CN106629800A - Method for producing cryolite from fluosilicic acid waste liquid - Google Patents
Method for producing cryolite from fluosilicic acid waste liquid Download PDFInfo
- Publication number
- CN106629800A CN106629800A CN201610869105.XA CN201610869105A CN106629800A CN 106629800 A CN106629800 A CN 106629800A CN 201610869105 A CN201610869105 A CN 201610869105A CN 106629800 A CN106629800 A CN 106629800A
- Authority
- CN
- China
- Prior art keywords
- fluosilicic acid
- liquid
- acid waste
- waste liquid
- ice crystal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/141—Preparation of hydrosols or aqueous dispersions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Dispersion Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a method for producing cryolite from fluosilicic acid waste liquid in the technical field of cryolite preparation. The method includes the steps of 1, adding the fluosilicic acid waste liquid and excessive 5-10% sodium carbonate into a reaction kettle, mixing to form material liquid, stirring the material liquid, heating to 70 DEG C, filtering out silica gel until a pH value of the material liquid reaches 8-9, and obtaining filtrate, namely a sodium fluoride solution; 2, pouring the fluosilicic acid waste liquid and aluminum oxide in a specific reaction ratio into the reaction kettle to form material liquid, stirring the material liquid, heating to 80 DEG C, filtering out silica gel until the material liquid is free of particles, and obtaining filtrate, namely an aluminum fluoride solution; 3, adding the sodium fluoride solution and the excessive 9-11% aluminum fluoride solution into a synthesis kettle to form mixed liquid, heating the mixed liquid to 95-100 DEG C until no crystal particle generates in the synthesis kettle, filtering the mixed liquid to obtain the cryolite, heating hot water to wash, spin-drying and drying so as to obtain a cryolite finished product. By the method, the utilization rate of the fluosilicic acid waste liquid and the yield of the cryolite are increased remarkably, and the quality of the cryolite can be improved remarkably.
Description
Technical field
The present invention relates to ice crystal preparing technical field, more particularly to a kind of side of utilization fluosilicic acid waste liquid production ice crystal
Method.
Background technology
Fluosilicic acid is typically the byproduct of the production such as phosphoric acid by wet process and general calcium, coarse whiting.Wet phosphoric acid by dihydrate, often produces
One ton of phosphoric acid by wet process (100%P2O5) about 0.06 ton of fluosilicic acid (100%H2SiF6) of by-product, often produces one ton of general calcium (100%
P2O5) about 0.06 ton of fluosilicic acid (100%H2SiF6) of by-product.China is production of phosphate fertilizer and consumes big country, national phosphate fertilizer industry pair
The fluosilicic acid incredible amount of product.Because the fluosilicic acid produced in phophatic fertilizer production process is mainly changed into fluosilicic acid by importing pond
Waste liquid, fluosilicic acid waste liquid has highly acid, it is directly discharged easily environment is damaged, while also result in fluosilicic acid money
The waste in source.And another aspect fluosilicic acid is one of important source material of generation ice crystal.
The use of the main method of fluosilicic acid production ice crystal is at present ammonium fluoride intermediate product and prodan intermediate product
Method, the former is to react with sodium aluminate again after fluosilicic acid and ammoniacal liquor ammonification and generate.The latter is by the waste gas containing fluoride in production of phosphate fertilizer
After recovered prodan, then Jing ammonifications synthesis etc. operation and be obtained.Above two method is required to by ammonification, and ammonification
Journey causes that the preparation process of ice crystal is loaded down with trivial details, conversion ratio is relatively low seriously increased production cost.
The content of the invention
The invention is intended to a kind of method that utilization fluosilicic acid waste liquid produces ice crystal is provided, to improve the profit of fluosilicic acid waste liquid
With rate and the quality and output capacity of ice crystal.
