CN103910373B - A kind of preparation method of cerium hydroxide and system - Google Patents
A kind of preparation method of cerium hydroxide and system Download PDFInfo
- Publication number
- CN103910373B CN103910373B CN201410134846.4A CN201410134846A CN103910373B CN 103910373 B CN103910373 B CN 103910373B CN 201410134846 A CN201410134846 A CN 201410134846A CN 103910373 B CN103910373 B CN 103910373B
- Authority
- CN
- China
- Prior art keywords
- lautertuns
- cerium hydroxide
- filter
- feed liquid
- airtight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Catalysts (AREA)
Abstract
A kind of preparation method of cerium hydroxide, it is characterized in that, taking the cerous carbonate of purity >99.99% as raw material, become cerous nitrate feed liquid with nitric acid dissolve, the removal of impurities that is hydrolyzed in course of dissolution, then carry out at least secondary filter, the filtrate of gained is filtered through accurate filter, proceed to reservoir vessel, leave standstill a couple of days, the general non-rare earth impurity <5ppm of the cerous nitrate feed liquid of gained; The feed liquid having purified is again taking ammoniacal liquor as transforming agent, and hydrogen peroxide is oxidant, through making the transition into cerium hydroxide, through highly basic degree immersion bubble, washing, to remove nitrate anion; Prepared cerium hydroxide is filtered, and filter cake through overheated intermediate water washing, is drained again; Put into baking oven being filtered dry material, through 90-95 DEG C of oven dry a few hours, thereby obtain cerium hydroxide product ultra-pure, superelevation total amount. The cerium hydroxide product that the present invention makes, nitrate anion <500ppm, Purity of Rare Earth >99.99%, general non-rare earth impurity <10ppm, CL-<10ppm，SO4 2-<10ppm, oxygenation efficiency is at 98-99.9%, oxide aggregate >90%.
Description
Technical field
The present invention relates to preparation method and system ultra-pure, superelevation total amount cerium hydroxide, belong to rare earth rawThe hydrometallurgy field of producing.
Background technology
Cerium hydroxide is a kind of important raw material of industry, as colour television flourescent screen additive, and canChange toughness, intensity and other optical properties of fluorescent glass, can also be for the preparation of ammonium ceric nitrate, withAnd other numerous purposes.
International market has proposed more and more higher requirement to the quality of cerium hydroxide, for example: rare earth is pureDegree>99.99%, non-rare earth impurity is general<10ppm, CL-<10ppm，SO4 2-< 10ppm, nitrate anion<2000ppm, the oxide aggregate of cerium hydroxide product>80%, acid-soluble good etc.
But in prior art, the technology of producing cerium hydroxide is difficult to reach so high requirement. EspeciallyThe requirement that is total amount of the rare earth oxide and nitrate anion is difficult to reach.
CN87100620A, CN1075171A, the disclosed production of CN1269327A, CN1048239AThe method of cerium hydroxide is from mishmetal feed liquid, and the cerium hydroxide obtaining is difficult to filter and produceThing purity is low, can carry parcel Na secretly+、Mn2+、SO4 2-With other rare earth impurities etc., make these methodsThe cerium hydroxide purity obtaining is on the low side. Can not be used for the field of having relatively high expectations for product impurity a lot,Such as automobile exhaust purifier, production ammonium ceric nitrate etc.
The disclosed cerium hydroxide preparation method of CN1635169A can improve the quality scale of product, but its productProduct oxygenation efficiency is on the low side, especially Cl-Height, total amount is low, and nitrate anion is high.
In the prior art, the total amount of rare earth of general cerium hydroxide is at 65% left and right, CL-?400-600ppm, nitrate anion is between 2.5-5%, and other non-rare earth impurity is between 100-200ppm.This can not meet domestic and international client's high-end quality requirement completely.
Summary of the invention
The preparation method and the system that the object of this invention is to provide a kind of cerium hydroxide, it can prepare superelevationThe cerium hydroxide of pure, superelevation total amount.
