CN1087604A - From zircon ore concentrate, prepare high-purity zirconium dioxide - Google Patents
From zircon ore concentrate, prepare high-purity zirconium dioxide Download PDFInfo
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- CN1087604A CN1087604A CN 93118428 CN93118428A CN1087604A CN 1087604 A CN1087604 A CN 1087604A CN 93118428 CN93118428 CN 93118428 CN 93118428 A CN93118428 A CN 93118428A CN 1087604 A CN1087604 A CN 1087604A
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- zirconium dioxide
- crystallization
- zircon
- calcium chloride
- concentration
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Abstract
The present invention relates to a kind of method that from zircon ore concentrate, prepares high-purity zirconium dioxide.Calcareous lime powder and zircon ore concentrate is baking mixed, embathe burned material with lower concentration cycle pickling waste liquid earlier, leach with high density pickling waste liquid again, leach liquor is through purifying, and twice crystallization obtains high-purity zirconium dioxide.It is short that the present invention has technical process, and production cost is low, ZrO
2Rate of recovery height, good product quality, advantages such as three-waste free pollution.
Description
The present invention relates to a kind of method that from zircon, prepares zirconium compounds, particularly from zircon ore concentrate, prepare the method for high purity zirconium dioxide.
From zircon, prepare zirconium white, generally adopt the caustic alkali melting method, for example use sodium hydroxide and yellow soda ash and zircon mixed sintering, make it to generate sodium zirconate and water glass product, also be the hydration zirconium dioxide with water extraction dissolves silicon acid sodium thereupon, further purify then with the hydrolysis sodium zirconate.In order to obtain high purity product, to have to use two or more inorganic bronsted lowry acids and bases bronsted lowries to dissolve purification repeatedly, thereby cause complex technical process, the cycle is long, and raw materials consumption is big, and the finished product zirconium white rate of recovery is low, generally has only about 35%.Even the method that Chinese patent application CN1063268A announces adopts white lime batching sintering, Technologies such as hydrochloric acid leaching are though can make ZrO
2The rate of recovery increase, but technological process do not shorten, and it is big to exist hydrochloric acid consumption, mother liquor and washing lotion have problems such as pending, this method only can be prepared into the zirconium dioxide of general industry level, is unsuitable for preparing high-purity zirconium dioxide.
The object of the present invention is to provide a kind of method for preparing high-purity zirconium dioxide, particularly improve ZrO
2The rate of recovery and quality product solve the comprehensive regulation of the three wastes and the processing method of utilization.
Technology of the present invention constitutes, adopt the aqueous solution, the zircon ore concentrate of calcareous lime (rhombspar) or Wingdale and calcium chloride to mix, roasting, described calcium chloride water are that the calcium chloride water for preparing from the waste liquid that low acidleach goes out contains CaO 15～20%, CaCl
245～60%.Make zirconium silicate be converted into the zirconate that can be decomposed by hydrochloric acid, burning till material uses mother liquor or spent acid from this technology to carry out the preextraction processing, remove soluble impurity calcium, iron and silicon etc., leach with the chloride solution that contains zirconium oxychloride and calcium chloride again, separate out ZrOCl through concentrating
2, 8H
2The O crystal then crystal recrystallization soluble in water, is further removed trace impurities such as micro-iron, calcium, titanium, at last with ZrOCl
2, 8H
2The O calcining makes the high purity zirconium dioxide.
Principle of Process of the present invention is zircon ore concentrate and flux roasting at high temperature, zirconium silicate changes into calcium zirconate and calcium-silicate, in their hydrochloric acid solns under different concns, temperature, has different solubility properties, utilize difference on its solubility property will burn till the material water and/or dilute hydrochloric acid leaches under 30～60 ℃ of temperature, can remove excessive CaO and calcium-silicate and magnesium salts, leach with chloride solution, zirconium enters solution with the zirconium oxychloride of solubility, utilize the different solubility of zirconium oxychloride in the hydrochloric acid soln under the differing temps again, make zirconium be ZrOCl
2, 8H
2The O crystallization is separated out, and zirconium is able to separate with impurity, reaches the effect of purification.Purified ZrOCl
2, 8H
2The O crystal burns under the differing temps gradient, changes into the not zirconium dioxide of isomorphous system structure.
In order to reach the purpose of purification zirconium dioxide, adopt two sections silica removals, heavy molten crystalline technical measures, promptly when leaching, adopt the chloride solution that contains basic zirconium chloride and calcium oxide to leach, can remove about 99% SiO
2Soluble impurity again through twice crystallization, can obtain 99.9% high-purity zirconium dioxide product.
Describe concrete processing condition of the present invention in detail below in conjunction with embodiment.
Fig. 1 is a process flow diagram of the present invention.
Technological process is mainly by four most of one-tenth such as roasting, leaching, purging by crystallization, calcining.
