CN103833064A - Preparation method for rare earth oxide through jet pyrolysis of rare earth chloride solution - Google Patents
Preparation method for rare earth oxide through jet pyrolysis of rare earth chloride solution Download PDFInfo
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Abstract
The invention brings forward a preparation method for a rare earth oxide through jetting low-temperature rapid pyrolysis of a rare earth chloride solution. The method comprises the following steps: (1) combusting combustion gas and O2 according to certain flow so as to form high temperature mixed tail gas which is used as a heat source and a working fluid for a pyrolytic reaction; (2) allowing the rare earth chloride solution to enter into a jet device and be heated by the high temperature mixed tail gas so as to realize gasification and form tiny bubbles in dispersed distribution and carrying out the pyrolytic reaction so as to obtain rare earth oxide powder and high temperature pyrolysis tail gas containing HCl gas; and (3) introducing a gas-solid mixture of the rare earth oxide powder and the pyrolysis tail gas obtained after pyrolysis into a cyclone separator, carrying out gas-solid separation so as to obtain the rare earth oxide powder, introducing the pyrolysis tail gas into an absorbing tower for absorption by an absorbent so as to obtain a hydrochloric acid solution and totally discharging residual purified tail gas. The method can substantially reinforce mass transfer and heat transfer efficiency, reduces pyrolysis energy consumption and enables the rare earth chloride solution to be rapidly pyrolyzed; and the obtained rare earth oxide powder has small granularity, uniform particle distribution and high purity.
Description
Technical field
The invention belongs to rare earth metallurgy field, be specifically related to a kind of method of being prepared rare earth oxide by rare earth chloride.
Background technology
Rare earth oxide has purposes very widely, for example, lanthanum trioxide is widely used in manufactures special alloy precision optics glass, high dioptrics fiberboard, is applicable to doing Kamera, photographic camera, microscope camera lens and high optics instrument prism, ceramic condenser and catalysts etc.Cerium oxide is widely used in oxygenant, the catalyzer of organic reaction, photo chromic glass and enamel glass etc.Praseodymium trioxide is for architectural pottery and domestic ceramics, and itself and ceramic glaze are mixed and made into color glaze, also can make separately under-glaze pigment, and the pigment of making is faint yellow, and tone is pure, simple and elegant.Neodymium trioxide is mainly used as the tinting material of glass, pottery, manufacture the raw material of neodymium metal and the raw material of ferromagnetism neodymium iron boron, in magnesium alloy or aluminium alloy, add 1.5%-2.5% Nanometer-sized Neodymium Oxide and can put forward heavy alloyed high-temperature behavior, resistance to air loss and erosion resistance, be widely used as aerospace material.Samarium trioxide can absorb ultrared fluorescent glass additive, the coating in sensitive materials, and samarium processed bores permanent magnet material and produces samarium metal etc.
At present, the main preparation methods of rare earth oxide is ammonium salt (or alkali metal hydroxide) precipitator method, join and in rare earth salts solution, obtain rare-earth hydroxide precipitation by ammoniacal liquor (or alkali metal hydroxide), filtration washing obtains rare earth hydrate precipitation, and then high temperature dehydration obtains rare earth oxide.In addition, oxalate or carbon ammonium precipitation method are to utilize oxalate or carbon ammonium directly to join in re chloride rare earth to be converted into rare earth oxalate precipitation, filter and obtain rare earth oxalate, then obtain rare earth oxide 800-900 DEG C of calcining.Above method all can produce a large amount of alkaline waste waters, and serious environment pollution can produce a large amount of CO 2 waste gas etc. in roasting process simultaneously.
Chinese utility model patent ZL200920203918 and Chinese invention patent ZL201010534886,201210081225 disclose and have adopted the direct pyrolysis of re chloride to prepare the method for rare earth oxide, and disclose the processing condition such as related solution concentration, airshed and maturing temperature.; first stoving oven is preheating to 500-1700 DEG C, then the re chloride of 10-300g/L is jetted in stoving oven with the flow of 2-8000L/h, roasting 1-40min; obtain rare earth oxide, adopt absorption tower to absorb through the HCl of cyclonic separation gained baking tail gases and obtain hydrochloric acid recycle.Due to adopted pyrolysis stoving oven limitation, cause this winding-up re chloride pyrolysis efficiency too low, therefore need high-temperature roasting (roasting time 1-40min) the guarantee pyrolytic reaction of long period fully to occur, and long firing cycle can cause the excessive and skewness of pyrolysis gained powder size, has a strong impact on its quality.In addition, pyrolysis is prepared and in the process of rare earth oxide, secondary side reaction also can be occurred and cause pyrolysis inefficiency, and prepared rare earth oxide purity declines.Side reaction is as follows: RECl
3+ RE
2o
3=3REOCl.
