CN102092766A - Preparation method of ultrafine lanthanum oxide powder - Google Patents

Preparation method of ultrafine lanthanum oxide powder Download PDF

Info

Publication number
CN102092766A
CN102092766A CN 201110053742 CN201110053742A CN102092766A CN 102092766 A CN102092766 A CN 102092766A CN 201110053742 CN201110053742 CN 201110053742 CN 201110053742 A CN201110053742 A CN 201110053742A CN 102092766 A CN102092766 A CN 102092766A
Authority
CN
China
Prior art keywords
preparation
lanthanum
lanthanum trioxide
superfine
powder
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.)
Granted
Application number
CN 201110053742
Other languages
Chinese (zh)
Other versions
CN102092766B (en
Inventor
雷少钦
陈楷翰
李来超
付金彪
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujian Jinlong Rare Earth Co ltd
Original Assignee
Fujian Changting Jinlong Rare Earth Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Fujian Changting Jinlong Rare Earth Co Ltd filed Critical Fujian Changting Jinlong Rare Earth Co Ltd
Priority to CN 201110053742 priority Critical patent/CN102092766B/en
Publication of CN102092766A publication Critical patent/CN102092766A/en
Application granted granted Critical
Publication of CN102092766B publication Critical patent/CN102092766B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

The invention discloses a preparation method of ultrafine rare earth lanthanum oxide powder. The method comprises the following steps of: quickly calcining precipitates which are produced in a reaction by a direct precipitation method and serve as a precursor at a high temperature; and putting the calcined precipitates into water for quenching to obtain high-purity lanthanum oxide ultrafine powder. By the method, the problems of difficulty in washing and low product purity during precipitation, hard agglomeration of rare earth oxide particles during calcining, wide particle distribution and the like in the prior art are solved, and more importantly, the problem of synthesis of precursors such as ultrafine lanthanum oxalate and the like with very high costs can be solved. The method can be directly applied on the basis of the original precipitation and calcining, complex grinding or smashing operation is not required, and the environmental protection pressure cannot be too high under the condition that an appropriate precipitating agent is selected; moreover, the method is low in preparation cost, and is easy to operate and popularize.

