the method that phosphorus ore association high price iodine prepares iodine in Wet-process Phosphoric Acid Production according to claim 1: step (2) sulfurous acid washings used concentration is 3 ~ 3.5g/l.
4. reclaim the method that phosphorus ore association height valency iodine prepares iodine in Wet-process Phosphoric Acid Production according to claim 1, it is characterized in that: contain concentration of hydrogen iodide in step (3) gained concentrated solution at 50 ~ 100g/l.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510434732.6A CN105110296B (en) | 2015-07-21 | 2015-07-21 | The method that phosphorus ore association chemical valence iodine high prepares iodine is reclaimed in Wet-process Phosphoric Acid Production |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510434732.6A CN105110296B (en) | 2015-07-21 | 2015-07-21 | The method that phosphorus ore association chemical valence iodine high prepares iodine is reclaimed in Wet-process Phosphoric Acid Production |
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| CN105110296B CN105110296B (en) | 2017-06-27 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1676461A (en) * | 2003-09-10 | 2005-10-05 | 陈肖虎 | Method for extracting iodine from rejected material generated during production of phosphor product from iodine-containing phosphorus ore |
| CN101318625A (en) * | 2008-07-10 | 2008-12-10 | 贵州大学 | Method for recycling iodine from diluted phosphoric acid for phosphoric acid manufacture with wet-process |
| 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 |
-
2015
- 2015-07-21 CN CN201510434732.6A patent/CN105110296B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1676461A (en) * | 2003-09-10 | 2005-10-05 | 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 |
| CN101318625A (en) * | 2008-07-10 | 2008-12-10 | 贵州大学 | Method for recycling iodine from diluted phosphoric acid for phosphoric acid manufacture with wet-process |
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