The method that a kind of utilization fluosilicic acid waste liquid in this programme produces ice crystal, comprises the following steps：
The preparation of step one, Fluorinse：
1）Fluosilicic acid waste liquid after decontamination is poured into steel lining plastic reactor, then to excessive addition 5% in steel lining plastic reactor ~
10% soda ash forms feed liquid, stirs feed liquid and is heated to 70 DEG C, until material liquid pH value is 8 ~ 9；Chemical equation is：H2SiF6+
3Na2CO3→6NaF+SiO2+3CO2+H2O；
2）Filter：Feed liquid after filtering and heating, leaches silica, and filtrate is Fluorinse；
The preparation of step 2, aluminun fluoride solution：
1）Fluosilicic acid waste liquid after decontamination is poured into steel lining plastic reactor, then is added in steel lining plastic reactor by reaction ratio
Plus alundum (Al2O3) forms feed liquid, stir feed liquid and be heated to 80 DEG C, until without particle in feed liquid；Chemical equation is：
H2SiF6+Al2O3→2AlF3+SiO2+H2O；
2）Filter：Feed liquid after filtering and heating, leaches silica, and filtrate is aluminun fluoride solution；
Step 3：The synthesis of ice crystal：
1）Fluorinse is put into in synthesis reactor, then adds excessive 9% ~ 11% aluminun fluoride solution to form mixing in synthesis reactor
Liquid, heating mixed liquor is to 95 DEG C ~ 100 DEG C, until there is no longer crystal grain generation in synthesis reactor；Chemical equation is：3NaF+AlF3→
Na3AlF6；
2）Filter mixed liquor, leaches ice crystal and adds hot wash, then dries, is dried, and obtains ice crystal finished product.
Beneficial effects of the present invention：This programme is obtained fluorine with soda ash and alundum (Al2O3) reaction respectively using fluosilicic acid waste liquid
Change sodium and aluminum fluoride, recycle the reaction between sodium fluoride and aluminum fluoride to generate ice crystal；The whole course of reaction time is short, and makes fluorine
Silicic acid waste liquid is fully reacted, so that the quality and conversion ratio of ice crystal are all greatly improved；Simultaneously in course of reaction
In generate available silica.In Fluorinse preparation process, excessive addition 5% ~ 10% in a kettle.
Soda ash fluosilicic acid is fully reacted, and the temperature of feed liquid is brought up into 70 degrees Celsius, further promote soda ash with
Reaction between fluosilicic acid waste liquid, while greatly reducing the reaction time, improves operating efficiency；PH value is 8 ~ 9 explanation fluosilicic acid
Obtain more sufficiently reacting.In the preparation process of aluminun fluoride solution, due to fluosilicic acid waste liquid concentration typically only 11% ~
12%, can fully be reacted with fluosilicic acid waste liquid from alundum (Al2O3), be conducive to improving the utilization rate of fluosilicic acid, while will
The reaction temperature of feed liquid is controlled at 80 DEG C, is significantly improved reaction speed and is improve the consumption of fluosilicic acid.In ice crystal
In preparation process, due to the concentration typically only 11% ~ 12% of fluosilicic acid waste liquid, so that obtained Fluorinse and aluminum fluoride
The concentration of solution is respectively at 18% ~ 22% and 11% ~ 13% or so, and because both concentration are relatively low, and aluminum fluoride is lazy with respect to sodium fluoride
Property it is higher, add excessive 9% ~ 11% aluminun fluoride solution to make both in the mixed liquor constituted to Fluorinse and aluminun fluoride solution
Between reactant reach equilibrium, be conducive to both fully to react, improve ice crystal conversion ratio, reduce the contaminative of filtrate；
And reacted at a temperature of 95 DEG C ~ 100 DEG C, significantly improve reaction speed between the two and improve the conversion of ice crystal
Rate.
Further, the concentration of fluosilicic acid waste liquid is that 12%, soda ash purity is more than 96%, three oxidations in ice crystal preparation process
The purity of two aluminium is more than 95%.It is all linked with one another between each reaction in due to the preparation process of ice crystal, wherein any one ring occurs
Problem can all cause the quality of ice crystal low with conversion ratio.The concentration for keeping fluosilicic acid ensure that remaining soda ash and three oxygen 12%
Change the reaction between two aluminium, while causing cost to improve from the addition fluosilicic acid in fluosilicic acid waste liquid is avoided；And soda ash and three oxygen
Change two aluminium purity be maintained at a high position be conducive to itself and the reaction between fluosilicic acid waste liquid, while guarantee react after sodium fluoride it is molten
Liquid has higher purity with aluminun fluoride solution, so as to save the reaction time for the generation of ice crystal, improves the quality of ice crystal
With conversion ratio.