For this reason, according to an aspect of the present invention, provide a kind of preparation method of cerium hydroxide, its spyLevy and be, taking purity 99.99% cerous carbonate is raw material, becomes cerous nitrate feed liquid with nitric acid dissolve, dissolvedThe removal of impurities that is hydrolyzed in journey, then carry out at least secondary filter, the filtrate of gained for example, through (passing through filter pump)Secondary filter, proceeds to reservoir vessel (for example storage tank), leaves standstill a couple of days (for example, about 15 days), the nitric acid of gainedGeneral non-rare earth impurity < the 5ppm of cerium feed liquid; The feed liquid having purified is again taking ammoniacal liquor as transforming agent, hydrogen peroxideFor oxidant, through making the transition into cerium hydroxide, through highly basic degree immersion bubble, washing, to remove nitrate anion;Prepared cerium hydroxide is filtered, and filter cake through overheated intermediate water washing, is drained again; Being filtered dry materialPut into baking oven, dry a few hours (for example 24 hours) through 90-95 DEG C of temperature, thereby obtain ultra-pure, superThe cerium hydroxide product of high total amount.
According to another aspect of the present invention, provide a kind of preparation method of cerium hydroxide, its featureBe, comprise the following steps:
1) by purity > 99.99% cerous carbonate quantitatively drops into reactor, and add nitric acid to dissolve and (dissolvedIn journey, drag for oil); After dissolving completely, regulate pH value to 4.5-5.5, and be adjusted to certain rare with intermediate waterSoil concentration; Heat up, removal of impurities is hydrolyzed;
2) the cerous nitrate feed liquid being hydrolyzed is inserted in the airtight lautertuns of one-level and filtered;
3) filtrate after single filter enters in the airtight lautertuns of secondary again and filters;
4) filtrate after cascade filtration is delivered into memory, through leaving standstill a couple of days, for subsequent use;
5) put into precipitation reaction still by leaving standstill good cerous nitrate feed liquid for subsequent use, stir, regulate with intermediate waterFinite concentration, for subsequent use;
6) under agitation control temperature, add ammoniacal liquor, allow cerous nitrate make the transition into Ce (OH)3, in alkali lyeOH-Ion and cerium ion mol ratio (3.5～4.5): 1;
7) continue at normal temperatures to stir, add hydrogen peroxide, make Ce (OH)3Be oxidized to Ce (OH)4OrCe(OH)3OOH；
8) be warming up to 90-100 DEG C, insulation, makes Ce (OH)3OOH all changes into Ce (OH)4, andUnnecessary hydrogen peroxide is removed;
9) leave standstill, remove supernatant, with the hot ammoniacal liquor stirring of 3-4N concentration, soak several minutes, leave standstill numberMinute, then remove supernatant, to remove nitrate anion;
10) feed liquid is put into lautertuns, with hot intermediate water washing several times, filter, drain;
11) filter cake of draining is proceeded to baking oven, through 90-95 DEG C of constant temperature drying a few hours;
12) material of having dried is sieved, batch mixing, the cerium hydroxide that makes thus ultra-pure, superelevation total amount producesProduct.
Preferably, comprise following technical characterictic at least one of them:
Step 1) in, the input ratio of cerous carbonate and nitric acid is mol ratio 1:3;
Step 1) in, after dissolving completely, regulate pH value to 5;
Step 1) in, the input ratio of intermediate water is for regulating feed liquid rare earth concentration to 1.0-1.5M.
