CN105236481B - A kind of method of low temperature liquid phase decomposing zircon sand - Google Patents
A kind of method of low temperature liquid phase decomposing zircon sand Download PDFInfo
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- CN105236481B CN105236481B CN201410323330.4A CN201410323330A CN105236481B CN 105236481 B CN105236481 B CN 105236481B CN 201410323330 A CN201410323330 A CN 201410323330A CN 105236481 B CN105236481 B CN 105236481B
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Abstract
The present invention relates to zircon sand to decompose field, in particular it relates to a kind of method of low temperature liquid phase decomposing zircon sand.The method of the low temperature liquid phase decomposing zircon sand of the present invention, comprises the following steps：(1) zircon sand is mixed with the solution of alkali metal hydroxide, stirred, carry out liquid phase reactor, reaction temperature is 250~350 DEG C, obtains liquid-phase reaction product；(2) after the liquid-phase reaction product cooling obtained step (1), add water pulping and washing, then filter, it is obtained zirconates midbody compound to obtain solid phase filter cake, the liquid phase of acquisition is containing aqueous slkali, and step (1) recycling is can return to after the purified concentration of the alkali lye.The inventive method can substantially reduce reaction temperature compared with conventional high-temperature alkali fusion technology, save energy consumption, and due to for liquid phase reactor, being polluted in the absence of alkali mist, operating environment can be improved, alkali can be realized and recycled, and reduce comprehensive alkaline consumption, be a kind of cleaning decomposition method of zircon sand.
Description
Technical field
The present invention relates to zircon sand to decompose field, in particular it relates to a kind of side of low temperature liquid phase decomposing zircon sand
Method.
Background technology
Zirconium chemicalses are national economy, the important materials of national defense construction, are widely used in ceramics, chemical industry, electronics, smelting
The industries such as gold, papermaking, printing and dyeing, industrial catalyst, purifying vehicle exhaust, military project, nuclear power station and nuclear industry.Zirconium oxychloride is as one
The important zirconates basic chemical industry product of kind, occupy the first place of zirconium chemicalses, its main purposes is as zirconium carbonate, sulfuric acid
The intermediate raw material of other zirconium compounds deep processings such as zirconium, zirconium dioxide, and can be used for producing nuclear-grade zirconium material.
Zircon sand is the primary raw material of zirconium oxychloride production and processing, and it is a kind of silicate (ZrSiO with zirconium4) based on
The mineral to be formed, physics and chemical very rotundity are high, it is difficult to decompose.At present, domestic decomposing zircon sand mainly use for
Alkali fusion (a sour alkaline process), the process of zirconium oxychloride is prepared by zircon sand includes high temperature alkali fuse reaction, washing, transition, acidolysis
The alkali fusion reaction of the processes such as flocculation, evaporative crystallization, wherein zircon sand and sodium hydroxide is one of key link.
In existing zirconium oxychloride production, alkali fusion decomposing zircon sand process is intermittently carried out typically in sintering pot, reaction
Process is to put into zircon sand after solid sodium hydroxide is heated into molten state in sintering pot, is entered by the natural subsidence of zircon sand
Go and react, be brought rapidly up after putting into zircon sand to the reaction temperature of needs (generally 750 DEG C), then insulation obtains for a period of time
Sintering feed, sintering feed can must wash material after being washed, its main component is the midbody compound of zirconates.
In conventional high-temperature alkali fusion course of reaction, the reaction mainly occurred can represent as follows：
ZrSiO4+ 2NaOH=Na2ZrSiO5+2H2O
ZrSiO4+ 4NaOH=Na2ZrO3+Na2SiO3+2H2O
ZrSiO4+ 6NaOH=Na2ZrO3+Na4SiO4+3H2O
In theory, the proportioning of sodium hydroxide and zircon sand is mol ratio 4：1 (mass ratio 0.87：1), examined based on dynamics
Consider, the alkali of generally use is excessive, i.e., in actual production, the proportioning of sodium hydroxide and zircon sand is generally mol ratio 6：1 (matter
Measure ratio 1.33：1), alkali number exceedes theoretical amount more than 50%, and excessive alkali forms substantial amounts of spent lye in water-washing process, according to
Statistics, often produce one ton of zirconium oxychloride and about produce 5~6 tons of alkali wasteliquids, because reaction needs are solid caustic soda, therefore, these salkali waste
Liquid can not economically be realized and recycled, and cause great hidden danger to periphery ecological environment, while also increase zirconium oxychloride
Production cost.