Further, in step one, the heating to feed liquid is until material liquid pH value is 9.Material liquid pH value is realized substantially after reaching 8
The abundant reaction of fluosilicic acid, but to guarantee the reaction completely of fluosilicic acid, is heated to after material liquid pH value reaches 9, the fluorine silicon in feed liquid
Acid has been realized reacting completely.
Further, in step 3, the aluminun fluoride solution excessive value of addition is 10%.10% aluminum fluoride excessive value can ensure that fluorine
Change the normal reaction between sodium and aluminum fluoride, while the aluminun fluoride solution for avoiding excessive addition causes mixed liquid concentration further to drop
It is low, reduce reaction speed between the two.
Description of the drawings
Fig. 1 is a kind of schematic flow sheet of the method for utilization fluosilicic acid waste liquid production ice crystal of the invention.
Specific embodiment
Below by specific embodiment, the present invention is further detailed explanation：
Embodiment 1：
The method that a kind of utilization fluosilicic acid waste liquid as shown in Figure 1 produces ice crystal, comprises the following steps：
The preparation of step one, Fluorinse：
1) the fluosilicic acid waste liquid after decontamination is made into silicate fluoride solution that concentration is 12% and is poured into steel lining plastic reactor, then
The soda ash of excessive addition 10% in steel lining plastic reactor（Soda ash purity is 98%）Feed liquid is formed, feed liquid is stirred and is heated to 70
DEG C, until material liquid pH value is 9；Chemical equation is：H2SiF6+3Na2CO3→6NaF+SiO2+3CO2+H2O；
2) filter：Feed liquid after filtering and heating, leaches silica, and filtrate is sodium fluoride liquid, then by sodium fluoride liquid system
It is standby for Fluorinse that concentration of sodium fluoride is 20%；
The preparation of step 2, aluminun fluoride solution：
1）Fluosilicic acid waste liquid after decontamination is made into silicate fluoride solution that concentration is 12% and is poured into steel lining plastic reactor, then
Add alundum (Al2O3) in steel lining plastic reactor by reaction ratio（The purity of alundum (Al2O3) is 96%）Form feed liquid, stirring
Feed liquid is simultaneously heated to 80 DEG C, until without particle in feed liquid；Chemical equation is：H2SiF6+Al2O3→2AlF3+SiO2+H2O；
2）Filter：Feed liquid after filtering and heating, leaches silica, and filtrate is as fluorinated aluminium liquid, then will fluorination aluminium liquid system
It is standby for Fluorinse that aluminum fluoride concentration is 12%；
Step 3：The synthesis of ice crystal：
1）Fluorinse is put into in synthesis reactor, then adds excessive 10% aluminun fluoride solution to form mixed liquor in synthesis reactor,
Heating mixed liquor is to 100 DEG C, until there is no longer crystal grain generation in synthesis reactor；Chemical equation is：3NaF+AlF3→Na3AlF6；
2）Filter mixed liquor, leaches ice crystal and adds hot wash, then dries, is dried, and obtains ice crystal finished product.
Embodiment 2：
Embodiment 2 is with the difference of embodiment 1, and it is 95% that the purity of soda ash is the purity of 96%, alundum (Al2O3)；Step
Feed liquid is heated to material liquid pH value for 8.5 in one；In step 3, the excessive value of aluminun fluoride solution addition is 9%, and heating-up temperature is 95
℃。
Embodiment 3：
Embodiment 3 is with the difference of embodiment 1, and it is 98% that the purity of soda ash is the purity of 97%, alundum (Al2O3)；Step
Feed liquid is heated to material liquid pH value for 8 in one；In step 3, the excessive value of aluminun fluoride solution addition is 11%, and heating-up temperature is 98
℃。
By preparing ice crystal using the present invention, the quality and conversion ratio of ice crystal can be effectively improved, while realizing fluorine silicon
The efficient utilization of acid waste liquid, it is to avoid the waste of fluosilicic acid in fluosilicic acid waste liquid, while environmental protection, is the development of enterprise
Create more values.
Above-described is only embodiments of the invention, and the general knowledge here such as known concrete structure and characteristic is not made in scheme
Excessive description.It should be pointed out that for a person skilled in the art, on the premise of without departing from present configuration, can be with
Some deformations and improvement are made, these should also be considered as protection scope of the present invention, these are implemented all without the impact present invention
Effect and practical applicability.This application claims protection domain should be defined by the content of its claim, in specification
Specific embodiment etc. records the content that can be used for explaining claim.