Description

A kind of preparation method of ultra-fine lanthanum trioxide powder
Technical field
The present invention relates to a kind of preparation method of ultra-fine lanthanum trioxide powder.
Technical background
The method for preparing the superfine rare-earth oxide compound has the precipitator method, sol-gel processing, hydrothermal method, microemulsion method, spray heating decomposition etc., and wherein the precipitator method are research and the production methods that the most generally adopt.This method has that raw materials cost is low, low for equipment requirements, technology is simple, easy and simple to handle, can accurately control chemical constitution, easily make the ultra-micro powder of multiple uniform component, control advantages such as coating of particles and granularity easily.
The precipitator method commonly used prepare the superfine rare-earth oxide compound to be had:
(1) direct precipitation method: add precipitation agents such as oxyhydroxide, oxalate or bicarbonate of ammonia in containing the solution of rare earth ion, directly reacting produces precipitation.But discover that during precipitation of hydroxide, the rare earth hydrate of generation is that a kind of height is assembled, the throw out of unformed, viscose glue, be difficult to washing, dry, calcining back produces hard coacervate, need grind, and can't directly generate the superfine rare-earth oxide compound; During oxalate precipitation, because Cl -More, very easily form crystal salt in the sintering process, form the solid phase bridge, make particle produce hard aggregation and big particle agglomerate, and under comparatively high temps, agglomeration is more serious, also can't directly generate the superfine rare-earth oxide powder; It is low that ammonium bicarbonate precipitation method has a raw materials cost, and the product yield advantages of higher can form the less rare earth oxide of particle diameter after calcining, but the high-concentration ammonia nitrogenous wastewater that ammonium bicarbonate method produced is difficult to handle, and therefore limited its application.
(2) sluggish precipitation: utilize a certain chemical reaction make in the solution configurational ion by in the solution lentamente, discharge equably, after washing, oven dry, calcining, can form epigranular, densification, rare earth oxide that purity is high, normal precipitation agent is a urea at present, but this production technique productive rate is lower, and environmental protection pressure is bigger.
(3) alkoxide hydrolysis: utilize the organic alkoxide of rare earth metal can be dissolved in organic solvent and hydrolysis takes place to generate oxyhydroxide preparation superfine rare-earth oxide powder.But this method expense of raw materials is very high, and the preparation alkoxide needs to react operational difficulty under anhydrous atmosphere.
(4) complex-precipitation method: complexing agents such as rare earth ion and EDTA generate the complex compound of ambient stable, and complex compound is destroyed under proper temperature and pH value, and rare earth ion discharges again, with the OH in the solution -And add precipitation agent effect generation throw out, further processing can prepare the superfine rare-earth oxide powder, but technology is loaded down with trivial details, is unsuitable for industrial production, and the cost height.
Summary of the invention
At above problem, the preparation method who the purpose of this invention is to provide a kind of ultra-fine lanthanum trioxide powder, can on original precipitation and incinerating basis, directly use, need not loaded down with trivial details grinding or fragmentation procedure, under the condition of selecting suitable precipitation agent, not only do not have too big environmental protection pressure, and cost of manufacture is low, simple to operate, be easy to promote.
In order to reach above-mentioned purpose, solution of the present invention is:
A kind of preparation method of superfine rare-earth lanthanum trioxide powder, the throw out that direct precipitation method reaction is produced is as presoma, and behind the high temperature quick burning, the entry quenching is prepared into the high purity lanthanum oxide superfine powder.
Described presoma is to add precipitation agent oxyhydroxide, oxalate or bicarbonate of ammonia, lanthanum oxalate, Phosbloc or lanthanum hydroxide that reaction produces in containing the solution of rare earth ion.
Described presoma lanthanum oxalate, Phosbloc or lanthanum hydroxide particle diameter are 5~6 μ m.
900~1000 ℃ of the temperature of described high temperature quick burning, time 1~3h.
The time 6h of described high temperature quick burning, the section that wherein heats up 3 h, holding-zone 3 h.
Described quenching water is the high purity water under room temperature or the low temperature.
