CN106277005B - A kind of method that ice crystal, calcium carbonate and sodium sulphate are reclaimed in the resource from calcium fluoride sludge - Google Patents
A kind of method that ice crystal, calcium carbonate and sodium sulphate are reclaimed in the resource from calcium fluoride sludge Download PDFInfo
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- CN106277005B CN106277005B CN201610757504.7A CN201610757504A CN106277005B CN 106277005 B CN106277005 B CN 106277005B CN 201610757504 A CN201610757504 A CN 201610757504A CN 106277005 B CN106277005 B CN 106277005B
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- sludge
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/50—Fluorides
- C01F7/54—Double compounds containing both aluminium and alkali metals or alkaline-earth metals
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/06—Preparation of sulfates by double decomposition
- C01D5/10—Preparation of sulfates by double decomposition with sulfates of magnesium, calcium, strontium, or barium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
Abstract
A kind of method that ice crystal, calcium carbonate and sodium sulphate are reclaimed in resource from calcium fluoride sludge, is comprised the following steps that：(1) sulfuric acid is added in calcium fluoride sludge, the calcium existed in its pH=1~3, sludge with calcium hydroxide and calcium carbonate form is adjusted and is converted into calcium sulfate, obtain solution A；(2) sodium aluminate solid is added in solution A, and is stirred leaching calcirm-fluoride is converted into fluoaluminic acid and calcium sulfate precipitation S1 and solution B；(3) sodium carbonate is added in solution B, makes its pH=0.1~2, and adds sodium sulphate promotes cryolite precipitation complete, obtains ice crystal and solution C；(4) add sodium bicarbonate solution in precipitation S1 to be handled, be filtrated to get calcium carbonate and solution D；(5) solution C and solution D are merged into evaporative crystallization and obtains sodium sulphate.The present invention has the advantages that easy control of process conditions, easy large-scale production, it is possible to achieve calcium fluoride sludge recycling.
Description
Technical field
The application is related to calcium fluoride sludge process field, and ice crystal is reclaimed from calcium fluoride sludge resource more particularly, to one kind
The method of stone, calcium carbonate and sodium sulphate.
Background technology
Fluorine element is indispensable in current industrial production due to its unique chemical property.Fluorine chemical wastewater usually through
The alkaline matter neutralization precipitations such as addition lime, carbide slag and the mode of flocculation are handled, and often to the several of different process generation
Stock waste water mixed processing, adds the difficulty of wastewater treatment and the complexity of sludge.It is mainly reflected in calcium fluoride sludge composition
Complexity, containing calcium carbonate, calcium hydroxide etc., conventional PAC flocculants can introduce aluminum metal, and a small amount of ferrous metal.So fluorination
The processing of calcium sludge is always one being emphasis of concern.
Calcium fluoride sludge recycling is a research direction for solving the problems, such as calcium fluoride sludge.Currently with approach it is main
Be by sell outside cement additire, paveio(u)r and make it is non-burning brick realize recycling, see CN01109444.3, but this
There is the major hidden danger of secondary pollution in Land use systems, and cause the waste of this non-renewable energy resources of fluorite, and it is long-range to be unfavorable for
Development.
Also someone studies a kind of increase fluorination mentioned in calcium fluoride sludge deep processing recycling, such as CN101941752B
The method of calcium precipitate particle diameter, with solid-liquid two-phase flowization bed for crystallization reactor, adds a certain amount of calcirm-fluoride brilliant in the reactor
Kind, fluoride waste and calcic precipitating reagent are sent into liquid-solid fluidized bed processing unit by reaction ratio, fluorine ion is deposited in fluorination
Calcium seed surface, reduces the moisture content of calcirm-fluoride, and Calcium Fluoride Content is higher.But program cost is higher, it is unfavorable for industrial metaplasia
Production.
CN201410116814 describes the side of a kind of fluoride wastewater treatment and its fluorine-containing sludge recycling of generation
Method, this method reacts fluoride waste and calcium chloride under the conditions of the slant acidity of spent acid acidic materials formation is added, crystalline deposit
The solubilised state calcirm-fluoride removed in the fluorine-containing sludge of most of fluorine ion formation high-purity in waste water, supernatant liquor is miscellaneous with other
Matter is removed by alkaline chemical precipitation, forms the low fluorine-containing sludge of a small amount of purity, afterwards supernatant liquor neutralized, water outlet, go out
Water fluorinion concentration is less than 10ppm, corrupt and evil discharging standards.Added after the fluorine-containing sludge drying of high concentration with excessive sulfuric acid
In reactor with agitating device, hydrogen fluoride is produced in progress reaction at 150~300 DEG C, and obtained thick hydrogen fluoride gas leads to
Cross condensation, rectifying and anhydrous hydrogen fluoride product is made.This method obtains fluorination hydrogen purity height, and product quality is high, but process conditions
Complexity, hydrogen fluoride gas toxicity itself is larger.
