CN104291270B - A kind of high temperature direct method is prepared the method for light rare earth hydride - Google Patents
A kind of high temperature direct method is prepared the method for light rare earth hydride Download PDFInfo
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- -1 rare earth hydride Chemical class 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 56
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 53
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 312
- 239000001257 hydrogen Substances 0.000 claims abstract description 312
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 300
- 238000010438 heat treatment Methods 0.000 claims abstract description 162
- 239000000843 powder Substances 0.000 claims abstract description 88
- 238000006243 chemical reaction Methods 0.000 claims abstract description 84
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 65
- 230000004941 influx Effects 0.000 claims abstract description 43
- 238000002360 preparation method Methods 0.000 claims abstract description 34
- 239000011261 inert gas Substances 0.000 claims abstract description 21
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 9
- 150000004678 hydrides Chemical class 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 201
- 238000005984 hydrogenation reaction Methods 0.000 claims description 152
- 150000002431 hydrogen Chemical class 0.000 claims description 49
- 239000010453 quartz Substances 0.000 claims description 44
- 238000003860 storage Methods 0.000 claims description 38
- 229910052684 Cerium Inorganic materials 0.000 claims description 33
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 33
- 239000000284 extract Substances 0.000 claims description 29
- 238000009461 vacuum packaging Methods 0.000 claims description 29
- 229910052746 lanthanum Inorganic materials 0.000 claims description 28
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 28
- 229910052693 Europium Inorganic materials 0.000 claims description 24
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 24
- 241000973497 Siphonognathus argyrophanes Species 0.000 claims description 23
- 229910052773 Promethium Inorganic materials 0.000 claims description 20
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 claims description 20
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 20
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 18
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 18
- 229910052772 Samarium Inorganic materials 0.000 claims description 16
- 239000012298 atmosphere Substances 0.000 claims description 10
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 9
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 9
- 238000005538 encapsulation Methods 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 400
- 229910052786 argon Inorganic materials 0.000 description 200
- 239000003708 ampul Substances 0.000 description 37
- 239000012300 argon atmosphere Substances 0.000 description 15
- 238000004140 cleaning Methods 0.000 description 13
- 238000007789 sealing Methods 0.000 description 11
- 238000000338 in vitro Methods 0.000 description 10
- 239000011521 glass Substances 0.000 description 8
- 229910052779 Neodymium Inorganic materials 0.000 description 7
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 7
- 238000004806 packaging method and process Methods 0.000 description 3
- LQOYQLDIKMDNER-UHFFFAOYSA-N VVSVLT Natural products CC(O)C(C(O)=O)NC(=O)C(CC(C)C)NC(=O)C(C(C)C)NC(=O)C(CO)NC(=O)C(NC(=O)C(N)C(C)C)C(C)C LQOYQLDIKMDNER-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 108010066069 cabin-3 Proteins 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052987 metal hydride Inorganic materials 0.000 description 2
- 150000004681 metal hydrides Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- AQLFYWZHKRHRAR-UHFFFAOYSA-N LVYDAY Natural products CC(C)CC(N)C(=O)NC(C(C)C)C(=O)NC(Cc1ccc(O)cc1)C(=O)NC(CC(=O)O)C(=O)NC(C)C(=O)NC(Cc2ccc(O)cc2)C(=O)O AQLFYWZHKRHRAR-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 241000720974 Protium Species 0.000 description 1
- SPBZADYXQCYFKE-UHFFFAOYSA-N VLQSSGLYS Natural products CC(C)C(N)C(=O)NC(CC(C)C)C(=O)NC(CCC(N)=O)C(=O)NC(CO)C(=O)NC(CO)C(=O)NCC(=O)NC(CC(C)C)C(=O)NC(C(=O)NC(CO)C(O)=O)CC1=CC=C(O)C=C1 SPBZADYXQCYFKE-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 108010066114 cabin-2 Proteins 0.000 description 1
- 108010066278 cabin-4 Proteins 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
- C01B6/02—Hydrides of transition elements; Addition complexes thereof
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Abstract
The invention belongs to materials science field, be specifically related to a kind of high temperature direct method and prepare the method for light rare earth hydride, its main implementation step is under inert gas shielding, get purity and be greater than 99%, particle diameter is that the light rare earth of 2～15mm is placed in quartz glass test tube, catch up with air in most cabin with inert gas simultaneously, then close evacuating valve, heating rate with 2～20 DEG C/min heats stove cabin temperature rapidly, stop heating up to 300～1000 DEG C, control hydrogen influx simultaneously and be 200～10000ml/min and keep this temperature to continue again reaction, thereby until the pressure in Hydrogen Vapor Pressure table and heating reaction furnace obtains required light rare earth hydride and corresponding light rare earth hydride powder in poised state completely. utilizing method of the present invention to prepare light rare earth hydride purity is 97～99.99%, and the conversion ratio of light rare earth hydride powder is 97～99.99%, has solved hydride in preparation of industrialization technology and has prepared purity problem, safe and reliable, pollution-free, for large-scale industrialization, to prepare light rare earth hydride significant.
Description
Technical field
The present invention relates to a kind of method of preparing light rare earth hydride, be specifically related to use the preparation of high temperature direct methodThe method of light rare earth hydride, belongs to hydrogen metal material preparation field.
Background technology
The energy is one of three large pillars of new worldwide technological revolution, along with human social development and scientific and technological progress,The mankind are increasing for the demand of the energy. Meanwhile, fossil fuel is because resource is non-renewable, simultaneouslyBe attended by serious environmental pollution, exist huge limitation, be difficult to adapt to the development of modern science and technologyNeed. The energy that scientist is devoted to find clean and effective always replaces fossil fuel, solar energy, wind energy,Therefore the clean energy resource such as Hydrogen Energy, nuclear energy arises at the historic moment. In these several energy harvesting forms, solar energy and windCan have weather limitation, the extensive controlled utilization of nuclear energy also needs Hen Chang road to walk, just at present,Hydrogen Energy combustion heat value is high, and the heat after the burning of every kg of hydrogen is about 3 times of gasoline, is 3.9 times of alcohol,Be 4.5 times of coke, aboundresources and clean and effective, adapt to global sustainability environmental protection joint instantly moreCan development need, be considered to have most the conventional chemical energy carrier of prospect of the application. The maximum that Hydrogen Energy is usedDifficulty and key problem in technology are how to solve large-scale industrialization safe storage and transportation problem.
The most promising way of Hydrogen Energy is by anti-under uniform temperature and pressure condition to some metal and hydrogenShould in conjunction with and generate metal hydride. LREE density of material is higher, and light rare earth and hydrogen atom have veryGood compatibility, light rare earth hydride unit volume be 1～3 times of liquid hydrogen density containing hydrogen density, be preparationThe fine selection of metal hydride. Meanwhile, LREE and protium all have very high combustion heat value,Rare earth hydride also has huge application potential as high energy material in energetic material field. Light rare earth hydrogenationThe preparation method of thing had many reports before this, was mainly the hydrogenation to lanthanum and a small amount of cerium, but mostlyNumber is that the form that rare earth is prepared into alloy is carried out hydrogenation again, and rare earth alloy is easily introduced impurity in rare earth,Cause being difficult to recycling, be unfavorable for long term growth; Also once there were pair simple substance lanthanum and cerium carry out direct hydrogenation and makeStandby hydride, but it mostly is diatomic hydrogen compound, and trivalent mostly is non-stoichiometry hydride, has no tetravalence rareReport prepared by soil hydride, because preparation difficulty problem large, that purity is lower has limited lanthanum and cerium hydrogen alwaysThe development of compound and application; Other light rare earths prepare hydride and application has no report, and high temperature direct hydrogenationPrepare method and the related-art process of high-purity light rare earth hydride and do not see bibliographical information.
Preparation method, preparative capacibility and the technology of preparing of light rare earth hydride is to determine its following scale developmentKey, not yet has light rare earth hydride to prepare the Patents of aspect at present. China has the abundantest in the worldRare earth mineral resources, this has established solid foundation for preparation and application of light rare earth hydride. The present inventionTechnology and the related process method for high-purity light rare earth hydride by high temperature direct hydrogenation legal system, with existingLanthanum compare with cerium hydride preparation method, there is essential distinction in difference, the invention solves industrialization systemStandby technology and hydride are prepared purity problem, solve the series of key techniques such as preparation facilities simultaneously, are industryThe extensive safety of change prepares light rare earth hydride and application is significant.
Summary of the invention
The present invention seeks in order to solve the key technology of puzzlement in light rare earth hydride preparation process, and send outBright a kind of high temperature direct method is prepared the method for light rare earth hydride. The present invention is standby by high temperature direct hydrogenation legal systemThe technology of high-purity light rare earth hydride and related process method, with existing lanthanum and cerium hydride preparation methodCompare, there is essential distinction in difference, the invention solves light rare earth hydride preparation of industrialization technology and hydrogenCompound is prepared purity problem, has solved the series of key techniques such as the preparation facilities of light rare earth hydride simultaneously,For large-scale industrialization is prepared safely light rare earth hydride and application provides technical support.
