CN101033067A - Method of eliminating arsenic by fluosilicic acid - Google Patents
Method of eliminating arsenic by fluosilicic acid Download PDFInfo
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- CN101033067A CN101033067A CN 200710077736 CN200710077736A CN101033067A CN 101033067 A CN101033067 A CN 101033067A CN 200710077736 CN200710077736 CN 200710077736 CN 200710077736 A CN200710077736 A CN 200710077736A CN 101033067 A CN101033067 A CN 101033067A
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- arsenic
- fluoride solution
- silicate fluoride
- sulfide
- fluosilicic acid
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Abstract
This invention discloses a method for eliminating As to fluosilicic acid, which puts a fluosilicic acid solution containing 50-100mg/L As in a reactor with a beater, heats it with a vapour to 30-90deg.C and mixes it in the speed of 50-400r/m and adds an As-elimination agent steadily to the reactor in the weight of 0.1-0.6% that of fluosilicic acid solution, then reacts them for 30-200m and puts the solution into a cleaifying tank to be idled for 1-6h to be filtered to separate sulfide deposition of As to get a fluosilicic acid solution with low As.
Description
Technical field
The invention belongs to chemical field, relate in particular to a kind of method of silicate fluoride solution arsenic removal.
Background technology
Fluorine is one of important associated resources of phosphorus ore.The fluorine content of phosphorus ore is generally 3～4%.Different with phosphorus ore working method and fluorine removal process, the impurity that contains in the by-product fluosilicic acid is also different.In Wet-process Phosphoric Acid Production, the fluorochemical major part that enters dilute phosphoric acid changes gas phase in the Phosphoric Acid Concentration process, through washing with absorb that to obtain concentration be 12～30% silicofluoric acid.The arsenic that contains in the phosphorus ore, it also enters dilute phosphoric acid, and partly enters silicofluoric acid, and the arsenic content that makes silicofluoric acid is more than dozens of mg/L.Silicofluoric acid is a basic raw material of producing many other fluorochemicalss, as silicofluorides such as Sodium Silicofluoride, potassium silicofluoride, magnesium silicofluoride, cuprichexafluorosilicate, barium silicofluoride, calcium silicofluoride, silicon tetrafluoride, Neutral ammonium fluoride, aluminum fluoride, hydrogen fluoride etc.Be used for the electrolytic refining, fluoridation of water of Metal plating, wood preservation, equipment disinfection, aluminium etc., can also be used as mordant, metal conditioner, tanning, glass etching, cement solidification, grease acidifying, textiles and remove rust staining, plumbous refining etc.The quality of silicofluoric acid has usually determined to produce the feasibility and the economy of these fluorochemicalss.
U.S. Pat 3592590 discloses a kind of silicate fluoride solution method of purification.The silicate fluoride solution of impure (Vanadium Pentoxide in FLAKES and organism) is used vitriolization earlier, heated mixt, and with the vapor space of superheated vapour purging mixture top, condensation purges steam, and water absorbs the silicate fluoride solution that all the other steams are purified again.U.S. Pat 3386892 discloses a kind of rare silicate fluoride solution and phosphoric acid forms the normal pressure continuous rectification method of purification that boiling point is about 120 ℃ mixture, reclaims purified silicate fluoride solution from the rectifying gas phase.English Patent GB1413905 discloses a kind of rare silicate fluoride solution method of enrichment.Evaporate the thick silicate fluoride solution that contains Vanadium Pentoxide in FLAKES earlier in first section, the steam that reclaims from first section under lower pressure in second section obtains purer silicate fluoride solution again.Japanese Patent JP6247708 discloses a kind of silicate fluoride solution method of purification.In silicate fluoride solution, add potassium permanganate oxidant, remove sulfide, phosphide, boride, arsenide etc. through adding thermal rectification again.
