CN105442047B - A kind of method that fluorine element is extracted from industrial gypsum - Google Patents
A kind of method that fluorine element is extracted from industrial gypsum Download PDFInfo
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- CN105442047B CN105442047B CN201510993009.1A CN201510993009A CN105442047B CN 105442047 B CN105442047 B CN 105442047B CN 201510993009 A CN201510993009 A CN 201510993009A CN 105442047 B CN105442047 B CN 105442047B
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/62—Whiskers or needles
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
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Abstract
The present invention relates to environmental protection and technical field of resource comprehensive utilization; specifically a kind of method that fluorine element is extracted from industrial gypsum; it is the method for the fluosilicate that crystal whisker of gypsum while separatin non-soluble are prepared using the normal pressure salt solustion mehtod of gypsum; prepare uniform in size; the preferable crystal whisker of gypsum of quality, while extract fluorine element.The present invention is purified industrial gypsum, while further obtains fluorine element and opened up new way.
Description
Technical field
The present invention relates to environmental protection and technical field of resource comprehensive utilization, is a kind of purified industrial gypsum specifically
The new method of fluorine element is extracted from industrial gypsum simultaneously.
Background technology
Industrial gypsum mainly includes ardealite and fluorgypsum, desulfurated plaster.Ardealite gives off when being phosphate fertilizer, phosphoric acid production
Solid waste.Production 1t phosphoric acid about produces 4.5~5t ardealites.In recent years, with the development of phosphate fertilizer industry, the row of ardealite
High-volume also increasingly increase.The discharge capacity of the annual ardealite in China is more than 10,000,000 t, and its utilization rate is very low, and ardealite takes
A large amount of soils, environment is polluted, very big burden is brought to manufacturing enterprise, the recycling of ardealite turns into phosphate fertilizer industry
Realize the key of sustainable development.Ardealite is mainly by CaSO4·2H2O is formed, and is a kind of important reclaimed gypsum resource.Phosphorus stone
Cream contains the impurity such as phosphorus, fluorine, and structure is also different from the natural gypsum, it is therefore necessary to could be used for building materials of gypsum after being pre-processed
Production.The application to ardealite domestic at present has carried out substantial amounts of research, also achieves certain achievement, ardealite building materials,
The industries such as agricultural, chemical industry are obtained for recycling.
The main chemical compositions of ardealite are CaO and SO3, contain P simultaneously2O5、F、Al2O3、Fe2O3、SiO2, organic matter etc.
The element such as impurity and a small amount of uranium, radium, cadmium, lead, copper.Ardealite is mainly with acicular crystal, platelike crystal, closely knit crystal, more nucleus
Four kinds of crystal forms such as crystal are present.The performance of ardealite adhesive bond has larger difference compared with the natural gypsum, is mainly shown as
Setting time is grown, and intensity is relatively low.Different manufacturing enterprises, chemical group Chengdu of ardealite of different batches are slightly different, and this is main
The kind of control and rock phosphate in powder with phosphoric acid production process conditions is relevant.China's phosphoric acid production passes through sulphur based on wet production
Sour decomposing phosphate rock stone generation extracts slurry, and then phosphoric acid is made in filtration washing, and ardealite is produced simultaneously during filtration washing.Its
Reaction equation is：
Ca5(PO4)F+5H2SO4+10H2O→3H3PO4+5CaSO4·2H2O+HF
In production process of phosphoric acid, part rock phosphate in powder is undecomposed, ardealite washing and filtering process is incomplete and produces
The additive added in journey be in ardealite containing the plurality of impurities such as phosphorus, fluorine the reason for, the ardealite that has been exactly these impurity effects
Performance, it is not directly applicable the production of building materials of gypsum, constrain the use of ardealite.Fluorine source in ardealite in
Rock phosphate in powder, when rock phosphate in powder is through sulfuric acid decomposition, the fluorine in rock phosphate in powder has 20%~40% to be mixed in ardealite, with soluble fluorine NaF
With indissoluble fluorine CaF2、Na2SiF6Three kinds of forms are present.Influence ardealite performance is soluble fluorine, and soluble fluorine has blood coagulation enhancing effect, but
When its content is more than 0.3%, the intensity of ardealite can be significantly reduced.Soluble fluorine can be eliminated by washing process.In ardealite
Fluorine also environment is damaged.There are some researches show the content of fluorine will higher than national standard in the leachate of new output ardealite
The threshold limit value asked, belongs to hazardous waste.After depositing a period of time in stockyard, a part of fluorine can flow because of rainfall leaching
Lose, a part of fluorine and the Ca in ardealite2+Stable calcirm-fluoride is formed so that the solvable Oil repellent in ardealite reduces, at this moment
Ardealite belong to unhazardous waste (important content of the invention is to reclaim the fluorine that is present in ardealite of this part).