Therefore, the fast direct pyrolytic process of exploitation rare-earth chloride solution, is to realize the key that high-quality rare earth oxide is prepared in the direct pyrolysis of rare-earth chloride solution.
Summary of the invention
The present invention is directed to the pyrolysis of rare-earth chloride solution direct roasting prepares rare earth oxide and exists pyrolysis efficiency low, the high-temperature roasting cycle is long, the RE oxide powder granularity of pyrolysis gained is large, skewness, and the shortcoming such as product purity is low, propose a kind of rare-earth chloride solution jet winding-up low temperature fast pyrogenation and prepared the method for rare earth oxide, the method is reinforcing mass transfer and heat transfer efficiency significantly, reduce pyrolysis energy consumption, make re chloride fast pyrogenation, the RE oxide powder granularity that obtains is little, even particle distribution, and purity is high.
For achieving the above object, technical scheme of the present invention is as follows:
A method for rare earth oxide is prepared in the pyrolysis of rare-earth chloride solution jet, comprises the following steps:
(1) high temperature mixed tail gas preparation
By combustion gas and O
2form high temperature mixed tail gas according to certain flow through burning, it is directly pumped in jet reactor, as thermal source and the working fluid of pyrolytic reaction; Described combustion gas and O
2volume flow ratio be 1:2～1:16, combustion gas total flux 5～3000Nm
3/ h, combustion gas jetting pressure 0.5MPa～1.5MPa;
(2) jet pyrolytic reaction
Concentration is that the rare-earth chloride solution that 50～300g/L, inhalation flow are 10～10000L/h enters ejector by the liquid inlet place that is transferred of jet reactor, it is the high temperature mixed tail gas heating and gasifying of 500 DEG C～1300 DEG C by the temperature producing in step (1), form the micro-bubble that disperse distributes, the high temperature pyrolysis tail gas that concurrent raw pyrolytic reaction obtains RE oxide powder and contains HCl gas;
The jet pyrolytic reaction that described rare earth chloride generates rare earth oxide is as follows:
Cerium II Chloride aqueous solution pyrolytic reaction formula:
2CeCl
3+3H
2O+0.5O
2=2CeO
2+6HCl (1)
Except solution of cerium chloride by oxidation, all the other trivalent rare earth chloride solution pyrolytic reaction formulas are as follows:
2RECl
3+3H
2O=RE
2O
3+6HCl (2)
(3) gas solid separation
The gas-solid mixing body that pyrolysis obtains rare earth oxide and pyrolysis tail gas is incorporated in cyclonic separator through the gas inlet of cyclonic separator with tangential manner, realizes gas solid separation, obtains pyrolysis tail gas and RE oxide powder;
(4) vent gas treatment
Pyrolysis tail gas leaves cyclonic separator through the pneumatic outlet at cyclonic separator top, is incorporated in packed absorber and absorbs and obtain hydrochloric acid soln through absorption agent, and residue cleaning of off-gas is emptying.
The method of rare earth oxide is prepared in above-mentioned a kind of rare-earth chloride solution jet pyrolysis, and described rare earth chloride comprises: LaCl
3, CeCl
3, PrCl
3, NdCl
3, SmCl
3, EuCl
3, GdCl
3, DyCl
3, HoCl
3, ErCl
3, TmCl
3, YbCl
3, LuCl
3, ScCl
3, YCl
3deng.
The method of rare earth oxide is prepared in above-mentioned a kind of rare-earth chloride solution jet pyrolysis, and described rare earth oxide comprises: La
2o
3, CeO
2, Pr
2o
3, Nd
2o
3, Sm
2o
3, Eu
2o
3, Gd
2o
3, Dy
2o
3, Ho
2o
3, Er
2o
3, Tm
2o
3, Yb
2o
3, Lu
2o
3, Sc
2o
3, Y
2o
3deng.