Step 2)-3) in, in the airtight lautertuns of one-level and/or the airtight lautertuns of secondary, be provided with double-layer filter cloth, inBetween cushioning filter paper;
Step 4) in, the filtrate after cascade filtration is delivered into storage vat with secondary filter pump, through leaving standstillMore than 15 days;
Step 5) in, put into precipitation reaction still by leaving standstill good cerous nitrate feed liquid for subsequent use, with agitator stirring,With intermediate water charging point regulate concentration to 0.2-0.4M;
Step 6) in, the temperature of under agitation controlling is (25-30 DEG C), the concentration that adds ammoniacal liquor is a 1.0M left sideRight;
Step 7) in, continue at normal temperatures to stir, add amount and the Ce (OH) of hydrogen peroxide3Amount moleThan being (2-5): 1, make Ce (OH)3Be oxidized to Ce (OH)4Or Ce (OH)3OOH；
Step 8) in, be warming up to 90-100 DEG C, be incubated 1 hour, make Ce (OH)3OOH all transformsBecome Ce (OH)4, and unnecessary hydrogen peroxide is removed;
Step 9) in, leave standstill, remove after supernatant, with the hot ammoniacal liquor stirring of 3-4N concentration, soak 5 pointsClock, then leave standstill 30 minutes, afterwards, then remove supernatant by siphon, to remove nitrate anion;
Step 10) in, feed liquid is put into lautertuns, with hot intermediate water washing two times, filter, drain.
Step 11) in, the filter cake of draining is proceeded to baking oven, 90-95 DEG C of constant temperature drying of process 24 hours;
Step 12) in, by the material of having dried sieve successively, batch mixing, inspection, pack, inspection declaration, warehouse-in,Make thus cerium hydroxide product ultra-pure, superelevation total amount.
According to another aspect of the present invention, provide a kind of preparation system of cerium hydroxide, its featureBe, comprise:
Reactor, its quantitative input port, nitric acid that is provided with high-purity carbonic acid cerium adds entrance, water filling port, heightThe input ratio csr controller of purity cerous carbonate, nitric acid and water;
The airtight lautertuns of one-level, it is arranged on the downstream of reactor, is communicated with reactor;
The airtight lautertuns of secondary, it is arranged on the downstream of the airtight lautertuns of one-level, with the airtight lautertuns of one-levelBe communicated with;
Filtrate memory, its upstream is communicated with by the airtight lautertuns of secondary filter pump and secondary;
Precipitation reaction still, its upstream is communicated with filtrate memory, and this precipitation reaction still has agitator, twoInferior water charging point, ammoniacal liquor injector, hydrogen peroxide injector, the dioxygen water yield and Ce (OH)3The mol ratio of amountController, hydrogen peroxide ejector, hot ammoniacal liquor injector, supernatant remover and ammonia concn controller;
Lautertuns, its upstream is communicated with precipitation reaction still, and this lautertuns has hot intermediate water injector and takes outDry device;
Baking oven, its upstream is communicated with lautertuns, has bake out temperature controller and drying time controller;
Cerium hydroxide product container, its upstream is communicated with baking oven, baking oven and cerium hydroxide product container itBetween be provided with cribellum and blender.
Preferably, reactor is also provided with pH value detector and temperature controller.
Preferably, the airtight lautertuns of one-level comprises double-layer filter cloth and middle cushioning filter paper; And/or secondary is airtightLautertuns comprises double-layer filter cloth and middle cushioning filter paper.
Preferably, filtrate memory is storage vat.
Preferably, when precipitation reaction still is also provided with whipping temp controller, holding temperature controller, insulationBetween controller, soak time controller and/or time of repose controller.
Preferably, hydrogen peroxide ejector and/or supernatant remover are siphon pipes.
Preferably, between blender and cerium hydroxide product container, be also provided with verifying attachment, sack-filling device,Inspection declaration device and cerium hydroxide product collecting device.
The cerium hydroxide product making according to the present invention, purity is high, Purity of Rare Earth > 99.99%, non-rare earth heteroMatter is low, general non-rare earth impurity < 10ppm, CL-<10ppm，SO4 2-<10ppm。
Cerium hydroxide produced according to the invention, particle is large, and shatter value is good, is easy to filtering drying, finalThe cerium hydroxide product granularity obtaining is even, and specific area is large.
Cerium hydroxide produced according to the invention, oxygenation efficiency is high, generally at 98-99.9% (Ce4+/∑Ce)。
The cerium hydroxide product making according to the present invention, oxide aggregate > 90%.