The present invention is achieved through the following technical solutions a kind of method that high temperature direct method is prepared light rare earth hydride,Concrete preparation process is as follows:
1), under inert gas shielding atmosphere, get purity and be greater than 99%, the light rare earth that particle diameter is 2～15mm100～5000g, is placed in quartz glass test tube, with rubber stopper seal test tube mouth;
2) by the 1st) step test tube is placed in the heating furnace cabin that can vacuumize and be connected with hydrogen and inert gas,Under inert gas atmosphere, take off rapidly rubber stopper, close stove cabin;
3) catch up with in most cabin with inert gas, repeatedly operate 2～10 times, extract gas in heating furnace, reach negativePress 0.010～0.001MPa, then close evacuating valve;
4) under negative pressure state, rapidly stove cabin temperature is heated with the heating rate of 2～20 DEG C/min, controlIn 5～60min, stove cabin temperature is heated to 200～600 DEG C, opens hydrogen valve, in reacting furnace, inputHigh-purity hydrogen, controlling hydrogen influx is 200～10000ml/min, continue programming rate to be heated to 300～1000 DEG C stop heating up;
5) constant hydrogen gas velocity, since the 4th) after step hydrogenation coreaction 100～500min, keep this temperatureDegree continues reaction again, until the pressure in Hydrogen Vapor Pressure table and heating reaction furnace is completely after balance; NowAgain heat up 2～50 DEG C, the still ripple disable of Hydrogen Vapor Pressure table, shows that in stove, hydrogenation reaches terminal;
6) when preparation high price rare earth hydride, when the pressure in Hydrogen Vapor Pressure table and heating reaction furnace completely inAfter balance, again heat up 50～200 DEG C, continue once again inputting hydrogen, Hydrogen Vapor Pressure table is still when ripple disable,Show that in stove, high price rare earth hydride hydrogenation reaches high price reaction end;
7) close hydrogen valve, heating furnace cabin temperature is cooled to normal temperature, under inert gas atmosphere, openStove cabin, uses rapidly rubber stopper seal test tube mouth, quartz test tube is taken out to the glove box that is put in inert gas shieldingIn;
8) by the 6th or 7) the light rare earth hydride that obtains of step grinds to form in the glove box of inert gas shieldingFine-powdered thing, sieves, and obtains being separated into the light rare earth hydride powder of required particle diameter, and powder is carried out to vacuumPackaging or other encapsulation can obtain the product of energy safe storage, and the method is prepared the conversion of light rare earth hydride powderRate is 97～99.99%, and light rare earth hydride purity is 97～99.99%;
Above-mentioned light rare earth hydride is: dihydro lanthanum (LaH2), lanthanum hydride (LaH3), tetrahydro cerium(CeH4), three hydrogenation cerium (CeH3), dihydro cerium (CeH2), three praseodymium hydride (PrH3), tetrahydro praseodymium (PrH4)、Three neodymium hydride (NdH3), three hydrogenation promethium (PmH3), dihydro samarium (SmH2), samaric hydride (SmH3), dihydroChange europium (EuH2), three hydrogenation europium (EuH3), three hydrogenation gadolinium (GdH3)。
Beneficial effect
The preparation method of light rare earth hydride of the present invention is without complicated production device, simple to operate, adapts to existing workIndustryization is produced; High-purity, the trivalent of high conversion, the industrially scalable of tetravalence light rare earth hydride are realizedPreparation, good product quality, stores safety and stability, has greatly improved the water of preparing of high valence state light rare earth hydrideFlat; Production process has the protection of inert gas argon gas, without high-temperature high-pressure apparatus operation, safe and reliable; ProducedJourney is without " three wastes " discharge, and to human body and environment, without harm, clean environment firendly is pollution-free.
Brief description of the drawings
Fig. 1 is light rare earth hydride preparation facilities schematic diagram.
Wherein, 1-2-3-4-5-6-7-8-9-
Specific embodiment
Below in conjunction with drawings and Examples, the present invention is elaborated.
Embodiment 1
In the glove box that is full of argon gas, the 500g praseodymium that is 99% by purity is loaded on quartz glass test tube, and usesRubber stopper seal. Test tube is placed in to the heating furnace cabin that can vacuumize, lead to hydrogen and argon gas, prior in cabinBe set to argon atmosphere. Pull up rapidly rubber stopper, and close stove cabin. Keep hydrogen, argon gas valve closing,Open evacuating valve, it is 0.026MPa that stove cabin pressure is evacuated to negative pressure; Close evacuating valve, open argon gas valveDoor is closed argon gas valve after stove cabin is inflated, and opens evacuating valve and vacuumizes, and repeatedly operates 2Inferior. Close all valves, rapidly stove cabin temperature is heated to 360 DEG C, open hydrogen valve, in reacting furnaceInput high-purity hydrogen, controlling hydrogen influx is that 770ml/min is constant, heats with 15 DEG C/min programming rate20min to 585 DEG C stops heating up, and constant hydrogen gas velocity, from hydrogenation starts coreaction 176min, keepsSaid temperature continues to react 35min again, until the pressure in Hydrogen Vapor Pressure table and heating reaction furnace is completely in flatWeighing apparatus; Now again heat up 25 DEG C, the still ripple disable of Hydrogen Vapor Pressure table, shows that in stove, hydrogenation reaches terminal,Common enter 12.10g hydrogen. Close hydrogen valve, heating furnace cabin temperature is cooled to normal temperature, open argon gas valveDoor is to inflating in cabin. Open stove cabin, use rapidly rubber stopper seal test tube mouth, test tube is taken out and is put in handIn casing, prepare praseodymium hydride (surface has a large amount of breaches crisscross, crisp hard, as the shape of blooming).In glove box, grind to form fine powder, obtain 510.63g praseodymium hydride powder. This powder is carried out to vacuum packaging can be obtainedTo the product of energy safe storage. The conversion ratio that the method is prepared praseodymium hydride is 99.85%, and praseodymium hydride purity is99.85％。
Embodiment 2
In the glove box that is full of argon gas, the 308g praseodymium that is 99% by purity is loaded on quartz glass test tube, and usesRubber stopper seal. Test tube is placed in to the heating furnace cabin that can vacuumize, lead to hydrogen and argon gas, prior in cabinBe set to argon atmosphere. Pull up rapidly rubber stopper, and close stove cabin. Keep hydrogen, argon gas valve closing,Open evacuating valve, it is 0.030MPa that stove cabin pressure is evacuated to negative pressure; Close evacuating valve, open argon gas valveDoor is closed argon gas valve after stove cabin is inflated, and opens evacuating valve and vacuumizes, and repeatedly operates 2Inferior. Close all valves, rapidly stove cabin temperature is heated to 375 DEG C, open hydrogen valve, in reacting furnaceInput high-purity hydrogen, controlling hydrogen influx is that 580ml/min is constant, heats with 12 DEG C/min programming rate18min to 565 DEG C stops heating up, and constant hydrogen gas velocity, from hydrogenation starts coreaction 125min, keepsSaid temperature continues to react 25min again, until the pressure in Hydrogen Vapor Pressure table and heating reaction furnace is completely in flatWeighing apparatus; Now again heat up 30 DEG C, the still ripple disable of Hydrogen Vapor Pressure table, shows that in stove, hydrogenation reaches terminal,Common enter 8.00g hydrogen. Close hydrogen valve, heating furnace cabin temperature is cooled to normal temperature, open argon gas valveDoor is to inflating in cabin. Open stove cabin, use rapidly rubber stopper seal test tube mouth, test tube is taken out and is put in handIn casing, prepare praseodymium hydride (surface has a large amount of breaches crisscross, crisp hard, as the shape of blooming).In glove box, grind to form fine powder, obtain 314.53g praseodymium hydride powder. This powder is carried out to vacuum packaging can be obtainedTo the product of energy safe storage. The conversion ratio that the method is prepared praseodymium hydride is 99.65%, and praseodymium hydride purity is99.66％。
Embodiment 3
In the glove box that is full of argon gas, the 1012g praseodymium that is 99% by purity is loaded on quartz glass test tube, and usesRubber stopper seal. Test tube is placed in to the heating furnace cabin that can vacuumize, lead to hydrogen and argon gas, prior in cabinBe set to argon atmosphere. Pull up rapidly rubber stopper, and close stove cabin. Keep hydrogen, argon gas valve closing,Open evacuating valve, it is 0.019MPa that stove cabin pressure is evacuated to negative pressure; Close evacuating valve, open argon gas valveDoor is closed argon gas valve after stove cabin is inflated, and opens evacuating valve and vacuumizes, and repeatedly operates 3Inferior. Close all valves, rapidly stove cabin temperature is heated to 395 DEG C, open hydrogen valve, in reacting furnaceInput high-purity hydrogen, controlling hydrogen influx is that 1318ml/min is constant, adds with 10 DEG C/min programming rateHot 25min to 605 DEG C stops heating up, and constant hydrogen gas velocity, from hydrogenation starts coreaction 195min, protectsHold said temperature and continue again to react 30min, until the pressure in Hydrogen Vapor Pressure table and heating reaction furnace completely inBalance; Now again heat up 15 DEG C, the still ripple disable of Hydrogen Vapor Pressure table, shows that in stove, hydrogenation reaches eventuallyPoint, common enter 22.96g hydrogen. Close hydrogen valve, heating furnace cabin temperature is cooled to normal temperature, open argonAir valve is to inflating in cabin. Open stove cabin, use rapidly rubber stopper seal test tube mouth, test tube is taken out and putIn glove box, (surface has a large amount of breaches crisscross, crisp hard, as the shape of blooming to prepare praseodymium hydrideShape). In glove box, grind to form fine powder, obtain 1033.49g praseodymium hydride powder. This powder is carried out to vacuum packetDress can obtain the product of energy safe storage. The conversion ratio that the method is prepared praseodymium hydride is 99.72%, and praseodymium hydride is pureDegree is 99.73%.