The method of rare earth oxide is prepared in above-mentioned a kind of rare-earth chloride solution jet pyrolysis, and the combustion gas described in step (1) is H
2, CH
4, C
2h
2, natural gas or kerosene,
When combustion of hydrogen: 2H
2(g)+O
2(g)=2H
2o (g) (3)
When methyl hydride combustion: CH
4(g)+2O
2(g)=CO
2(g)+2H
2o (g) (4)
When acetylene combustion: 2C
2h
2(g)+5O
2(g)=4CO
2(g)+2H
2o (g) (5)
When natural gas burning: available equation (3) approximate representation,
When kerosene burning: C
8h
18(g)+12.5O
2(g)=8CO
2(g)+9H
2o (g) (6).
The method of rare earth oxide is prepared in above-mentioned a kind of rare-earth chloride solution jet pyrolysis, in order to improve pyrolysis transformation efficiency, reduce pyrolysis temperature, in can the rare-earth chloride solution in described step (2), add mass concentration and be 20%～30% hydrogen peroxide or hypochlorous acid solution, its add-on is 10%～20% of rare-earth chloride solution volume; Now, described high temperature mixed tail gas temperature is 400 DEG C～1000 DEG C;
Under hydrogen peroxide system, the reaction formula of solution of cerium chloride by oxidation pyrolytic process is:
2CeCl
3+3H
2O
2=2CeO
2+6HCl+O
2 （7）
Under hydrogen peroxide system, all the other trivalent re chloride pyrolytic reaction formulas except solution of cerium chloride by oxidation:
2RECl
3+6H
2O
2=RE
2O
3+6HCl+3O
2 （8）
Under hypochlorous acid system, the reaction formula of solution of cerium chloride by oxidation pyrolytic process is
2CeCl
3+HClO+3H
2O=2CeO
2+7HCl （9）
Under hypochlorous acid system, all the other trivalent re chloride pyrolytic reaction formulas except solution of cerium chloride by oxidation:
2RECl
3+2HClO+3H
2O=RE
2O
3+8HCl+O
2 （10）。
The method of rare earth oxide is prepared in above-mentioned a kind of rare-earth chloride solution jet pyrolysis, more than RE oxide powder purity >=99% in described step (3).
The method of rare earth oxide is prepared in above-mentioned a kind of rare-earth chloride solution jet pyrolysis, and the cyclonic separator of described step (3) is CZT type standard cyclonic separator, and processing power is definite according to pyrolysis flow, and available other models substitute.
The method of rare earth oxide is prepared in above-mentioned a kind of rare-earth chloride solution jet pyrolysis, it is characterized in that, in described step (4), packed absorber model is CST type.
Compared with prior art, feature of the present invention and advantage:
1, adopt jet winding-up pyrolytic technique, rare-earth chloride solution can be formed the ultra-fine bubble of even dispersion when heating and gasifying rapidly by working fluid (high-temperature fuel gas), has greatly increased reaction interface, has ensured that pyrolytic reaction is abundant.
2, adopt jet winding-up pyrolytic technique, working fluid can pass through jet reactor fast, the pyrolytic reaction time is 0.1s left and right only, realize fast pyrogenation, avoid existing rare-earth chloride solution roasting heat solution to prepare the generation of oxychloride by product in rare earth oxide process, improved the purity of pyrolysis transformation efficiency and rare earth oxide.
3,, because rare-earth chloride solution gasification forms the ultra-fine bubble of even dispersion, therefore the method is prepared RE oxide powder to have granularity little, the advantages such as even particle distribution.
4, carry re chloride taking high-temperature fuel gas as working fluid and carry out jet pyrolysis, re chloride is carried when entering ejector by high-temperature fuel gas can be by heating and gasifying rapidly, and significantly reinforcing mass transfer and heat transfer efficiency, reduces pyrolysis energy consumption.
5, present method adopt rare-earth chloride solution be that rare earth oxide is prepared in the direct pyrolysis of raw material, pyrolysis tail gas through absorb obtain hydrochloric acid soln, can return to re chloride preparation technology, realized rare earth oxide without useless cleaner production.
