CN109761255A - A method of ice crystal, nitric acid and sodium sulphate are prepared using fluorine-containing nitric acid waste - Google Patents
A method of ice crystal, nitric acid and sodium sulphate are prepared using fluorine-containing nitric acid waste Download PDFInfo
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- CN109761255A CN109761255A CN201910220580.8A CN201910220580A CN109761255A CN 109761255 A CN109761255 A CN 109761255A CN 201910220580 A CN201910220580 A CN 201910220580A CN 109761255 A CN109761255 A CN 109761255A
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Abstract
The invention discloses a kind of methods for preparing ice crystal, nitric acid and sodium sulphate using fluorine-containing nitric acid waste, it the described method comprises the following steps: (1) being added in fluorine-containing nitric acid waste containing aluminium and containing the substance of sodium element, adjust pH value of solution 5~8, it heats and stirs in water-bath, obtain solution A；(2) ice crystal solid and solution B are filtered to obtain to solution A；(3) after being adjusted with acid the pH of solution B, solution is first concentrated under reduced pressure into a certain concentration, then continuously add sulfuric acid during reduced pressure, obtains nitric acid and solution C；(4) solution C is cooling, it is centrifuged to obtain sodium bisulfate crystallization and solution D, solution D reuse；(5) pH of solution is crystallized and controlled with alkali soluble solution sodium bisulfate, will be centrifuged after solution freezing and crystallizing, and sal glauberi crystallization is obtained；(6) after to sal glauberi crystallizing and drying, anhydrous sodium sulfate crystallization is obtained.Equipment needed for present invention process is simple, easy to operate, generates without secondary waste, reduces the discharge of the three wastes.
Description
Technical field
The present invention relates to waste water recycling device technical fields, prepare ice crystal by fluorine-containing nitric acid waste more particularly, to one kind
The method of stone, nitric acid and sodium sulphate.
Background technique
A large amount of fluorine-containing and nitric acid mixing spent acid can be generated in the production of photovoltaic solar cell and semiconductor crystal wafer, wherein
Funing tablet is 200ppm~5000ppm, and concentration of nitric acid differs for 10%~30%.Main harm in waste water is fluorine ion and total
Nitrogen, current processing method are usually to neutralize this liquid, form calcium fluoride precipitate with lime and fluorine, liquid enters life
Change pond to be denitrogenated, this is a kind of wasting of resources to fluorine and nitric acid.
CN201610755665.2 discloses a kind of method for recycling product in fluorine-containing nitric acid, mainly using multicomponent
Fluorine removal particle fluorine removal and potassium nitrate consolidate fluorine, then pass through a series of available nitre of processes such as the solid after hydrofluoric acid dissolution fluorine removal
Acid, calcirm-fluoride and potassium fluosilicate.Although feasible on this theoretical method, fluorine removal particulate component used is complicated, the fluorine of synthesis
Potassium silicate solution purity is not high；Particle after fluorine removal is smaller, needs to walk during plant operations using flocculant flocculating setting
It is rapid more complex；When preparing calcirm-fluoride and potassium fluosilicate using hydrofluoric acid, to the more demanding of equipment, it is necessary to select fluorine-resistant material
Reactor tank, and used raw material hydrofluoric acid danger coefficient is larger.
CN105948083A discloses a kind of using magnesium-containing compound as precipitating reagent fluorine removal, and this method is not in industry
The reason of upper extensive use is mainly that the magnesium fluoride sediment generated after reacting needs to generate hydrogen fluorine with sulfuric acid reaction at high temperature
Acid, required equipment material requirement is harsh, and operational hazards factor is also more.
CN106430267A and CN107720795A discloses the synthetic method of ice crystal, is all made of and adds into fluorine-containing waste liquid
Enter aluminium salt and sodium salt, guarantees sodium aluminium fluorine ratio in 3:1:6 or so, this scheme is possible in theory, but has a problem that be exactly when three
When kind substance is largely present in system, it can be quickly generated the lesser ice crystal of particle, one side filters pressing is difficult, on the other hand
Impurities are more in the ice crystal of synthesis, are not able to satisfy requirement of certain industries to ice crystal.
In addition, sodium nitrate storage condition requires strictly, so many dangerous waste enterprises attempt to be translated into sodium sulphate, still
Industrially using less, it is important to the more difficult control of technology controlling and process point.
