CN85106015A - Mixed rare earth of lanthanum and cerium - Google Patents
Mixed rare earth of lanthanum and cerium Download PDFInfo
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- CN85106015A CN85106015A CN198585106015A CN85106015A CN85106015A CN 85106015 A CN85106015 A CN 85106015A CN 198585106015 A CN198585106015 A CN 198585106015A CN 85106015 A CN85106015 A CN 85106015A CN 85106015 A CN85106015 A CN 85106015A
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- lanthanum
- cerium
- rare earth
- ceo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/253—Halides
- C01F17/271—Chlorides
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Abstract
A kind of rare earth compound.Existing product is to contain the mishmetal that LaCePrNd is the master, has both wasted the praseodymium neodium resource, can not bring into play the effect of lanthanum cerium again fully.The present invention is a mixed rare earth of lanthanum and cerium, its La
2O
3+ CeO
2Amount accounts for more than 95% of total rare earth (TRE), La
2O
3/ CeO
2Ratio is 1: 4～10: 1, can be used for sparking alloy, the additive that metal or alloy such as iron and steel, aluminum bronze zinc are smelted, hydrogen storage material, abrasive substance, glass melts clarify and decolorize, the manufacturing of catalyzer and agricultural micro fertilizer have improved the economic benefit of four rare earth elements of LaCePrNd.
Description
The present invention is a kind of rare earth compound.
Rare earth element is lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd) ... general name Deng 17 elements.General they be from bastnasite, solitary stone ore and China Baotou rare earth ore deposit (bastnasite that contains monazite) through processing such as sodium hydroxide, sulfuric acid, oxidizing roasting-mineral acid leaching or carburizing chlorinations, obtain mixed rare earth chlorides and (use RECL
3Expression, RE represents La+Ce+Pr+Nd in the formula ...).Then with RECL
3Be raw material, directly apply to or after being processed into norium, oxide compound, oxyhydroxide, fluorochemical, carbonate, nitrate or vitriol, be applied to sparking alloy, additive hydrogen storage material when metal or alloy such as iron and steel, aluminum bronze zinc are smelted, abrasive substance, the glass clarifying decolouring, the manufacturing of catalyzer and agricultural micro fertilizer.
These RECL
3Deng metallic compound, mainly elementary composition by La, Ce, four of Pr, Nd, their total content (in oxide compound) accounts for more than 90% of whole rare earths, wherein lanthanum trioxide (La
2O
3) be 23～28%, cerium oxide 45～50%, Praseodymium trioxide (Pr
6O
11) 3～8%, Neodymium trioxide (Nd
2O
3) 13～18%, with different change different with the product working method of rare-earth mineral, remainder is other rare earth.
RECL
3In above-mentioned application,, make product application uneconomical, Deng metallic compound because the praseodymium neodymium is the magneticsubstance of high value: (Smpr) Co owing to contain 20% the praseodymium neodymium of having an appointment in the product
5Nd
15Fe
77B
8, glass-ceramic coloured material: the raw material of the additive of praseodymium yellow, neodymium purple, variable color neodymium glass etc. and color TV face glass; Moreover, higher praseodymium neodymium content in above-mentioned some are used, causes injurious effects toward contact, reduces effect.As by crystallization RECL
3When norium was produced in fused salt electrolysis, neodymium was a detrimental impurity, and it reduces electrolytic current efficiency in abrasive substance, in the sosoloid that forms during high temperature sintering, often because the hexagonal system of too much neodymium, and reduced polishing ability to glass.Therefore, need a kind of new norium compound, make them can be used for above-mentioned Application Areas, can strengthen effect again, increase economic efficiency.For this reason, invented mixed rare earth of lanthanum and cerium, and according to the difference of Application Areas, it can be a metal, oxide compound, the muriate of hydration or non-hydrated, fluorochemical, oxyhydroxide, carbonate, nitrate or vitriol.