6, compared with carbonic acid or oxalic acid (poisonous) precipitator method, the present invention does not need to precipitate pre-treatment, has avoided the generation of ammonia nitrogen waste water, has significantly reduced the pollution to environment.
Brief description of the drawings
Fig. 1 re chloride jet pyrolysis scheme figure
Embodiment
Re chloride is that to adopt purity to be not less than 99.9% rare earth chloride formulated, and rare earth chloride is all purchased from Qufu City group of the lanthanides Chemical Co., Ltd..
Cyclonic separator is CZT type standard cyclonic separator, and processing power is definite according to pyrolysis flow, and available other models substitute.
Tail gas absorbs packed absorber, the model C ST type of adopting.
Embodiment 1
A kind of by LaCl
3preparation La
2o
3method, its step is as follows:
1, CH
4with O
2form CO through the burning of jet combustion device
2and H
2the high temperature mixed tail gas of O, directly pumps into the thermal source as working fluid and pyrolytic reaction in jet pyrolysis reactor, combustion gas total flux 3000Nm using it
3/ h, combustion gas jetting pressure 1.5MPa, CH
4with O
2throughput ratio be 1:2, the two combustion reactions formula is:
CH
4(g)+2O
2(g)=CO
2(g)+2H
2O(g)+△H
1；
2, the LaCl of 50g/L
3solution is carried and is entered the heated gasification of reactor by the liquid inlet that is transferred of jet pyrolysis reactor with the flow of 10000L/h, and pyrolysis temperature reaches 1250～1300 DEG C, pyrolytic reaction occurs rapidly and obtain La
2o
3powder and contain HCl gas, water vapour, CO
2and the high temperature pyrolysis tail gas of process variable oxygen; LaCl
3aqueous solution pyrolytic reaction formula is as follows:
2LaCl
3+3H
2O=La
2O
3+6HCl；
3, by La
2o
3the gas-solid mixing system of powder and high temperature pyrolysis tail gas composition is incorporated into cyclonic separator and carries out gas solid separation and obtain pyrolysis tail gas and La through the gas inlet of cyclonic separator with tangential manner
2o
3powder;
4, pyrolysis tail gas absorbs and obtains hydrochloric acid soln recycle through absorption tower, purifies the rear tail gas of absorption emptying.
Through chemical composition analysis, the La that pyrolysis obtains
2o
3powder purity is 99.7%.
Embodiment 2
A kind of by CeCl
3preparation CeO
2method, its step is as follows:
1, kerosene and O
2form CO through the burning of jet combustion device
2and H
2the high temperature mixed tail gas of O, directly pumps into the thermal source as working fluid and pyrolytic reaction in jet pyrolysis reactor, combustion gas total flux 5Nm using it
3/ h, combustion gas jetting pressure 1.5MPa, kerosene and O
2throughput ratio be 1:16, the two combustion reactions formula is:
C
8H
18(g)+12.5O
2(g)=8CO
2(g)+9H
2O(g)+△H
1；
2, the CeCl of 175g/L
3solution is carried and is entered the heated gasification of reactor by the liquid inlet that is transferred of jet pyrolysis reactor with the flow of 10L/h, and pyrolysis temperature reaches 500～30 DEG C, pyrolytic reaction occurs and obtain CeO
2powder and contain HCl gas, water vapour, CO
2and the high temperature pyrolysis tail gas of process variable oxygen; CeCl
3aqueous solution pyrolytic reaction formula is as follows:
2CeCl
3+3H
2O+0.5O
2=2CeO
2+6HCl；
3, by CeO
2the gas-solid mixing system of powder and high temperature pyrolysis tail gas composition is incorporated into cyclonic separator with tangential manner through the gas inlet of cyclonic separator and carries out gas solid separation, obtains pyrolysis tail gas and CeO
2powder;
4, pyrolysis tail gas absorbs and obtains hydrochloric acid soln recycle through absorption tower, purifies the rear tail gas of absorption emptying.
Through chemical composition analysis, the CeO that pyrolysis obtains
2powder purity is 99.5%.