Claims (4)
1. a kind of method that utilization fluosilicic acid waste liquid produces ice crystal, it is characterised in that comprise the following steps：
The preparation of step one, Fluorinse：
Fluosilicic acid waste liquid after decontamination is poured into steel lining plastic reactor, then to excessive addition 5% ~ 10% in steel lining plastic reactor
Soda ash form feed liquid, stirring feed liquid is simultaneously heated to 70 DEG C, until material liquid pH value is 8 ~ 9；Chemical equation is：H2SiF6+
3Na2CO3→6NaF+SiO2+3CO2+H2O；
Filter：Feed liquid after filtering and heating, leaches silica, and filtrate is Fluorinse；
The preparation of step 2, aluminun fluoride solution：
Fluosilicic acid waste liquid after decontamination is poured into steel lining plastic reactor, then is added in steel lining plastic reactor by reaction ratio
Alundum (Al2O3) forms feed liquid, stirs feed liquid and is heated to 80 DEG C, until without particle in feed liquid；Chemical equation is：H2SiF6+
Al2O3→2AlF3+SiO2+H2O；
Filter：Feed liquid after filtering and heating, leaches silica, and filtrate is aluminun fluoride solution；
Step 3：The synthesis of ice crystal：
Fluorinse is put into in synthesis reactor, then adds excessive 9% ~ 11% aluminun fluoride solution to form mixing in synthesis reactor
Liquid, heating mixed liquor is to 95 DEG C ~ 100 DEG C, until there is no longer crystal grain generation in synthesis reactor；Chemical equation is：3NaF+AlF3→
Na3AlF6；
Filter mixed liquor, leaches ice crystal and adds hot wash, then dries, is dried, and obtains ice crystal finished product.
2. the method that utilization fluosilicic acid waste liquid according to claim 1 produces ice crystal, it is characterised in that：It is prepared by ice crystal
During fluosilicic acid waste liquid concentration be 12%, purity that soda ash purity is more than 96%, alundum (Al2O3) be more than 95%.
3. the method that utilization fluosilicic acid waste liquid according to claim 2 produces ice crystal, it is characterised in that：In step one,
Heating to feed liquid is until material liquid pH value is 9.
4. the method that utilization fluosilicic acid waste liquid according to claim 3 produces ice crystal, it is characterised in that：In step 3,
The aluminun fluoride solution excessive value of addition is 10%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610869105.XA CN106629800A (en) | 2016-09-30 | 2016-09-30 | Method for producing cryolite from fluosilicic acid waste liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610869105.XA CN106629800A (en) | 2016-09-30 | 2016-09-30 | Method for producing cryolite from fluosilicic acid waste liquid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106629800A true CN106629800A (en) | 2017-05-10 |
Family
ID=58853955
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610869105.XA Pending CN106629800A (en) | 2016-09-30 | 2016-09-30 | Method for producing cryolite from fluosilicic acid waste liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106629800A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107857286A (en) * | 2017-12-11 | 2018-03-30 | 达州励志环保科技有限公司 | A kind of method that ice crystal is produced using fluosilicic acid waste liquid |
| CN109231247A (en) * | 2018-11-28 | 2019-01-18 | 达州励志环保科技有限公司 | A kind of method that the by-product of fluosilicic acid legal system aluminum fluoride prepares ice crystal |
| CN115196660A (en) * | 2022-06-22 | 2022-10-18 | 中石化南京工程有限公司 | Method and system for producing cryolite from fluosilicic acid |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101269816A (en) * | 2008-05-16 | 2008-09-24 | 夏克立 | Method for producing fluorine series compounds and white carbon black |
| CN101391793A (en) * | 2008-11-05 | 2009-03-25 | 湖南有色氟化学有限责任公司 | Method for preparing kryocide |
| CN102718244A (en) * | 2012-07-13 | 2012-10-10 | 六九硅业有限公司 | Preparation method of cryolite |
| CN104030317A (en) * | 2014-06-25 | 2014-09-10 | 江西渠成氟化学有限公司 | White carbon black production process for producing sodium fluoride and co-producing cryolite by using fluorosilicic acid |
| CN105645447A (en) * | 2015-12-29 | 2016-06-08 | 湖北祥福化工科技有限公司 | Method for producing high-molecular ratio cryolite by utilizing low-concentration fluosilicic acid |