The fluorine being lost in rainfall leaching can be penetrated into the water body around stockyard, made Funing tablet in water too high, caused environmental pollution.
Fluorgypsum is that the byproduct after hydrofluoric acid is produced using fluorite and the concentrated sulfuric acid.The production of 1 ton of hydrofluoric acid can produce 3.6
The anhydrous fluorgypsum of ton.Wherein CaSO4Content is up to more than 90%, is high-grade gypsum resource.It is more rare, wherein fluorine
Change content 1.2~4.0% (dry method gypsum), 2.7~6.8% (the wet method gypsum) of calcium.If reasonably utilized, will turn into
One of important sources of fluorine.
(Calcium Sulfate Whisker, also known as calcium sulphate micro-fibre, international commodity are entitled for calcium sulfate crystal whiskers
ONODA-GPF) it is a kind of new inorganic material with very high combination property.In papermaking, precise part mould, construction material
Part, cement mortar, polymer carrier, friction means etc. are all widely used.
Following patent is to prepare relevant China and foreign countries' patent document with wastewaters with modified calcium sulfate whiskers：
WO2009150037A1 discloses a kind of organosilicon compound composition granule and prepares hydrophobic gypsum as additive, wherein
Silanes are silane, siloxanes and some silicon-containing compounds.
CN102337703A discloses a kind of method using titanate coupling agent surface modified gypsum whisker, will be a certain amount of
Crystal whisker of gypsum suspension in the ethanol solution of 3%~5% titanate coupling agent, be heated to 60 DEG C~90 DEG C modifications 10~
30min.
CN102634847A discloses a kind of method using quaternary ammonium salt surface modified gypsum whisker, and calcium sulfate crystal whiskers are first
It is dried, then calcium sulfate crystal whiskers, polyquaternium, octadecylamine and absolute ethyl alcohol is mixed to the pH in regulation liquid by a certain percentage
To 6~9, then filter, modified product calcium sulfate crystal whiskers will be obtained after filter residue and drying.
CN1283548A, ZL200610051140.7, ZL200610051178.4 are to prepare to reclaim with fluorine with crystal whisker of gypsum
Relevant Chinese patent literature.
But on a kind of short-cut method and technique that fluorine is extracted from ardealite, fluorgypsum, so far there are no reports.
The content of the invention
It is an object of the invention to provide a kind of short-cut method and technique that fluorine is extracted from ardealite, fluorgypsum.
The first aspect of the present invention, there is provided a kind of method that fluorine element is extracted from industrial gypsum, be using the normal of gypsum
The method that pressure salt solustion mehtod prepares the fluosilicate of crystal whisker of gypsum while separatin non-soluble, comprises the following steps：
(1) fine prepares ardealite or fluorgypsum particle：By ball milling or air-flow crushing by ardealite or fluorgypsum
Manage into ultra-fine ardealite or the fluorgypsum particle (part A) of 1~20 μm or so of particle diameter；
(2) ultra-fine ardealite or the fluorgypsum particle (part A) for preparing step (1), water, cosolvent, crystal formation is added and is adjusted
Save agent to mix, regulation pH is 0.5~2.5 (preferably 0.5~1.5), is reacted in 95~100 DEG C (preferably 95~98)；
Described cosolvent is selected from more than one or both of sodium chloride, potassium chloride, sodium sulphate, potassium sulfate (preferably chlorine
Change sodium)；The one kind of described crystal structure adjusting agent in tartaric acid, citric acid, malic acid, edta and its sodium salt
(optimization citric acid sodium)；Described ultra-fine ardealite or fluorgypsum particle, water, cosolvent, the parts by weight difference of crystal structure adjusting agent
For：
(3) by the reaction solution of step (2), calcium sulfate crystal whiskers mixed-powder, 50-80 DEG C of aeration-drying are filtrated to get；Utilize
Screen cloth or grading plant carry out gradation, sift out draw ratio 1：1~3：1 whisker particle (part B), beyond this size
Solid particle, which merges to obtain, is rich in fluosilicate, villiaumite, the mixed powder (C portion) of silicate and other metallic salts, utilizes
The technology of existing extraction fluorine, fluorine element is extracted from above-mentioned mixed powder.