At present in the industrial production, zircon sand alkali fusion process is intermittently carried out typically in sintering pot, and reaction temperature is up to 750
DEG C, therefore, decomposable process high energy consumption is also one of problem of zircon sand decomposable process.
The content of the invention
It is an object of the present invention to solve the above problems, improving the deficiency of traditional alkali fusion technique, there is provided a kind of Low Temperature Liquid
The new method of phase decomposition zircon sand.By the application of new method, reaction temperature can be substantially reduced, reduces energy consumption, improves operation ring
Border, alkaline media recycle, and reduce comprehensive alkaline consumption, are a kind of cleaning decomposition techniques of zircon sand.
The method of the low temperature liquid phase decomposing zircon sand of the present invention, comprises the following steps：
(1) zircon sand is mixed with the solution of alkali metal hydroxide, stirred, carry out liquid phase reactor, reaction temperature
For 250~350 DEG C, liquid-phase reaction product is obtained；
(2) after the liquid-phase reaction product cooling obtained step (1), add water pulping and washing, then filter, obtain solid phase filter
Cake is obtained zirconates midbody compound, and the liquid phase of acquisition is containing aqueous slkali.
The method according to the invention, for reaction effect is better achieved, preferably step (1) described zircon sand can be put into
Ball mill carries out ball milling, obtains the zircon sand after ball milling；The particle mean size of zircon sand after ball milling is 2~70 μm.
The method according to the invention, the alkali metal hydroxide that step (1) uses can be potassium hydroxide or sodium hydroxide
Or two kinds of combination, the concentration of the solution of used alkali metal hydroxide is 50%~90% (w/w).
The method according to the invention, in the liquid phase reactor mass ratio of alkali metal hydroxide and zircon sand for (1~
7)：1；Reaction time is 0.5~10h.
According to the low temperature liquid phase decomposing zircon sand method of the present invention, described liquid phase reactor can also use heat stepwise mode
Reacted, i.e., in the case that (0.5~10h) is constant in the W-response time, some front and rear reaction temperature will be divided into the reaction time
The different periods is spent, the reaction temperature of each period is in the range of 250~350 DEG C.
In the liquid phase reactor of the present invention, pressure can be normal pressure, and mixing speed is 50~300r/min.The liquid phase is anti-
It is able to should be carried out preferably in the reactor with agitating paddle.
In the present invention, the amount of water of washing and the mass ratio of liquid-phase reaction product are (2~10) in step (2):1, pulp
Time is 5~30min.
Contain aqueous slkali for what step (2) obtained, after desiliconization purification can be carried out to it using conventional method, further pass through
It is concentrated by evaporation to the solution concentration of step (1) alkali metal hydroxide, realization and recycles.
Traditional zircon sand decomposes for sodium hydroxide alkali fusion, the problems such as high energy consumption, alkaline consumption is high be present, as country is to resource
Energy resource consumption, environmental protection, pollution control emission control system are more and more tighter, and the research to zircon sand decomposition technique also result in the country
The attention of outer researcher, it is representative for mixing alkali fusion and hydro-thermal method.
(Novel decomposition method for zircon, the Journal of Alloys such as Abdelkader
and Compounds,2008,460:577) proposed for alkali fusion decomposable process reaction temperature the problem of high using low melting point
KOH and NaOH fused salt mixts substitute NaOH or Na2CO3The decomposition of zircon sand is carried out, at 550 DEG C, excessive 20% alkali ore deposit compares condition
Under, the resolution ratio of zircon sand is up to more than 96%.(CaO-NaOH mixed base decomposing zircon sands prepare the new work of zirconium oxychloride to Zhang Jiandong
Skill research, Beijing Non-Fervoous Metal Inst., Ph.D. Dissertation, 2012), Chen Weidong (CaCl2With the compound decomposing zircon sands of NaOH
Technical study, Ti industry progress, 2013,30 (1)：37), Wang Lijun etc. (CN201010553198.8) decomposed for zircon sand
The problem of journey alkaline consumption is high, Batch Process, propose to prepare zirconium oxychloride new technology using the compound decomposing zircon sand of additive-caustic soda,
Used additive such as CaCl2, NaCl, CaO etc., reduce base amount to a certain extent, and alkali is realized based on rotary furnace
The serialization of molten process, but the reaction temperature needed is still higher, is 750~850 DEG C.
Relative to traditional alkali fusion, mixing alkali fusion is reducing alkaline consumption, temperature and is realizing that continuous reaction etc. has one
It is a little to improve, but due to being still based on traditional high temperature alkali fuse reaction system, can not fundamentally solve reaction temperature height and alkali lye
The problem that medium economic circulation utilizes.