Embodiment 3
A kind of by NdCl
3preparation Nd
2o
3method, its step is as follows:
1, Sweet natural gas and O
2form high temperature mixed tail gas through the burning of jet combustion device, it is directly pumped into the thermal source as working fluid and pyrolytic reaction in jet pyrolysis reactor, combustion gas total flux 500Nm
3/ h, combustion gas jetting pressure 0.5MPa, Sweet natural gas and O
2throughput ratio is 1:3.0;
2, the NdCl that compound concentration is 300g/L
3solution 3000L, then be 30% hydrogen peroxide solution 300L to adding mass concentration in solution;
3, mixing solutions is carried and entered reactor by the liquid inlet that is transferred of jet pyrolysis reactor with the flow of 500L/h, heated gasification, pyrolysis temperature reaches 400～420 DEG C, pyrolytic reaction occurs rapidly and obtain Nd
2o
3powder and contain HCl gas, water vapour, CO
2and the high temperature pyrolysis tail gas of process variable oxygen; NdCl under this system
3the reaction formula of solution pyrolytic process is:
2NdCl
3+3H
2O=Nd
2O
3+6HCl(g)
2NdCl
3+6H
2O
2=Nd
2O
3+6HCl+3O
2；
4, by Nd
2o
3the gas-solid mixing system of powder and high temperature pyrolysis tail gas composition is incorporated into cyclonic separator and carries out gas solid separation and obtain pyrolysis tail gas and Nd through the gas inlet of cyclonic separator with tangential manner
2o
3powder;
5, pyrolysis tail gas absorbs and obtains hydrochloric acid soln recycle through absorption tower, purifies the rear tail gas of absorption emptying.Through chemical composition analysis, the Nd that pyrolysis obtains
2o
3powder purity is 99.8%.
Embodiment 4
A kind of by ErCl
3preparation Er
2o
3method, its step is as follows:
1, C
2h
2with O
2form high temperature air mixture through the burning of jet combustion device, it is directly pumped into the thermal source as working fluid and pyrolytic reaction in jet pyrolysis reactor, combustion gas total flux 2000Nm
3/ h, combustion gas jetting pressure 1.0MPa, C
2h
2with O
2throughput ratio is 1:2.5, and the two combustion reactions formula is:
2C
2H
2(g)+5O
2(g)=4CO
2(g)+2H
2O(g)+△H
1；
2, the ErCl that compound concentration is 200g/L
3solution 30000L, then to add concentration in solution be 20% hypochlorous acid solution 6000L and mix;
3, mixing solutions is carried and entered reactor by the liquid inlet that is transferred of jet pyrolysis reactor with the flow of 5000L/h, heated gasification, pyrolysis temperature reaches 960～1000 DEG C, pyrolytic reaction occurs rapidly and obtain Er
2o
3powder and contain HCl gas, water vapour, CO
2and the high temperature pyrolysis tail gas of process variable oxygen; ErCl under this system
3the reaction formula of solution pyrolytic process is:
2ErCl
3+3H
2O=Er
2O
3+6HCl
2ErCl
3+HClO=Er
2O
3+HCl+O
2；
4, by Er
2o
3the gas-solid mixing system of powder and high temperature pyrolysis tail gas composition is incorporated into cyclonic separator and carries out gas solid separation and obtain pyrolysis tail gas and Er through the gas inlet of cyclonic separator with tangential manner
2o
3powder;
5, pyrolysis tail gas absorbs and obtains hydrochloric acid soln recycle through absorption tower, purifies the rear tail gas of absorption emptying.
Through chemical composition analysis, the Er that pyrolysis obtains
2o
3powder purity is 99.3%.