The prepared cerium hydroxide according to the present invention, solubility in acid is good, Yi Rong, and solution is as clear as crystal,Without greasy dirt and insoluble matter.
Nitrate anion < the 500ppm of prepared cerium hydroxide according to the present invention, is far smaller than according to existing skillThe nitrate radical content 2.5-5% of the cerium hydroxide that the nitric acid system of art is produced.
Reaction condition gentleness of the present invention, the reaction time is short, productive rate is high, needed raw material is cheap.
Brief description of the drawings
Fig. 1 is according to the preparation method's of cerium hydroxide of the present invention schematic flow sheet;
Fig. 2 is according to the structure principle chart of the preparation system of cerium hydroxide of the present invention.
Detailed description of the invention
As shown in Figure 1, according to the preparation method of cerium hydroxide of the present invention, with high-purity cerous carbonate (> 99.99%)For raw material, become cerous nitrate feed liquid with nitric acid dissolve, the removal of impurities that is hydrolyzed in course of dissolution, then carry out secondaryFilter, the filtrate of gained, through filter pump secondary filter, proceeds to reservoir vessel (for example storage tank), leaves standstill a couple of days(for example, about 15 days), the general non-rare earth impurity < 5ppm of the cerous nitrate feed liquid of gained.
The feed liquid having purified is again taking ammoniacal liquor as transforming agent, and hydrogen peroxide is oxidant, through making the transition into hydroxideCerium, through highly basic degree liquid washing by soaking, to remove nitrate anion, prepared cerium hydroxide filters, and filter cake is warp againOverheated intermediate water washing, drains, and puts into baking oven being filtered dry material, dry 24 hours through 90-95 DEG C of temperature,Obtain cerium hydroxide product ultra-pure, superelevation total amount.
As shown in Figure 1-2, in one embodiment, comprise according to the preparation method of cerium hydroxide of the present inventionThe following step:
1. by high-purity carbonic acid cerium 1 (> 99.99%) quantitatively drop into reactor 2, add nitric acid 3 to dissolve,In course of dissolution, note dragging for oil, after dissolving completely, (by 3 water fillings of note ammoniacal liquor mouth) regulate pH value to arrive4.5-5.5 (for example 5 left and right), heats up, and removal of impurities is hydrolyzed. The input ratio of high-purity carbonic acid cerium and nitric acid1:3 left and right in molar ratio.
2. the feed liquid (injecting intermediate water by water filling port 4) being hydrolyzed to 1-1.5M (for example regulates feed concentration1 left and right), put into the airtight lautertuns 5 of one-level and filter (preferably, cushioning filter paper in the middle of double-layer filter cloth).
3. the filtrate after single filter enters in the airtight lautertuns 6 of secondary again and filters (preferably, bilayerCushioning filter paper in the middle of filter cloth).
4. the filtrate after cascade filtration (for example using secondary filter pump 7) is delivered into memory 8 (for example storingBucket), leave standstill a couple of days (for example, more than 15 days) through row, for subsequent use.
5. put into precipitation reaction still 9 by leaving standstill good cerous nitrate feed liquid for subsequent use, stir use with agitator 10Intermediate water charging point 11 regulates finite concentration (scope: 0.2-0.4M), for subsequent use.
6. under agitation control certain temperature (25-30 DEG C), add finite concentration by ammoniacal liquor injector 12The ammoniacal liquor of (1.0M left and right), allows cerous nitrate make the transition into Ce (OH) 3, OH-ion and cerium ion in alkali lyeMol ratio (3.5～4.5): 1.
7. continue at normal temperatures to stir, [for example, add a certain amount of hydrogen peroxide by hydrogen peroxide injector 13Add amount and the Ce (OH) of hydrogen peroxide3The mol ratio of amount be (2-5): 1], make Ce (OH)3Be oxidized toCe(OH)4Or Ce (OH)3OOH。
8. be warming up to 90-100 DEG C, insulation a period of time (for example 1 hour), makes Ce (OH)3OOH is completePortion changes into Ce (OH)4, and by hydrogen peroxide ejector 14, unnecessary hydrogen peroxide is removed.
