CN104370277A - Method for recycling fluorine from phosphorus-containing fluorine slag and cogenerating calcium superphosphate - Google Patents
Method for recycling fluorine from phosphorus-containing fluorine slag and cogenerating calcium superphosphate Download PDFInfo
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- CN104370277A CN104370277A CN201410580753.4A CN201410580753A CN104370277A CN 104370277 A CN104370277 A CN 104370277A CN 201410580753 A CN201410580753 A CN 201410580753A CN 104370277 A CN104370277 A CN 104370277A
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- Prior art keywords
- fluorine
- containing slag
- phosphor
- fluorine containing
- calcium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/055—Peroxyhydrates; Peroxyacids or salts thereof
- C01B15/16—Peroxyhydrates; Peroxyacids or salts thereof containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
- C01B7/191—Hydrogen fluoride
Abstract
The invention discloses a method for recycling fluorine from a phosphorus-containing fluorine slag and cogenerating calcium superphosphate. The method comprises the following steps: adding a phosphorus-containing fluorine slag and concentrated sulfuric acid to a defluorination reaction tank according to the ratio of 1 to (0.6-1.1), stirring and reacting at 60-200 DEG C for 0.1-3 hours; recovering escaped fluorine-containing gas in the reaction process and preparing fluoride products such as hydrofluoric acid and the like to recover fluorine resources; stirring and reacting the phosphorus-containing fluorine slag and the concentrated sulfuric acid in the defluorination reaction tank for 0.1-3 hours; adding a phosphorus-containing calcium material to reaction slurry, stirring and reacting for 0.1-5 hours, and neutralizing free acids in the slurry; and drying the reactants after reacting, so as to obtain a calcium superphosphate product. Compared with the prior art, the method has the characteristics of being simple in process, mild in operation condition, high in recovery rate of phosphorus-fluorine resources, and free of 'three wastes' on the whole.
Description
Technical field
The present invention relates to phosphorous chemical industry field of waste treatment, relate in particular to a kind of method reclaiming fluorine co-production calcium superphosphate from phosphor fluorine containing slag.
Background technology
China's sulphur dioxide of phosphor chemical industry can produce a large amount of phosphor fluorine containing waste water in Wet-process Phosphoric Acid Production process, and in the process of process phosphor fluorine containing fluorinion in waste water, main employing adds the calcium salt such as milk of lime, calcium carbonate to precipitate the fluorion in waste water, and filtering-depositing slag obtains P
2o
5content is about 15% ~ 28%, F content be about 15% ~ 30% phosphor fluorine containing slag.This phosphor fluorine containing slag, due to containing a large amount of F, directly may cause dunsiekte as fertilizer application in farm crop; And be citric acid soluble phosphorus because institute in this phosphor fluorine containing slag is phosphorous, can be subject to adding restriction because of the requirement of water-soluble phosphorus content in fertilizer for the production of during fertilizer.Based on above reason, this phosphor fluorine containing slag mainly stores up process as waste at present, does not only utilize the phosphorus fluorine resource in slag, also stores up land occupation, pays expensive maintenance cost, and also causes certain pollution to environment.
Be disclose in the patent documentation of 201110319555.9 " a kind of method reclaiming phosphorus and fluorine in defluorination residues " at application number, this patent is with reference to the phosphorus in the method recovery defluorination residues of traditional sulfuric acid decomposition phosphorus ore and fluorine resource, but complex process, facility investment is large, and the rate of recovery of fluorine resource is lower.
Be disclose " preparing hydrogen fluoride by Calcium Fluoride (Fluorspan) and sulfuric acid " in the patent documentation of 200880003959.3 at application number, fine powder and the sulfuric acid reaction of this patent fluorinated calcium produce hydrogen fluoride, but sulfuric acid dosage is greatly excessive, temperature of reaction is high, and equipment and materials requires high.
Summary of the invention
The object of the invention is to overcome above-mentioned shortcoming and provide a kind of method reclaiming fluorine co-production calcium superphosphate from phosphor fluorine containing slag, the method has that technique is simple, operational condition is gentle, phosphorus fluorine resource recovery is high, substantially without the feature that " three wastes " produce.