Embodiment 5
A kind of by CeCl
3preparation CeO
2method, its step is as follows:
1, hydrogen and O
2form high temperature mixed tail gas through the burning of jet combustion device, it is directly pumped into the thermal source as working fluid and pyrolytic reaction in jet pyrolysis reactor, combustion gas total flux 50Nm
3/ h, combustion gas jetting pressure 1.0MPa, hydrogen and O
2throughput ratio is 4:3, and the two combustion reactions formula is:
2H
2(g)+O
2(g)=2H
2O(g)+△H
1；
2, the CeCl that compound concentration is 100g/L
3solution 8000L, then be 25% hydrogen peroxide solution 1200L to adding mass concentration in solution;
3, mixing solutions is carried and entered reactor by the liquid inlet that is transferred of jet pyrolysis reactor with the flow of 1000L/h, heated gasification, pyrolysis temperature reaches 690～710 DEG C, pyrolytic reaction occurs rapidly and obtain CeO
2powder and contain HCl gas, water vapour, CO
2and the high temperature pyrolysis tail gas of process variable oxygen; CeCl under this system
3the reaction formula of solution pyrolytic process is:
2CeCl
3+3H
2O+0.5O
2=2CeO
2+6HCl
2CeCl
3+3H
2O
2=2CeO
2+6HCl+O
2；
4, by CeO
2the gas-solid mixing system of powder and high temperature pyrolysis tail gas composition is incorporated into cyclonic separator and carries out gas solid separation and obtain pyrolysis tail gas and CeO through the gas inlet of cyclonic separator with tangential manner
2powder;
5, pyrolysis tail gas absorbs and obtains hydrochloric acid soln recycle through absorption tower, purifies the rear tail gas of absorption emptying.
Through chemical composition analysis, the CeO that pyrolysis obtains
2powder purity is 99.7%.
Embodiment 6
A kind of by PrCl
3preparation Pr
2o
3method, its step is as follows:
1, CH
4with O
2form CO through the burning of jet combustion device
2and H
2the high temperature mixed tail gas of O, directly pumps into the thermal source as working fluid and pyrolytic reaction in jet pyrolysis reactor, combustion gas total flux 1000Nm using it
3/ h, combustion gas jetting pressure 0.5MPa, CH
4with O
2throughput ratio be 1:2, the two combustion reactions formula is:
CH
4(g)+2O
2(g)=CO
2(g)+2H
2O(g)+△H
1；
2, the PrCl of 250g/L
3solution is carried and is entered the heated gasification of reactor by the liquid inlet that is transferred of jet pyrolysis reactor with the flow of 50L/h, and pyrolysis temperature reaches 820～840 DEG C, pyrolytic reaction occurs rapidly and obtain Pr
2o
3powder and contain HCl gas, water vapour, CO
2and the high temperature pyrolysis tail gas of process variable oxygen; PrCl
3aqueous solution pyrolytic reaction formula is as follows:
2PrCl
3+3H
2O=Pr
2O
3+6HCl；
3, by Pr
2o
3the gas-solid mixing system of powder and high temperature pyrolysis tail gas composition is incorporated into cyclonic separator and carries out gas solid separation and obtain pyrolysis tail gas and Pr through the gas inlet of cyclonic separator with tangential manner
2o
3powder;
4, pyrolysis tail gas absorbs and obtains hydrochloric acid soln recycle through absorption tower, purifies the rear tail gas of absorption emptying.
Through chemical composition analysis, the Pr that pyrolysis obtains
2o
3powder purity is 99.7%.
Embodiment 7
A kind of by SmCl
3preparation Sm
2o
3method: the SmCl that compound concentration is 50g/L
3solution, according to the method jet pyrolysis of embodiment 1, the Sm obtaining
2o
3powder is through chemical composition analysis, and purity is 99.6%
Embodiment 8
A kind of by EuCl
3preparation Eu
2o
3method: the EuCl that compound concentration is 150g/L
3solution, according to the method jet pyrolysis of embodiment 3, the Eu obtaining
2o
3powder is through chemical composition analysis, and purity is 99.4%.
Embodiment 9
A kind of by GdCl
3preparation Gd
2o
3method: the GdCl that compound concentration is 150g/L
3solution, according to the method jet pyrolysis of embodiment 4, the Gd obtaining
2o
3powder is through chemical composition analysis, and purity is 99.2%.
Embodiment 10
A kind of by DyCl
3preparation Dy
2o
3method: the DyCl that compound concentration is 300g/L
3solution, according to the method jet pyrolysis of embodiment 6, the Dy obtaining
2o
3powder is through chemical composition analysis, and purity is 99.3%.
Embodiment 11
A kind of by HoCl
3preparation Ho
2o
3method: the HoCl that compound concentration is 100g/L
3solution, according to the method jet pyrolysis of embodiment 1, the Ho obtaining
2o
3powder is through chemical composition analysis, and purity is 99.5%.