9. leave standstill, for example, remove after supernatant by supernatant remover 16 (siphon pipe), use 3-4N concentrationThe hot ammoniacal liquor that hot ammoniacal liquor injector 15 injects that passes through stir, soak several minutes (for example 5 minutes), more quietPut several minutes (for example 30 minutes), afterwards, then (for example, by siphon) remove supernatant, to remove nitrate anion.
10. feed liquid is put into lautertuns 17, used the hot intermediate water injecting by hot intermediate water injector 18Wash several times (for example two times), filter, drain by draining device 19 again.
The filter cake of draining is proceeded to baking oven 20 by 11., and through 90-95 DEG C of constant temperature drying a few hours, (for example 24 is littleTime).
12. by the material of having dried sieve successively, batch mixing (follow-up inspection, pack, inspection declaration, the warehouse-in of comprising21), make thus cerium hydroxide product ultra-pure, superelevation total amount.
As shown in Figure 2, comprise according to the preparation system of cerium hydroxide of the present invention:
Reactor 2, its quantitative input port 1, nitric acid that is provided with high-purity carbonic acid cerium adds entrance 3, water filling port4, the input ratio csr controller of high-purity carbonic acid cerium, nitric acid and water;
The airtight lautertuns 5 of one-level, it is arranged on the downstream of reactor 2, is communicated with reactor 2;
The airtight lautertuns 6 of secondary, it is arranged on the downstream of the airtight lautertuns 5 of one-level, with the airtight filtration of one-levelGroove 5 is communicated with;
Filtrate memory 8, its upstream is communicated with by the airtight lautertuns 6 of secondary filter pump 7 and secondary;
Precipitation reaction still 9, its upstream is communicated with filtrate memory 8, and this precipitation reaction still 9 has agitator10, intermediate water charging point 11, ammoniacal liquor injector 12, hydrogen peroxide injector 13, the dioxygen water yield and Ce (OH)3Mol ratio controller, hydrogen peroxide ejector 14, hot ammoniacal liquor injector 15, the supernatant remover 16 of amountWith ammonia concn controller;
Lautertuns 17, its upstream is communicated with precipitation reaction still 9, and this lautertuns 17 has hot intermediate water and injectsDevice 18 and drain device 19;
Baking oven 20, its upstream is communicated with lautertuns 17, has bake out temperature controller and drying time controlDevice;
Cerium hydroxide product container 21, its upstream is communicated with baking oven 20, produces at baking oven 20 and cerium hydroxideBetween product container 21, be provided with cribellum and blender.
Preferably, reactor 2 is also provided with pH value detector and temperature controller;
The airtight lautertuns 5 of one-level comprises double-layer filter cloth and middle cushioning filter paper;
The airtight lautertuns 6 of secondary comprises double-layer filter cloth and middle cushioning filter paper;
Filtrate memory 8 is storage vat;
Precipitation reaction still 9 is also provided with whipping temp controller, holding temperature controller, temperature retention time controlDevice, soak time controller and/or time of repose controller;
Hydrogen peroxide ejector 14 and/or supernatant remover 16 are siphon pipes;
Between blender and cerium hydroxide product container 21, be also provided with verifying attachment, sack-filling device, inspection declarationDevice and cerium hydroxide product collecting device.
Example 1:
The cerous carbonate that is 4N by purity adds intermediate water sizes mixing, and with nitric acid dissolve, after hydrolysis is good, is configured toContaining CeO2The feed liquid of 170g/l left and right is carried out secondary filter, forwards storage tank to store with secondary filter pump, leaves standstillAbout 15 days. The feed liquid having left standstill is proceeded to precipitation reaction still, is transferred to concentration 0.2-0.4M with intermediate water,After complete with ammoniacal liquor hydrogen peroxide oxidation transition, about 100 DEG C are incubated one hour, with the hot ammoniacal liquor of 3-5NSoak, reusable heat intermediate water washing 2 times, drains and proceeds to baking oven, and 90-95 DEG C of constant temperature drying a few hours (for example24 hours).