The raw material composition (weight %, down together.): zircon contains ZrO
260～65, SiO
231～34, TiO
2, 1.21, Fe
2O
30.45.
Calcareous lime contains (%): CaO 63.47, and Mg 2.27, Fe
20.15.
Hydrochloric acid HCl30～31, Fe 0.073.
1, roasting
By ratio of components (weight %),,, make roasting material in 1100 ℃ of following roastings 5 hours with described zircon ore concentrate 100 and calcareous lime 160.
Embathe:, embathe liquid with containing Ca for the first time described roasting material
サ60 grams per liters, [Cl
-]
TThe recycle acid washing lotion of concentration 3.1 mol, the furnishing pulp density is 35% washes, embathes 0.5 hour; Second and third time washing lotion adopts and contains [Ca
サ] be 80 grams per liters, [Cl
-]
TBe the recycle acid washing lotion of 5.8 mol, transferring pulp density is 30% to embathe 1～1.5 hour.
Leach: the roasting material that will embathe is with containing [Ca
サ] be 50～56 grams per liters, [Cl
-] be the solution of 10 mol, be 85～95 ℃ in temperature and leach down that be respectively with solid-to-liquid ratio under the condition of 1: 3.5 and 1: 3 and leach 2 times, the time is 1～1.5 hour.Leach and finish 0.3 kilogram/cubic metre of the preceding 3# of adding flocculation agent.
Purging by crystallization: before the condensing crystal, solution contains ZrO for the first time
2180～200kg/m
3, [Cl
-] 9.5～10.24mol/L, temperature is a normal temperature; The crystalline feed liquid contains ZrO for the second time
2800～950kg/m
3, mother liquor contains [Cl after the crystallization
-] 6.8～7.2mol/L, normal temperature; Crystal behind the recrystallization is with containing [Cl
-]
TBe the solution washing of 9mol/L, crystal washing solid-to-liquid ratio is 1: 1.4～1.6.
5, calcining: the recrystallized product after will washing places calcining furnace to calcine, 800～950 ℃ of calcining temperatures, 3 hours time.
By technology condition of the present invention, obtain ZrO2Content is greater than 99.9% product, ZrO2Direct yield 73.2%, overall recovery is greater than 90%. By the method for preparing high-purity zirconium dioxide of the present invention, have shortlyer than causticity alkali solution technique process cycle, raw materials consumption is few, and spent acid liquid and waste slag produced (being the three wastes) can be fully utilized, zirconium rate of recovery height, good product quality, the advantage such as production cost is low.
Claims (9)
1, a kind of zirconium dioxide preparation method who constitutes with lime, zircon and calcium chloride mixed sintering, hydrochloric acid leaching, condensing crystal, calcining step, it is characterized in that adopting calcareous lime powder, zircon and calcium chloride mixed sintering, pickling and leaching adopt precipitation to separate out the spent acid solution of zirconium crystal and calcination process generation, described crystallization is the once concentration crystallization, recrystallization removal of impurity Si, Fe, Ca, wherein recrystallization is the high purity hydrochloric acid with self-control ion-exchange, calcine then product.
2, the method for claim 1, wherein said calcareous lime be contain CaO63-80%(weight, down with) material.
3, the method for claim 1, wherein said pickling are with containing Ca
サ60 grams per liters, [Cl
-]
TBe the recycle acid washing lotion of 3.1 mol, pulp density is 35%, embathes 0.5 hour.
4, as the method for claim 1 or 3, wherein said pickling is with containing Ca
サ80 grams per liters.[Cl
-]
TThe recycle acid washing lotion of concentration 5.8 mol is regulated pulp density and is under 30% the condition and embathed 1～1.5 hour.
5, the method for claim 1, wherein leach liquor is to adopt to contain Ca
サ50～56 grams per liters, [Cl
-] concentration is the solution of 10 mol, leaches solid-to-liquid ratio and is respectively 1: 3～5 and 1: 3,85～95 ℃ of temperature, leach twice at 1～1.5 hour time.
6, the method for claim 1, wherein said twice crystallization, solution contains ZrO for the first time
2180～200kg/m
3, [Cl
-] be 9.5～10.24mol/L; Solution contains ZrO for the second time
2800～950kg/m
3, [the Cl after the crystallization
-] concentration is 6.8～7.2mol/L, all is normal temperature.
7, the method for claim 1, wherein calcining temperature is 800～950 ℃, 3 hours time.
8, the method for claim 1, wherein leach liquor adds 3
#Flocculation agent.
