CN102826601A - Method for preparing high-purity zirconium oxide through purifying silicon removed zirconium - Google Patents

Method for preparing high-purity zirconium oxide through purifying silicon removed zirconium Download PDF

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CN102826601A
CN102826601A CN2012100329749A CN201210032974A CN102826601A CN 102826601 A CN102826601 A CN 102826601A CN 2012100329749 A CN2012100329749 A CN 2012100329749A CN 201210032974 A CN201210032974 A CN 201210032974A CN 102826601 A CN102826601 A CN 102826601A
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zirconium
zirconia
obtains
purity
temperature
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王光强
陈杰
刘学燕
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ZIBOCITY ZHOUCUN LEIBAO REFRACTRIES CO Ltd
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ZIBOCITY ZHOUCUN LEIBAO REFRACTRIES CO Ltd
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Abstract

The invention relates to a method for preparing high-purity zirconium oxide through purifying silicon removed zirconium, and belongs to the technical field of chemical engineering material preparation. The method for preparing the high-purity zirconium oxide through purifying the silicon removed zirconium comprises the following steps: acidifying the silicon removed zirconium to convert zirconium oxide therein into zirconium sulfate, and roasting the zirconium sulfate at a high temperature to obtain the high-purity zirconium oxide. The method has the advantages of energy saving, production technology simplification, air pollution avoiding, and production efficiency improvement; and the zirconium oxide obtained after the purification of the silicon removed zirconium has the advantages of white color, realization of the ZrO2 mass content of not less than 99.8%, and low impurity content.