Add the acid for adjusting pH value of mass percent 25% in described step (2), the reaction time be 1~4 hour (preferably
2 hours).
Described part B is draw ratio 1：1~3：1 calcium sulfate crystal whiskers, can be used for high strength gypsum and calcium sulfate crystal whiskers
Other application.
Described C portion mixed powder is the mixed powder rich in fluosilicate, villiaumite, silicate and other metallic salts
Body, using the technology of existing ripe extraction fluorine, further it can extract fluorine element from this part powder.It is described it is existing into
The technology of ripe extraction fluorine includes：1) direct method (Bath company of Switzerland BASS AG)；2) indirect method：Among sodium hydroxide (potassium)
Method；3) indirect method：Ammonium fluoride method (liquefied ammonia).(bibliography：Tribute is long-living,《Modern Phosphating work technology and application》, chemical industry
Publishing house, Beijing：2013 pp532-543.)
The present invention is prepared uniform in size using ardealite, fluorgypsum as raw material using normal pressure salt solustion mehtod, and quality is preferable
Crystal whisker of gypsum.Gypsum equally follows the reaction mechanism of " dissolve-repreparation " in salting liquid, i.e. dihydrate gypsum is molten in salting liquid
Calcium ion and sulfate ion are solved, because solubility of the semi-hydrated gypsum in salting liquid is more molten than dihydrate gypsum and anhydrous gypsum
Xie Du is small, so as to cause calcium ion and sulfate ion to recrystallize, generates semi-hydrated gypsum crystal.Impurity in gypsum with
The dissolving of gypsum and escape in gypsum crystal, the purifying to the crystal structure of gypsum produces wholesome effect.The present invention is selecting
During crystal structure adjusting agent, it is contemplated that the factor that impurity influences on crystal structure, crystal formation tune has been additionally contemplates that while the removal of impurity is gone
Save the impact effect of the dosage of agent and the crystal to gypsum.The present invention is using organic acids such as citric acids as crystal structure adjusting agent, so as to make
It is purified industrial gypsum for uniform in size, the higher crystal whisker of gypsum of quality is gone out, while further obtains fluorine element and opened up new way
Footpath.
Embodiment
Embodiment provided by the invention is elaborated with reference to embodiment.
Embodiment 1
288mL water is added in the three-necked flask with thermometer that volume is 500mL, sodium chloride 72g, then weighs one
Quantitative ardealite 60g, with dilute H2SO4PH with NaOH solution regulation salting liquid is 2, is eventually adding 0.36g containing sodium citrate
Aqueous solution 5mL, adjust 95 DEG C of the temperature of reaction, reacted under the mixing speed of setting, 2 hours reaction time, cooling,
It is rapid to filter, with the deionized water washes clean of heat, dry, 5-20 μm of whisker particle is separated using Vibration Screen.In this chi
Solid particle beyond very little merges, as the component rich in fluosilicate.Obtained calcium sulfate crystal whiskers are uniform in size, particle diameter distribution
It see the table below 1.
Embodiment 2
288mL water is added in the three-necked flask with thermometer that volume is 500mL, sodium chloride 72g, then weighs one
Quantitative fluorgypsum 60g, with dilute H2SO4PH with NaOH solution regulation salting liquid is 2.5, is eventually adding containing sodium citrate
0.50g aqueous solution 5mL, 99 DEG C of the temperature of reaction is adjusted, is reacted under the mixing speed of setting, 2 hours reaction time,
Cooling, it is rapid to filter, with the deionized water washes clean of heat, dry, 5-60 μm of whisker particle is separated using Vibration Screen.
Solid particle beyond this size merges, as rich in fluosilicate, villiaumite component.Obtained calcium sulfate crystal whiskers size is equal
Even, particle diameter distribution see the table below 1.
Embodiment 3
240mL water is added in the three-necked flask with thermometer that volume is 500mL, sodium chloride 60g, then weighs one
Quantitative ardealite 50g, with dilute H2SO4PH with NaOH solution regulation salting liquid is 1.5, is eventually adding containing sodium citrate
0.55g aqueous solution 5mL, 100 DEG C of the temperature of reaction is adjusted, is reacted under the mixing speed of setting, the reaction time 2.5 is small
When, cooling is rapid to filter, and with the deionized water washes clean of heat, dries, 5-60 μm of whisker is separated using Vibration Screen
Grain.Solid particle beyond this size merges, as the component rich in fluosilicate.Obtained calcium sulfate crystal whiskers size is equal
Even, particle diameter distribution see the table below 1.