The high purity water that described quenching water is 10~40 ℃ (under low temperature) (water that chemical purity is high, the content of impurity wherein is less than 0.1mg/L).
Described high purity lanthanum oxide superfine powder D 50=0.8~0.9 μ m.
Described quenching water is the recirculated water of recycling.
After adopting such scheme, doing presoma with lanthanum oxalate is example, and step of the present invention is:
(1) oxalate precipitation.Oxalate precipitation technology is simple, the cycle is short, productive rate is high, but because during oxalic acid precipitation, the crystal grain formation speed is very fast, usually obtain oarse-grained oxalate, generate, improve aggregating state in order to suppress crystal grain, add organic dispersing agent in the precipitation process of being everlasting, and in the oxalate as contain more Cl -, be easy to generate hard aggregation during calcining, so cost is higher, and is difficult to prepare the superfine rare-earth oxide compound.Adopt technology of the present invention, not only the control of condition does not need very accurately in the oxalate precipitation process, and need not add dispersion agent, makes things convenient for manual operation, and has reduced production cost.
(2) suction filtration and washing.The oxalate particle is bigger, make things convenient for suction filtration, but contained chlorine root easily forms parcel, difficult the washing, adopt the ultra-fine lanthanum trioxide of prepared of the present invention, most of impurity can be discharged, therefore can reduce the washing times of chlorine root and impurity by the fracture of quenching, enhance productivity, reduce production costs.
(3) calcining and liquid cooling.In the industrial production, the temperature of calcining lanthanum oxalate is generally 1000 ℃, the lanthanum trioxide granularity that generates under this temperature is big (3-10 μ m), if lanthanum oxalate is oven dry not, more be easy to generate agglomeration, it is bigger that granularity becomes, and skewness, technology of the present invention can be under existing working condition, the lanthanum trioxide chamber of pouring into behind the high-temp combustion is overflow or low temperature under high purity water in, pass through quenching, make it to produce the fracture of quenching, but repeated hardening makes it to produce repeated stress failure in case of necessity, and it is minimum to get granularity, the lanthanum trioxide powder that is evenly distributed.
(4) oven dry and batch mixing packing.According to the practical situation of producing, dry and batch mixing is packed and got final product by existing technology.
In a word, the present invention is compared with prior art: traditional technology calcining lanthanum oxalate etc. needs higher temperature, and be preferably under the competent atmosphere of oxygen, calcination process is difficult to avoid the particle agglomeration phenomenon, therefore the ultra-fine lanthanum trioxide powder of preparation all needs trickleer precursor particle at present, cause the production operation difficulty, facility investment and technology cost are very high.Part company adopts calcining back ground method, not only workman's complex operation, severe operational environment, energy consumption height, and also product particle distributes widely, often brings pollution substance when grinding simultaneously into.The present invention is by this technology, and when the temperature quenching, the lanthanum trioxide coacervate ruptures automatically, and drying can make superfine lanthanum trioxide powder.Industrial production is convenient in the present invention, and grinding or fragmentation procedure that prepared lanthanum trioxide need not be loaded down with trivial details, and high purity water reusable edible can reduce production costs significantly.
Washing difficulty when the invention solves present precipitation, problem such as product purity is not high, prepares the rare earth oxide particles hard aggregation during calcination, and size distribution is wide be the more important thing is the composition problem of the precursors such as ultra-fine lanthanum oxalate that avoidable cost is very high.
For the use-pattern of technology of the present invention is described, take following specific embodiment to be elaborated.
Embodiment
Embodiment 1
Get 2 Kg lanthanum oxalates (not oven dry), under the anoxybiotic atmosphere, put into 900 ℃ of calcinings of retort furnace, 6 h(intensification section, 3 h, holding-zone 3 h), without temperature descending section, directly the lanthanum trioxide that burns till is taken out, in 2/3 high purity water of pouring under 20 ℃ of 5 L, suction filtration, 100 ℃ of oven dry 12 h down then, the lanthanum trioxide with remaining 1/3 and the detection granularity of taking away through the lanthanum trioxide of the fracture back oven dry of quenching, the result is: without the lanthanum trioxide D of the fracture of quenching 50=8.78, D 90=18.50, through the lanthanum trioxide D of the fracture of quenching 50=0.80, D 90=0.87, and experimental repeatability is good.