The content of the invention
In view of the above-mentioned problems existing in the prior art, the applicant provides one kind and reclaims ice from calcium fluoride sludge resource
The method of spar, calcium carbonate and sodium sulphate.The present invention has the advantages that easy control of process conditions, easy large-scale production, can be with
Realize calcium fluoride sludge recycling.
Technical scheme is as follows：
A kind of method that ice crystal, calcium carbonate and sodium sulphate are reclaimed in resource from calcium fluoride sludge, is comprised the following steps that：
(1) sulfuric acid is added in calcium fluoride sludge, is adjusted in its pH=1~3, sludge with calcium hydroxide and calcium carbonate form
The calcium of presence is converted into calcium sulfate, obtains solution A；
(2) sodium aluminate solid is added in solution A, and is stirred leaching calcirm-fluoride is converted into fluoaluminic acid and calcium sulfate
Precipitate S1 and solution B；
(3) sodium carbonate is added in solution B, makes its pH=0.1~2, and add sodium sulphate to promote cryolite to precipitate
Entirely, ice crystal and solution C are obtained；
(4) add sodium bicarbonate solution in precipitation S1 to be handled, be filtrated to get calcium carbonate and solution D；
(5) solution C and solution D are merged into evaporative crystallization and obtains sodium sulphate.
When being acidified in the step (1) using sulfuric acid to sludge, the time is 1~2h.
In the step (2), in the solution B of sulfuric acid and sodium aluminate, the mass ratio of the sodium aluminate and calcium fluoride sludge
For 1~2:5.
In the step (3), sodium carbonate amount is 1.1~1.5 times of calcium sulfate, 1~2h of mixing time.
In the step (3), the addition of sodium sulphate is 30~70g/L.
Sodium sulphate in the step (3) uses the sodium sulphate that step (5) is obtained.
The concentration of sodium bicarbonate solution is 20wt% in the step (4)；The amount of sodium bicarbonate solution is added to make solid-liquid
Mass ratio is 1:0.5~2.
The present invention is beneficial to be had technical effect that：
The present invention takes full advantage of the property of calcium fluoride sludge each component, and respectively obtains corresponding product；Realize fluorine
Fluorine, the extraction respectively of calcium resource in change calcium sludge；With easy control of process conditions, the conversion ratio rate of recovery is high, easy scale
The advantage of metaplasia production.
The production of ice crystal is from hydrofluoric acid as Fluorine source making ice crystal in conventional method, and the present invention discloses method
It is the special complex performance that make use of fluorine to aluminium, directly can be dissolved calcirm-fluoride.The wound of another protrusion of the present invention
New point is that using sulfuric acid as medium, calcium can be converted into calcium sulfate, and calcium is separated with fluorine, possess ice crystal made of stones
Another premise made, the presence of predominantly fluoaluminic acid and sodium after calcium is isolated is i.e. available in conjunction with conventional fluorine aluminum ratio adjustment
Ice crystal product.The method introduced in prior art 200710168535.X is limited only to the fluorine-containing acid waste water containing aluminium, should
It is equivalent effect that waste water adds aluminium with hydrofluoric acid, very big with this method difference.
This method addition different agents obtain different product, and main thought is the recycling for seeking calcium fluoride sludge, is existed side by side
The difference recycling of fluorine resource and calcium resource is enough to, ice crystal can be sold as product, reclaiming obtained calcium carbonate can continue
For fluorine removal, resources circulation is realized, sodium sulphate is the medium as separation fluorine and calcium, and process is mainly used in reuse and reduces ice crystal
Solubility step, more than needed can also sell as byproduct.
Brief description of the drawings
Fig. 1 is preparation technology schematic flow sheet of the present invention.
Embodiment
Below in conjunction with the accompanying drawings 1 and embodiment, the present invention is specifically described.
Embodiment 1
A kind of the applicant reclaims ice crystal, calcium carbonate and sodium sulphate method in providing resource from calcium fluoride sludge,
Comprise the following steps that：
(1) sulfuric acid is added in calcium fluoride sludge 1000g, adjusts its pH=2, when being acidified using sulfuric acid to sludge,
Time is 1.5h；The calcium existed in sludge with calcium hydroxide and calcium carbonate form is converted into calcium sulfate, obtains solution A.