The cerium hydroxide sample oxygenation efficiency that step obtains is thus 99.9%, is soluble in nitric acid, total amount 90.5%,Glassy yellow powder, mobility is fabulous, general non-rare earth impurity < 10ppm, CL-<10ppm，SO4 2-< 10ppm, nitrate anion < 500ppm.
Example 2:
The cerous carbonate that is 4N by purity adds intermediate water sizes mixing, and with nitric acid dissolve, after hydrolysis is good, is configured toContaining CeO2The feed liquid of 170g/l left and right is carried out secondary filter, forwards storage tank to store with secondary filter pump, leaves standstillAbout 15 days. The feed liquid having left standstill is proceeded to precipitation reaction still, is transferred to concentration 0.2-0.4M with intermediate water,After complete with ammoniacal liquor hydrogen peroxide oxidation transition, about 100 DEG C are incubated one hour, directly with hot secondary washingWash 2-3 time, drain and proceed to baking oven, 90-95 DEG C of constant temperature drying a few hours (for example 24 hours).
The cerium hydroxide sample oxygenation efficiency that step obtains is thus 99.9%, is soluble in nitric acid, total amount 90.5%,Glassy yellow powder, mobility is fabulous, general non-rare earth impurity < 10ppm, CL-<10ppm，SO4 2-< 10ppm, but nitrate anion 38000ppm. Do not soak nitrate anion with hot ammonia scrubbing very high.Example 3:
The cerous carbonate that is 4N by purity adds intermediate water sizes mixing, and with nitric acid dissolve, after hydrolysis is good, is configured toContaining CeO2The feed liquid of 170g/l left and right is carried out secondary filter, forwards storage tank to store with secondary filter pump, leaves standstillAbout 15 days. The feed liquid having left standstill is proceeded to precipitation reaction still, is transferred to concentration 0.2-0.4M with intermediate water,After complete with ammoniacal liquor hydrogen peroxide oxidation transition, about 100 DEG C are incubated one hour, with the hot ammoniacal liquor of 3-5NSoak, reusable heat intermediate water washing 2 times, drains and proceeds to baking oven, more than 100 or 100 DEG C constant temperature drying numberHour (for example 24 hours).
The cerium hydroxide sample oxygenation efficiency that step obtains is thus 99.9%, total amount 90.5%, nitric acid dissolveSlightly poor, glassy yellow powder, the mobility of easily reuniting is poor, general non-rare earth impurity < 10ppm, CL-<10ppm，SO4 2-< 10ppm, nitrate anion < 500ppm.
Example 4:
The cerous carbonate that is 4N by purity adds intermediate water sizes mixing, and with nitric acid dissolve, after hydrolysis is good, is configured toContaining CeO2The feed liquid of 170g/l left and right, carries out secondary filter, forwards storage tank to store with secondary filter pump, quietPut about 15 days. The feed liquid having left standstill is proceeded to precipitation reaction still, is transferred to concentration 0.2-0.4M with intermediate water,After complete with ammoniacal liquor hydrogen peroxide oxidation transition, directly soak the washing of reusable heat secondary with the hot ammoniacal liquor of 3-5NWash 2 times, drain and proceed to baking oven, 90-95 DEG C of constant temperature drying a few hours (for example 24 hours).
The cerium hydroxide sample that step obtains is thus due to not through 100 DEG C of left and right insulations in 1 hour, manyRemaining hydrogen peroxide is not discharged, cause being oxidized oxygenation efficiency low < 95%. Be soluble in nitric acid, total amount 90.5%, brightYellow powder, mobility is fabulous, general non-rare earth impurity < 10ppm, CL-<10ppm，SO4 2-<10ppm，Nitrate anion < 500ppm.