To contain La
2O
3Be 23～28%, CeO
245～50%, Pr
6O
113～8%, Nd
2O
313～18% crystallization RECL is water-soluble, regulate certain rare earth concentration and acidity, use the method know altogether: solvent collection agent method, ion exchange method or selective precipitation crystallization process separate the mixed rare earth of lanthanum and cerium muriate, through condensing crystal, must contain the mixed rare earth of lanthanum and cerium muriate of 4～6 crystal water.The outward appearance of this product is the light gray crystallization, and easily tide is situated between in air, soluble in water and mineral acid.The total amount of lanthanum cerium (in oxide compound) accounts for more than 95% of total rare earth (TRE) oxide compound, wherein La in the product
2O
3With CeO
2Weight ratio regulate between can 1: 4～10: 1, to be fit to the different application needs.Through fused salt electrolysis, can get the mixed rare earth of lanthanum and cerium metal by the mixed rare earth of lanthanum and cerium muriate; Also can be by sodium hydroxide, the yellow soda ash precipitation gets lanthanum cerium oxyhydroxide, lanthanum cerium carbonate; Also can by hydrofluoric acid precipitate lanthanum cerium fluorochemical, sulfuric acid conversion gets the lanthanum cerium sulphate, nitric acid transform lanthanum cerium nitrate; The oxalate precipitation calcination of lanthanum cerium or other lanthanum cerium salt calcination get the lanthanum cerium oxide, and they can be used for following purposes.
The main application of mixed rare earth of lanthanum and cerium is:
(1) to contain CeO
260～80%, La
2O
320～40% mixed rare earth of lanthanum and cerium muriate gets the mixed rare earth of lanthanum and cerium metal through fused salt electrolysis, makes the sparking alloy material.With 78～82 parts of mixed rare earth of lanthanum and cerium metals, 15～20 parts of metallic irons, 3～5 parts of MAGNESIUM METAL+copper+zinc mixed be smelted into alloy and be sparking alloy.Sparking alloy mainly is to utilize the burning-point of cerium lower (165 ℃), promptly burns and emits big calorimetric principle once friction.Because the CeO in the mixed rare earth of lanthanum and cerium metal
2Content compares RECL
3In exceed 10～35%, therefore get angry the efficient height.
(2) with the mixed rare earth of lanthanum and cerium metal of (1) gained additive as metal or alloy such as iron and steel, aluminum bronze zinc, make grain refining, the iron and steel deoxidization desulfuration changes inclusion morphology etc. and makes their sex change, improve the physicals of metal or alloy, improve use value.Metal for this purpose also can be by 40～60% La
2O
3With 40～60% CeO
2The mixed rare earth of lanthanum and cerium metal of forming.
(3) to contain La
2O
380～90%, CeO
210～20% mixed rare earth of lanthanum and cerium muriate gets the mixed rare earth of lanthanum and cerium metal through fused salt electrolysis.By (LaCe) Ni
5(atomic ratio) gets mixed rare earth of lanthanum and cerium metal and metallic nickel, founds, and gets hydrogen storage material after the processing.
(4) to contain 50～70%CeO
2, 30～50%La
2O
3Lanthanum cerium carbonate or oxide form directly add in the industrial aluminum electrolysis bath, to produce the Al rare earth alloy that contains rare earth 1～5%.
(5) produce abrasive substance, will contain CeO
2Be 70～80%, La
2O
320～30% mixed rare earth of lanthanum and cerium muriate etc., through molten Jie, precipitation, alkali transforms, calcination, technologies such as screening are made abrasive substance, are used for spectacle glass, camera gun, the polishing of picture tube panel.The glass polishing ability is the physics of cerium oxide and the result of chemical action, and it strengthens with the increase of cerium oxide content.Because CeO in the mixed rare earth of lanthanum and cerium
2Content compares RECL
3In height, the polishing effect of glass might as well.
(6) make the glass clarifying discoloring agent.To contain CeO
2Be 70～80%, La
2O
3Be that 20～30% mixed rare earth of lanthanum and cerium adds in the glass melt, cerium is with Fe in the frit
++Be oxidized to Fe
+++, emit oxygen simultaneously to increase oxygen partial pressure in the melt, make small bubbles change air pocket and play the clarify and decolorize effect.
(7) making of catalyzer.To contain La
2O
380～90%, CeO
210～20% mixed rare earth of lanthanum and cerium muriate is adsorbed on the silicon aluminium particle, makes Y zeolite microballoon cracking catalyst, is used for oil and splits Jie, improves the activity of gasoline.
