CN105129820A - Method of recycling phosphorite-associated high-valence iodine from wet-method phosphoric acid production to prepare iodized salt - Google Patents
Method of recycling phosphorite-associated high-valence iodine from wet-method phosphoric acid production to prepare iodized salt Download PDFInfo
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- CN105129820A CN105129820A CN201510434696.3A CN201510434696A CN105129820A CN 105129820 A CN105129820 A CN 105129820A CN 201510434696 A CN201510434696 A CN 201510434696A CN 105129820 A CN105129820 A CN 105129820A
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- iodine
- phosphoric acid
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- gas
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Abstract
The invention discloses a method of recycling phosphorite-associated high-valence iodine from wet-method phosphoric acid production to prepare iodized salt. In an acidolysis process, SO2 gas is continuously or intermittently fed into a phosphoric ore pulp acidolysis tank. In an phosphoric concentration process, free iodine molecules entering the gas phase are circularly eluted through a sulfurous acid washing liquid, wherein the circulated washing liquid is concentrated and then is added with a precipitating agent for removing impurities and filtering the washing liquid, and then sodium oxide, potassium hydroxide, sodium carbonate or potassium carbonate is added, and finally the liquid is filtered to obtain solid iodized salt. By feeding the SO2 gas, which is strong in reducing property, into the phosphoric ore pulp acidolysis tank, high-valence double iodates in phosphorite are reduced into the free iodine molecules, so that the high-valence iodine is recycled. The method reduces emission of the high-valence double iodates and environment pollution, does not change the original wet-method phosphoric acid process, is simple in processes, is low in recycling cost and is high in additional value of the iodized salt.
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 salt compounded of 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, the patent No. be ZL03135817.9 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.The patent No. is that ZL200510003058.2 patent document discloses a kind of method utilizing Wet Processes of Phosphoric Acid to extract iodine from the dilute phosphoric acid produced containing iodine phosphorus ore.
Above-mentioned research is only limitted to reclaim the iodine in negative monovalence.
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 salt compounded of 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 salt compounded of 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;
(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) circulating cleaning solution being rich in hydrogen iodide step (2) obtained concentrates, until concentration of hydrogen iodide rises to 20 ~ 150g/l in concentrated solution;
(4) get the supernatant liquor of step (3) gained concentrated solution, in supernatant liquor, add the Ba (OH) that excessive weight percent concentration is 1 ~ 3%
2solution, filters;
(5) add excessive sodium oxide or potassium hydroxide or sodium carbonate or salt of wormwood in the filtered liquid obtained to step (4), filter, obtain the corresponding salt compounded of iodine of solid phase.
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
Ba(OH)
2+H
2SO
4→H
2O+BaSO
4
HI+NaOH→NaI+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
3washings recycling elution Phosphoric Acid Concentration technique evaporation water vapor, free I can be made
2molecule enters gas phase, and realize being separated of iodine and phosphoric acid, compared with the technique reclaiming iodine with other phosphorus ore, technical process is simple; Without Roots's wind, function consumption is low; Cost recovery is low; Three is that the iodine absorption liquid of recovery is directly prepared salt compounded of iodine, can improving product added value.
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 fluid;
(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 Ba (OH) that weight percent concentration is 1%
2solution, until no longer produce precipitation in solution, filters;
(5) sodium oxide or potassium hydroxide or sodium carbonate or salt of wormwood is slowly added in the filtered liquid obtained to step (4), calculate with molar weight, the add-on of sodium oxide or potassium hydroxide or sodium carbonate or salt of wormwood in and 1.1 times of theoretical amount needed for HI, filter, obtain the corresponding salt compounded of iodine of solid phase.
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 fluid;
(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 Ba (OH) that weight percent concentration is 3%
2solution, until no longer produce precipitation in solution, filters;
(5) sodium oxide or potassium hydroxide or sodium carbonate or salt of wormwood is slowly added in the filtered liquid obtained to step (4), calculate with molar weight, the add-on of sodium oxide or potassium hydroxide or sodium carbonate or salt of wormwood in and 1.05 times of theoretical amount needed for HI, filter, obtain the corresponding salt compounded of iodine of solid phase.