Adopt reactor, lautertuns, filter pump, drying baker, the blender that sieves, ICP detector, colorimetricThe testing equipments such as instrument are tested. Result of the test shows:
1. the cerium hydroxide product purity that the present invention makes is high, Purity of Rare Earth > 99.99%. Non-rare earth impurityLow, general non-rare earth impurity < 10ppm, CL-<10ppm，SO4 2-<10ppm。
2. cerium hydroxide produced according to the invention, particle is large, and shatter value is good, is easy to filtering drying,The cerium hydroxide product granularity obtaining is eventually even, and specific area is large.
3. cerium hydroxide produced according to the invention, oxygenation efficiency is high, generally at 98-99.9% (Ce4+/∑Ce)。
4. the cerium hydroxide product making according to the present invention, oxide aggregate > 90%.
5. the prepared cerium hydroxide according to the present invention, solubility in acid is good, Yi Rong, and solution is as clear as crystal,Without greasy dirt and insoluble matter.
6. according to high-end particular/special requirement, nitrate anion is less than 2000ppm, and according to the nitre of prior artThe nitrate anion of the cerium hydroxide that acid system is produced is between 2.5-5%. The prepared cerium hydroxide of the present inventionNitrate anion < 500ppm.
Reaction condition gentleness of the present invention, the reaction time is short, productive rate is high, needed raw material is cheap.
Claims (9)
1. a preparation method for cerium hydroxide, is characterized in that, taking purity > 99.99% cerous carbonate asRaw material, becomes cerous nitrate feed liquid with nitric acid dissolve, the removal of impurities that is hydrolyzed in course of dissolution, and after dissolving completely,Regulate pH value to 4.5-5.5 with ammoniacal liquor; Be adjusted to the rare earth concentration of 1.0-1.5mol/L with intermediate water, heat up,Removal of impurities is hydrolyzed; Carry out again at least secondary filter, the cerous nitrate feed liquid being hydrolyzed is inserted to one-level airtightIn lautertuns, filter; Filtrate after single filter enters in the airtight lautertuns of secondary again and filters;The filtrate of gained, through secondary filter, proceeds to reservoir vessel, leaves standstill a couple of days, the cerous nitrate feed liquid of gainedGeneral non-rare earth impurity < 5ppm; The feed liquid having purified is again taking ammoniacal liquor as transforming agent, and hydrogen peroxide is oxidant,Through making the transition into cerium hydroxide, through highly basic degree soaked with liquid, washing, to remove nitrate anion; To obtainedCerium hydroxide filter, filter cake through the washing of overheated intermediate water, is drained again; Put into baking oven being filtered dry material,Dry a few hours through 90-95 DEG C of temperature, thereby obtain cerium hydroxide product ultra-pure, superelevation total amount.
2. preparation method as claimed in claim 1, is characterized in that, the filtrate of gained is through filter pumpSecondary filter.
3. preparation method as claimed in claim 2, is characterized in that, reservoir vessel is storage tank.
4. preparation method as claimed in claim 2, is characterized in that, leaves standstill 15 days.
5. preparation method as claimed in claim 2, is characterized in that, dries 24 hours.