Description

From desilicated zirconia, purify and produce the method for high-purity zirconia
Technical field
The present invention relates to a kind of from desilicated zirconia, the purification and produce the method for high-purity zirconia, belong to technical field of chemical material preparation.
Background technology
Desilicated zirconia is a kind of sosoloid of a kind of zirconium of processing through the high-temperature fusion desiliconization; Have no idea at present dissolution in low temperature check; Can only pass through simple processing now uses as low-grade refractory materials; We have invented a kind of new process method and have solved this difficult problem for the use value that improves it, make it obtain purifying and realized its true value.Zirconium white after the purification is a kind of high grade refractory, and thermostability is preferably arranged, and purified zirconium white is a white solid, can manifest grey or faint yellow when containing impurity.Because zirconia material has high firmness; HS; H.T., the physical and chemical performance that high wear resistance and chemical resistance or the like are good, zirconium white obtain to use widely in pottery, refractory materials, machinery, electronics, optics, aerospace, biology, chemistry or the like various fields.
Be to make high-purity zirconia in the common process through methods such as alkaline earth metal oxide decomposition method, carbonization chlorination and plasma thermal decomposition methods; Reaction is purified under degree more than 2000, needs to consume a large amount of energy a large amount of chlorine of discharging in the production process; And complex process; Not only make troubles to production operation, and cause the pollution to environment, the products obtained therefrom color is dark and foreign matter content is high.
Summary of the invention
Technical problem to be solved by this invention provides a kind of from desilicated zirconia, the purification and produces the method for high-purity zirconia, and this method has been practiced thrift the energy, has simplified production technique, has avoided atmospheric pollution, and the zirconium white product purity that makes is high.
Of the present invention from desilicated zirconia, the purification produced the method for high-purity zirconia, is to make zirconium white composition wherein be converted into zirconium sulfate through acidification reaction desilicated zirconia, and zirconium sulfate obtains high-purity zirconia through high-temperature roasting.
Said acidification reaction is the roasting reaction of under the ammonium sulfate katalysis, being carried out by desilicated zirconia and sulfuric acid.
Said desilicated zirconia, ammonium sulfate and sulfuric acid mix according to mass fraction 1: 2～4: 3～5.
The maturing temperature of said acidification reaction is 120～1100 ℃.
Product behind the acidification reaction obtains the zirconium sulfate crystal through leaching in the water, solid-liquid separation, the clear liquid evaporation concentration that obtains, liquid concentrator crystallization, spinning mother liquor successively, obtains zirconium white through washing, roasting zirconium sulfate crystal.
Leaching temperature is 50～70 ℃, and acidity is 5～8mol/L during leaching, and leaching time is 2～3h, and solid-to-liquid ratio is 1: 2～1: 6 during leaching.
Said liquid concentrator degree Beaume is 30～40 ° of B é, and the liquid concentrator Tc is 40～50 ℃.
Centrifugal speed is 1400～1500 rev/mins.
Said zirconium sulfate high-temperature roasting temperature is 750～1200 ℃ and obtains zirconium white.
The mass content of said high-purity zirconia is more than 99.8%.
Desilicated zirconia is Powdered among the present invention, red-brown, and granularity is less than 60 orders, ZrO 2Mass content>=96%, Fe 2O 3Mass content≤0.1%, SiO 2Mass content≤1%, surplus are impurity.Sulfuric acid mass content >=93%, industrial sulphuric acid ammonium N content >=20%.
The chemical equation that the present invention relates to is:
ZrO 2+2H 2SO 4＝Zr(SO 4) 2+2H 2O
Reaction principle: the staple of desiliconization zirconium powder is ZrO 2, at (NH 4) 2SO 4Catalysis down and sulfuric acid reaction, making zirconium change into vitriol is Zr (SO 4) 2, the sulfate mixture that generates added in the entry leach, the leach liquor press filtration is got the zirconium clear liquid and carries out evaporation concentration, the zirconium in the zirconium clear liquid is separated out with the zirconium sulfate crystal, goes out the zirconium sulfate crystal with whizzer is centrifugal, through roasting acquisition high-purity zirconia.
The beneficial effect that the present invention had is:
The present invention has practiced thrift the energy, has simplified production technique, has avoided atmospheric pollution, has improved production efficiency, and gained zirconium white product colour was white after desilicated zirconia was purified, ZrO 2Mass content>=99.8%, foreign matter content is low.
Description of drawings
Fig. 1 is technological process of production figure of the present invention.
Embodiment
Below in conjunction with embodiment the present invention is done and to further describe.
Desilicated zirconia is Powdered among the present invention, red-brown, and granularity is less than 60 orders, ZrO 2Mass content>=96%, Fe 2O 3Mass content≤0.1%, SiO 2Mass content≤1%, surplus are impurity.Sulfuric acid mass content >=93%, industrial sulphuric acid ammonium N content >=20%.
Embodiment 1
(1) batching: desilicated zirconia, ammonium sulfate and sulfuric acid are mixed according to mass fraction at 1: 3: 4;
(2) acidification reaction: above mixture 650 ℃ of roastings, is made it reacting generating salt, and transformation efficiency is 93.9%;
(3) leach: vitriol is added in the entry leach, solid-to-liquid ratio is 1: 6, and temperature is controlled at 55 ℃, and acidity control is at 7mol/L, and extraction time is controlled at 2.5h;
(4) press filtration: leach the end back and carry out solid-liquid separation with board and frame machine, press filtration goes out clear liquid;