For achieving the above object, the technical solution used in the present invention is: a kind of method reclaiming fluorine co-production calcium superphosphate from phosphor fluorine containing slag, comprises the following steps:
(1) by all in butt P
2o
5content is 15% ~ 28%, F content is 15% ~ 30%, water content be 20% ~ 100% phosphor fluorine containing slag and the vitriol oil to join in defluorination reaction groove stirring reaction 0.1 ~ 3h at 60 ~ 200 DEG C, phosphor fluorine containing slag (in butt) and the vitriol oil (pure H
2sO
4) add-on be 1:0.6 ~ 1.1, adopt in reaction process the traditional method known by those skilled in the art reclaim effusion fluoro-gas make fluorochemical Product recycling fluorine resource.
(2) phosphor fluorine containing slag and the vitriol oil are in defluorination reaction groove after stirring reaction 0.1 ~ 3h, add in phosphorous calcium thing stirring reaction 0.1 ~ 5h and free acid in slip, after reaction, reactants dry is obtained calcium superphosphate product in reaction slurry.
In above-mentioned phosphor fluorine containing slag, phosphorus exists with one or more forms in secondary calcium phosphate, monocalcium phosphate, tricalcium phosphate, and fluorine exists with the form of Calcium Fluoride (Fluorspan).
The above-mentioned vitriol oil is 70% ~ 100% H by weight
2sO
4sulfuric acid.
Above-mentioned fluorochemical can be one or more in Sodium Fluoride, Neutral ammonium fluoride, ammonium bifluoride, aluminum fluoride, Calcium Fluoride (Fluorspan), anhydrous hydrogen fluoride and hydrofluoric acid.
Above-mentioned phosphorous calcium thing is one or both in ground phosphate rock, secondary calcium phosphate.
The add-on of above-mentioned phosphorous calcium thing is 10% ~ 50% of phosphor fluorine containing slag butt weight, and makes calcium superphosphate product Free Acid (with P
2o
5meter) massfraction be less than 5.5%.
Contriver points out: relative under about 300 DEG C of high temperature of routine, Calcium Fluoride (Fluorspan) and sulfuric acid react under anhydrous system produces the technique that hydrogen fluoride reclaims fluorine resource, the present invention is in an Aquo System and make Calcium Fluoride (Fluorspan) and sulfuric acid reaction under lesser temps, mixing of materials is even, react quick and complete, and because water-content in reaction system limits, fluorine is overflowed effective, can up to 95% by the fluoro-gas fluorine rate of recovery reclaiming effusion.In the process of fluorine effusion, the phosphor resource in phosphor fluorine containing slag also completes the transformation from citric acid soluble phosphorus to water-soluble phosphorus, and finally namely the free acid supplemented in appropriate ground phosphate rock or secondary calcium phosphate neutralization reaction system obtains calcium superphosphate product.By the present invention, separate fluorine resource and conversion phosphor resource are organically combined in a technique and complete, not only avoid tediously long technical process, also effectively reclaimed phosphorus fluorine resource.
Compared with prior art, tool of the present invention has the following advantages:
(1) the present invention just can reclaim the phosphorus fluorine resource in phosphor fluorine containing slag by main two processing steps, and realize phosphorus fluorine and be separated, and obtain phosphorus fluorine related products respectively, technique is simple.
(2) compare fluorite to add sulfuric acid pyroreaction and produce hydrofluoric technology, the operational condition of present invention process is relatively gentle.
(3), in the specific aqueous reaction system of the present invention, material can react comparatively fully, keeps higher boiling point; Meanwhile, novelty reaction product is converted into calcium superphosphate product, reclamation of phosphorus resource is complete.
(4) phosphorus fluorine resource in phosphor fluorine containing slag is separately converted to phosphorus fluorine product by the present invention, substantially produces without " three wastes ", environmental friendliness.By the present invention, can avoid storing up of phosphor fluorine containing slag, thus avoid the maintenance in appropriation of land and stockyard, reduce the harm to environment, environmental benefit is obvious.
Accompanying drawing explanation
Fig. 1 is present invention process FB(flow block).