Embodiment 4
240mL water is added in the three-necked flask with thermometer that volume is 500mL, sodium chloride 55g, then weighs one
Quantitative ardealite 60g, with dilute H2SO4PH with NaOH solution regulation salting liquid is 2, is eventually adding 0.20g containing sodium citrate
Aqueous solution 5mL, adjust 95 DEG C of the temperature of reaction, reacted under the mixing speed of setting, 2 hours reaction time, cooling,
It is rapid to filter, with the deionized water washes clean of heat, drying, obtain long 10-50 μm, draw ratio 10：1 calcium sulfate crystal whiskers mark
Quasi- Vibration Screen separates.Solid particle beyond this size merges, as the component rich in fluosilicate.Obtained calcium sulfate
Whisker is uniform in size, and particle diameter distribution see the table below 1.
Embodiment 5
240mL water is added in the three-necked flask with thermometer that volume is 500mL, sodium chloride 55g, then weighs one
Quantitative fluorgypsum 70g, with dilute H2SO4PH with NaOH solution regulation salting liquid is 2.5, is eventually adding containing sodium citrate
0.25g aqueous solution 5mL, 99 DEG C of the temperature of reaction is adjusted, is reacted under the mixing speed of setting, 2 hours reaction time,
Cooling, it is rapid to filter, with the deionized water washes clean of heat, drying, obtain long 5-60 μm, draw ratio 10：1 calcium sulfate crystal whiskers
Sieved with standard vibration.Solid particle beyond this size merges, as rich in fluosilicate, villiaumite component.
The calcium sulfate crystal whiskers arrived are uniform in size, and particle diameter distribution see the table below 1.
The laser particle size analyzer method particle diameter distribution % of table 1.
The rate of recovery of the F contents before and after the processing of table 2. and F
Note：Content in this table does not include SO2, the crystallization water and other minor metallic elements.F elements refer to fluorine-containing silicic acid
Salt, the fluorine element in villiaumite.
From table 1, table 2, the gypsum crystal being prepared by embodiment 1-5, particle diameter distribution Relatively centralized is in 5~50 μm
Scope is higher for the rate of recovery of F elements.
The present invention is when from crystal modifier, it is contemplated that the factor that impurity influences on crystal structure, while the removal of impurity is gone
It has been additionally contemplates that the impact effect of the dosage of crystal modifier and the crystal to gypsum.The present invention is using organic acids such as citric acids as a turn crystalline substance
Agent, quality higher crystal whisker of gypsum uniform in size so as to prepare, it is to having a competition below on crystal modifier (crystal structure adjusting agent)
Test：
Comparative example 1
288mL water is added in the three-necked flask with thermometer that volume is 500mL, sodium chloride 72g, then weighs one
Quantitative ardealite 60g, with dilute H2SO4PH with NaOH solution regulation salting liquid is 2, is eventually adding the 0.36g's containing malonic acid
Aqueous solution 5mL, 95 DEG C of the temperature of reaction is adjusted, is reacted under the mixing speed of setting, in 2 hours reaction time, cooling is fast
Speed filters, and with the deionized water washes clean of heat, dries, 5-20 μm of whisker particle is screened out with standard.Beyond this size
Solid particle merge, the as component rich in fluosilicate.Obtained calcium sulfate crystal whiskers size is irregular, and size distribution is shown in
Table 3；The F rate of recovery 43%.
Comparative example 2
288mL water is added in the three-necked flask with thermometer that volume is 500mL, sodium chloride 72g, then weighs one
Quantitative fluorgypsum 60g, with dilute H2SO4PH with NaOH solution regulation salting liquid is 2.5, is eventually adding containing 0.5 gram of glutaric acid
Aqueous solution 5mL, adjust 99 DEG C of the temperature of reaction, reacted under the mixing speed of setting, 2 hours reaction time, cooling,
It is rapid to filter, with the deionized water washes clean of heat, dry, 5-20 μm of whisker particle is screened out with standard.This size with
Outer solid particle merges, as rich in fluosilicate, villiaumite component.Obtained calcium sulfate crystal whiskers size is irregular, grain
Degree distribution is shown in Table 3, the F rate of recovery 38%.