Embodiment 4
In the glove box that is full of argon gas, the 3005g praseodymium that is 99% by purity is loaded on quartz glass test tube, and usesRubber stopper seal. Test tube is placed in to the heating furnace cabin that can vacuumize, lead to hydrogen and argon gas, prior in cabinBe set to argon atmosphere. Pull up rapidly rubber stopper, and close stove cabin. Keep hydrogen, argon gas valve closing,Open evacuating valve, it is 0.014MPa that stove cabin pressure is evacuated to negative pressure; Close evacuating valve, open argon gas valveDoor is closed argon gas valve after stove cabin is inflated, and opens evacuating valve and vacuumizes, and repeatedly operates 4Inferior. Close all valves, rapidly stove cabin temperature is heated to 405 DEG C, open hydrogen valve, in reacting furnaceInput high-purity hydrogen, controlling hydrogen influx is that 2450ml/min is constant, heats with 8 DEG C/min programming rate26min to 590 DEG C stops heating up, and constant hydrogen gas velocity, from hydrogenation starts coreaction 299min, keepsSaid temperature continues to react 40min again, until the pressure in Hydrogen Vapor Pressure table and heating reaction furnace is completely in flatWeighing apparatus; Now again heat up 10 DEG C, the still ripple disable of Hydrogen Vapor Pressure table, shows that in stove, hydrogenation reaches terminal,Common enter 65.26g hydrogen. Close hydrogen valve, heating furnace cabin temperature is cooled to normal temperature, open argon gas valveDoor is to inflating in cabin. Open stove cabin, use rapidly rubber stopper seal test tube mouth, test tube is taken out and is put in handIn casing, prepare praseodymium hydride (surface has a large amount of breaches crisscross, crisp hard, as the shape of blooming).In glove box, grind to form fine powder, obtain 3068.79g praseodymium hydride powder. This powder is carried out to vacuum packaging can be obtainedTo the product of energy safe storage. The conversion ratio that the method is prepared praseodymium hydride is 99.70%, and praseodymium hydride purity is99.71％。
Embodiment 5
In the glove box that is full of argon gas, the 800g praseodymium that is 99% by purity is loaded on quartz glass test tube, and usesRubber stopper seal. Test tube is placed in to the heating furnace cabin that can vacuumize, lead to hydrogen and argon gas, prior in cabinBe set to argon atmosphere. Pull up rapidly rubber stopper, and close stove cabin. Keep hydrogen, argon gas valve closing,Open evacuating valve, it is 0.020MPa that stove cabin pressure is evacuated to negative pressure; Close evacuating valve, open argon gas valveDoor is closed argon gas valve after stove cabin is inflated, and opens evacuating valve and vacuumizes, and repeatedly operates 3Inferior. Close all valves, rapidly stove cabin temperature is heated to 550 DEG C, open hydrogen valve, in reacting furnaceInput high-purity hydrogen, controlling hydrogen influx is that 1020ml/min is constant, heats with 8 DEG C/min programming rate24min to 720 DEG C stops heating up, and constant hydrogen gas velocity, from hydrogenation starts coreaction 265min, keepsSaid temperature continues to react 35min again, until the pressure in Hydrogen Vapor Pressure table and heating reaction furnace is completely in flatWeighing apparatus; Now again heat up 10 DEG C, the still ripple disable of Hydrogen Vapor Pressure table, shows that in stove, hydrogenation reaches terminal,Common enter 24.12g hydrogen. Close hydrogen valve, heating furnace cabin temperature is cooled to normal temperature, open argon gas valveDoor is to inflating in cabin. Open stove cabin, use rapidly rubber stopper seal test tube mouth, test tube is taken out and is put in handIn casing, (there are a large amount of crisscross breaches on surface, and quality is crisp hard, as blooms to prepare tetravalence praseodymium hydrideShape). In glove box, grind to form fine powder, obtain 820.2g tetravalence praseodymium hydride powder. This powder is carried out veryEmpty package can obtain the product of energy safe storage. The conversion ratio that the method is prepared tetravalence praseodymium hydride is 99.75%,Purity is 99.76%.
Embodiment 6
In the glove box of argon shield, the 500g neodymium that is 99% by purity is loaded on quartz glass test tube, and usesRubber stopper seals. Test tube is placed in the heating furnace that vacuumizes and can lead to inert gas, pulls up stopper,And close rapidly stove cabin valve. Keep hydrogen, argon gas valve closing, extract all gas in heating furnace, extremelyNegative pressure is 0.025MPa, closes evacuating valve, again to stove cabin applying argon gas, with gas in argon replaces stove cabin2 times. Close all valves, rapidly stove cabin temperature be heated to 450 DEG C, in reacting furnace, input high-purity hydrogen,Controlling hydrogen influx is that 675ml/min is constant, with 14 DEG C/min programming rate, stove cabin temperature is heated simultaneously20min to 650 DEG C stops heating up, and constant hydrogen gas velocity, from hydrogenation starts coreaction 175min, keepsSaid temperature continues to react 25min again, until the pressure in Hydrogen Vapor Pressure table and heating reaction furnace is completely in flatWeighing apparatus; Now again heat up 30 DEG C, the still ripple disable of Hydrogen Vapor Pressure table, shows that in stove, hydrogenation reaches terminal,Common enter 11.88g hydrogen. Stop hydrogen input, heating furnace cabin temperature is cooled to normal temperature, will in cabin, be full ofArgon gas. Open stove cabin, seal test tube mouth with rubber stopper and take out, and be put in rapidly in glove box, obtain hydrogenChange neodymium (surface has a large amount of breaches crisscross, is the shape of blooming). In glove box, grind to form fine powder, to obtain final productTo 510.39g neodymium hydride powder. By this powder carry out vacuum packaging can obtain can safe storage product. The methodThe conversion ratio of preparing neodymium hydride is 99.93%, and neodymium hydride purity is 99.93%.
Embodiment 7
In the glove box of argon shield, the 802g neodymium that is 99% by purity is loaded on quartz glass test tube, and usesRubber stopper seals. Test tube is placed in the heating furnace that vacuumizes and can lead to inert gas, pulls up stopper,And close rapidly stove cabin valve. Keep hydrogen, argon gas valve closing, extract all gas in heating furnace, extremelyNegative pressure is 0.020MPa, closes evacuating valve, again to stove cabin applying argon gas, with gas in argon replaces stove cabin3 times. Close all valves, rapidly stove cabin temperature be heated to 452 DEG C, in reacting furnace, input high-purity hydrogen,Controlling hydrogen influx is that 883ml/min is constant, with 12 DEG C/min programming rate, stove cabin temperature is heated simultaneously23min to 685 DEG C stops heating up, and constant hydrogen gas velocity, from hydrogenation starts coreaction 230min, keepsSaid temperature continues to react 20min again, until the pressure in Hydrogen Vapor Pressure table and heating reaction furnace is completely in flatWeighing apparatus; Now again heat up 20 DEG C, the still ripple disable of Hydrogen Vapor Pressure table, shows that in stove, hydrogenation reaches terminal,Common enter 18.15g hydrogen. Stop hydrogen input, heating furnace cabin temperature is cooled to normal temperature, will in cabin, be full ofArgon gas. Open stove cabin, seal test tube mouth with rubber stopper and take out, and be put in rapidly in glove box, obtain hydrogenChange neodymium (surface has a large amount of breaches crisscross, is the shape of blooming). In glove box, grind to form fine powder, to obtain final productTo 88.66g neodymium hydride powder. By this powder carry out vacuum packaging can obtain can safe storage product. The party's legal systemThe conversion ratio of standby neodymium hydride is 99.87%, and neodymium hydride purity is 99.87%.
Embodiment 8
In the glove box of argon shield, the 1007g neodymium that is 99% by purity is loaded on quartz glass test tube, and usesRubber stopper seals. Test tube is placed in the heating furnace that vacuumizes and can lead to inert gas, pulls up stopper,And close rapidly stove cabin valve. Keep hydrogen, argon gas valve closing, extract all gas in heating furnace, extremelyNegative pressure is 0.018MPa, closes evacuating valve, again to stove cabin applying argon gas, with gas in argon replaces stove cabin3 times. Close all valves, rapidly stove cabin temperature be heated to 502 DEG C, in reacting furnace, input high-purity hydrogen,Controlling hydrogen influx is that 1450ml/min is constant, with 10 DEG C/min programming rate, stove cabin temperature is added simultaneouslyHot 19min to 677 DEG C stops heating up, and constant hydrogen gas velocity, from hydrogenation starts coreaction 173min, protectsHold said temperature and continue again to react 25min, until the pressure in Hydrogen Vapor Pressure table and heating reaction furnace completely inBalance; Now again heat up 10 DEG C, the still ripple disable of Hydrogen Vapor Pressure table, shows that in stove, hydrogenation reaches eventuallyPoint, common enter 22.40g hydrogen. Stop hydrogen input, heating furnace cabin temperature is cooled to normal temperature, in cabinBe full of argon gas. Open stove cabin, seal test tube mouth with rubber stopper and take out, and be put in rapidly in glove box, to obtain final productTo neodymium hydride (surface has a large amount of breaches crisscross, is the shape of blooming). In glove box, grind to form fine powder,Obtain 1027.91g neodymium hydride powder. By this powder carry out vacuum packaging can obtain can safe storage product. ShouldThe conversion ratio that method is prepared neodymium hydride is 99.84%, and neodymium hydride purity is 99.85%.
Embodiment 9
In the glove box of argon shield, the 4121g neodymium that is 99% by purity is loaded on quartz glass test tube, and usesRubber stopper seals. Test tube is placed in the heating furnace that vacuumizes and can lead to inert gas, pulls up stopper,And close rapidly stove cabin valve. Keep hydrogen, argon gas valve closing, extract all gas in heating furnace, extremelyNegative pressure is 0.012MPa, closes evacuating valve, again to stove cabin applying argon gas, with gas in argon replaces stove cabin4 times. Close all valves, rapidly stove cabin temperature be heated to 495 DEG C, in reacting furnace, input high-purity hydrogen,Controlling hydrogen influx is that 3750ml/min is constant, with 8 DEG C/min programming rate, stove cabin temperature is heated simultaneously27min to 692 DEG C stops heating up, and constant hydrogen gas velocity, from hydrogenation starts coreaction 260min, keepsSaid temperature continues to react 40min again, until the pressure in Hydrogen Vapor Pressure table and heating reaction furnace is completely in flatWeighing apparatus; Now again heat up 18 DEG C, the still ripple disable of Hydrogen Vapor Pressure table, shows that in stove, hydrogenation reaches terminal,Common enter 87.07g hydrogen. Stop hydrogen input, heating furnace cabin temperature is cooled to normal temperature, will in cabin, be full ofArgon gas. Open stove cabin, seal test tube mouth with rubber stopper and take out, and be put in rapidly in glove box, obtain hydrogenChange neodymium (surface has a large amount of breaches crisscross, is the shape of blooming). In glove box, grind to form fine powder, to obtain final productTo 4206.58g neodymium hydride powder. By this powder carry out vacuum packaging can obtain can safe storage product. The methodThe conversion ratio of preparing neodymium hydride is 99.85%, and neodymium hydride purity is 99.86%.
Embodiment 10
Having under argon gas atmosphere, getting purity and be 99% lanthanum 505g, be placed in vacuumizing and can leading to inertiaIn the heating furnace of gas, valve-off, extracts all gas in heating furnace, and making negative pressure is 0.02MPa. ThenWith argon cleaning 3 times, valve-off, while being heated to rapidly 390 DEG C, connect High Purity Hydrogen, to defeated in reacting furnaceEnter hydrogen, controlling hydrogen influx is 563ml/min, and control programming rate is 12 DEG C/min simultaneously, heating30min to 692 DEG C stops heating up, and constant hydrogen gas velocity, from hydrogenation starts coreaction 246min, keepsUnder said temperature again continue reaction 40min, until the pressure in Hydrogen Vapor Pressure table and heating reaction furnace completely inBalance; Now again heat up 15 DEG C, the ripple disable of Hydrogen Vapor Pressure table, shows that in stove, hydrogenation reaches terminal,Common enter 12.37g hydrogen. Cut off hydrogen influx, while being cooled to normal temperature with furnace temperature, under argon shield,The hydrogenation lanthanum (now surface is the hard shape of blooming that is highly brittle) that takes out preparation grinds to form fine powder in glove boxShape thing, obtains 515.90g hydrogenation lanthanum powder. By this powder carry out vacuum packaging can obtain can safe storage productProduct. The conversion ratio that the method is prepared hydrogenation lanthanum is 99.97%, and hydrogenation lanthanum purity is 99.97%.