The evaporation concentration behavior of silicate fluoride solution is very complicated.The steam that evaporation enters the silicofluoric acid in the gas phase almost completely is decomposed into hydrogen fluoride and silicon tetrafluoride.Since the difference of initial silicate fluoride solution concentration, and hydrofluoric volatility is lower, and the ratio of contained hydrogen fluoride and silicon tetrafluoride is just different in the steam.Concentration is lower than 13% silicate fluoride solution, and the overhead product that rectifying obtains contains more hydrogen fluoride than silicofluoric acid, and concentration is higher than 13% silicate fluoride solution, and the overhead product that rectifying obtains contains still less hydrogen fluoride than silicofluoric acid.In addition, when silicofluoric acid concentration reached 45%, silicofluoric acid and water can form an azeotrope with maximum boiling point.When producing high-pure anhydrous hydrogen fluoride with silicofluoric acid, arsenic is an impurity that is harmful to and must removes.Therefore, for guaranteeing the quality of anhydrous hydrogen fluoride, must be to the arsenic removal of raw material silicate fluoride solution.
In the above-mentioned patent relevant, have only Japanese Patent JP6247708 to relate to arsenic removal with the silicate fluoride solution purification.It adopts the method for oxidation in conjunction with rectifying, flow process complexity; Potassium permanganate also can cause forming insoluble potassium silicofluoride and the loss that brings silicofluoric acid.
Because chemical precipitation method technology is simple, invest low, the prefered method of arsenic removal often.To the silicate fluoride solution arsenic removal, be dearsenic agent as adopting sodium sulphite, because silicofluoric acid and sodium ion can form the very low Sodium Silicofluoride of solubleness, can cause the silicofluoric acid unnecessary loss; As to adopt thiophosphoric anhydride be dearsenic agent, can increase undesirable foreign matter of phosphor in the silicate fluoride solution.
Therefore, during the silicate fluoride solution arsenic removal, should guarantee that total effect of arsenic removal satisfies the requirement of silicofluoric acid following process, consider the simplification of arsenic removal process again, and reduce the loss of silicofluoric acid as far as possible.
Summary of the invention
The silicate fluoride solution dearsenification that the objective of the invention is to overcome above-mentioned shortcoming and provide is effective, and technical process is simple, less investment and can not cause the method for eliminating arsenic by fluosilicic acid of the on-mechanical loss of silicofluoric acid.
The method of a kind of eliminating arsenic by fluosilicic acid of the present invention may further comprise the steps:
(1) silicate fluoride solution with the about 50-100 mg/litre of arsenic content places in the reactor of belt stirrer;
(2) heat to 30～90 ℃ with steam, under stirring state, stirring velocity is 50～400 rev/mins, in reactor, progressively add arsenic removing agent, its addition is 0.1～0.6% (sulfide precipitation that makes arsenic in the silicate fluoride solution form arsenic is separated out) of silicate fluoride solution weight, the silicate fluoride solution of reactor internal reaction after 30～200 minutes is put into clarifying tank leave standstill and display;
(3) in clarifying tank, send to filtration, separate the sulfide precipitation of arsenic, obtain the low silicate fluoride solution of arsenic content through the silicate fluoride solution that leaves standstill after displaying 1～6 hour.
The method of above-mentioned eliminating arsenic by fluosilicic acid, wherein arsenic removing agent comprises the sulfide of period of element Table VIII family's metal and heavy metal and/or their mixture, as Iron sulfuret, nickelous sulfide, cobaltous sulfide, zinc sulphide, manganese sulfide, hydrogen sulfide etc.
The method of above-mentioned eliminating arsenic by fluosilicic acid, wherein arsenic removing agent is an Iron sulfuret.
Method of the present invention compared with prior art, arsenic has several forms that exist in the aqueous solution, depend on the pH and the oxidation position of water, but is trivalent arsenic and pentavalent arsenic pattern.Be lower than at 2 o'clock at pH, arsenic is with H
3AsO
3And H
3AsO
4Exist, and be dissociative not.Therefore, silicate fluoride solution adopts the sulfide arsenic removal, and what mainly form is Yellow arsenic sulfide and Diarsenic pentasulfide.Because the arsenic content of silicate fluoride solution is not high, the arsenic removal dosage of interpolation is few, and the silicofluoride precipitation that can not form associated metal causes the silicofluoric acid loss.The silicate fluoride solution effect of removing arsenic is good, need not oxidation, and technical process is simpler, less investment.