Comparative example 3
240mL water is added in the three-necked flask with thermometer that volume is 500mL, sodium chloride 60g, then weighs one
Quantitative ardealite 50g, with dilute H2SO4PH with NaOH solution regulation salting liquid is 1.5, is eventually adding containing 0.55 gram of oxalic acid
Aqueous solution 5mL, adjust 100 DEG C of the temperature of reaction, reacted under the mixing speed of setting, it is 2.5 hours reaction time, cold
But, it is rapid to filter, with the deionized water washes clean of heat, dry, 5-40 μm of whisker particle is screened out with standard.In this size
Solid particle in addition merges, as the component rich in fluosilicate.Obtained calcium sulfate crystal whiskers size is irregular, size distribution
It is shown in Table 3；The F rate of recovery 36%.
The laser particle size analyzer method particle diameter distribution % of table 3.
The rate of recovery of the F contents before and after the processing of table 4. and F
From table 3, table 4, the gypsum crystal being prepared by comparative example 1-3, particle diameter distribution relative distribution, for F members
The rate of recovery of element is relatively low.
The preferred embodiment to the invention is illustrated above, but the invention be not limited to it is described
Embodiment, those skilled in the art can also make a variety of equivalent on the premise of without prejudice to the invention spirit
Modification or replacement, these equivalent modifications or replacement are all contained in the application claim limited range.
Claims (5)
- A kind of 1. method that fluorine element is extracted from industrial gypsum, it is characterised in that be the normal pressure salting liquid legal system using gypsum The method of standby crystal whisker of gypsum while the fluosilicate of separatin non-soluble, comprises the following steps：(1) fine prepares ardealite or fluorgypsum particle：Ardealite or fluorgypsum are processed into by ball milling or air-flow crushing Ultra-fine ardealite or the fluorgypsum particle of 1~20 μm of particle diameter；(2) ultra-fine ardealite or the fluorgypsum particle for preparing step (1), water, cosolvent, crystal structure adjusting agent is added and mixes and stirs Mix, regulation pH is 0.5~2.5, in 95~100 DEG C of reactions；Described cosolvent is selected from more than one or both of sodium chloride, potassium chloride, sodium sulphate, potassium sulfate；Described crystal formation The one kind of conditioning agent in tartaric acid, citric acid, malic acid, edta and its sodium salt；Described ultra-fine ardealite Or the parts by weight of fluorgypsum particle, water, cosolvent, crystal structure adjusting agent are respectively：(3) by the reaction solution of step (2), calcium sulfate crystal whiskers mixed-powder, 50-80 DEG C of aeration-drying are filtrated to get；Utilize screen cloth Or grading plant carries out gradation, 5-60 μm of whisker particle is sifted out, the solid particle beyond this size merges to obtain richness The mixed powder of fluorine-containing silicate, villiaumite, silicate and other metallic salts, using the technology of existing extraction fluorine, from above-mentioned Fluorine element is extracted in mixed powder.
- 2. the method according to claim 1 that fluorine element is extracted from industrial gypsum, it is characterised in that described step (2) acid for adjusting pH value of mass percent 25% is added in.
- 3. the method according to claim 1 that fluorine element is extracted from industrial gypsum, it is characterised in that described step (2) reaction time in is 1~4 hour.
- 4. the method according to claim 1 that fluorine element is extracted from industrial gypsum, it is characterised in that described cosolvent For sodium chloride.
- 5. the method according to claim 1 that fluorine element is extracted from industrial gypsum, it is characterised in that described crystal formation is adjusted Section agent is sodium citrate.
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| CN106319631B (en) * | 2016-08-30 | 2019-02-22 | 湖北永绍科技股份有限公司 | The joint disposal of a kind of sulfuric acid waste and hydrochloride waste utilizes method |
| CN108467016B (en) * | 2018-06-11 | 2021-04-23 | 华东理工大学 | Method for extracting fluorine element from industrial gypsum by using flotation technology |
| CN109137084B (en) * | 2018-09-10 | 2021-06-18 | 昆明理工大学 | Method for producing calcium sulfate dihydrate crystal whisker by salting-out method |
| CN110453286B (en) * | 2019-09-18 | 2021-05-04 | 云南凝创环保科技有限公司 | Method for producing calcium sulfate dihydrate crystal whisker by semi-permeable membrane method |
| CN115784238B (en) * | 2022-10-18 | 2024-03-12 | 宜都兴发化工有限公司 | Method for recycling soluble fluorine in phosphogypsum |
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