Embodiment 11
Having under argon gas atmosphere, getting purity and be 99% lanthanum 412g, be placed in vacuumizing and can leading to inertiaIn the heating furnace of gas, valve-off, extracts all gas in heating furnace, and making negative pressure is 0.018MPa. SoAfter use argon cleaning 2 times, valve-off, while being heated to rapidly 362 DEG C, connect High Purity Hydrogen, in reacting furnaceInputting hydrogen, controlling hydrogen influx is 724ml/min, control programming rate is 8 DEG C/min simultaneously, heating40min to 685 DEG C stops heating up, and constant hydrogen gas velocity, from hydrogenation starts coreaction 160min, keepsUnder said temperature again continue reaction 35min, until the pressure in Hydrogen Vapor Pressure table and heating reaction furnace completely inBalance; Now again heat up 20 DEG C, the ripple disable of Hydrogen Vapor Pressure table, shows that in stove, hydrogenation reaches terminal,Common enter 10.34g hydrogen. Cut off hydrogen influx, while being cooled to normal temperature with furnace temperature, under argon shield,The hydrogenation lanthanum (now surface is the hard shape of blooming that is highly brittle) that takes out preparation grinds to form fine powder in glove boxShape thing, obtains 420.86g hydrogenation lanthanum powder. By this powder carry out vacuum packaging can obtain can safe storage productProduct. The conversion ratio that the method is prepared hydrogenation lanthanum is 99.75%, and hydrogenation lanthanum purity is 99.76%.
Embodiment 12
Having under argon gas atmosphere, getting purity and be 99% lanthanum 998g, be placed in vacuumizing and can leading to inertiaIn the heating furnace of gas, valve-off, extracts all gas in heating furnace, and making negative pressure is 0.022MPa. SoAfter use argon cleaning 3 times, valve-off, while being heated to rapidly 380 DEG C, connect High Purity Hydrogen, in reacting furnaceInputting hydrogen, controlling hydrogen influx is 766ml/min, control programming rate is 15 DEG C/min simultaneously, addsHot 40min to 702 DEG C stops heating up, and constant hydrogen gas velocity, from hydrogenation starts coreaction 336min, protectsHold under said temperature and continue again reaction 20min, until the pressure in Hydrogen Vapor Pressure table and heating reaction furnace is located completelyIn balance; Now again heat up 5 DEG C, the ripple disable of Hydrogen Vapor Pressure table, shows that in stove, hydrogenation reaches terminal,Common enter 22.99g hydrogen. Cut off hydrogen influx, while being cooled to normal temperature with furnace temperature, under argon shield,The hydrogenation lanthanum (now surface is the hard shape of blooming that is highly brittle) that takes out preparation grinds to form fine powder in glove boxShape thing, obtains 1019.52g hydrogenation lanthanum powder. By this powder carry out vacuum packaging can obtain can safe storage productProduct. The conversion ratio that the method is prepared hydrogenation lanthanum is 99.82%, and hydrogenation lanthanum purity is 99.82%.
Embodiment 13
Having under argon gas atmosphere, getting purity and be 99% lanthanum 5002g, be placed in vacuumizing and can leading to inertiaIn the heating furnace of gas, valve-off, extracts all gas in heating furnace, and making negative pressure is 0.015MPa. SoAfter use argon cleaning 4 times, valve-off, while being heated to rapidly 356 DEG C, connect High Purity Hydrogen, in reacting furnaceInputting hydrogen, controlling hydrogen influx is 4708ml/min, control programming rate is 7 DEG C/min simultaneously, addsHot 50min to 695 DEG C stops heating up, and constant hydrogen gas velocity, from hydrogenation starts coreaction 260min, protectsHold under said temperature and continue again reaction 30min, until the pressure in Hydrogen Vapor Pressure table and heating reaction furnace is located completelyIn balance; Now again heat up 10 DEG C, the ripple disable of Hydrogen Vapor Pressure table, shows that in stove, hydrogenation reaches terminal,Common enter 109.30g hydrogen. Cut off hydrogen influx, while being cooled to normal temperature with furnace temperature, under argon shield,The hydrogenation lanthanum (now surface is the hard shape of blooming that is highly brittle) that takes out preparation grinds to form fine powder in glove boxShape thing, obtains 5109.83g hydrogenation lanthanum powder. By this powder carry out vacuum packaging can obtain can safe storage productProduct. The conversion ratio that the method is prepared hydrogenation lanthanum is 99.81%, and hydrogenation lanthanum purity is 99.82%.
Embodiment 14
Under argon atmosphere protection, get purity and be 99% cerium 509g, be loaded in quartz glass test tube, use rubberPlug sealing test tube mouth. Test tube is placed in to the heating furnace cabin that can vacuumize, lead to hydrogen and argon gas, in cabinBe set in advance argon atmosphere. Pull up rapidly rubber stopper, and close stove cabin. Keep hydrogen, argon gas valve to closeClose, extract all gas in heating furnace, making negative pressure is 0.025MPa, then closes evacuating valve, opens argonAir valve, until being full of in cabin after argon gas, again closing argon gas valve and opens evacuating valve and vacuumize,Repeatedly operate 2 times. Close all valves, under negative pressure state, rapidly stove cabin temperature be heated to 352 DEG C,Open hydrogen valve, in reacting furnace, input high-purity hydrogen, controlling hydrogen influx is that 731ml/min is constant,Stop heating up with 25min to 520 DEG C of 10 DEG C/min programming rate heating, constant hydrogen gas velocity, opens from hydrogenationAfter beginning coreaction 190min, keep this temperature to continue again to react 25min, until Hydrogen Vapor Pressure table is anti-with heatingAnswer pressure in stove completely in balance; Now again heat up 25 DEG C, the still ripple disable of Hydrogen Vapor Pressure table, tableHydrogenation reaches terminal in open oven, common enter 12.40g hydrogen. Close hydrogen valve, by heating furnace cabin temperatureDegree is cooled to normal temperature, opens argon gas valve, makes in cabin and to be in vitro full of argon gas. Open stove cabin, rapidlyWith rubber stopper seal test tube mouth, quartz test tube is taken out and is put in the glove box of argon shield. In vitro beThe hydrogenation cerium (there is very how crisp hard breach in length and breadth on surface, is the shape of blooming) preparing. In glove box, grindWear into fine-powdered thing, obtain 519.89g hydrogenation cerium powder. This powder is carried out to vacuum packaging and can obtain energy safetyThe product of storage. The conversion ratio that the method is prepared hydrogenation cerium is 99.96%, and hydrogenation cerium purity is 99.96%.
Embodiment 15
Under argon atmosphere protection, get purity and be 99% cerium 401g, be loaded in quartz glass test tube, use rubberPlug sealing test tube mouth. Test tube is placed in to the heating furnace cabin that can vacuumize, lead to hydrogen and argon gas, in cabinBe set in advance argon atmosphere. Pull up rapidly rubber stopper, and close stove cabin. Keep hydrogen, argon gas valve to closeClose, extract all gas in heating furnace, making negative pressure is 0.027MPa, then closes evacuating valve, opens argonAir valve, until being full of in cabin after argon gas, again closing argon gas valve and opens evacuating valve and vacuumize,Repeatedly operate 2 times. Close all valves, under negative pressure state, rapidly stove cabin temperature be heated to 375 DEG C,Open hydrogen valve, in reacting furnace, input high-purity hydrogen, controlling hydrogen influx is that 869ml/min is constant,Stop heating up with 20min to 550 DEG C of 12 DEG C/min programming rate heating, constant hydrogen gas velocity, opens from hydrogenationAfter beginning coreaction 130min, keep this temperature to continue again to react 20min, until Hydrogen Vapor Pressure table is anti-with heatingAnswer pressure in stove completely in balance; Now again heat up 20 DEG C, the still ripple disable of Hydrogen Vapor Pressure table, tableHydrogenation reaches terminal in open oven, common enter 10.09g hydrogen. Close hydrogen valve, by heating furnace cabin temperatureDegree is cooled to normal temperature, opens argon gas valve, makes in cabin and to be in vitro full of argon gas. Open stove cabin, rapidlyWith rubber stopper seal test tube mouth, quartz test tube is taken out and is put in the glove box of argon shield. In vitro beThe hydrogenation cerium (there is very how crisp hard breach in length and breadth on surface, is the shape of blooming) preparing. In glove box, grindWear into fine-powdered thing, obtain 409.58g hydrogenation cerium powder. This powder is carried out to vacuum packaging and can obtain energy safetyThe product of storage. The conversion ratio that the method is prepared hydrogenation cerium is 99.92%, and hydrogenation cerium purity is 99.92%.
Embodiment 16
Under argon atmosphere protection, get purity and be 99% cerium 995g, be loaded in quartz glass test tube, use rubberPlug sealing test tube mouth. Test tube is placed in to the heating furnace cabin that can vacuumize, lead to hydrogen and argon gas, in cabinBe set in advance argon atmosphere. Pull up rapidly rubber stopper, and close stove cabin. Keep hydrogen, argon gas valve to closeClose, extract all gas in heating furnace, making negative pressure is 0.02MPa, then closes evacuating valve, opens argon gasValve, until being full of in cabin after argon gas, again closing argon gas valve and opens evacuating valve and vacuumize, anti-Operate again 3 times. Close all valves, under negative pressure state, rapidly stove cabin temperature is heated to 380 DEG C, beatOpen hydrogen valve, in reacting furnace, input high-purity hydrogen, controlling hydrogen influx is that 1265ml/min is constant,Stop heating up with 30min to 590 DEG C of 8 DEG C/min programming rate heating, constant hydrogen gas velocity, from hydrogenationAfter coreaction 202min, keep this temperature to continue again to react 30min, until Hydrogen Vapor Pressure table with add thermal responsePressure in stove is completely in balance; Now again heat up 15 DEG C, the still ripple disable of Hydrogen Vapor Pressure table, showsHydrogenation reaches terminal in stove, common enter 22.79g hydrogen. Close hydrogen valve, by heating furnace cabin temperatureBe cooled to normal temperature, open argon gas valve, make in cabin and to be in vitro full of argon gas. Open stove cabin, use rapidlyRubber stopper seal test tube mouth, takes out quartz test tube to be put in the glove box of argon shield. In vitro be systemThe hydrogenation cerium (there is very how crisp hard breach in length and breadth on surface, is the shape of blooming) of getting ready. In glove box, grindBecome fine-powdered thing, obtain 1016.28g hydrogenation cerium powder. This powder is carried out to vacuum packaging can be obtained storing safelyThe product of depositing. The conversion ratio that the method is prepared hydrogenation cerium is 99.89%, and hydrogenation cerium purity is 99.90%.