Embodiment
Specific embodiment of the invention process is as follows:
From phosphor fluorine containing slag, reclaim a method for fluorine co-production calcium superphosphate, comprise the following steps:
(1) by all in butt P
2o
5content is 15% ~ 28%, F content is 15% ~ 30%, water content be 20% ~ 100% phosphor fluorine containing slag and the vitriol oil to join in defluorination reaction groove stirring reaction 0.1 ~ 3h at 60 ~ 200 DEG C, phosphor fluorine containing slag (in butt) and the vitriol oil (pure H
2sO
4) add-on be 1:0.6 ~ 1.1, adopt in reaction process the traditional method known by those skilled in the art reclaim effusion fluoro-gas make the fluorochemical Product recycling fluorine resources such as hydrofluoric acid.
(2) phosphor fluorine containing slag and the vitriol oil are in defluorination reaction groove after stirring reaction 0.1 ~ 3h, add in phosphorous calcium thing stirring reaction 0.1 ~ 5h and free acid in slip, after reaction, reactants dry is obtained calcium superphosphate product in reaction slurry.
In above-mentioned phosphor fluorine containing slag, phosphorus exists with one or more forms in secondary calcium phosphate, monocalcium phosphate, tricalcium phosphate, and fluorine exists with the form of Calcium Fluoride (Fluorspan).
The above-mentioned vitriol oil is 70% ~ 100% H by weight
2sO
4sulfuric acid.
Above-mentioned fluorochemical can be one or more in Sodium Fluoride, Neutral ammonium fluoride, ammonium bifluoride, aluminum fluoride, Calcium Fluoride (Fluorspan), anhydrous hydrogen fluoride and hydrofluoric acid.
Above-mentioned phosphorous calcium thing is one or both in ground phosphate rock, secondary calcium phosphate.
The add-on of above-mentioned phosphorous calcium thing is 10% ~ 50% of phosphor fluorine containing slag butt weight, and makes calcium superphosphate product Free Acid (with P
2o
5meter) massfraction be less than 5.5%.
For the ease of understanding the present invention, below examples of implementation set forth content of the present invention, content of the present invention is not limited only to the following examples.
embodiment 1
By all in butt P
2o
5content is 22%, F content is 24%, water content is the 1.7t phosphor fluorine containing slag of 70% and the 98%H of 950kg
2sO
4the vitriol oil to join in defluorination reaction groove at 90 DEG C stirring reaction 25 minutes, i.e. phosphor fluorine containing slag (in butt) and the vitriol oil (pure H
2sO
4) add-on be 1:0.93, the fluoro-gas of overflowing in reaction adopts fluorine absorber to reclaim and generates hydrofluoric acid (HF content about 20%) about 1.1t, is used further to produce the fluorochemicals such as anhydrous hydrogen fluoride.
Phosphor fluorine containing slag and vitriol oil stirring reaction in defluorination reaction groove, after 25 minutes, adds P in reaction slurry
2o
5free acid in the ground phosphate rock 300kg stirring reaction 4h of about 30% and in slip, obtains the effective P of about 2.2t after reaction by reactants dry
2o
5be 14%, water-soluble P
2o
5be 12% and free acid (with P
2o
5meter) be less than 5.5% calcium superphosphate product.
embodiment 2
By all in butt P
2o
5content is 28%, F content is 15%, water content is the 1.2t phosphor fluorine containing slag of 20% and the 70%H of 1t
2sO
4the vitriol oil to join in defluorination reaction groove at 200 DEG C stirring reaction 40 minutes, i.e. phosphor fluorine containing slag (in butt) and the vitriol oil (pure H
2sO
4) add-on be 1:0.7, the fluoro-gas of overflowing in reaction adopts fluorine absorber to reclaim and generates hydrofluoric acid (HF content about 15%) about 0.94t, is used further to produce the fluorochemicals such as anhydrous hydrogen fluoride.
Phosphor fluorine containing slag and vitriol oil stirring reaction in defluorination reaction groove, after 40 minutes, adds P in reaction slurry
2o
5free acid in the ground phosphate rock 340kg stirring reaction 4.5h of about 25% and in slip, obtains the effective P of about 2.0t after reaction by reactants dry
2o
5be 18%, water-soluble P
2o
5be 16% and free acid (with P
2o
5meter) be less than 5.5% calcium superphosphate product.
embodiment 3
By all in butt P
2o
5content is 15%, F content is 30%, water content is the 2t phosphor fluorine containing slag of 100% and the 100%H of 1.1t
2sO
4the vitriol oil to join in defluorination reaction groove stirring reaction 3h at 95 DEG C, i.e. phosphor fluorine containing slag (in butt) and the vitriol oil (pure H
2sO
4) add-on be 1:1.1, the fluoro-gas of overflowing in reaction adopts fluorine absorber to reclaim and generates hydrofluoric acid (HF content about 25%) about 1.2t, is used further to produce the fluorochemicals such as anhydrous hydrogen fluoride.