Embodiment 12
A kind of by TmCl
3preparation Tm
2o
3method: the TmCl that compound concentration is 100g/L
3solution, according to the method jet pyrolysis of embodiment 3, the Tm obtaining
2o
3powder is through chemical composition analysis, and purity is 99.5%.
Embodiment 13
A kind of by YbCl
3preparation Yb
2o
3method: the YbCl that compound concentration is 100g/L
3solution, according to the method jet pyrolysis of embodiment 4, the Yb obtaining
2o
3powder is through chemical composition analysis, and purity is 99.7%.
Embodiment 14
A kind of by LuCl
3preparation Lu
2o
3method: the LuCl that compound concentration is 100g/L
3solution, according to the method jet pyrolysis of embodiment 6, the Lu obtaining
2o
3powder is through chemical composition analysis, and purity is 99.6%.
Embodiment 15
A kind of by ScCl
3preparation Sc
2o
3method: the ScCl that compound concentration is 200g/L
3solution, according to the method jet pyrolysis of embodiment 1, the Sc obtaining
2o
3powder is through chemical composition analysis, and purity is 99.4%.
Embodiment 16
A kind of by YCl
3preparation Y
2o
3method: the YCl that compound concentration is 200g/L
3solution, according to the method jet pyrolysis of embodiment 3, the Y obtaining
2o
3powder is through chemical composition analysis, and purity is 99.8%.
Claims (8)
1. a method for rare earth oxide is prepared in the pyrolysis of rare-earth chloride solution jet, it is characterized in that, comprises the following steps:
(1) high temperature mixed tail gas preparation
By combustion gas and O
2form high temperature mixed tail gas according to certain flow through burning, it is directly pumped in jet reactor, as thermal source and the working fluid of pyrolytic reaction; Described combustion gas and O
2volume flow ratio be 1:2～1:16, combustion gas total flux 5～3000Nm
3/ h, combustion gas jetting pressure 0.5MPa～1.5MPa;
(2) jet pyrolytic reaction
Concentration is that the rare-earth chloride solution that 50～300g/L, inhalation flow are 10～10000L/h enters ejector by the liquid inlet place that is transferred of jet reactor, it is the high temperature mixed tail gas heating and gasifying of 500 DEG C～1300 DEG C by the temperature producing in step (1), form the micro-bubble that disperse distributes, the high temperature pyrolysis tail gas that concurrent raw pyrolytic reaction obtains RE oxide powder and contains HCl gas;
The jet pyrolytic reaction that described rare earth chloride generates rare earth oxide is as follows:
Cerium II Chloride aqueous solution pyrolytic reaction formula:
2CeCl
3+3H
2O+0.5O
2=2CeO
2+6HCl (1)
Except solution of cerium chloride by oxidation, all the other trivalent rare earth chloride solution pyrolytic reaction formulas are as follows:
2RECl
3+3H
2O=RE
2O
3+6HCl (2)
(3) gas solid separation
The gas-solid mixing body that pyrolysis obtains rare earth oxide and pyrolysis tail gas is incorporated in cyclonic separator through the gas inlet of cyclonic separator with tangential manner, realizes gas solid separation, obtains pyrolysis tail gas and RE oxide powder;
(4) vent gas treatment
Pyrolysis tail gas leaves cyclonic separator through the pneumatic outlet at cyclonic separator top, is incorporated in packed absorber and absorbs and obtain hydrochloric acid soln through absorption agent, and residue cleaning of off-gas is emptying.
2. the method for rare earth oxide is prepared in a kind of rare-earth chloride solution jet according to claim 1 pyrolysis, it is characterized in that, described rare earth chloride comprises: LaCl
3, CeCl
3, PrCl
3, NdCl
3, SmCl
3, EuCl
3, GdCl
3, DyCl
3, HoCl
3, ErCl
3, TmCl
3, YbCl
3, LuCl
3, ScCl
3and YCl
3.
3. the method for rare earth oxide is prepared in a kind of rare-earth chloride solution jet according to claim 1 pyrolysis, it is characterized in that, described rare earth oxide comprises: La
2o
3, CeO
2, Pr
2o
3, Nd
2o
3, Sm
2o
3, Eu
2o
3, Gd
2o
3, Dy
2o
3, Ho
2o
3, Er
2o
3, Tm
2o
3, Yb
2o
3, Lu
2o
3, Sc
2o
3and Y
2o
3.