Embodiment 17
Under argon atmosphere protection, get purity and be 99% cerium 4001g, be loaded in quartz glass test tube, use rubberPlug sealing test tube mouth. Test tube is placed in to the heating furnace cabin that can vacuumize, lead to hydrogen and argon gas, in cabinBe set in advance argon atmosphere. Pull up rapidly rubber stopper, and close stove cabin. Keep hydrogen, argon gas valve to closeClose, extract all gas in heating furnace, making negative pressure is 0.015MPa, then closes evacuating valve, opens argonAir valve, until being full of in cabin after argon gas, again closing argon gas valve and opens evacuating valve and vacuumize,Repeatedly operate 4 times. Close all valves, under negative pressure state, rapidly stove cabin temperature be heated to 385 DEG C,Open hydrogen valve, in reacting furnace, input high-purity hydrogen, controlling hydrogen influx is that 3756ml/min is constant,Stop heating up with 40min to 605 DEG C of 6 DEG C/min programming rate heating, constant hydrogen gas velocity, from hydrogenationAfter coreaction 260min, keep this temperature to continue again to react 35min, until Hydrogen Vapor Pressure table with add thermal responsePressure in stove is completely in balance; Now again heat up 10 DEG C, the still ripple disable of Hydrogen Vapor Pressure table, showsHydrogenation reaches terminal in stove, common enter 87.08g hydrogen. Close hydrogen valve, by heating furnace cabin temperatureBe cooled to normal temperature, open argon gas valve, make in cabin and to be in vitro full of argon gas. Open stove cabin, use rapidlyRubber stopper seal test tube mouth, takes out quartz test tube to be put in the glove box of argon shield. In vitro be systemThe hydrogenation cerium (there is very how crisp hard breach in length and breadth on surface, is the shape of blooming) of getting ready. In glove box, grindBecome fine-powdered thing, obtain 4086.555g hydrogenation cerium powder. This powder is carried out to vacuum packaging and can obtain energy safetyThe product of storage. The conversion ratio that the method is prepared hydrogenation cerium is 99.87%, and hydrogenation cerium purity is 99.87%.
Embodiment 18
Under argon atmosphere protection, get purity and be 99% cerium 600g, be loaded in quartz glass test tube, use rubberPlug sealing test tube mouth. Test tube is placed in to the heating furnace cabin that can vacuumize, lead to hydrogen and argon gas, in cabinBe set in advance argon atmosphere. Pull up rapidly rubber stopper, and close stove cabin. Keep hydrogen, argon gas valve to closeClose, extract all gas in heating furnace, making negative pressure is 0.020MPa, then closes evacuating valve, opens argonAir valve, until being full of in cabin after argon gas, again closing argon gas valve and opens evacuating valve and vacuumize,Repeatedly operate 3 times. Close all valves, under negative pressure state, rapidly stove cabin temperature be heated to 520 DEG C,Open hydrogen valve, in reacting furnace, input high-purity hydrogen, controlling hydrogen influx is that 812ml/min is constant,Stop heating up with 31min to 682 DEG C of 6 DEG C/min programming rate heating, constant hydrogen gas velocity, from hydrogenationAfter coreaction 258min, keep this temperature to continue again to react 32min, until Hydrogen Vapor Pressure table with add thermal responsePressure in stove is completely in balance; Now again heat up 8 DEG C, the still ripple disable of Hydrogen Vapor Pressure table, shows stoveInterior hydrogenation reaches terminal, common enter 18.70g hydrogen. Close hydrogen valve, by cold heating furnace cabin temperatureBut to normal temperature, open argon gas valve, make in cabin and to be in vitro full of argon gas. Open stove cabin, use rapidly rubberPlug sealing test tube mouth, takes out quartz test tube to be put in the glove box of argon shield. In vitro be preparationGood tetravalence hydrogenation cerium (there is very how crisp hard breach in length and breadth on surface, is the shape of blooming). In glove box, grindWear into fine-powdered thing, obtain 620.19g tetravalence hydrogenation cerium powder. This powder is carried out to vacuum packaging and can obtain energyThe product of safe storage. The conversion ratio that the method is prepared tetravalence hydrogenation cerium is 99.87%, and purity is 99.87%.
Embodiment 19
Having in argon gas glove box, get purity and be 99% 521g promethium, be placed in quartz glass tube, use rubberPlug seals the mouth of pipe. Glass tube is placed in and can be vacuumized and the heating furnace of logical hydrogen, argon gas, pull up rubberPlug is also closed rapidly stove cabin valve, opens vacuum valve, extracts all gas in heating furnace, makes negative pressure be0.025MPa. Be used alternatingly vacuum valve and argon gas valve, repeatedly use after argon cleaning 2 times, close allValve. Rapidly stove cabin temperature is heated to 450 DEG C, opens hydrogen valve, in reacting furnace, input high-purity hydrogen,Controlling hydrogen influx is 857ml/min, and control programming rate is 15 DEG C/min simultaneously, heats 18min alwaysStop heating up to 665 DEG C, constant hydrogen gas velocity, from hydrogenation starts coreaction 160min, keeps above-mentioned temperatureDegree continues reaction 35min again, until the pressure in Hydrogen Vapor Pressure table and heating reaction furnace is completely in balance; ThisShi Zaici heats up 25 DEG C, and the still ripple disable of Hydrogen Vapor Pressure table shows that in stove, hydrogenation reaches terminal, commonEnter 12.26g hydrogen. Close hydrogen valve, stove cabin temperature is cooled to normal temperature, in cabin, pass into argon gas, at argonUnder gas protection, open hatch door and seal the glass mouth of pipe with rubber stopper rapidly, by the hydrogenation promethium of preparation (now tableFace is the shape of blooming of loosening very much) be put in glove box. In glove box, grind to form fine-powdered thing, to obtain final productTo 531.77g hydrogenation promethium powder. By this powder carry out vacuum packaging can obtain can safe storage product. The methodThe conversion ratio of preparation hydrogenation promethium is 99.83%, and purity is 99.83%.
Embodiment 20
Having in argon gas glove box, get purity and be 99% 407g promethium, be placed in quartz glass tube, use rubberPlug seals the mouth of pipe. Glass tube is placed in and can be vacuumized and the heating furnace of logical hydrogen, argon gas, pull up rubberPlug is also closed rapidly stove cabin valve, opens vacuum valve, extracts all gas in heating furnace, makes negative pressure be0.027MPa. Be used alternatingly vacuum valve and argon gas valve, repeatedly use after argon cleaning 2 times, close allValve. Rapidly stove cabin temperature is heated to 445 DEG C, opens hydrogen valve, in reacting furnace, input high-purity hydrogen,Controlling hydrogen influx is 781ml/min, and control programming rate is 12 DEG C/min simultaneously, heats 23min alwaysStop heating up to 687 DEG C, constant hydrogen gas velocity, from hydrogenation starts coreaction 142min, keeps above-mentioned temperatureDegree continues reaction 30min again, until the pressure in Hydrogen Vapor Pressure table and heating reaction furnace is completely in balance; ThisShi Zaici heats up 20 DEG C, and the still ripple disable of Hydrogen Vapor Pressure table shows that in stove, hydrogenation reaches terminal, commonEnter 9.89g hydrogen. Close hydrogen valve, stove cabin temperature is cooled to normal temperature, in cabin, pass into argon gas, at argonUnder gas protection, open hatch door and seal the glass mouth of pipe with rubber stopper rapidly, by the hydrogenation promethium of preparation (now tableFace is the shape of blooming of loosening very much) be put in glove box. In glove box, grind to form fine-powdered thing, to obtain final productTo 415.41 hydrogenation promethium powder. By this powder carry out vacuum packaging can obtain can safe storage product. The party's legal systemThe conversion ratio of standby hydrogenation promethium is 99.86%, and purity is 99.87%.
Embodiment 21
Having in argon gas glove box, get purity and be 99% 1000g promethium, be placed in quartz glass tube, use rubberPlug seals the mouth of pipe. Glass tube is placed in and can be vacuumized and the heating furnace of logical hydrogen, argon gas, pull up rubberPlug is also closed rapidly stove cabin valve, opens vacuum valve, extracts all gas in heating furnace, makes negative pressure be0.020MPa. Be used alternatingly vacuum valve and argon gas valve, repeatedly use after argon cleaning 3 times, close allValve. Rapidly stove cabin temperature is heated to 480 DEG C, opens hydrogen valve, in reacting furnace, input high-purity hydrogen,Controlling hydrogen influx is 1326ml/min, and control programming rate is 10 DEG C/min simultaneously, heats 25min alwaysStop heating up to 695 DEG C, constant hydrogen gas velocity, from hydrogenation starts coreaction 189min, keeps above-mentioned temperatureDegree continues reaction 40min again, until the pressure in Hydrogen Vapor Pressure table and heating reaction furnace is completely in balance; ThisShi Zaici heats up 15 DEG C, and the still ripple disable of Hydrogen Vapor Pressure table shows that in stove, hydrogenation reaches terminal, commonEnter 22.37g hydrogen. Close hydrogen valve, stove cabin temperature is cooled to normal temperature, in cabin, pass into argon gas, at argonUnder gas protection, open hatch door and seal the glass mouth of pipe with rubber stopper rapidly, by the hydrogenation promethium of preparation (now tableFace is the shape of blooming of loosening very much) be put in glove box. In glove box, grind to form fine-powdered thing, to obtain final productTo 1031.89g hydrogenation promethium powder. By this powder carry out vacuum packaging can obtain can safe storage product. The methodThe conversion ratio of preparation hydrogenation promethium is 99.81%, and purity is 99.81%.