(5) evaporation concentration: clear liquid is carried out evaporation concentration, and control concentrate feed liquid degree Beaume obtains liquid concentrator at 40 ° of B é;
(6) crystallization: will concentrate the feed liquid crystallization, cooling temperature is controlled at 45 ℃, separates mother liquor and obtains the zirconium sulfate crystal;
(7) washing: 1500 rev/mins centrifugal after, with sulfuric acid leacheate washing crystal, iron and impurity are washed out;
(8) roasting: make zirconium white through 850 ℃ of roastings.
The product colour that the present invention makes is white, ZrO 2Mass content is 99.8%, Fe 2O 3Mass content 0.021%, SiO 2Mass content 0.035%, surplus are impurity.
Embodiment 2
(1) batching: desilicated zirconia, ammonium sulfate and sulfuric acid are mixed according to mass fraction at 1: 2.5: 5;
(2) acidification reaction: above mixture 850 ℃ of roastings, is made it reacting generating salt, and transformation efficiency is 93.5%;
(3) leach: vitriol is added in the entry leach, solid-to-liquid ratio is 1: 4, and temperature is controlled at 65 ℃, and acidity control is at 6mol/L, and extraction time is controlled at 2h;
(4) press filtration: leach the end back and carry out solid-liquid separation with board and frame machine, press filtration goes out clear liquid;
(5) evaporation concentration: clear liquid is carried out evaporation concentration, and control concentrate feed liquid degree Beaume obtains liquid concentrator at 35 ° of B é;
(6) crystallization: will concentrate the feed liquid crystallization, cooling temperature is controlled at 40 ℃, separates mother liquor and obtains the zirconium sulfate crystal;
(7) washing: 1500 rev/mins centrifugal after, with sulfuric acid leacheate washing crystal, iron and impurity are washed out;
(8) roasting: make zirconium white through 850 ℃ of roastings.
The product colour that the present invention makes is white, ZrO 2Mass content is 99.8%, Fe 2O 3Mass content 0.02%, SiO 2Mass content 0.03%, surplus are impurity.
Embodiment 3
(1) batching: desilicated zirconia, ammonium sulfate and sulfuric acid are mixed according to mass fraction at 1: 3.5: 3;
(2) acidification reaction: above mixture 230 ℃ of roastings, is made it reacting generating salt, and transformation efficiency is 93.8%;
(3) leach: vitriol is added in the entry leach, solid-to-liquid ratio is 1: 2, and temperature is controlled at 70 ℃, and acidity control is at 5mol/L, and extraction time is controlled at 3h;
(4) press filtration: leach the end back and carry out solid-liquid separation with board and frame machine, press filtration goes out clear liquid;
(5) evaporation concentration: clear liquid is carried out evaporation concentration, and control concentrate feed liquid degree Beaume obtains liquid concentrator at 30 ° of B é;
(6) crystallization: will concentrate the feed liquid crystallization, cooling temperature is controlled at 50 ℃, separates mother liquor and obtains the zirconium sulfate crystal;
(7) washing: 1500 rev/mins centrifugal after, with sulfuric acid leacheate washing crystal, iron and impurity are washed out;
(8) roasting: make zirconium white through 950 ℃ of roastings.
The product colour that the present invention makes is white, ZrO 2Mass content is 99.9%, Fe 2O 3Mass content 0.02%, SiO 2Mass content 0.02%, surplus are impurity.
Embodiment 4
(1) batching: desilicated zirconia, ammonium sulfate and sulfuric acid are mixed according to mass fraction at 1: 3.5: 3;
(2) acidification reaction: above mixture 450 ℃ of roastings, is made it reacting generating salt, and transformation efficiency is 93.7%;
(3) leach: vitriol is added in the entry leach, solid-to-liquid ratio is 1: 2, and temperature is controlled at 70 ℃, and acidity control is at 5mol/L, and extraction time is controlled at 3h;
(4) press filtration: leach the end back and carry out solid-liquid separation with board and frame machine, press filtration goes out clear liquid;
(5) evaporation concentration: clear liquid is carried out evaporation concentration, and control concentrate feed liquid degree Beaume obtains liquid concentrator at 30 ° of B é;
(6) crystallization: will concentrate the feed liquid crystallization, cooling temperature is controlled at 50 ℃, separates mother liquor and obtains the zirconium sulfate crystal;
(7) washing: 1500 rev/mins centrifugal after, with sulfuric acid leacheate washing crystal, iron and impurity are washed out;
(8) roasting: make zirconium white through 1150 ℃ of roastings.
The product colour that the present invention makes is white, ZrO 2Mass content is 99.9%, Fe 2O 3Mass content 0.023%, SiO 2Mass content 0.02%, surplus are impurity.
Embodiment 5
(1) batching: desilicated zirconia, ammonium sulfate and sulfuric acid are mixed according to mass fraction at 1: 3.5: 3;
(2) acidification reaction: above mixture 1050 ℃ of roastings, is made it reacting generating salt, and transformation efficiency is 93.85%;
(3) leach: vitriol is added in the entry leach, solid-to-liquid ratio is 1: 2, and temperature is controlled at 70 ℃, and acidity control is at 5mol/L, and extraction time is controlled at 3h;
(4) press filtration: leach the end back and carry out solid-liquid separation with board and frame machine, press filtration goes out clear liquid;
(5) evaporation concentration: clear liquid is carried out evaporation concentration, and control concentrate feed liquid degree Beaume obtains liquid concentrator at 30 ° of B é;
(6) crystallization: will concentrate the feed liquid crystallization, cooling temperature is controlled at 50 ℃, separates mother liquor and obtains the zirconium sulfate crystal;
(7) washing: 1500 rev/mins centrifugal after, with sulfuric acid leacheate washing crystal, iron and impurity are washed out;
(8) roasting: make zirconium white through 750 ℃ of roastings.
The product colour that the present invention makes is white, ZrO 2Mass content is 99.85%, Fe 2O 3Mass content 0.022%, SiO 2Mass content 0.03%, surplus are impurity.