9, the method for claim 1, wherein described calcium chloride sinter additives is the calcium chloride water for preparing from the waste liquid that low acidleach goes out, and contains CaO 15～20%, CaCl
245～60%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93118428 CN1032965C (en) | 1993-09-27 | 1993-09-27 | Preparation high-purity zirconium dioxide from zircon ore concentrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93118428 CN1032965C (en) | 1993-09-27 | 1993-09-27 | Preparation high-purity zirconium dioxide from zircon ore concentrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1087604A true CN1087604A (en) | 1994-06-08 |
| CN1032965C CN1032965C (en) | 1996-10-09 |
Family
ID=4992464
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93118428 Expired - Fee Related CN1032965C (en) | 1993-09-27 | 1993-09-27 | Preparation high-purity zirconium dioxide from zircon ore concentrate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1032965C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1039805C (en) * | 1995-03-31 | 1998-09-16 | 广东工学院 | Method for prepn. of electronic grade ZrO2 by Zircon |
| WO2001064586A1 (en) * | 2000-03-01 | 2001-09-07 | Joseph Mizrahi | Process for the manufacture of substantially pure zirconium oxide from raw materials containing zirconium |
| CN101113019B (en) * | 2007-07-03 | 2010-06-30 | 李树昌 | Method for reclaiming zirconium oxide and yttrium oxide from zirconium-containing solid waste |
| CN102060326A (en) * | 2010-11-22 | 2011-05-18 | 北京有色金属研究总院 | Alkali fusion continuous decomposing process method of zirconite |
| CN103253702A (en) * | 2012-02-15 | 2013-08-21 | 淄博市周村磊宝耐火材料有限公司 | Method for purification of waste zirconium brick to prepare high purity zirconia |
| CN104003438A (en) * | 2013-02-26 | 2014-08-27 | 中国科学院过程工程研究所 | Method for desiliconization of zirconium oxychloride acidolysis solution |
| CN104003441A (en) * | 2013-02-26 | 2014-08-27 | 中国科学院过程工程研究所 | Method for desiliconization by hydrochloric acid decomposition during alkali fusion process zirconium oxychloride production |
| CN107055609A (en) * | 2016-12-29 | 2017-08-18 | 宣城晶瑞新材料有限公司 | A kind of preparation method of ultra-pure 3Y yttrium stable zirconium oxides |
| CN109536718A (en) * | 2018-12-07 | 2019-03-29 | 江苏科技大学 | A method of zr element in recycling abraum salt containing zirconium monochloride |
-
1993
- 1993-09-27 CN CN 93118428 patent/CN1032965C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1039805C (en) * | 1995-03-31 | 1998-09-16 | 广东工学院 | Method for prepn. of electronic grade ZrO2 by Zircon |
| WO2001064586A1 (en) * | 2000-03-01 | 2001-09-07 | Joseph Mizrahi | Process for the manufacture of substantially pure zirconium oxide from raw materials containing zirconium |
| CN101113019B (en) * | 2007-07-03 | 2010-06-30 | 李树昌 | Method for reclaiming zirconium oxide and yttrium oxide from zirconium-containing solid waste |
| CN102060326A (en) * | 2010-11-22 | 2011-05-18 | 北京有色金属研究总院 | Alkali fusion continuous decomposing process method of zirconite |
| CN102060326B (en) * | 2010-11-22 | 2013-03-27 | 北京有色金属研究总院 | Alkali fusion continuous decomposing process method of zirconite |
| CN103253702B (en) * | 2012-02-15 | 2016-01-27 | 山东磊宝锆业科技股份有限公司 | To purify from zirconium gives up brick the zirconic method of high purity |
| CN103253702A (en) * | 2012-02-15 | 2013-08-21 | 淄博市周村磊宝耐火材料有限公司 | Method for purification of waste zirconium brick to prepare high purity zirconia |
| CN104003438A (en) * | 2013-02-26 | 2014-08-27 | 中国科学院过程工程研究所 | Method for desiliconization of zirconium oxychloride acidolysis solution |
| CN104003441A (en) * | 2013-02-26 | 2014-08-27 | 中国科学院过程工程研究所 | Method for desiliconization by hydrochloric acid decomposition during alkali fusion process zirconium oxychloride production |
| CN104003438B (en) * | 2013-02-26 | 2016-04-06 | 中国科学院过程工程研究所 | The method of a kind of zirconium oxychloride acid hydrolysis solution desiliconization |
| CN107055609A (en) * | 2016-12-29 | 2017-08-18 | 宣城晶瑞新材料有限公司 | A kind of preparation method of ultra-pure 3Y yttrium stable zirconium oxides |
| CN107055609B (en) * | 2016-12-29 | 2018-06-08 | 宣城晶瑞新材料有限公司 | A kind of preparation method of ultra-pure 3Y yttrium stable zirconium oxides |
| CN109536718A (en) * | 2018-12-07 | 2019-03-29 | 江苏科技大学 | A method of zr element in recycling abraum salt containing zirconium monochloride |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1032965C (en) | 1996-10-09 |
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