In addition, there is the new method researched and proposed and zircon sand decomposition is carried out using hydro-thermal method.Yin Shu etc. is to prepare dioxy
Hydro-thermal method decomposing zircon sand is used for the purpose of change zirconium, is 330 DEG C in reaction temperature, in 35% alkali lye, realizes that zircon sand is efficient
Decompose.All great waves etc. (CN201310010214.2) use hydro-thermal method decomposing zircon sand, but due to it is desirable that zircon sand superfine powder
(1-5 μm), and reaction pressure is 3~7MPa, is also unfavorable for large-scale industrial application.Hydro-thermal method have corrosivity it is small, reaction temperature
The advantages that relatively low is spent, and offer feasibility is recycled for alkali lye, but the problem of needing high-tension apparatus be present.
For the present invention using the alkali metal hydroxide aqueous solution of higher concentration as reaction medium, it has low-steam pressure, boiling point
The high, characteristic of good fluidity, strengthen mass transport process by chemical fields, the efficient of mineral is realized in realization at relatively low temperature
Decompose.The process that zircon sand reacts in the highly concentrated alkaline medias of KOH and/or NaOH is that a typical liquid-solid two-phase on-catalytic is anti-
Should, it is thermodynamically identical with high temperature alkali fuse reaction principle, and product is the zirconates or silicon zirconates of alkali metal.With high concentrated base
Liquid (50%~90% KOH and/or NaOH) is also referred to as sub-molten salt technology for the reinforcing mineral decomposition technique of reaction medium, at present
It is successfully applied to decompose the difficult decomposition mineral such as chromite, ilmenite.
In the present invention, the proportioning of alkali metal hydroxide and zircon sand, reaction time, reaction temperature are taking after optimization
Value is appropriate up and down within the scope of the present invention to adjust as long as will not have adverse consequences to invention on the premise of reaction can be promoted to carry out
Whole proportioning, reaction time and reaction temperature can be with.
The inventive method can substantially reduce reaction temperature compared with conventional high-temperature alkali fusion technology, save energy consumption, and due to for
Liquid phase reactor, polluted in the absence of alkali mist, operating environment can be improved, alkali can be realized and recycled, and reduced comprehensive alkaline consumption, be a kind of zirconium
The cleaning decomposition method of sand.
Embodiment
The method of the low temperature liquid phase decomposing zircon sand of the present invention, is described in detail by following examples.
Embodiment 1
Zircon sand be milled to particle mean size as 10 μm, 50g zircon sands are taken, according to KOH and ZrSiO4Mass ratio is
3：1 proportioning, 150g KOH are weighed, potassium hydroxide is configured to the aqueous slkali that mass concentration is 60%, then entered with zircon sand
Row mixing, the reactor with stirring is inserted, mixing speed 50r/min, it is 320 DEG C to set reaction temperature, reacts 0.5h, then will
Obtained reaction product is cooled down, and 1000g water is added after cooling, pulping and washing 30min, then filters, obtains in potassium zirconium
Intermediate compounds therefor, after tested, zircon sand resolution ratio are 96%.Alkali lye adds appropriate milk of lime and carries out desiliconization, is evaporated to after separation
Concentration utilizes for 60% Posterior circle.
Embodiment 2
Zircon sand be milled to particle mean size as 70 μm, 50g zircon sands are taken, according to KOH and ZrSiO4Mass ratio is
7：1 proportioning, 350g KOH are weighed, potassium hydroxide is configured to the aqueous slkali that mass concentration is 90%, then entered with zircon sand
Row mixing, the reactor of band stirring is inserted, mixing speed 100r/min, it is 300 DEG C to set one section of reaction temperature, and the reaction time is
1h, second-stage reaction temperature are 350 DEG C, react 1h, and three sections of reaction temperatures are 280 degree, react 30min, obtain reaction product, will be anti-
Answer product to add 3000g water after being cooled down, pulping and washing 20min, then filter, obtain potassium zirconium midbody compound, pass through
Test, zircon sand resolution ratio are 98%.
Embodiment 3
Zircon sand be milled to particle mean size as 20 μm, 50g zircon sands are taken, according to NaOH and ZrSiO4Mass ratio is
6：1 proportioning, 200g NaOH are weighed, sodium hydroxide is configured to the aqueous slkali that mass concentration is 50%, then entered with zircon sand
Row mixing, the reactor with stirring is inserted, mixing speed 100r/min, it is 250 DEG C to set reaction temperature, reacts 7h, then will
Obtained reaction product is cooled down, and 800g water is added after cooling, pulping and washing 10min, then filters, obtains among potassium zirconium
Body compound, after tested, zircon sand resolution ratio are 96%.Alkali liquor desiliconization, concentration is evaporated to after separation and is utilized for 60% Posterior circle.