Embodiment 2
Get 2 Kg Phosblocs (not oven dry), under the anoxybiotic atmosphere, put into 1000 ℃ of calcinings of retort furnace, 6 h(intensification section, 3 h, holding-zone 3 h), without temperature descending section, directly the lanthanum trioxide that burns till is taken out, in 2/3 high purity water of pouring under 20 ℃ of 5 L, suction filtration, 100 ℃ of oven dry 12 h down then, the lanthanum trioxide with remaining 1/3 and the detection granularity of taking away through the lanthanum trioxide of the fracture back oven dry of quenching, the result is: without the lanthanum trioxide D of the fracture of quenching 50=13.42, D 90=28.92, through the lanthanum trioxide D of the fracture of quenching 50=0.76, D 90=0.87, and experimental repeatability is good.
Embodiment 3
Get 2 Kg lanthanum hydroxides (not oven dry), under the anoxybiotic atmosphere, put into 900 ℃ of calcinings of retort furnace, 6 h(intensification section, 3 h, holding-zone 3 h), without temperature descending section, directly the lanthanum trioxide that burns till is taken out, in 2/3 high purity water of pouring under 20 ℃ of 5 L, suction filtration, 100 ℃ of oven dry 12 h down then, the lanthanum trioxide with remaining 1/3 and the detection granularity of taking away through the lanthanum trioxide of the fracture back oven dry of quenching, the result is: without the lanthanum trioxide D of the fracture of quenching 50=1.21, D 90=1.64, through the lanthanum trioxide D of the fracture of quenching 50=0.79, D 90=0.91, and experimental repeatability is good.
Embodiment 4
Get 2 Kg lanthanum oxalates (not oven dry), under the anoxybiotic atmosphere, put into 1000 ℃ of calcinings of retort furnace, 6 h(intensification section, 3 h, holding-zone 3 h), without temperature descending section, directly the lanthanum trioxide that burns till is taken out, pour water temperature respectively into and be in 10 ℃, 20 ℃, 30 ℃ the high purity water, when experiment finds that water temperature is 10 ℃, by the lanthanum trioxide D of the fracture generation of quenching 50=0.95, D 90=1.12; When water temperature is 20 ℃, by the lanthanum trioxide D of the fracture generation of quenching 50=0.81, D 90=0.88; When water temperature is 30 ℃, by the lanthanum trioxide D of the fracture generation of quenching 50=0.91, D 90=1.07, illustrate that normal conditions at room temperature can use this technology.
Key of the present invention is the control of calcining temperature and the selection of calcining heating curve, also different through the granularity of the prepared lanthanum trioxide of repeated stress failure under the highest calcining temperature of difference, heat-up rate and whether be incubated the lanthanum trioxide particle size influences very big, satisfying on the basis that lanthanum oxalate fully decomposes, heat-up rate is fast more, soaking time is short more, and quenched products granularity and distribution are thin more.
Experiment by repeatedly finds that calcining temperature is 800 ℃, and during 20 ℃ of water temperatures, the lanthanum trioxide great majority that generate by the fracture of quenching concentrate on D 50=1.39, D 90=1.89; Calcining temperature is 900 ℃, during 20 ℃ of water temperatures, and the lanthanum trioxide D that generates by the fracture of quenching 50=0.80, D 90=0.87; Calcining temperature is 1000 ℃, during 20 ℃ of water temperatures, and the lanthanum trioxide D that generates by the fracture of quenching 50=0.81, D 90=0.88; Calcining temperature is 1100 ℃, during 20 ℃ of water temperatures, and the lanthanum trioxide D that generates by the fracture of quenching 50=0.83, D 90=0.87, this process repeatability is good,
But the present invention's repeated hardening diplomatic corps aggressiveness in case of necessity produces the fracture of quenching further to reduce product cut size, and drying can make superfine lanthanum trioxide powder.
High purity water of the present invention can recycle.Because this process using oxalic acid precipitation, the lanthanum trioxide purity of calcining out is higher, it is less to produce the impurity that discharges when quenching fracture, but so high purity water recycled for multiple times, in addition, because lanthanum trioxide is slightly soluble in water, so, can return sour molten workshop again and dissolve again when if high purity water middle-weight rare earths content and foreign matter content are higher.
It below only is preferred implementation of the present invention; it is not qualification to protection scope of the present invention; all and of the present invention gordian techniquies do not have to produce difference in essence, to the deduction or replace of above-mentioned embodiment, all should be regarded as falling within the protection domain of this case.