-
2016
- 2016-09-30 CN CN201610869105.XA patent/CN106629800A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101269816A (en) * | 2008-05-16 | 2008-09-24 | 夏克立 | Method for producing fluorine series compounds and white carbon black |
| CN101391793A (en) * | 2008-11-05 | 2009-03-25 | 湖南有色氟化学有限责任公司 | Method for preparing kryocide |
| CN102718244A (en) * | 2012-07-13 | 2012-10-10 | 六九硅业有限公司 | Preparation method of cryolite |
| CN104030317A (en) * | 2014-06-25 | 2014-09-10 | 江西渠成氟化学有限公司 | White carbon black production process for producing sodium fluoride and co-producing cryolite by using fluorosilicic acid |
| CN105645447A (en) * | 2015-12-29 | 2016-06-08 | 湖北祥福化工科技有限公司 | Method for producing high-molecular ratio cryolite by utilizing low-concentration fluosilicic acid |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107857286A (en) * | 2017-12-11 | 2018-03-30 | 达州励志环保科技有限公司 | A kind of method that ice crystal is produced using fluosilicic acid waste liquid |
| CN109231247A (en) * | 2018-11-28 | 2019-01-18 | 达州励志环保科技有限公司 | A kind of method that the by-product of fluosilicic acid legal system aluminum fluoride prepares ice crystal |
| CN115196660A (en) * | 2022-06-22 | 2022-10-18 | 中石化南京工程有限公司 | Method and system for producing cryolite from fluosilicic acid |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101555033B (en) | Method for preparing cryolite and coproducing soluble glass by using hydrof luorosilicic acid | |
| CN105645447B (en) | A kind of method that cryolite with high molecular ratio is produced using low dose fluoride silicic acid | |
| CN106629800A (en) | Method for producing cryolite from fluosilicic acid waste liquid | |
| CN103601217B (en) | Sodium fluoride production process and sodium fluoride mother liquor recycling process | |
| CN105502451B (en) | A kind of method for producing aluminum fluoride coproduction cryolite with high molecular ratio | |
| CN101289195B (en) | Process for preparing potassium borofluoride and co-production of white carbon black and sodium fluosilicate | |
| CN102887528B (en) | Production technology of ammonium bifluoride | |
| CN108358213A (en) | A kind of magnesium silicon hydrate bonding agent and preparation method thereof based on salt lake bittern | |
| CN106966418A (en) | A kind of low-density aluminum fluoride and its production technology | |
| WO2013020396A1 (en) | Cycled preparation method that uses sodium fluoborate as intermediate raw material and produces boron element and simultaneously sodium cryolite | |
| CN107857286A (en) | A kind of method that ice crystal is produced using fluosilicic acid waste liquid | |
| CN102718244B (en) | Preparation method of cryolite | |
| CN102633269A (en) | Preparation method of aerogel | |
| CN102115092A (en) | Method for producing high-modulus sodium silicate by adopting liquid phase method | |
| CN103303974B (en) | Method for recycling waste silicon slag discharged in production of zirconyl chloride | |
| CN102180470B (en) | Method for recycling silicon tetrachloride as by-product of polycrystalline silicon | |
| CN102874868B (en) | Method for preparing potassium fluozirconate through fluosilicic acid | |
| CN101391793A (en) | Method for preparing kryocide | |
| CN102874855B (en) | Lithium-containing sodium cryolite and preparation method thereof | |
| CN102167376B (en) | Technique for purifying cryolite | |
| WO2013123722A1 (en) | Method for cyclically preparing elemental boron and simultaneously producing potassium cryolite using potassium fluoroborate as an intermediate material | |
| CN102211784B (en) | Method for producing low silicon dry-method aluminum fluoride by using high silicon flousper powder | |
| CN102107900B (en) | Method for comprehensively utilizing chemical byproduct single cryolite | |
| CN101891213A (en) | Method for preparing water glass from byproduct silicon tetrachloride | |
| CN104192852A (en) | Method for performing gas phase desilication on silicon-containing minerals and recycling halogen-containing substances |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170510 |
|
| RJ01 | Rejection of invention patent application after publication |