Embodiment
Embodiment 1-9
Get arsenic content that the phosphoric acid by wet process concentration process reclaims and be 67.2 mg/litre, weight concentration and be 18.2% silicate fluoride solution 10 liters (density is 1.17 kilograms/liter) in reactor, 60 ℃ of controlled temperature.Stirring velocity is 200 rev/mins.After reaching specified temperature, under agitation add Iron sulfuret 32.5～52.5 gram, reacted 30～110 minutes, leave standstill to display after 22 hours and refilter, the arsenic content that obtains the dearsenification silicate fluoride solution sees Table 1.
The reaction conditions and the result of the arsenic removal of table 1 silicate fluoride solution
| Embodiment | Dearsenification dosage (gram) | Reaction times (minute) | Arsenic content (mg/litre) |
| 1 | 32.5 | 70 | 4.63 |
| 2 | 35.0 | 40 | 5.09 |
| 3 | 35.0 | 100 | 1.55 |
| 4 | 42.5 | 30 | 3.91 |
| 5 | 42.5 | 70 | 0.67 |
| 6 | 42.5 | 110 | 0.37 |
| 7 | 50.0 | 40 | 2.98 |
| 8 | 50.0 | 100 | 0.34 |
| 9 | 52.5 | 70 | 0.39 |
Embodiment 10
The silicate fluoride solution 10 liters (density is 1.20 kilograms/liter) of getting arsenic content that the phosphoric acid by wet process concentration process reclaims and be 90.0 mg/litre, weight concentration 19.5% is in reactor, and controlled temperature is 50 ℃, and stirring velocity is 50 rev/mins.After reaching specified temperature, under agitation add Iron sulfuret 50.0 gram, reacted 100 minutes, leave standstill to display after 1 hour and refilter, the arsenic content that obtains concentration 19.7% dearsenification silicate fluoride solution is 0.4 mg/litre.
Embodiment 11-18
Get about 54.5 mg/litre of arsenic content, weight concentration that the phosphoric acid by wet process concentration process reclaims and be 19.1% silicate fluoride solution 10 liters (density is 1.19 kilograms/liter) in reactor, controlled temperature is 40～80 ℃, and stirring velocity is 400 rev/mins.After reaching specified temperature, under agitation add Iron sulfuret 45 gram, reacted 30～110 minutes, leave standstill to display after 6 hours and refilter.The arsenic content that obtains the dearsenification silicate fluoride solution sees Table 2.
The reaction conditions and the result of the arsenic removal of table 2 silicate fluoride solution
| Embodiment | Temperature (℃) | Reaction times ((minute)) | Arsenic content (mg/litre) |
| 11 | 40 | 70 | 17.31 |
| 12 | 45 | 100 | 11.63 |
| 13 | 60 | 30 | 9.04 |
| 14 | 60 | 70 | 0.47 |
| 15 | 60 | 110 | 0.04 |
| 16 | 75 | 40 | 0.22 |
| 17 | 75 | 100 | 4.88 |
| 18 | 80 | 70 | 0.88 |
Embodiment 19
Get about 54.5 mg/litre of arsenic content, weight concentration that the phosphoric acid by wet process concentration process reclaims and be 19.1% silicate fluoride solution 10 liters (density is 1.19 kilograms/liter) in reactor, controlled temperature is 70 ℃.Stirring velocity is 300 rev/mins.After reaching specified temperature, under agitation add zinc sulphide 60 gram, reacted 100 minutes, leave standstill to display after 4 hours and refilter.The arsenic content that obtains the dearsenification silicate fluoride solution is 0.9 mg/litre.
Embodiment 20
Get about 54.5 mg/litre of arsenic content, weight concentration that the phosphoric acid by wet process concentration process reclaims and be 19.1% silicate fluoride solution 10 liters (density is 1.19 kilograms/liter) in reactor, controlled temperature is 30 ℃.Stirring velocity is 200 rev/mins.After reaching specified temperature, under agitation bubbling feeds hydrogen sulfide, reacts to refilter after 60 minutes.The arsenic content that obtains the dearsenification silicate fluoride solution is 0.8 mg/litre.