Claims (9)

1. the preparation method of a superfine rare-earth lanthanum trioxide powder is characterized in that: the throw out that the direct precipitation method reaction is produced is as presoma, and behind the high temperature quick burning, the entry quenching is prepared into the high purity lanthanum oxide superfine powder.
2. a kind of according to claim 1 preparation method of superfine rare-earth lanthanum trioxide powder, it is characterized in that: described presoma is to add precipitation agent oxyhydroxide, oxalate or bicarbonate of ammonia, lanthanum oxalate, Phosbloc or lanthanum hydroxide that reaction produces in containing the solution of rare earth ion.
3. a kind of according to claim 1 preparation method of superfine rare-earth lanthanum trioxide powder is characterized in that: described presoma lanthanum oxalate, Phosbloc or lanthanum hydroxide particle diameter are 5~6 μ m.
4. a kind of according to claim 1 preparation method of superfine rare-earth lanthanum trioxide powder is characterized in that: 900~1000 ℃ of the temperature of described high temperature quick burning, time 1~3h.
5. as the preparation method of a kind of superfine rare-earth lanthanum trioxide powder as described in the claim 4, it is characterized in that: the time 6h of described high temperature quick burning, the section that wherein heats up 3 h, holding-zone 3 h.
6. a kind of according to claim 1 preparation method of superfine rare-earth lanthanum trioxide powder is characterized in that: described quenching water is the high purity water under room temperature or the low temperature.
7. as the preparation method of a kind of superfine rare-earth lanthanum trioxide powder as described in the claim 6, it is characterized in that: described quenching water is 10~40 ℃ a high purity water.
8. a kind of according to claim 1 preparation method of superfine rare-earth lanthanum trioxide powder is characterized in that: described high purity lanthanum oxide superfine powder D 50=0.8~0.9 μ m.
9. a kind of according to claim 1 preparation method of superfine rare-earth lanthanum trioxide powder is characterized in that: described quenching water is the recirculated water of recycling.
CN 201110053742 2011-03-07 2011-03-07 Preparation method of ultrafine lanthanum oxide powder Active CN102092766B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 201110053742 CN102092766B (en) 2011-03-07 2011-03-07 Preparation method of ultrafine lanthanum oxide powder

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 201110053742 CN102092766B (en) 2011-03-07 2011-03-07 Preparation method of ultrafine lanthanum oxide powder

Publications (2)

Publication Number Publication Date
CN102092766A true CN102092766A (en) 2011-06-15
CN102092766B CN102092766B (en) 2013-03-13

Family

ID=44126057

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 201110053742 Active CN102092766B (en) 2011-03-07 2011-03-07 Preparation method of ultrafine lanthanum oxide powder

Country Status (1)

Country Link
CN (1) CN102092766B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105271353A (en) * 2015-09-23 2016-01-27 内蒙古生一伦稀土材料有限责任公司 Calcination method for raising daily output of rare earth carbonate
CN108585015A (en) * 2018-06-19 2018-09-28 四川江铜稀土有限责任公司 A kind of method that microwave calcination prepares lanthana
CN111115675A (en) * 2018-10-11 2020-05-08 有研稀土新材料股份有限公司 High-purity light lanthanum carbonate or lanthanum oxide and preparation method thereof
CN115010163A (en) * 2022-05-20 2022-09-06 全南县新资源稀土有限责任公司 Rare earth oxide with low apparent density and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101151214A (en) * 2004-12-28 2008-03-26 纳米科技创造私人有限公司 Nanostructured zinc oxide and a method of producing the same

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101151214A (en) * 2004-12-28 2008-03-26 纳米科技创造私人有限公司 Nanostructured zinc oxide and a method of producing the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
《稀有金属快报》 20011231 韩江 碳酸氢铵沉淀生产碳酸镧氧化镧 17-19 1-9 , 第11期 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105271353A (en) * 2015-09-23 2016-01-27 内蒙古生一伦稀土材料有限责任公司 Calcination method for raising daily output of rare earth carbonate
CN105271353B (en) * 2015-09-23 2017-01-18 北方稀土生一伦高科技有限公司 Calcination method for raising daily output of rare earth carbonate
CN108585015A (en) * 2018-06-19 2018-09-28 四川江铜稀土有限责任公司 A kind of method that microwave calcination prepares lanthana
CN111115675A (en) * 2018-10-11 2020-05-08 有研稀土新材料股份有限公司 High-purity light lanthanum carbonate or lanthanum oxide and preparation method thereof
CN115010163A (en) * 2022-05-20 2022-09-06 全南县新资源稀土有限责任公司 Rare earth oxide with low apparent density and preparation method thereof
CN115010163B (en) * 2022-05-20 2024-04-09 全南县新资源稀土有限责任公司 Rare earth oxide with low apparent density and preparation method thereof