In order to realize the recycling of resource, the synthesis industrial product that purity is higher, property is stable, and meet behaviour
Make simple, the low technique requirement of danger coefficient, designing a kind of method that fluorine and nitric acid is separately recovered for fluorine-containing nitric acid waste is
It is very necessary.
Summary of the invention
In view of the above-mentioned problems existing in the prior art, it is prepared the applicant provides a kind of using fluorine-containing nitric acid waste
The method of ice crystal, nitric acid and sodium sulphate.Equipment needed for present invention process is simple, easy to operate, generates, subtracts without secondary waste
The discharge for having lacked the three wastes can obtain ice crystal, nitric acid and sodium sulphate three by techniques such as fluorine removal, distillation, crystallisation by cooling simultaneously
Kind chemical products, and product purity is higher, realizes the good combination of economic benefit and environmental benefit.
Technical scheme is as follows:
A method of ice crystal, nitric acid and sodium sulphate being prepared using fluorine-containing nitric acid waste, the method includes following steps
It is rapid:
(1) it is added in fluorine-containing nitric acid waste containing aluminium and containing the substance of sodium element, pH value of solution 5~8 is adjusted, in water-bath
It heats and stirs, obtain solution A；
(2) ice crystal solid and solution B are filtered to obtain to solution A；
(3) after being adjusted with acid the pH of solution B, solution is first concentrated under reduced pressure into a certain concentration, then during reduced pressure
Sulfuric acid continuously is added, obtains nitric acid and solution C；
(4) solution C is cooling, it is centrifuged to obtain sodium bisulfate crystallization and solution D, solution D reuse；
(5) pH of solution is crystallized and controlled with alkali soluble solution sodium bisulfate, will be centrifuged after solution freezing and crystallizing, is obtained ten water sulfuric acid
Sodium crystallization；
(6) after to sal glauberi crystallizing and drying, anhydrous sodium sulfate crystallization is obtained.
Substance containing aluminium element described in step (1) be one of aluminum nitrate, aluminium hydroxide, aluminium oxide, aluminum sulfate or
A variety of, the dosage of the substance containing aluminium element is to make aluminium, fluorine molar ratio 1:4.8~5.2, after mixing evenly, is added containing sodium member
The substance of element；The substance containing sodium element be one of sodium hydroxide, sodium sulphate, sodium nitrate, sodium carbonate, sodium bicarbonate or
A variety of, the dosage of the substance containing sodium element is to make sodium, 1.8~2.2:1 of al mole ratio；The water bath temperature be 60~
80 DEG C, being stirred to react the time is 3~5h.
Filter type described in step (2) is filters pressing, using rinsing type filter press.
Acid described in step (3) is sulfuric acid, adjusts pH=5~7；Specific gravity after solution B concentration is 1.34~
1.36g/mL。
The mass fraction that sulfuric acid is added described in step (3) is 60~70wt%, added sulfuric acidVolume is solution B volume 0.85~0.95 times, striking point control gravity in 1.75~1.85g/mL。
The type of cooling described in step (4) is circulating water in collet, and cooling temperature is 45~50 DEG C.
Alkali described in step (5) is the sodium hydroxide solution of 5~10wt%, and the pH of adjusting is 5~7, solution freezing mode
To freeze in collet, refrigerant is ethylene glycol, and cryogenic temperature is -10~5 DEG C, 4~8h of cooling time.
The equipment that drying process described in step (6) uses is continous way liquidation drying equipment.
The present invention is beneficial to be had the technical effect that
In order to realize the abundant recycling of resource, the applicant has devised one kind to fluorine-containing by a large amount of experiment
The method that nitric acid waste recycles.This technique generates fluorination using the substance containing aluminium element first in conjunction with the fluorine in waste liquid
Aluminium, recycling sodium-containing material reacts generation ice crystal under certain condition and saline solns, saline solns are being concentrated under reduced pressure
The available nitric acid of sulfuric acid and sodium bisulfate are continuously added down, and sodium bisulfate can obtain after supercooling and centrifugation
Crystallized to sodium bisulfate, crystallization obtains metabisulfite solution by dissolution and after neutralizing again, metabisulfite solution by freezing, centrifugation and
After drying, anhydrous sodium sulfate crystallization is obtained.Raw materials used type is simple and easy to operate；It provides a kind of novel by sodium nitrate
It is converted into the commercial run of sodium sulphate；It does not need to can be obtained by economy using the higher hydrofluoric acid of danger coefficient and fluorine-containing material
Costly product, and the purity of the ice crystal and sodium sulphate product synthesized is all higher and conversion ratio of nitric acid is also higher.