Embodiment 23
Having in argon gas glove box, get purity and be 99% 5050g promethium, be placed in quartz glass tube, use rubberPlug seals the mouth of pipe. Glass tube is placed in and can be vacuumized and the heating furnace of logical hydrogen, argon gas, pull up rubberPlug is also closed rapidly stove cabin valve, opens vacuum valve, extracts all gas in heating furnace, makes negative pressure be0.015MPa. Be used alternatingly vacuum valve and argon gas valve, repeatedly use after argon cleaning 4 times, close allValve. Rapidly stove cabin temperature is heated to 490 DEG C, opens hydrogen valve, in reacting furnace, input high-purity hydrogen,Controlling hydrogen influx is 4266ml/min, and control programming rate is 8 DEG C/min simultaneously, heats 29min alwaysStop heating up to 705 DEG C, constant hydrogen gas velocity, from hydrogenation starts coreaction 278min, keeps above-mentioned temperatureDegree continues reaction 35min again, until the pressure in Hydrogen Vapor Pressure table and heating reaction furnace is completely in balance; ThisShi Zaici heats up 10 DEG C, and the still ripple disable of Hydrogen Vapor Pressure table shows that in stove, hydrogenation reaches terminal, commonEnter 105.89g hydrogen. Close hydrogen valve, stove cabin temperature is cooled to normal temperature, in cabin, pass into argon gas,Under argon shield, open hatch door and seal the glass mouth of pipe with rubber stopper rapidly, by the hydrogenation promethium of preparation (nowSurface is the very loose shape of blooming) be put in glove box. In glove box, grind to form fine-powdered thing,Obtain 5154.41 hydrogenation promethium powder. By this powder carry out vacuum packaging can obtain can safe storage product. The partyLegal system is 99.87% for the conversion ratio of hydrogenation promethium, and purity is 99.88%.
Embodiment 23
In the glove box that is filled with argon shield, the block samarium of the 520g that is 99% by purity is placed in quartz ampoule alsoSeal with rubber stopper. Quartz ampoule is placed in to stove cabin and is full of the heating furnace of argon gas, heating furnace with vacuum valve,Hydrogen valve, argon gas valve. Pull up rubber stopper and close rapidly heating furnace cabin valve, opening vacuum valve,By stove cabin internal pressure extract to negative pressure be 0.025MPa. Open argon gas valve, again vacuumize after passing into argon gas,Repeatedly use argon cleaning 2 times, close all valves. Rapidly stove cabin temperature is heated to 450 DEG C, opens hydrogenValve is inputted high-purity hydrogen in reacting furnace, and controlling hydrogen influx is 898ml/min, controls and heats up simultaneouslySpeed is 13 DEG C/min, heats 15min to 585 DEG C always and stops heating up, and constant hydrogen gas velocity, from hydrogenationStart after coreaction 148min, keep said temperature to continue again to react 32min, until Hydrogen Vapor Pressure table with addPressure in thermal response stove is completely in balance; Now again heat up 25 DEG C, the still ripple disable of Hydrogen Vapor Pressure table,Show in stove that hydrogenation reaches terminal, common enter 11.87g hydrogen. Close hydrogen valve, by stove cabin temperatureBe cooled to normal temperature, under argon shield, open hatch door, seal the quartzy mouth of pipe with rubber stopper rapidly, take out stoneEnglish pipe is placed in glove box. (now surface is highly brittle firmly the hydrogenation samarium of preparation, and breach is a lot, is the shape of bloomingShape) in glove box, take out. In glove box, grind to form fine-powdered thing, obtain 530.36g hydrogenation samarium powder.By this powder carry out vacuum packaging can obtain can safe storage product. The conversion ratio that the method is prepared hydrogenation samarium is99.87%, purity is 99.87%.
Embodiment 24
In the glove box that is filled with argon shield, the block samarium of the 397g that is 99% by purity is placed in quartz ampoule alsoSeal with rubber stopper. Quartz ampoule is placed in to stove cabin and is full of the heating furnace of argon gas, heating furnace with vacuum valve,Hydrogen valve, argon gas valve. Pull up rubber stopper and close rapidly heating furnace cabin valve, opening vacuum valve,By stove cabin internal pressure extract to negative pressure be 0.028MPa. Open argon gas valve, again vacuumize after passing into argon gas,Repeatedly use argon cleaning 2 times, close all valves. Rapidly stove cabin temperature is heated to 435 DEG C, opens hydrogenValve is inputted high-purity hydrogen in reacting furnace, and controlling hydrogen influx is 864ml/min, controls and heats up simultaneouslySpeed is 15 DEG C/min, heats 12min to 582 DEG C always and stops heating up, and constant hydrogen gas velocity, from hydrogenationStart after coreaction 122min, keep said temperature to continue again to react 25min, until Hydrogen Vapor Pressure table with addPressure in thermal response stove is completely in balance; Now again heat up 28 DEG C, the still ripple disable of Hydrogen Vapor Pressure table,Show in stove that hydrogenation reaches terminal, common enter 9.42g hydrogen. Close hydrogen valve, by stove cabin temperatureBe cooled to normal temperature, under argon shield, open hatch door, seal the quartzy mouth of pipe with rubber stopper rapidly, take out stoneEnglish pipe is placed in glove box. (now surface is highly brittle firmly the hydrogenation samarium of preparation, and breach is a lot, is the shape of bloomingShape) in glove box, take out. In glove box, grind to form fine-powdered thing, obtain 404.91g hydrogenation samarium powder.By this powder carry out vacuum packaging can obtain can safe storage product. The conversion ratio that the method is prepared hydrogenation samarium is99.84%, purity is 99.85%.
Embodiment 25
In the glove box that is filled with argon shield, the block samarium of the 1009g that is 99% by purity is placed in quartz ampoule alsoSeal with rubber stopper. Quartz ampoule is placed in to stove cabin and is full of the heating furnace of argon gas, heating furnace with vacuum valve,Hydrogen valve, argon gas valve. Pull up rubber stopper and close rapidly heating furnace cabin valve, opening vacuum valve,By stove cabin internal pressure extract to negative pressure be 0.020MPa. Open argon gas valve, again vacuumize after passing into argon gas,Repeatedly use argon cleaning 3 times, close all valves. Rapidly stove cabin temperature is heated to 458 DEG C, opens hydrogenValve is inputted high-purity hydrogen in reacting furnace, and controlling hydrogen influx is 1180ml/min, controls and rises simultaneouslyTemperature speed is 10 DEG C/min, heats 16min to 595 DEG C always and stops heating up, and constant hydrogen gas velocity, from addingHydrogen starts after coreaction 193min, keep said temperature continue again to react 35min, until Hydrogen Vapor Pressure table withPressure in heating reaction furnace is completely in balance; Now again heat up 15 DEG C, Hydrogen Vapor Pressure table is still calmMoving, show that in stove, hydrogenation reaches terminal, common enter 21.61g hydrogen. Close hydrogen valve, by stove cabinTemperature is cooled to normal temperature, under argon shield, opens hatch door, seals the quartzy mouth of pipe rapidly with rubber stopper, getsGoing out quartz ampoule is placed in glove box. (now surface is highly brittle firmly the hydrogenation samarium of preparation, and breach is a lot, for openingFlower shape) in glove box, take out. In glove box, grind to form fine-powdered thing, obtain 1029.10g hydrogenationSamarium powder. By this powder carry out vacuum packaging can obtain can safe storage product. The method is prepared turning of hydrogenation samariumRate is 99.88%, and purity is 99.88%.
Embodiment 26
In the glove box that is filled with argon shield, the block samarium of the 4300g that is 99% by purity is placed in quartz ampoule alsoSeal with rubber stopper. Quartz ampoule is placed in to stove cabin and is full of the heating furnace of argon gas, heating furnace with vacuum valve,Hydrogen valve, argon gas valve. Pull up rubber stopper and close rapidly heating furnace cabin valve, opening vacuum valve,By stove cabin internal pressure extract to negative pressure be 0.015MPa. Open argon gas valve, again vacuumize after passing into argon gas,Repeatedly use argon cleaning 4 times, close all valves. Rapidly stove cabin temperature is heated to 447 DEG C, opens hydrogenValve is inputted high-purity hydrogen in reacting furnace, and controlling hydrogen influx is 4207ml/min, controls and rises simultaneouslyTemperature speed is 8 DEG C/min, heats 23min to 605 DEG C always and stops heating up, and constant hydrogen gas velocity, from hydrogenationStart after coreaction 232min, keep said temperature to continue again to react 40min, until Hydrogen Vapor Pressure table with addPressure in thermal response stove is completely in balance; Now again heat up 10 DEG C, the still ripple disable of Hydrogen Vapor Pressure table,Show in stove that hydrogenation reaches terminal, common enter 87.14g hydrogen. Close hydrogen valve, by stove cabin temperatureBe cooled to normal temperature, under argon shield, open hatch door, seal the quartzy mouth of pipe with rubber stopper rapidly, take out stoneEnglish pipe is placed in glove box. (now surface is highly brittle firmly the hydrogenation samarium of preparation, and breach is a lot, is the shape of bloomingShape) in glove box, take out. In glove box, grind to form fine-powdered thing, obtain 4385.63g hydrogenation samarium powder.By this powder carry out vacuum packaging can obtain can safe storage product. The conversion ratio that the method is prepared hydrogenation samarium is99.83%, purity is 99.84%.
Embodiment 27
In the glove box that is filled with argon shield, the block samarium of the 804g that is 99% by purity is placed in quartz ampoule alsoSeal with rubber stopper. Quartz ampoule is placed in to stove cabin and is full of the heating furnace of argon gas, heating furnace with vacuum valve,Hydrogen valve, argon gas valve. Pull up rubber stopper and close rapidly heating furnace cabin valve, opening vacuum valve,By stove cabin internal pressure extract to negative pressure be 0.018MPa. Open argon gas valve, again vacuumize after passing into argon gas,Repeatedly use argon cleaning 3 times, close all valves. Rapidly stove cabin temperature is heated to 320 DEG C, opens hydrogenValve is inputted high-purity hydrogen in reacting furnace, and controlling hydrogen influx is 750ml/min, controls and heats up simultaneouslySpeed is 6 DEG C/min, heats 22min to 405 DEG C always and stops heating up, and constant hydrogen gas velocity, opens from hydrogenationAfter beginning coreaction 182min, keep said temperature to continue again to react 25min, until Hydrogen Vapor Pressure table and heatingPressure in reacting furnace is completely in balance; Now again heat up 5 DEG C, the still ripple disable of Hydrogen Vapor Pressure table, tableHydrogenation reaches terminal in open oven, common enter 12.19g hydrogen. Close hydrogen valve, by cold stove cabin temperatureBut to normal temperature, under argon shield, open hatch door, seal the quartzy mouth of pipe with rubber stopper rapidly, take out quartzPipe is placed in glove box. (now surface is highly brittle firmly the divalence hydrogenation samarium of preparation, and breach is a lot, for bloomingShape) in glove box, take out. In glove box, grind to form fine-powdered thing, obtain 814.68g diatomic hydrogenChange samarium powder. By this powder carry out vacuum packaging can obtain can safe storage product. The method is prepared divalence hydrogenationThe conversion ratio of samarium is 99.89%, and purity is 99.89%.