Embodiment 4
Zircon sand be milled to particle mean size as 2 μm, 50g zircon sands are taken, according to NaOH and ZrSiO4Mass ratio is
1：1 proportioning, 50g NaOH are weighed, sodium hydroxide is configured to the aqueous slkali that mass concentration is 70%, then entered with zircon sand
Row mixing, insert band stirring reactor, mixing speed 200r/min, set one section of reaction temperature be 180 degree, reaction 2h, two
Section reaction temperature is 280 DEG C, reacts 5h, is then cooled down obtained reaction product, and 1000g water, pulp are added after cooling
30min is washed, then filters, obtains potassium zirconium midbody compound, after tested, zircon sand resolution ratio is 95%.
Embodiment 5
Zircon sand be milled to particle mean size as 20 μm, 50g zircon sands are taken, according to alkali and ZrSiO4Mass ratio is 4：
1 proportioning, weigh 100gNaOH and 100g KOH, by mixed base be configured to mass concentration be 70% aqueous slkali, then with zirconium
Sand is mixed, and inserts the reactor with stirring, and mixing speed 300r/min, it is 310 DEG C to set reaction temperature, reacts 4h,
Then obtained reaction product is cooled down, 1200g water is added after cooling, pulping and washing 10min, then filters, obtains zirconium
Sour potassium midbody compound, after tested, zircon sand resolution ratio are 98%.
Non-elaborated part of the present invention belongs to techniques well known.
Certainly, the present invention can also have various embodiments, in the case of without departing substantially from spirit of the invention and its essence, be familiar with
Those skilled in the art can be made according to disclosure of the invention it is various it is corresponding change and deformation, but these it is corresponding change and
Deformation should all belong to the scope of the claims of the present invention.
Claims (7)
1. a kind of method of low temperature liquid phase decomposing zircon sand, comprises the following steps：
(1) zircon sand is mixed with the solution of alkali metal hydroxide, stirs, carry out liquid phase reactor at ambient pressure, reacted
Temperature is 250~350 DEG C, obtains liquid-phase reaction product；Wherein, the mass percent of the solution of the alkali metal hydroxide is dense
Spend for 50%~90%；The alkali metal hydroxide is potassium hydroxide or sodium hydroxide or two kinds of combination；
(2) after the liquid-phase reaction product cooling obtained step (1), add water pulping and washing, then filter, obtaining solid phase filter cake is
Obtained zirconates midbody compound, the liquid phase of acquisition is containing aqueous slkali.
2. according to the method for claim 1, it is characterised in that step (1) described zircon sand is put into ball mill and carries out ball
Mill, obtains the zircon sand after ball milling；The particle mean size of zircon sand after ball milling is 2~70 μm.
3. according to the method for claim 1, it is characterised in that the mass ratio of alkali metal hydroxide and zircon sand for (1~
7)：1.
4. according to the method for claim 1, it is characterised in that in step (1) the liquid reactive reaction time be 0.5~
10h。
5. the method according to claim 1 or 4, it is characterised in that in step (1) liquid phase reactor mixing speed be 50~
300r/min。
6. according to the method for claim 1, it is characterised in that the amount of water and liquid-phase reaction product of washing in step (2)
Mass ratio be (2~10):1, slurry time is 5~30min.
7. according to the method for claim 1, it is characterised in that carry out desiliconization purification containing aqueous slkali by what step (2) obtained
Afterwards, through being concentrated by evaporation to the solution concentration of step (1) alkali metal hydroxide, recycle.
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| CN115321593A (en) * | 2022-07-26 | 2022-11-11 | 乐昌东锆新材料有限公司 | Preparation method of zirconium oxychloride |
Citations (1)
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| CN101481141A (en) * | 2008-01-08 | 2009-07-15 | 河南佰利联化学股份有限公司 | Method for decomposing zircon sand |
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| CN101481141A (en) * | 2008-01-08 | 2009-07-15 | 河南佰利联化学股份有限公司 | Method for decomposing zircon sand |
Non-Patent Citations (1)
| Title |
|---|
| A new technique for extracting zirconium form Egyptian zircon concentrate;Aly M.Abdel-Rehim;《Int.J.Miner.Process.》;20051231;第76卷;第236页第2.3节，第242页右栏倒数第12行至倒数第7行，图2，摘要 * |
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