Detailed description of the invention
Fig. 1 is present invention process flow diagram.
Specific embodiment
With reference to the accompanying drawings and examples, the present invention is specifically described.
Embodiment 1
Take fluorine-containing nitric acid waste 1000mL (fluorine content 10g/L, the nitric acid content of certain manufacture of solar cells producer production line
50%) 8.552g aluminium hydroxide, is first added in waste liquid, control aluminium fluorine ratio is that 1:4.8 adds 11.086g after mixing evenly
Sodium nitrate and 2.676g piece alkali control sodium aluminium ratio 1.8:1, guarantee pH value of solution=5, stir 4h in 60 DEG C of water-baths, filter
18.22g ice crystal solid and liquid, liquid are concentrated under reduced pressure into specific gravity 1.34g/mL at 0.02Mpa, 100 DEG C, continuously add
The sulfuric acid of the 70wt% of 0.85 times of volume of the concentrated liquid obtains 1819mL25% nitric acid and mother liquor, after mother liquor is cooled to 45 DEG C, mistake
Filter obtains sodium bisulfate crystallization and return water, and return water continues reuse, the sodium hydroxide solution of 5wt% is added to adjust in sodium bisulfate crystallization
PH=5, centrifugation obtains sal glauberi crystallization and it is anhydrous to obtain 558.89g after dry after progress freezing and crystallizing 6h at -10 DEG C
Sulfate crystal.
After measured, fluorine utilization rate is 98.9% in fluorine-containing nitric acid waste, and fluorine content is 52.2% in ice crystal product, and aluminium contains
Amount is 12.5%, sodium content 32.4%, and hygroscopic moisture content is 0.35%, reaches state quality standard；Nitric acid purity 25% is returned
Yield 89.5%；Sodium sulphate purity 99.2%, water content 0.51%, meets national standard.
Embodiment 2
Take fluorine-containing nitric acid waste 1000mL (fluorine content 12g/L, the nitric acid content of certain manufacture of solar cells producer production line
45%) 21.6g aluminum sulfate, is first added in waste liquid, control aluminium fluorine ratio is that 1:5 adds 9.26g sodium sulphate after mixing evenly
Sodium aluminium ratio 2:1 is controlled with 4.886g piece alkali, guarantees pH value of solution=5, stirs 3h in 70 DEG C of water-baths, filter to obtain 19.51g ice crystal
Stone solid and liquid, liquid are concentrated under reduced pressure into specific gravity 1.35g/mL at 0.03Mpa, 105 DEG C, continuously add 0.95 times of concentrate
60% sulfuric acid of volume, obtains 1450mL28% nitric acid and mother liquor, and after mother liquor is cooled to 48 DEG C, sodium bisulfate is obtained by filtration
Crystallization and solution, solution reuse, sodium bisulfate crystallization in plus 8wt% sodium hydroxide solution adjust pH=6, carried out at -5 DEG C
Centrifugation obtains sal glauberi crystallization after freezing and crystallizing 5h, after dry, obtains the crystallization of 507.14g anhydrous sodium sulfate.
After measured, fluorine utilization rate is 98.6% in fluorine-containing nitric acid waste, and fluorine content is 52.5% in ice crystal product, and aluminium contains
Amount is 12.7%, sodium content 32.4%, and hygroscopic moisture content is 0.35%, reaches state quality standard；Nitric acid purity 28% is returned
Yield 90.2%；Sodium sulphate purity 99.5%, water content 0.49%, meets national standard.
Embodiment 3
Take fluorine-containing nitric acid waste 1000mL (fluorine content 20g/L, the nitric acid content of certain manufacture of solar cells producer production line
55%) 43.12g aluminum nitrate, is first added in waste liquid, control aluminium fluorine ratio is that 1:5.2 adds 17.81g piece after mixing evenly
Alkali control sodium aluminium ratio 2.2:1, guarantee pH value of solution=7, stir 5h in 80 DEG C of water-baths, filter 32.72g ice crystal solid and
Liquid, liquid carry out being concentrated under reduced pressure into specific gravity 1.36g/mL at 0.04Mpa, 108 DEG C, continuously add 0.90 times of volume of the concentrated liquid
65% sulfuric acid, obtain 1839mL27% nitric acid and mother liquor, after mother liquor is cooled to 50 DEG C, be obtained by filtration sodium bisulfate crystallization
And solution, solution reuse, sodium bisulfate crystallization in plus 10wt% sodium hydroxide solution adjust pH=7, freezed at 0 DEG C
Centrifugation obtains sal glauberi crystallization after crystallization 8h, after dry, obtains the crystallization of 619.84g anhydrous sodium sulfate.