Embodiment 28
In the glove box that is full of argon gas, the block europium of the 400g that is 99% by purity is loaded in quartz ampoule, and usesRubber stopper sealing orifice. Quartz ampoule is placed in to the heating furnace with vacuum valve, hydrogen valve, argon gas valve,Stove cabin is full of argon gas. Take off rubber stopper rapid closing chamber valve, open vacuum valve, simultaneously in stove cabinAll gas extract out, to negative pressure be 0.022MPa. Open argon gas valve, after argon gas is full of, again vacuumize,Repeatedly operate after 2 times, close all valves. Rapidly stove cabin temperature is heated to 368 DEG C, to defeated in reacting furnaceEnter high-purity hydrogen, controlling hydrogen influx is 370ml/min, and control programming rate is 7 DEG C/min simultaneously, oneDirectly heat 29min to 539 DEG C and stop heating up, constant hydrogen gas velocity, from hydrogenation starts coreaction 166min,Keep said temperature to continue again to react 34min, until the pressure in Hydrogen Vapor Pressure table and heating reaction furnace is located completelyIn balance; Now again heat up 10 DEG C, the still ripple disable of Hydrogen Vapor Pressure table, shows that in stove, hydrogenation reachesTerminal, common enter 6.8g hydrogen. Close hydrogen valve, stove cabin temperature is cooled to normal temperature, in cabin, be full of argonAfter gas, open hatch door, seal the quartzy mouth of pipe with rubber stopper rapidly, take out and be placed in glove box. By quartzDivalence hydrogenation europium (there are a lot of cracks on surface, crisp hard, is the shape of blooming) in pipe takes out in glove box,And grind to form fine-powdered thing, obtain 404.8g divalence hydrogenation europium powder. This powder is carried out to vacuum packaging can be obtainedThe product of energy safe storage. The conversion ratio that the method is prepared divalence hydrogenation europium is 99.87%, and purity is 99.84%.
Embodiment 29
In the glove box that is full of argon gas, the block europium of the 500g that is 99% by purity is loaded in quartz ampoule, and usesRubber stopper sealing orifice. Quartz ampoule is placed in to the heating furnace with vacuum valve, hydrogen valve, argon gas valve,Stove cabin is full of argon gas. Take off rubber stopper rapid closing chamber valve, open vacuum valve, simultaneously in stove cabinAll gas extract out, to negative pressure be 0.025MPa. Open argon gas valve, after argon gas is full of, again vacuumize,Repeatedly operate after 2 times, close all valves. Rapidly stove cabin temperature is heated to 435 DEG C, to defeated in reacting furnaceEnter high-purity hydrogen, controlling hydrogen influx is 972ml/min, and control programming rate is 15 DEG C/min simultaneously,Heat 20min to 650 DEG C always and stop heating up, constant hydrogen gas velocity, starts coreaction 132min from hydrogenationAfter, keep said temperature to continue again to react 30min, until the pressure in Hydrogen Vapor Pressure table and heating reaction furnace is completeEntirely in balance; Now again heat up 20 DEG C, the still ripple disable of Hydrogen Vapor Pressure table, shows hydrogenation in stoveReach terminal, common enter 11.44g hydrogen. Close hydrogen valve, stove cabin temperature is cooled to normal temperature, in cabinBe full of after argon gas, open hatch door, seal the quartzy mouth of pipe with rubber stopper rapidly, take out and be placed in glove box.By the hydrogenation europium in quartz ampoule (now surface is highly brittle firmly, and breach is a lot, is the shape of blooming) at glove boxInterior taking-up, and grind to form fine-powdered thing, obtain 509.98g hydrogenation europium powder. This powder is carried out to vacuum packagingCan obtain the product of energy safe storage. The conversion ratio that the method is prepared hydrogenation europium is 99.95%, and purity is99.95％。
Embodiment 30
In the glove box that is full of argon gas, the block europium of the 1009g that is 99% by purity is loaded in quartz ampoule, and usesRubber stopper sealing orifice. Quartz ampoule is placed in to the heating furnace with vacuum valve, hydrogen valve, argon gas valve,Stove cabin is full of argon gas. Take off rubber stopper rapid closing chamber valve, open vacuum valve, simultaneously in stove cabinAll gas extract out, to negative pressure be 0.02MPa. Open argon gas valve, after argon gas is full of, again vacuumize,Repeatedly operate after 2 times, close all valves. Rapidly stove cabin temperature is heated to 395 DEG C, to defeated in reacting furnaceEnter high-purity hydrogen, controlling hydrogen influx is 1415ml/min, and control programming rate is 12 DEG C/min simultaneously,Heat 26min to 635 DEG C always and stop heating up, constant hydrogen gas velocity, starts coreaction 171min from hydrogenationAfter, keep said temperature to continue again to react 40min, until the pressure in Hydrogen Vapor Pressure table and heating reaction furnace is completeEntirely in balance; Now again heat up 15 DEG C, the still ripple disable of Hydrogen Vapor Pressure table, shows hydrogenation in stoveReach terminal, common enter 21.60g hydrogen. Close hydrogen valve, stove cabin temperature is cooled to normal temperature, in cabinBe full of after argon gas, open hatch door, seal the quartzy mouth of pipe with rubber stopper rapidly, take out and be placed in glove box.By the hydrogenation europium in quartz ampoule (now surface is highly brittle firmly, and breach is a lot, is the shape of blooming) at glove boxInterior taking-up, and grind to form fine-powdered thing, obtain 1029.14g hydrogenation europium powder. This powder is carried out to vacuum packagingCan obtain the product of energy safe storage. The conversion ratio that the method is prepared hydrogenation europium is 99.93%, and purity is99.93％。
Embodiment 31
In the glove box that is full of argon gas, the block europium of the 3000g that is 99% by purity is loaded in quartz ampoule, and usesRubber stopper sealing orifice. Quartz ampoule is placed in to the heating furnace with vacuum valve, hydrogen valve, argon gas valve,Stove cabin is full of argon gas. Take off rubber stopper rapid closing chamber valve, open vacuum valve, simultaneously in stove cabinAll gas extract out, to negative pressure be 0.015MPa. Open argon gas valve, after argon gas is full of, again vacuumize,Repeatedly operate after 2 times, close all valves. Rapidly stove cabin temperature is heated to 377 DEG C, to defeated in reacting furnaceEnter high-purity hydrogen, controlling hydrogen influx is 3054ml/min, and control programming rate is 10 DEG C/min simultaneously,Heat 35min to 648 DEG C always and stop heating up, constant hydrogen gas velocity, starts coreaction 225min from hydrogenationAfter, keep said temperature to continue again to react 38min, until the pressure in Hydrogen Vapor Pressure table and heating reaction furnace is completeEntirely in balance; Now again heat up 5 DEG C, the still ripple disable of Hydrogen Vapor Pressure table, shows that in stove, hydrogenation reachesTo terminal, common enter 61.34g hydrogen. Close hydrogen valve, stove cabin temperature is cooled to normal temperature, in cabin, fillAfter full argon gas, open hatch door, seal the quartzy mouth of pipe with rubber stopper rapidly, take out and be placed in glove box. WillHydrogenation europium (now surface is highly brittle firmly, and breach is a lot, is the shape of blooming) in quartz ampoule is in glove boxTake out, and grind to form fine-powdered thing, obtain 3059.89g hydrogenation europium powder. This powder is carried out to vacuum packaging canObtain the product of energy safe storage. The conversion ratio that the method is prepared hydrogenation europium is 99.94%, and purity is 99.94%.
Embodiment 32
In the glove box that is full of argon gas, the block europium of the 4988g that is 99% by purity is loaded in quartz ampoule, and usesRubber stopper sealing orifice. Quartz ampoule is placed in to the heating furnace with vacuum valve, hydrogen valve, argon gas valve,Stove cabin is full of argon gas. Take off rubber stopper rapid closing chamber valve, open vacuum valve, simultaneously in stove cabinAll gas extract out, to negative pressure be 0.010MPa. Open argon gas valve, after argon gas is full of, again vacuumize,Repeatedly operate after 2 times, close all valves. Rapidly stove cabin temperature is heated to 368 DEG C, to defeated in reacting furnaceEnter high-purity hydrogen, controlling hydrogen influx is 4025ml/min, and control programming rate is 8 DEG C/min simultaneously,Heat 38min to 636 DEG C always and stop heating up, constant hydrogen gas velocity, starts coreaction 281min from hydrogenationAfter, keep said temperature to continue again to react 45min, until the pressure in Hydrogen Vapor Pressure table and heating reaction furnace is completeEntirely in balance; Now again heat up 8 DEG C, the still ripple disable of Hydrogen Vapor Pressure table, shows that in stove, hydrogenation reachesTo terminal, common enter 100.98g hydrogen. Close hydrogen valve, stove cabin temperature is cooled to normal temperature, in cabinBe full of after argon gas, open hatch door, seal the quartzy mouth of pipe with rubber stopper rapidly, take out and be placed in glove box.By the hydrogenation europium in quartz ampoule (now surface is highly brittle firmly, and breach is a lot, is the shape of blooming) at glove boxInterior taking-up, and grind to form fine-powdered thing, obtain 5087.52g hydrogenation europium powder. This powder is carried out to vacuum packagingCan obtain the product of energy safe storage. The conversion ratio that the method is prepared hydrogenation europium is 99.89%, and purity is99.90％。
Embodiment 33
In glove box, the block gadolinium of the 580g that is 99% by purity is loaded in quartz ampoule, and seals pipe with stopperMouthful. Quartz ampoule is placed in and can be vacuumized and the heating furnace of logical hydrogen, argon gas, and stove cabin is full of argon gas.Take off stopper and close rapidly stove cabin. Open vacuum valve, all gas in stove cabin is extracted out, to negative pressure be0.025MPa. Open argon gas valve, after being full of argon gas in stove cabin, again vacuumize, repeatedly operate after 2 times,Close all valves. Under negative pressure state, rapidly stove cabin temperature is heated to 550 DEG C, opens hydrogen valve, toInput high-purity hydrogen in reacting furnace, controlling hydrogen influx is 905ml/min, controls programming rate simultaneously and is15 DEG C/min, heat 15min to 715 DEG C always and stop heating up, constant hydrogen gas velocity, starts anti-altogether from hydrogenationAnswer after 155min, keep said temperature to continue again to react 35min, until Hydrogen Vapor Pressure table and heating reaction furnaceInterior pressure is completely in balance; Now again heat up 25 DEG C, the still ripple disable of Hydrogen Vapor Pressure table, shows stoveInterior hydrogenation reaches terminal, common enter 12.52g hydrogen. Close hydrogen valve, stove cabin temperature is cooled toNormal temperature, is full of in cabin after argon gas, opens hatch door, seals the quartzy mouth of pipe rapidly with stopper, takes out and be placed in handIn casing. By the hydrogenation gadolinium in quartz ampoule (now surface is highly brittle firmly, and breach is a lot, is the shape of blooming)In glove box, take out, and grind to form fine-powdered thing, obtain 591.03g hydrogenation gadolinium powder. This powder is carried outVacuum packaging can obtain the product of energy safe storage. The conversion ratio that the method is prepared hydrogenation gadolinium is 99.70%, pureDegree is 99.71%.