(2) 200g sodium aluminate solids are added in solution A, and are stirred leaching calcirm-fluoride is converted into fluoaluminic acid and sulphur
Sour calcium precipitate S1 and solution B；
(3) sodium carbonate is added in solution B, makes its pH=0.1, and add 70g sodium sulphate to promote cryolite to precipitate
Entirely, mixing time 1h, obtains 100g ice crystals and solution C；Sodium carbonate amount is 1.3 times of calcium sulfate.
(4) precipitation S1 in add 100mL 20wt% sodium bicarbonate solutions handled, be filtrated to get 30g calcium carbonate and
Solution D；
(5) solution C and solution D are merged into evaporative crystallization and obtains sodium sulphate product 200g.
Sodium sulphate in the step (3) uses the sodium sulphate that step (5) is obtained.
Embodiment 2
A kind of the applicant reclaims ice crystal, calcium carbonate and sodium sulphate method in providing resource from calcium fluoride sludge,
Comprise the following steps that：
(1) sulfuric acid is added in calcium fluoride sludge 1000g, adjusts its pH=1, when being acidified using sulfuric acid to sludge,
Time is 1h；The calcium existed in sludge with calcium hydroxide and calcium carbonate form is converted into calcium sulfate, obtains solution A.
(2) 285g sodium aluminate solids are added in solution A, and are stirred leaching calcirm-fluoride is converted into fluoaluminic acid and sulphur
Sour calcium precipitate S1 and solution B；
(3) sodium carbonate is added in solution B, makes its pH=1, and adds 30g sodium sulphate promotes cryolite precipitation complete,
Mixing time 1.5h, obtains 100g ice crystals and solution C；Sodium carbonate amount is 1.1 times of calcium sulfate.
(4) precipitation S1 in add 100mL 20wt% sodium bicarbonate solutions handled, be filtrated to get 30g calcium carbonate and
Solution D；
(5) solution C and solution D are merged into evaporative crystallization and obtains sodium sulphate product 200g.
Sodium sulphate in the step (3) uses the sodium sulphate that step (5) is obtained.
Embodiment 3
A kind of the applicant reclaims ice crystal, calcium carbonate and sodium sulphate method in providing resource from calcium fluoride sludge,
Comprise the following steps that：
(1) sulfuric acid is added in calcium fluoride sludge 1000g, adjusts its pH=3, when being acidified using sulfuric acid to sludge,
Time is 2h；The calcium existed in sludge with calcium hydroxide and calcium carbonate form is converted into calcium sulfate, obtains solution A.
(2) 500g sodium aluminate solids are added in solution A, and are stirred leaching calcirm-fluoride is converted into fluoaluminic acid and sulphur
Sour calcium precipitate S1 and solution B；
(3) sodium carbonate is added in solution B, makes its pH=2, and adds 50g sodium sulphate promotes cryolite precipitation complete,
Mixing time 2h, obtains 100g ice crystals and solution C；Sodium carbonate amount is 1.5 times of calcium sulfate.
(4) precipitation S1 in add 100mL 20wt% sodium bicarbonate solutions handled, be filtrated to get 30g calcium carbonate and
Solution D；
(5) solution C and solution D are merged into evaporative crystallization and obtains sodium sulphate product 200g.
Sodium sulphate in the step (3) uses the sodium sulphate that step (5) is obtained.
It is described above, it is illustrative rather than limited, therefore be not limited thereto in protection scope of the present invention,
Any one skilled in the art is in the technical scope that the present invention is disclosed, the change that can be readily occurred in or replacement,
It should all be included within the scope of the present invention.
Claims (7)
1. the method for ice crystal, calcium carbonate and sodium sulphate is reclaimed in a kind of resource from calcium fluoride sludge, it is characterised in that specific step
It is rapid as follows：
(1) sulfuric acid is added in calcium fluoride sludge, is adjusted in its pH=1~3, sludge with calcium hydroxide and calcium carbonate form presence
Calcium be converted into calcium sulfate, obtain solution A；
(2) sodium aluminate solid is added in solution A, and is stirred leaching calcirm-fluoride is converted into fluoaluminic acid and calcium sulfate precipitation
S1 and solution B；
(3) sodium carbonate is added in solution B, makes its pH=0.1~2, and adds sodium sulphate promotes cryolite precipitation complete, obtains
To ice crystal and solution C；
(4) add sodium bicarbonate solution in precipitation S1 to be handled, be filtrated to get calcium carbonate and solution D；
(5) solution C and solution D are merged into evaporative crystallization and obtains sodium sulphate.