Claims (10)

1. from desilicated zirconia, purify and produce the method for high-purity zirconia for one kind, it is characterized in that making zirconium white composition wherein be converted into zirconium sulfate through acidification reaction desilicated zirconia, zirconium sulfate obtains high-purity zirconia through high-temperature roasting.
2. method according to claim 1 is characterized in that said acidification reaction is the roasting reaction of under the ammonium sulfate katalysis, being carried out by desilicated zirconia and sulfuric acid.
3. method according to claim 2 is characterized in that said desilicated zirconia, ammonium sulfate and sulfuric acid mix according to mass fraction 1: 2～4: 3～5.
4. method according to claim 2, the maturing temperature that it is characterized in that said acidification reaction is 120～1100 ℃.
5. method according to claim 1; It is characterized in that the product behind the acidification reaction obtains the zirconium sulfate crystal through leaching in the water, solid-liquid separation, the clear liquid evaporation concentration that obtains, liquid concentrator crystallization, spinning mother liquor successively, obtains zirconium white through washing, roasting zirconium sulfate crystal.
6. method according to claim 5 is characterized in that leaching temperature is 50～70 ℃, and acidity is 5～8mol/L during leaching, and leaching time is 2～3h.
7. method according to claim 5 is characterized in that said liquid concentrator degree Beaume is 30～40 ° of B é, and the liquid concentrator Tc is 40～50 ℃.
8. method according to claim 5 is characterized in that centrifugal speed is 1400～1500 rev/mins.
9. according to claim 1 or 5 described methods, it is characterized in that said zirconium sulfate high-temperature roasting temperature is 750～1200 ℃ and obtains zirconium white.
10. method according to claim 1, the mass content that it is characterized in that said high-purity zirconia is more than 99.8%.
CN2012100329749A 2011-06-15 2012-02-15 Method for preparing high-purity zirconium oxide through purifying silicon removed zirconium Pending CN102826601A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103539203A (en) * 2013-11-04 2014-01-29 李树昌 Method for preparing zirconium dioxide from zirconium-containing solid waste
CN108002441A (en) * 2017-12-20 2018-05-08 山东磊宝锆业科技股份有限公司 The method that high purity tetrahydrated zirconium sulfate is purified from desilicated zirconia
CN115448362A (en) * 2022-08-29 2022-12-09 焦天棋 Method for separating and preparing zirconium salt and preparing zirconium oxide solid from zirconium oxychloride mother liquor

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1559982A (en) * 2004-02-17 2005-01-05 哈尔滨工程大学 Preparation process for superfine powder of zirconium oxide
CN101244843A (en) * 2008-03-18 2008-08-20 李树昌 Method for recycling zirconium oxide and yttrium oxide from yttrium oxide steady zirconium oxide solid fused mass waste matter
US20090011239A1 (en) * 2007-07-06 2009-01-08 Hitachi Maxell, Ltd. Zirconium oxide hydrate particles and method for producing the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1559982A (en) * 2004-02-17 2005-01-05 哈尔滨工程大学 Preparation process for superfine powder of zirconium oxide
US20090011239A1 (en) * 2007-07-06 2009-01-08 Hitachi Maxell, Ltd. Zirconium oxide hydrate particles and method for producing the same
CN101244843A (en) * 2008-03-18 2008-08-20 李树昌 Method for recycling zirconium oxide and yttrium oxide from yttrium oxide steady zirconium oxide solid fused mass waste matter

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103539203A (en) * 2013-11-04 2014-01-29 李树昌 Method for preparing zirconium dioxide from zirconium-containing solid waste
CN103539203B (en) * 2013-11-04 2014-11-05 李树昌 Method for preparing zirconium dioxide from zirconium-containing solid waste
CN108002441A (en) * 2017-12-20 2018-05-08 山东磊宝锆业科技股份有限公司 The method that high purity tetrahydrated zirconium sulfate is purified from desilicated zirconia
CN115448362A (en) * 2022-08-29 2022-12-09 焦天棋 Method for separating and preparing zirconium salt and preparing zirconium oxide solid from zirconium oxychloride mother liquor
CN115448362B (en) * 2022-08-29 2024-01-16 焦天棋 Method for separating and preparing zirconium salt from zirconium oxychloride mother solution and preparing zirconium oxide solid

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Application publication date: 20121219