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 fluid;
(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 Ba (OH) that weight percent concentration is 2%
2solution, until no longer produce precipitation in solution, filters;
(5) sodium oxide or potassium hydroxide or sodium carbonate or salt of wormwood is slowly added in the filtered liquid obtained to step (4), calculate with molar weight, the add-on of sodium oxide or potassium hydroxide or sodium carbonate or salt of wormwood in and 1.05 times of theoretical amount needed for HI, filter, obtain the corresponding salt compounded of iodine of solid phase.
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 fluid;
(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 Ba (OH) that weight percent concentration is 2.5%
2solution, until no longer produce precipitation in solution, filters;
(5) sodium oxide or potassium hydroxide or sodium carbonate or salt of wormwood is slowly added in the filtered liquid obtained to step (4), calculate with molar weight, the add-on of sodium oxide or potassium hydroxide or sodium carbonate or salt of wormwood in and 1.02 times of theoretical amount needed for HI, filter, obtain the corresponding salt compounded of iodine of solid phase.
Claims (4)
1. reclaim the method that phosphorus ore association height valency iodine prepares salt compounded of 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) circulating cleaning solution being rich in iodine step (2) obtained concentrates, until concentration of hydrogen iodide rises to 20 ~ 150g/l in concentrated solution;
(4) get the supernatant liquor of step (3) gained concentrated solution, in supernatant liquor, add the Ba (OH) that excessive weight percent concentration is 1 ~ 3%
2solution, filters;
(5) add excessive sodium oxide or potassium hydroxide or sodium carbonate or salt of wormwood in the filtered liquid obtained to step (4), filter, obtain the corresponding salt compounded of iodine of solid phase.
2. reclaim the method that phosphorus ore association height valency iodine prepares salt compounded of 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 height valency iodine prepares salt compounded of 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 salt compounded of 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 |
|---|---|---|---|
| CN201510434696.3A CN105129820B (en) | 2015-07-21 | 2015-07-21 | Method of recycling phosphorite-associated high-valence iodine from wet-method phosphoric acid production to prepare iodized salt |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510434696.3A CN105129820B (en) | 2015-07-21 | 2015-07-21 | Method of recycling phosphorite-associated high-valence iodine from wet-method phosphoric acid production to prepare iodized salt |
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| Publication Number | Publication Date |
|---|---|
| CN105129820A true CN105129820A (en) | 2015-12-09 |
| CN105129820B CN105129820B (en) | 2017-01-25 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04176169A (en) * | 1990-11-08 | 1992-06-23 | Sony Corp | Semiconductor memory |
| 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 |
| CN1706744A (en) * | 2005-04-29 | 2005-12-14 | 贵州宏福实业开发有限总公司 | Process of extracting iodine from dilute phosphoric acid produced in iodine-containing phosphate ore production |
| 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 |
| CN102502504A (en) * | 2011-10-26 | 2012-06-20 | 瓮福（集团）有限责任公司 | Method for preparing iodized salt from iodine-contained absorption solution |
-
2015
- 2015-07-21 CN CN201510434696.3A patent/CN105129820B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04176169A (en) * | 1990-11-08 | 1992-06-23 | Sony Corp | Semiconductor memory |
| 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 |
| CN1706744A (en) * | 2005-04-29 | 2005-12-14 | 贵州宏福实业开发有限总公司 | Process of extracting iodine from dilute phosphoric acid produced in iodine-containing phosphate ore production |
| 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 |
| CN102502504A (en) * | 2011-10-26 | 2012-06-20 | 瓮福（集团）有限责任公司 | Method for preparing iodized salt from iodine-contained absorption solution |
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| CN105129820B (en) | 2017-01-25 |
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