2. according to the method described in claim 1, it is characterised in that：Sludge is acidified using sulfuric acid in the step (1)
When, the time is 1~2h.
3. according to the method described in claim 1, it is characterised in that：In the step (2), in the solution B of sulfuric acid and sodium aluminate
In, the mass ratio of the sodium aluminate and calcium fluoride sludge is 1~2:5.
4. according to the method described in claim 1, it is characterised in that：In the step (3), sodium carbonate amount is calcium sulfate
1.1~1.5 times, 1~2h of mixing time.
5. according to the method described in claim 1, it is characterised in that：In the step (3), the addition of sodium sulphate for 30~
70g/L。
6. according to the method described in claim 1, it is characterised in that：Sodium sulphate in the step (3) is obtained using step (5)
Sodium sulphate.
7. according to the method described in claim 1, it is characterised in that：The concentration of sodium bicarbonate solution is in the step (4)
20wt%；The amount of sodium bicarbonate solution is added to make solid-liquid mass ratio be 1:0.5~2.
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| CN107188142A (en) * | 2017-06-28 | 2017-09-22 | 盛隆资源再生（无锡）有限公司 | A kind of method that phosphorus waste liquid containing ambrose alloy prepares phosphoric acid, gypsum, sodium sulphate, nickel sulfate and metallic copper |
| CN109851132A (en) * | 2019-03-22 | 2019-06-07 | 盛隆资源再生（无锡）有限公司 | A method of recycling ice crystal, fluorite and ammonium sulfate from the high ammonia nitrogen acid waste water of high fluorine |
| CN112310500B (en) * | 2019-07-31 | 2021-12-03 | 中国科学院过程工程研究所 | Method for separating aluminum element from waste lithium iron phosphate material |
| TWI721823B (en) * | 2020-03-12 | 2021-03-11 | 淡江大學 | Method for treating fluorine-containing wastewater |
| CN111392754B (en) * | 2020-04-21 | 2022-05-03 | 深圳市考拉生态科技有限公司 | Method and equipment for purifying calcium chloride from fluorine-containing solid waste |
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| FR2788053B1 (en) * | 1998-12-30 | 2001-03-16 | Atochem Elf Sa | PROCESS FOR RECYCLING FINE POWDER OF CALCIUM FLUORIDE |
| TWI233428B (en) * | 2000-03-09 | 2005-06-01 | Ming-Huei Liau | Method for treating fluoro-containing wastewater and treating agent thereof |
| CN100537077C (en) * | 2005-08-29 | 2009-09-09 | 株洲冶炼集团有限责任公司 | Slag-forming constituents used for lead and lead-base alloy fusion casting |
| CN100482816C (en) * | 2007-09-24 | 2009-04-29 | 昆明理工大学 | Method for reclaiming valuable element from zinc kiln slag |
| CN102307816A (en) * | 2009-02-13 | 2012-01-04 | 株式会社神钢环境舒立净 | Method for processing waste water containing fluorine and silicon, method for producing calcium fluoride, and facility for processing fluorine-containing waste water |
| CN102328945A (en) * | 2009-08-03 | 2012-01-25 | 中昊晨光化工研究院 | Device for preparing calcium fluoride from fluorine-containing wastewater and application method thereof |
| CN102312104A (en) * | 2011-10-14 | 2012-01-11 | 南南铝业股份有限公司 | Refining agent for aluminium and aluminium alloy melting |
| CN102887535A (en) * | 2012-10-09 | 2013-01-23 | 湖北富邦科技股份有限公司 | Method for recycling high-purity fluorine and phosphorus from wastewater of phosphogypsum residue field |
| CN103848522B (en) * | 2014-03-26 | 2015-06-10 | 南京大学环境规划设计研究院有限公司 | Method for treating fluorine-containing wastewater and recycling fluorine-containing sludge produced by treatment of fluorine-containing wastewater |
| CN104131169B (en) * | 2014-08-07 | 2016-08-24 | 陕西煤业化工集团陕南投资开发有限公司 | Flyash acidleach synthetical recovery vanadium, the method for potassium |
| CN104498726B (en) * | 2015-01-06 | 2016-11-30 | 云南云铝润鑫铝业有限公司 | A kind of slagging agent with aluminum ash as raw material and preparation method thereof |
| CN105836783B (en) * | 2016-03-24 | 2017-11-03 | 上海交通大学 | A kind of high-concentration fluorine-containing waste water multistep treatment original position prepares high-purity CaF2Method |
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