Claims (4)
1, a kind of method of eliminating arsenic by fluosilicic acid may further comprise the steps:
(1) silicate fluoride solution with arsenic content 50-100 mg/litre places in the reactor of belt stirrer;
(2) heat to 30～90 ℃ with steam, under stirring state, stirring velocity is 50～400 rev/mins, in reactor, progressively add arsenic removing agent, its addition is 0.1～0.6% of a silicate fluoride solution weight, the silicate fluoride solution of reactor internal reaction after 30～200 minutes is put into clarifying tank leave standstill and display;
(3) in clarifying tank, send to filtration, separate the sulfide precipitation of arsenic, obtain the low silicate fluoride solution of arsenic content through the silicate fluoride solution that leaves standstill after displaying 1～6 hour.
2, the method for eliminating arsenic by fluosilicic acid as claimed in claim 1, wherein arsenic removing agent comprises the sulfide of period of element Table VIII family's metal and heavy metal and/or their mixture.
3, the method for eliminating arsenic by fluosilicic acid as claimed in claim 1 or 2, wherein arsenic removing agent is Iron sulfuret, nickelous sulfide, cobaltous sulfide, zinc sulphide, manganese sulfide, hydrogen sulfide.
4, the method for eliminating arsenic by fluosilicic acid as claimed in claim 3, wherein arsenic removing agent is an Iron sulfuret.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100777369A CN100480181C (en) | 2007-04-20 | 2007-04-20 | Method of eliminating arsenic by fluosilicic acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100777369A CN100480181C (en) | 2007-04-20 | 2007-04-20 | Method of eliminating arsenic by fluosilicic acid |
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| CN101033067A true CN101033067A (en) | 2007-09-12 |
| CN100480181C CN100480181C (en) | 2009-04-22 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110921711A (en) * | 2019-10-31 | 2020-03-27 | 郴州丰越环保科技有限公司 | Preparation method and application of nanoscale manganese sulfide |
| CN115259441A (en) * | 2022-07-05 | 2022-11-01 | 铜陵有色金属集团股份有限公司 | Process for removing arsenic from waste acid |
| US11639302B2 (en) | 2016-11-10 | 2023-05-02 | Mexichem Fluor S.A. De C.V. | Process for reducing the concentration of arsenic in an aqueous solution comprising a fluoroacid |
| CN116251561A (en) * | 2023-05-02 | 2023-06-13 | 瓮福（集团）有限责任公司 | Synthesis method and application of carbon nitride composite oxidation adsorbent |
-
2007
- 2007-04-20 CN CNB2007100777369A patent/CN100480181C/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11639302B2 (en) | 2016-11-10 | 2023-05-02 | Mexichem Fluor S.A. De C.V. | Process for reducing the concentration of arsenic in an aqueous solution comprising a fluoroacid |
| CN110921711A (en) * | 2019-10-31 | 2020-03-27 | 郴州丰越环保科技有限公司 | Preparation method and application of nanoscale manganese sulfide |
| CN115259441A (en) * | 2022-07-05 | 2022-11-01 | 铜陵有色金属集团股份有限公司 | Process for removing arsenic from waste acid |
| CN115259441B (en) * | 2022-07-05 | 2023-11-24 | 铜陵有色金属集团股份有限公司 | Process for removing arsenic in waste acid |
| CN116251561A (en) * | 2023-05-02 | 2023-06-13 | 瓮福（集团）有限责任公司 | Synthesis method and application of carbon nitride composite oxidation adsorbent |
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|---|---|
| CN100480181C (en) | 2009-04-22 |
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Application publication date: 20070912 Assignee: Guizhou Wengfu Lantian Fluoride Chemicals Co., Ltd. Assignor: Urn Fu (Group) limited liability company|Guizhou University Contract record no.: 2010520000007 Denomination of invention: Method of eliminating arsenic by fluosilicic acid Granted publication date: 20090422 License type: Common License Record date: 20100419 |