(8) agricultural micro fertilizer.To contain La
2O
340～60%, CeO
240～60% mixed rare earth of lanthanum and cerium nitrate to crop fertilizations such as wheat, cotton, watermelon, tealeaves, promotes increasing crop yield with the consumption of every mu of field 40～60 gram.
Because in the mixed rare earth of lanthanum and cerium mainly is the lanthanum Ce elements, its total content (in oxide compound) is than corresponding RECL
3In high by 20～30%, and can be according to different purposes, easily with La
2O
3/ CeO
2Ratio adjust to 1: 4～10: 1.Like this, the additive in metal or alloy such as sparking alloy, iron and steel, aluminum bronze zinc are smelted, hydrogen storage material, abrasive substance, the glass clarifying decolouring, in the manufacturing of catalyzer and the application of agricultural little fertilizer, effect has improved.Because in these were used, what of lanthanum cerium content the height of its effect depended primarily on, and as sparking alloy, mainly is to utilize the burning-point of cerium low, but do not wish it is pure cerium, not so with spontaneous combustion.Contain a certain amount of lanthanum in the alloy now, the burning-point of lanthanum is lower than cerium height ratio neodymium, and with cerium, after metals such as iron fitted in alloy, sparking rate is high but also safety not only.When producing metal,, electrolytic current efficiency is improved more than 10%, the also corresponding increase of metal output of unit electrolyzer simultaneously because of neodymium content significantly reduces by the mixed rare earth of lanthanum and cerium electrolysis of chloride.In abrasive substance is made, because cerium content is brought up to more than 70% in the product, the crystallographic system structure of the sosoloid of sintering gained has become centroid cubic crystal system, rather than former face-centered cubic adds hexagonal system, when the polishing of glass surface, what need is exactly this centroid cubic crystal system.And at hydrogen storage material, oil splits in Jie's catalyzer, because product contains the lanthanum height and promoted the storage hydrogen effect of material and the transformation efficiency of oil.Moreover, because mixed rare earth of lanthanum and cerium is by RECL
3In isolate praseodymium neodymium gained, the praseodymium neodymium is again a magneticsubstance, the height when valuable materials of television industry and glass-ceramic industry, its economic worth are mixed more than them and lanthanum cerium.With the muriate is example, one kilogram of RECL
3Only 4～5 yuan of crystallizations, and one kilogram of Pr
6O
11, Nd
2O
3Then be worth 200～300 yuan.As they being used to make (SmPr) CO
5, Nd
15Fe
77B
8Magneticsubstance, or make tinting material in the glass-ceramic, the additive of colour TV glass panel, its economic benefit also will increase exponentially.And tell the mixed rare earth of lanthanum and cerium muriate of gained behind the lanthanum neodymium, one liter price is not higher than RECL again
3, even can descend slightly.As seen, mixed rare earth of lanthanum and cerium is a kind of cheap and good-quality material, and it had both utilized the lanthanum Ce elements fully, brings into play their effects in each is used; Utilize the lanthanum neodymium element again fully, brought into play their vital role, improved the economic benefit of mixed rare earth of lanthanum and cerium and praseodymium neodymium greatly.
Embodiment
1, with crystallization RECL
3(contain La
2O
323～28%, CeO
245～50%, Pr
6O
113～8%, Nd
2O
313～18%) water-soluble, adjust RE1.0～1.5M in the solution, PH3～5, be extraction agent with 1MP507-kerosene then, extraction phase is than O/A=2-3/1, and 10～20 extracting stages extract, with PrNd ... collection is gone into organic phase LaCe and is stayed water, through 120 ℃ of condensing crystals, must contain the mixed rare earth of lanthanum and cerium muriate of 4～6 crystal water, wherein La
2O
3+ CeO
2Account for more than 95% of total rare earth (TRE), La
2O
3/ CeO
2=25～40/60～75.Product appearance is a light gray, places Yi Chaojie in air, soluble in water and mineral acid.