Embodiment 34
In glove box, the block gadolinium of the 600g that is 99% by purity is loaded in quartz ampoule, and seals pipe with stopperMouthful. Quartz ampoule is placed in and can be vacuumized and the heating furnace of logical hydrogen, argon gas, and stove cabin is full of argon gas.Take off stopper and close rapidly stove cabin. Open vacuum valve, all gas in stove cabin is extracted out, to negative pressure be0.025MPa. Open argon gas valve, after being full of argon gas in stove cabin, again vacuumize, repeatedly operate after 2 times,Close all valves. Under negative pressure state, rapidly stove cabin temperature is heated to 551 DEG C, opens hydrogen valve, toInput high-purity hydrogen in reacting furnace, controlling hydrogen influx is 963ml/min, controls programming rate simultaneously and is13 DEG C/min, heat 17min to 752 DEG C always and stop heating up, constant hydrogen gas velocity, starts anti-altogether from hydrogenationAnswer after 172min, keep said temperature to continue again to react 30min, until Hydrogen Vapor Pressure table and heating reaction furnaceInterior pressure is completely in balance; Now again heat up 15 DEG C, the still ripple disable of Hydrogen Vapor Pressure table, shows stoveInterior hydrogenation reaches terminal, common enter 14.78g hydrogen. Close hydrogen valve, stove cabin temperature is cooled toNormal temperature, is full of in cabin after argon gas, opens hatch door, seals the quartzy mouth of pipe rapidly with stopper, takes out and be placed in handIn casing. By the hydrogenation gadolinium in quartz ampoule (now surface is highly brittle firmly, and breach is a lot, is the shape of blooming)In glove box, take out, and grind to form fine-powdered thing, obtain 712.30g hydrogenation gadolinium powder. This powder is carried outVacuum packaging can obtain the product of energy safe storage. The conversion ratio that the method is prepared hydrogenation gadolinium is 99.71%, pureDegree is 99.72%.
Embodiment 35
In glove box, the block gadolinium of the 2008g that is 99% by purity is loaded in quartz ampoule, and seals pipe with stopperMouthful. Quartz ampoule is placed in and can be vacuumized and the heating furnace of logical hydrogen, argon gas, and stove cabin is full of argon gas.Take off stopper and close rapidly stove cabin. Open vacuum valve, all gas in stove cabin is extracted out, to negative pressure be0.020MPa. Open argon gas valve, after being full of argon gas in stove cabin, again vacuumize, repeatedly operate after 3 times,Close all valves. Under negative pressure state, rapidly stove cabin temperature is heated to 583 DEG C, opens hydrogen valve, toInput high-purity hydrogen in reacting furnace, controlling hydrogen influx is 2543ml/min, controls programming rate simultaneously and is10 DEG C/min, heat 24min to 781 DEG C always and stop heating up, constant hydrogen gas velocity, starts anti-altogether from hydrogenationAnswer after 175min, keep said temperature to continue again to react 20min, until Hydrogen Vapor Pressure table and heating reaction furnaceInterior pressure is completely in balance; Now again heat up 10 DEG C, the still ripple disable of Hydrogen Vapor Pressure table, shows stoveInterior hydrogenation reaches terminal, common enter 39.73g hydrogen. Close hydrogen valve, stove cabin temperature is cooled toNormal temperature, is full of in cabin after argon gas, opens hatch door, seals the quartzy mouth of pipe rapidly with stopper, takes out and be placed in handIn casing. By the hydrogenation gadolinium in quartz ampoule (now surface is highly brittle firmly, and breach is a lot, is the shape of blooming)In glove box, take out, and grind to form fine-powdered thing, obtain 2046.24g hydrogenation gadolinium powder. This powder is carried outVacuum packaging can obtain the product of energy safe storage. The conversion ratio that the method is prepared hydrogenation gadolinium is 99.83%, pureDegree is 99.83%.
Embodiment 36
In glove box, the block gadolinium of the 5080g that is 99% by purity is loaded in quartz ampoule, and seals pipe with stopperMouthful. Quartz ampoule is placed in and can be vacuumized and the heating furnace of logical hydrogen, argon gas, and stove cabin is full of argon gas.Take off stopper and close rapidly stove cabin. Open vacuum valve, all gas in stove cabin is extracted out, to negative pressure be0.015MPa. Open argon gas valve, after being full of argon gas in stove cabin, again vacuumize, repeatedly operate after 4 times,Close all valves. Under negative pressure state, rapidly stove cabin temperature is heated to 570 DEG C, opens hydrogen valve, toInput high-purity hydrogen in reacting furnace, controlling hydrogen influx is 4491ml/min, controls programming rate simultaneously and is8 DEG C/min, heat 30min to 780 DEG C always and stop heating up, constant hydrogen gas velocity, starts anti-altogether from hydrogenationAnswer after 245min, keep said temperature to continue again to react 25min, until Hydrogen Vapor Pressure table and heating reaction furnaceInterior pressure is completely in balance; Now again heat up 5 DEG C, the still ripple disable of Hydrogen Vapor Pressure table, shows in stoveHydrogenation reaches terminal, common enter 98.25g hydrogen. Close hydrogen valve, stove cabin temperature is cooled to oftenTemperature, is full of in cabin after argon gas, opens hatch door, seals the quartzy mouth of pipe rapidly with stopper, takes out and be placed in glovesIn case. Hydrogenation gadolinium in quartz ampoule (now surface is highly brittle firmly, and breach is a lot, is the shape of blooming) is existedIn glove box, take out, and grind to form fine-powdered thing, obtain 5176.76g hydrogenation gadolinium powder. This powder is carried out veryEmpty package can obtain the product of energy safe storage. The conversion ratio that the method is prepared hydrogenation gadolinium is 99.84%, purityBe 99.85%.
Claims (2)
1. high temperature direct method is prepared a method for light rare earth hydride, it is characterized in that, concrete steps are achieved as follows:
1) under inert gas shielding atmosphere, get purity and be greater than 99%, light rare earth 100～5000g that particle diameter is 2～15mm, is placed in quartz glass test tube, with rubber stopper seal test tube mouth;
2) by the 1st) step test tube is placed in the heating furnace cabin that can vacuumize and be connected with hydrogen and inert gas, takes off rapidly rubber stopper under inert gas atmosphere, closes stove cabin;
3) catch up with in most cabin with inert gas, repeatedly operate 2～10 times, extract gas in heating furnace, reach negative pressure 0.010～0.001MPa, then close evacuating valve;
4) under negative pressure state, heating rate with 2～20 DEG C/min heats stove cabin temperature rapidly, be controlled in 5～60min stove cabin temperature is heated to 200～600 DEG C, open hydrogen valve, in reacting furnace, input high-purity hydrogen, controlling hydrogen influx is 200～10000ml/min, and continuation programming rate is heated to 300～1000 DEG C to be stopped heating up;
5) constant hydrogen gas velocity, since the 4th) after step hydrogenation coreaction 100～500min, keep this temperature to continue again reaction, until the pressure in Hydrogen Vapor Pressure table and heating reaction furnace is completely after balance; Now again heat up 2～50 DEG C, the still ripple disable of Hydrogen Vapor Pressure table, shows that in stove, hydrogenation reaches terminal;
6) when preparation high price rare earth hydride, when the pressure in Hydrogen Vapor Pressure table and heating reaction furnace is completely after balance, again heat up 50～200 DEG C, continue once again inputting hydrogen, Hydrogen Vapor Pressure table still when ripple disable, shows that in stove, high price rare earth hydride hydrogenation reaches high price reaction end;
7) close hydrogen valve, heating furnace cabin temperature is cooled to normal temperature, under inert gas atmosphere, open stove cabin, use rapidly rubber stopper seal test tube mouth, quartz test tube is taken out and is put in the glove box of inert gas shielding;
8) by the 6th or 7) the light rare earth hydride that obtains of step grinds to form fine-powdered thing in the glove box of inert gas shielding; sieve; obtain being separated into the light rare earth hydride powder of required particle diameter; by powder carry out vacuum packaging or other encapsulation can obtain can safe storage product; the conversion ratio that the method is prepared light rare earth hydride powder is 97～99.99%, and light rare earth hydride purity is 97～99.99%.
2. the method for preparing light rare earth hydride according to a kind of high temperature direct method described in claims 1, is characterized in that, the light rare earth hydride of preparation is: dihydro lanthanum (LaH2), lanthanum hydride (LaH3), tetrahydro cerium (CeH4), three hydrogenation cerium (CeH3), dihydro cerium (CeH2), three praseodymium hydride (PrH3), tetrahydro praseodymium (PrH4), three neodymium hydride (NdH3), three hydrogenation promethium (PmH3), dihydro samarium (SmH2), samaric hydride (SmH3), dihydro europium (EuH2), three hydrogenation europium (EuH3), three hydrogenation gadolinium (GdH3)。
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