Phosphor fluorine containing slag and the vitriol oil after stirring reaction 3h, add P in defluorination reaction groove in reaction slurry
2o
5free acid in the ground phosphate rock 500kg stirring reaction 5h of about 32% and in slip, obtains the effective P of about 2.4t after reaction by reactants dry
2o
5be 12%, water-soluble P
2o
5be 10% and free acid (with P
2o
5meter) be less than 5.5% calcium superphosphate product.
embodiment 4
By all in butt P
2o
5content is 24%, F content is 17%, water content is the 1.32t phosphor fluorine containing slag of 32% and the 98%H of 610kg
2sO
4the vitriol oil to join in defluorination reaction groove stirring reaction 0.1h at 110 DEG C, i.e. phosphor fluorine containing slag (in butt) and the vitriol oil (pure H
2sO
4) add-on be 1:0.6, the fluoro-gas of overflowing in reaction adopts fluorine absorber to reclaim and generates hydrofluoric acid (HF content about 18%) about 0.82t, is used further to produce the fluorochemicals such as anhydrous hydrogen fluoride.
Phosphor fluorine containing slag and the vitriol oil after stirring reaction 0.1h, add P in defluorination reaction groove in reaction slurry
2o
5free acid in the secondary calcium phosphate 100kg stirring reaction 0.1h of about 34% and in slip, obtains the effective P of about 1.7t after reaction by reactants dry
2o
5be 16%, water-soluble P
2o
5be 15% and free acid (with P
2o
5meter) be less than 5.5% calcium superphosphate product.
embodiment 5
By all in butt P
2o
5content is 18%, F content is 20%, water content is the 1.5t phosphor fluorine containing slag of 50% and the 95%H of 840kg
2sO
4the vitriol oil to join in defluorination reaction groove stirring reaction 2.5h at 60 DEG C, i.e. phosphor fluorine containing slag (in butt) and the vitriol oil (pure H
2sO
4) add-on be 1:0.8, the fluoro-gas of overflowing in reaction adopts fluorine absorber to reclaim and generates hydrofluoric acid (HF content about 21%) about 0.87t, is used further to produce the fluorochemicals such as anhydrous hydrogen fluoride.
Phosphor fluorine containing slag and the vitriol oil after stirring reaction 2.5h, add P in defluorination reaction groove in reaction slurry
2o
5ground phosphate rock 250kg and P of about 28%
2o
5free acid in the secondary calcium phosphate 150kg stirring reaction 3h of about 36% and in slip, obtains the effective P of about 2.2t after reaction by reactants dry
2o
5be 13%, water-soluble P
2o
5be 11% and free acid (with P
2o
5meter) be less than 5.5% calcium superphosphate product.
The above, it is only preferred embodiment of the present invention, not any pro forma restriction is done to the present invention, anyly do not depart from technical solution of the present invention content, the any simple modification done above embodiment according to technical spirit of the present invention, equivalent variations and modification, all still belong in the scope of technical solution of the present invention.
Claims (6)
1. from phosphor fluorine containing slag, reclaim a method for fluorine co-production calcium superphosphate, it is characterized in that it comprises the following steps:
(1) by all in butt P
2o
5content is 15% ~ 28%, F content is 15% ~ 30%, water content be 20% ~ 100% phosphor fluorine containing slag and the vitriol oil to join in defluorination reaction groove stirring reaction 0.1 ~ 3h at 60 ~ 200 DEG C, the add-on of phosphor fluorine containing slag and the vitriol oil is 1:0.6 ~ 1.1, described phosphor fluorine containing slag is in butt, and the described vitriol oil is with pure H
2sO
4meter, the fluoro-gas adopting the traditional method known by those skilled in the art to reclaim effusion in reaction process makes fluorochemical Product recycling fluorine resource;
(2) phosphor fluorine containing slag and the vitriol oil after stirring reaction 0.1 ~ 3h, add phosphorous calcium thing stirring reaction 0.1 ~ 5h in defluorination reaction groove in reaction slurry, in and slip in free acid, after reaction, reactants dry is obtained calcium superphosphate product.