2, get the salpeter solution (La, Ce, Pr, Nd oxide content are with embodiment 1) of 1.5～2.0MRE concentration, free acidity is 0.5～1NHNO
3, be extraction agent with 200 grams per liter N263-heavy solvents, extraction phase comes together the lanthanum cerium into organic phase than O/A=2～4/1,5～10 extracting stages extraction, and organic phase gets the mixed rare earth of lanthanum and cerium muriate with 0.5～1.0NHCL back extraction, and it is formed with embodiment 1.
3, with crystallization RECL
3(content is with embodiment 1) is water-soluble, RE concentration 1.0～1.2M in the solution, and PH3～5 are with the chlorine bleach liquor who contains 5%, with the Ce in the solution
+ 3Be oxidized to Ce
+ 4, water is situated between, and generates Ce(OH)
4Precipitation.Sedimentation and filtration cleans to be placed.This moment solution in CeO
2Concentration drops to 2～3%, adjusts PH4～5, is extraction agent with 25% naphthenic acid-15% alcohol mixture-60% kerosene, compares O/A=3-4/1, with PrNd ... collection is gone into organic phase, and remaining La Ce stays water.La
2O
3/ CeO
2Ratio is 10: 1.
4, with CeO
2Content 60～80%, La
2O
3The mixed rare earth of lanthanum and cerium muriate of content 20～40% gets the mixed rare earth of lanthanum and cerium metal through fused salt electrolysis.Get this metal 78～80 grams, metallic iron 15～18 grams, MAGNESIUM METAL+copper+zinc 3～5 grams; in 300 kilovolts of middle frequency furnaces, be smelted into alloy; on 100 tons of water pressure engine, be squeezed into the strip of 2.1～2.4 millimeters of φ again, be cut into the particle of 4.2～4.5 millimeters long on the dicing machine, be the lighter calcium carbide.Product is tested through sparking rate, sparking rate 〉=96%(national standard 〉=95%).
5, with CeO
2Content 70～80%, La
2O
3The mixed rare earth of lanthanum and cerium muriate of content 20～30%, being made into lanthanum cerium oxide concentration is the solution of 100～130 grams per liters, adds (NH then
4)
2SO
4, get lanthanum sulfat cerium ammonium double salt precipitation.Sedimentation and filtration, washing, change into the precipitation of hydroxide of lanthanum cerium with 30%NaOH again, sedimentation and filtration washing back adds the 7%(weight percent) NaF, calcination two hours under 850 ℃ of temperature then is chilled to room temperature, screening, get polishing powder from rare earth, through spectacle glass polishing test, glass is thrown erosion amount 〉=0.095 and is restrained/10 minutes.
6, with CeO
2Content 50～70%, La
2O
330～50% mixed rare earth of lanthanum and cerium muriate is made into 100～150 grams per liter rare earth oxides, adds Na then
2CO
3Generate the mixed rare earth of lanthanum and cerium carbonate deposition, sedimentation and filtration, washing, 100～200 ℃ of dryings, the lanthanum cerium carbonate of gained directly adds in the industrial aluminum electrolysis bath, and add-on is 3～5% of an aluminium weight, makes the Al rare earth alloy that contains lanthanum cerium 1～3%.
7, with La
2O
3Content 80～90%, CeO
2The mixed rare earth of lanthanum and cerium muriate of content 10～20% is adsorbed on the sial microballon, makes Y zeolite microballoon cracking catalyst, and be used for oil catalysis and split Jie, yield of gasoline＞46%, total conversion rate＞80%(is weight percentage).
8, with CeO
2Content 50～80%, La
2O
320～50% mixed rare earth of lanthanum and cerium nitrate is used for wheat fertilizing.Consumption: 40～50 gram/mus, with the wheat contrast of not executing rare earth, the per mu yield of executing mixed rare earth of lanthanum and cerium nitrate improves 5～10%.
Claims (10)
1, a kind of rare earth compound, it is by the mishmetal that lanthanum, cerium, praseodymium, neodymium are formed, and technical characterictic of the present invention is lanthanum, cerium mishmetal, the total content of its lanthanum cerium (in oxide compound)＞95%, La
2O
3/ CeO
2Ratio is 1: 4-10: 1.
2, the mixed rare earth of lanthanum and cerium of claim 1 indication can be a metal, oxide compound, the muriate of hydration or non-hydrated, oxyhydroxide, fluorochemical, carbonate, nitrate, vitriol.