4. the method for rare earth oxide is prepared in a kind of rare-earth chloride solution jet according to claim 1 pyrolysis, it is characterized in that, the combustion gas described in step (1) is H
2, CH
4, C
2h
2, natural gas or kerosene.
5. the method for rare earth oxide is prepared in a kind of rare-earth chloride solution jet according to claim 1 pyrolysis, it is characterized in that, in described step (2), be 20%～30% hydrogen peroxide or hypochlorous acid solution to adding mass concentration in rare-earth chloride solution, its add-on is 10%～20% of rare-earth chloride solution volume; Now, the described high temperature mixed tail gas temperature range for high temperature pyrolysis reaction is 400 DEG C～1000 DEG C;
Under hydrogen peroxide system, the reaction formula of solution of cerium chloride by oxidation pyrolytic process is:
2CeCl
3+3H
2O
2=2CeO
2+6HCl+O
2 （3）
Under hydrogen peroxide system, all the other trivalent re chloride pyrolytic reaction formulas except solution of cerium chloride by oxidation:
2RECl
3+6H
2O
2=RE
2O
3+6HCl+3O
2 （4）
Under hypochlorous acid system, the reaction formula of solution of cerium chloride by oxidation pyrolytic process is
2CeCl
3+HClO+3H
2O=2CeO
2+7HCl （5）
Under hypochlorous acid system, all the other trivalent re chloride pyrolytic reaction formulas except solution of cerium chloride by oxidation:
2RECl
3+2HClO+3H
2O=RE
2O
3+8HCl+O
2 （6）。
6. the method for rare earth oxide is prepared in a kind of rare-earth chloride solution jet according to claim 1 pyrolysis, it is characterized in that RE oxide powder purity >=99% obtaining in described step (3).
7. the method for rare earth oxide is prepared in a kind of rare-earth chloride solution jet according to claim 1 pyrolysis, it is characterized in that, the cyclonic separator in described step (4) is the standard cyclonic separator of CZT type standard cyclonic separator or other models.
8. the method for rare earth oxide is prepared in a kind of rare-earth chloride solution jet according to claim 1 pyrolysis, it is characterized in that, in described step (4), packed absorber model is CST type.
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| CN104591254A (en) * | 2015-02-16 | 2015-05-06 | 包头市锦园化工科技有限公司 | Method for directly preparing rare earth chloride powder from rare earth chloride solution |
| CN108423702A (en) * | 2018-06-22 | 2018-08-21 | 东北大学秦皇岛分校 | The production equipment and preparation method of rare earth oxide |
| CN113697840A (en) * | 2020-05-21 | 2021-11-26 | 江西理工大学 | Method for preparing rare earth oxide by subcritical/supercritical steam pyrolysis method |
| CN114873626A (en) * | 2021-12-31 | 2022-08-09 | 中国工程物理研究院核物理与化学研究所 | A kind of 176 Yb 2 O 3 And 160 Gd 2 O 3 target material recovery method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104591254A (en) * | 2015-02-16 | 2015-05-06 | 包头市锦园化工科技有限公司 | Method for directly preparing rare earth chloride powder from rare earth chloride solution |
| CN108423702A (en) * | 2018-06-22 | 2018-08-21 | 东北大学秦皇岛分校 | The production equipment and preparation method of rare earth oxide |
| CN113697840A (en) * | 2020-05-21 | 2021-11-26 | 江西理工大学 | Method for preparing rare earth oxide by subcritical/supercritical steam pyrolysis method |
| CN113697840B (en) * | 2020-05-21 | 2023-08-15 | 江西理工大学 | Method for preparing rare earth oxide by subcritical/supercritical steam pyrolysis method |
| CN114873626A (en) * | 2021-12-31 | 2022-08-09 | 中国工程物理研究院核物理与化学研究所 | A kind of 176 Yb 2 O 3 And 160 Gd 2 O 3 target material recovery method |
| CN114873626B (en) * | 2021-12-31 | 2023-09-19 | 中国工程物理研究院核物理与化学研究所 | The method comprises the following steps of 176 Yb 2 O 3 And 160 Gd 2 O 3 target material recovery method |
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