2. a kind of method reclaiming fluorine co-production calcium superphosphate from phosphor fluorine containing slag according to claim 1, it is characterized in that in described phosphor fluorine containing slag, phosphorus exists with one or more forms in secondary calcium phosphate, monocalcium phosphate, tricalcium phosphate, fluorine exists with the form of Calcium Fluoride (Fluorspan).
3. a kind of method reclaiming fluorine co-production calcium superphosphate from phosphor fluorine containing slag according to claim 1, is characterized in that the described vitriol oil is for 70% ~ 100% H by weight
2sO
4sulfuric acid.
4. a kind of method reclaiming fluorine co-production calcium superphosphate from phosphor fluorine containing slag according to claim 1, is characterized in that described fluorochemical can be one or more in Sodium Fluoride, Neutral ammonium fluoride, ammonium bifluoride, aluminum fluoride, Calcium Fluoride (Fluorspan), anhydrous hydrogen fluoride and hydrofluoric acid.
5. a kind of method reclaiming fluorine co-production calcium superphosphate from phosphor fluorine containing slag according to claim 1, is characterized in that described phosphorous calcium thing is one or both in ground phosphate rock, secondary calcium phosphate.
6. a kind of method reclaiming fluorine co-production calcium superphosphate from phosphor fluorine containing slag according to claim 1, is characterized in that the add-on of described phosphorous calcium thing is 10% ~ 50% of phosphor fluorine containing slag butt weight, and makes in calcium superphosphate product, with P
2o
5the massfraction of meter free acid is less than 5.5%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410580753.4A CN104370277A (en) | 2014-10-27 | 2014-10-27 | Method for recycling fluorine from phosphorus-containing fluorine slag and cogenerating calcium superphosphate |
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|---|---|---|---|
| CN201410580753.4A CN104370277A (en) | 2014-10-27 | 2014-10-27 | Method for recycling fluorine from phosphorus-containing fluorine slag and cogenerating calcium superphosphate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104843642A (en) * | 2015-04-24 | 2015-08-19 | 瓮福（集团）有限责任公司 | Method for dry process rapid extraction of fluorine resources from defluorination residue by microwave decomposition |
| CN107381578A (en) * | 2017-07-17 | 2017-11-24 | 贵州川恒化工股份有限公司 | The method that defluorination residues purification prepares prodan |
| CN110255502A (en) * | 2019-06-14 | 2019-09-20 | 贵州新东浩化工材料科技有限公司 | White fertilizer hydrogen fluoride coproduction richness calcium and general calcium technique |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1207366A (en) * | 1998-08-22 | 1999-02-10 | 杨显庆 | Process for producing calcium hydrogen phosphate by once-through defluorination |
| CN1554570A (en) * | 2003-12-22 | 2004-12-15 | 云南三环化工有限公司 | Method for comprehensively utilizing phosphate fertilizer by-product |
| CN102502551A (en) * | 2011-10-20 | 2012-06-20 | 瓮福（集团）有限责任公司 | Method for recycling phosphorus and fluorine in defluorination residues |
-
2014
- 2014-10-27 CN CN201410580753.4A patent/CN104370277A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1207366A (en) * | 1998-08-22 | 1999-02-10 | 杨显庆 | Process for producing calcium hydrogen phosphate by once-through defluorination |
| CN1554570A (en) * | 2003-12-22 | 2004-12-15 | 云南三环化工有限公司 | Method for comprehensively utilizing phosphate fertilizer by-product |
| CN102502551A (en) * | 2011-10-20 | 2012-06-20 | 瓮福（集团）有限责任公司 | Method for recycling phosphorus and fluorine in defluorination residues |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104843642A (en) * | 2015-04-24 | 2015-08-19 | 瓮福（集团）有限责任公司 | Method for dry process rapid extraction of fluorine resources from defluorination residue by microwave decomposition |
| CN107381578A (en) * | 2017-07-17 | 2017-11-24 | 贵州川恒化工股份有限公司 | The method that defluorination residues purification prepares prodan |
| CN110255502A (en) * | 2019-06-14 | 2019-09-20 | 贵州新东浩化工材料科技有限公司 | White fertilizer hydrogen fluoride coproduction richness calcium and general calcium technique |
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Application publication date: 20150225 |