After measured, fluorine utilization rate is 99.2% in fluorine-containing nitric acid waste, and fluorine content is 52.3% in ice crystal product, and aluminium contains
Amount is 12.5%, sodium content 32.5%, and hygroscopic moisture content is 0.36%, reaches state quality standard；Nitric acid purity 27% is returned
Yield 90.3%；Sodium sulphate purity 98.9%, water content 0.45%, meets national standard.
Each raw material cited by the present invention can realize that the bound value of the present invention and each raw material, interval value can
It realizes the present invention, embodiment is just not listed one by one herein.The bound of technological parameter (such as temperature, time) of the invention takes
Value, interval value can realize the present invention, embodiment numerous to list herein.
Claims (8)
1. a kind of method for preparing ice crystal, nitric acid and sodium sulphate using fluorine-containing nitric acid waste, which is characterized in that the method packet
Include following steps:
(1) it is added in fluorine-containing nitric acid waste containing aluminium and containing the substance of sodium element, adjusts pH value of solution 5~8, heated in water-bath
And stir, obtain solution A；
(2) ice crystal solid and solution B are filtered to obtain to solution A；
(3) after being adjusted with acid the pH of solution B, solution is first concentrated under reduced pressure into a certain concentration, then during reduced pressure continuously
Sulfuric acid is added, nitric acid and solution C are obtained；
(4) solution C is cooling, it is centrifuged to obtain sodium bisulfate crystallization and solution D, solution D reuse；
(5) pH of solution is crystallized and controlled with alkali soluble solution sodium bisulfate, will be centrifuged after solution freezing and crystallizing, is obtained sal glauberi knot
It is brilliant；
(6) after to sal glauberi crystallizing and drying, anhydrous sodium sulfate crystallization is obtained.
2. the method according to claim 1, wherein the substance containing aluminium element described in step (1) be aluminum nitrate,
One of aluminium hydroxide, aluminium oxide, aluminum sulfate are a variety of, and the dosage of the substance containing aluminium element is to make aluminium, fluorine molar ratio 1:
4.8~5.2, after mixing evenly, add the substance containing sodium element；The substance containing sodium element be sodium hydroxide, sodium sulphate,
One of sodium nitrate, sodium carbonate, sodium bicarbonate are a variety of, and the dosage of the substance containing sodium element is to make sodium, al mole ratio
For 1.8~2.2:1；The water bath temperature is 60~80 DEG C, and being stirred to react the time is 3~5h.
3. the method according to claim 1, wherein filter type described in step (2) is filters pressing, using washing
Formula filter press.
4. adjusting pH=5~7 the method according to claim 1, wherein acid described in step (3) is sulfuric acid；
Specific gravity after the solution B concentration is 1.34~1.36g/mL.
5. the method according to claim 1, wherein the mass fraction for adding sulfuric acid described in step (3) is 60
~70wt%, added sulfuric acidVolume is 0.85~0.95 times of solution B volume, striking point control gravity 1.75~ 1.85g/mL。
6. the method according to claim 1, wherein the type of cooling described in step (4) is circulation in collet
Water is cooling, and cooling temperature is 45~50 DEG C.
7. the method according to claim 1, wherein alkali described in step (5) is the sodium hydroxide of 5~10wt%
Solution, the pH of adjusting are 5~7, and solution freezing mode is freezing in collet, and refrigerant is ethylene glycol, and cryogenic temperature is -10~5 DEG C,
4~8h of cooling time.
8. the method according to claim 1, wherein the equipment that drying process described in step (6) uses is company
Continuous formula liquidation drying equipment.
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| CN201910220580.8A CN109761255B (en) | 2019-03-22 | 2019-03-22 | Method for preparing cryolite, nitric acid and sodium sulfate by using fluorine-containing nitric acid waste liquid |
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| CN201910220580.8A CN109761255B (en) | 2019-03-22 | 2019-03-22 | Method for preparing cryolite, nitric acid and sodium sulfate by using fluorine-containing nitric acid waste liquid |
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Cited By (1)
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| CN115536049A (en) * | 2022-10-19 | 2022-12-30 | 广东臻鼎环境科技有限公司 | Method for preparing cryolite |
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