3, claim 1, the mixed rare earth of lanthanum and cerium of 2 indications contains CeO
260～80%, La
2O
320～40% metal can be used for making sparking alloy.
4, claim 1, the mixed rare earth of lanthanum and cerium of 2 indications contains CeO
260～80%, La
2O
320～40% metal can be used for iron and steel, additive when metal or alloy such as aluminum bronze zinc are smelted.
5, claim 1, the mixed rare earth of lanthanum and cerium of 2 indications contains La
2O
380～90%, CeO
210～20% metal is used to make hydrogen storage material.
6, claim 1, the mixed rare earth of lanthanum and cerium of 2 indications contains 50～70%CeO
2, 30～50%La
2O
3Carbonate or oxide compound can directly add in the industrial aluminum electrolysis bath, produce Al rare earth alloy.
7, claim 1, the mixed rare earth of lanthanum and cerium of 2 indications contains CeO
2Be 70～80%, La
2O
320～30% hydride etc. can be made the polishing (ophthalmic lens, camera gun, picture tube panel) that abrasive substance is used for glass surface.
8, claim 1, the mixed rare earth of lanthanum and cerium of 2 indications contains CeO
270～80%, La
2O
3Clarify and decolorize agent during 20～30% the glass smelting done.
9, claim 1, the mixed rare earth of lanthanum and cerium of 2 indications contains La
2O
380～90%, CeO
210～20% muriate can be done the manufacturing of catalyzer.
10, claim 1, the mixed rare earth of lanthanum and cerium of 2 indications contains La
2O
340～60%, CeO
240～60% nitrate can be used as agricultural micro fertilizer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN198585106015A CN85106015A (en) | 1985-07-23 | 1985-07-23 | Mixed rare earth of lanthanum and cerium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN198585106015A CN85106015A (en) | 1985-07-23 | 1985-07-23 | Mixed rare earth of lanthanum and cerium |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN85106015A true CN85106015A (en) | 1987-01-21 |
Family
ID=4794830
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN198585106015A Pending CN85106015A (en) | 1985-07-23 | 1985-07-23 | Mixed rare earth of lanthanum and cerium |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN85106015A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102395643A (en) * | 2009-04-15 | 2012-03-28 | 罗地亚(中国)有限公司 | A cerium-based particle composition and the preparation thereof |
| CN102787257A (en) * | 2012-08-20 | 2012-11-21 | 梁建烈 | Novel mixed rare earth pyrophoric alloy and preparation method thereof |
| CN102925106A (en) * | 2012-11-14 | 2013-02-13 | 内蒙古科技大学 | Rare earth polishing powder and preparation method thereof |
| CN108026433A (en) * | 2015-09-25 | 2018-05-11 | 昭和电工株式会社 | Cerium based abrasive material and its manufacture method |
| CN109158792A (en) * | 2018-10-15 | 2019-01-08 | 广东美的制冷设备有限公司 | Weld-ring, workpiece, heat exchanger and air conditioner |
-
1985
- 1985-07-23 CN CN198585106015A patent/CN85106015A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102395643A (en) * | 2009-04-15 | 2012-03-28 | 罗地亚(中国)有限公司 | A cerium-based particle composition and the preparation thereof |
| CN102787257A (en) * | 2012-08-20 | 2012-11-21 | 梁建烈 | Novel mixed rare earth pyrophoric alloy and preparation method thereof |
| CN102925106A (en) * | 2012-11-14 | 2013-02-13 | 内蒙古科技大学 | Rare earth polishing powder and preparation method thereof |
| CN108026433A (en) * | 2015-09-25 | 2018-05-11 | 昭和电工株式会社 | Cerium based abrasive material and its manufacture method |
| EP3354705A4 (en) * | 2015-09-25 | 2019-06-12 | Showa Denko K.K. | Cerium-based abrasive material and process for producing same |
| US10717909B2 (en) | 2015-09-25 | 2020-07-21 | Showa Denko K.K. | Cerium-based abrasive material and process for producing same |
| CN109158792A (en) * | 2018-10-15 | 2019-01-08 | 广东美的制冷设备有限公司 | Weld-ring, workpiece, heat exchanger and air conditioner |
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