Also Published As

Publication number Publication date
CN102092766B (en) 2013-03-13

Similar Documents

Publication Publication Date Title
CN101234750B (en) Method of preparing superfine micro-particle and nano granule
CN103028735B (en) Preparation method of semi-micrometer cobalt powder
KR20140131998A (en) PROCESS FOR THE COMPREHENSIVE RECOVERY OF METAL COBALT, RUTHENIUM AND ALUMINUM FROM WASTE CATALYST Co-Ru/Al2O3 IN FISCHER-TROPSCH SYNTHESIS
CN103088205B (en) Beryllium oxide production process
CN103317141A (en) Method for preparing metal nanoparticles
CN102092766B (en) Preparation method of ultrafine lanthanum oxide powder
CN102001693B (en) Process for preparing light magnesium oxide and calcium carbonate powder by utilizing dolomite acid method
CN101260464A (en) Stone coal vanadium-extracting ore decomposition method
CN104528787B (en) A kind of method preparing fine grain size alumina powder
CN103351017A (en) Preparation method of fine-grained, high-bulk-density, ball-shaped, rare earth carbonate and oxide thereof
CN104743613A (en) Method for continuously preparing large-particle-size spherical cobalt carbonate
CN101983925B (en) Preparation method of cerium oxide powder
KR20240055829A (en) Novel green lithium iron phosphate precursor, method for making same, and use thereof
CN108439473A (en) A kind of method that tungstenic scrap hard alloy prepares nanometer tungsten oxide
CN102764662B (en) Preparation method of special titanium-tungsten powder for SCR (selective catalytic reduction) denitrification catalyst
CN110282651B (en) Method for preparing high-purity rare earth oxide by using composite precipitator
CN111115675B (en) High-purity light lanthanum carbonate or lanthanum oxide and preparation method thereof
CN102698749A (en) Ruthenium ammonia synthesis catalyst taking ruthenium ammonia complex as precursor
CN104556175B (en) The method of preparing hydrogen aluminium oxide from potassium feldspar decomposition tailings
CN110857222A (en) Preparation method of vanadium trioxide powder
WO2017073392A1 (en) Method for producing seed crystal of cobalt powder
CN101229924B (en) Method for preparing high-purity magnesium hydroxide by using atomized ammonia as precipitator
CN103449511A (en) Strontium titanate submicron crystal and preparation method thereof
CN103952534B (en) A kind of method utilizing nickel-molybdenum ore to prepare Sodium orthomolybdate
CN105886772A (en) Comprehensive recycling method of waste rare earth type Y molecular sieve catalyst

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
EE01 Entry into force of recordation of patent licensing contract

Application publication date: 20110615

Assignee: GUANGZHOU ZHUJIANG PHOTOELECTRIC NEW MATERIALS Co.,Ltd.

Assignor: FUJIAN CHANGTING GOLDEN DRAGON RARE-EARTH Co.,Ltd.

Contract record no.: 2013990000326

Denomination of invention: Preparation method of ultrafine lanthanum oxide powder

Granted publication date: 20130313

License type: Exclusive License

Record date: 20130619

LICC Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model
CP03 Change of name, title or address
CP03 Change of name, title or address

Address after: 366300 new industrial zone, Changting Economic Development Zone, Longyan City, Fujian Province

Patentee after: Fujian Jinlong Rare Earth Co.,Ltd.

Country or region after: China

Address before: 366300 Changting Jinlong Rare Earth Co., Ltd., Industrial New District, Changting Economic Development Zone, Longyan City, Fujian Province

Patentee before: FUJIAN CHANGTING GOLDEN DRAGON RARE-EARTH Co.,Ltd.

Country or region before: China