6. a preparation method for cerium hydroxide, is characterized in that, comprises the following steps:
1) by purity > 99.99% cerous carbonate quantitatively drops into reactor, adds nitric acid to dissolve; DissolveCompletely, regulate pH value to 4.5-5.5 with ammoniacal liquor; The rare earth that is adjusted to 1.0-1.5mol/L with intermediate water is denseDegree, heats up, and removal of impurities is hydrolyzed;
2) the cerous nitrate feed liquid being hydrolyzed is inserted in the airtight lautertuns of one-level and filtered;
3) filtrate after single filter enters in the airtight lautertuns of secondary again and filters;
4) filtrate after cascade filtration is delivered into memory, through leaving standstill a couple of days, for subsequent use;
5) put into precipitation reaction still by leaving standstill good cerous nitrate feed liquid for subsequent use, stir, regulate with intermediate waterFinite concentration, for subsequent use;
6) under agitation control temperature, add ammoniacal liquor, allow cerous nitrate make the transition into Ce (OH)3, in alkali lyeOH-Ion and cerium ion mol ratio (3.5～4.5): 1;
7) continue at normal temperatures to stir, add hydrogen peroxide, make Ce (OH)3Be oxidized to Ce (OH)4OrCe(OH)3OOH；
8) be warming up to 90-100 DEG C, insulation, makes Ce (OH)3OOH all changes into Ce (OH)4, andUnnecessary hydrogen peroxide is removed;
9) leave standstill, remove after supernatant, with the hot ammoniacal liquor stirring of 3-4N concentration, soak several minutes, more quietAfter putting several minutes, then remove supernatant, to remove nitrate anion;
10) feed liquid is put into lautertuns, with hot intermediate water washing several times, filter, drain;
11) filter cake of draining is proceeded to baking oven, through 90-95 DEG C of constant temperature drying a few hours;
12) material of having dried is sieved, batch mixing, the cerium hydroxide that makes thus ultra-pure, superelevation total amount producesProduct.
7. preparation method as claimed in claim 6, is characterized in that, the mistake that adds nitric acid to dissolveIn journey, drag for oil.
8. preparation method as claimed in claim 6, is characterized in that, also comprises following technical characterictic extremelyLack one of them:
Step 1) in, the input ratio of cerous carbonate and nitric acid is mol ratio 1:3;
Step 1) in, after dissolving completely, regulate pH value to 5;
Step 2)-3) in, in the airtight lautertuns of one-level and/or the airtight lautertuns of secondary, be provided with double-layer filter cloth, inBetween cushioning filter paper;
Step 4) in, the filtrate after cascade filtration is delivered into storage vat with secondary filter pump, leave standstill through rowMore than 15 days;
Step 5) in, put into precipitation reaction still by leaving standstill good cerous nitrate feed liquid for subsequent use, with agitator stirring,With intermediate water charging point regulate concentration to 0.2-0.4M;
Step 6) in, the temperature of under agitation controlling is 25-30 DEG C, the concentration that adds ammoniacal liquor is 1.0M;
Step 7) in, add amount and the Ce (OH) of hydrogen peroxide3The mol ratio of amount be (2-5): 1;
Step 8) in, be incubated 1 hour;
Step 9) in, soak 5 minutes, then after leaving standstill 30 minutes, then remove supernatant by siphon,To remove nitrate anion;
Step 10) in, with hot intermediate water washing two times;
Step 11) in, the filter cake of draining is proceeded to baking oven, 90-95 DEG C of constant temperature drying of process 24 hours;
Step 12) in, further the material of having dried is checked successively, pack, inspection declaration, warehouse-in, thus systemObtain cerium hydroxide product ultra-pure, superelevation total amount.
9. a preparation system for cerium hydroxide, is characterized in that, comprising:
Reactor, its quantitative input port, nitric acid that is provided with high-purity carbonic acid cerium adds entrance, water filling port, heightThe input ratio csr controller of purity cerous carbonate, nitric acid and water, reactor is also provided with pH value detector and temperatureDegree controller;
The airtight lautertuns of one-level, it is arranged on the downstream of reactor, is communicated with reactor;
The airtight lautertuns of secondary, it is arranged on the downstream of the airtight lautertuns of one-level, with the airtight lautertuns of one-levelBe communicated with;
Filtrate memory, its upstream is communicated with by the airtight lautertuns of secondary filter pump and secondary;
Precipitation reaction still, its upstream is communicated with filtrate memory, and this precipitation reaction still has agitator, twoInferior water charging point, ammoniacal liquor injector, hydrogen peroxide injector, the dioxygen water yield and Ce (OH)3The mol ratio of amountController, hydrogen peroxide ejector, hot ammoniacal liquor injector, supernatant remover and ammonia concn controller;
Lautertuns, its upstream is communicated with precipitation reaction still, and this lautertuns has hot intermediate water injector and takes outDry device;
Baking oven, its upstream is communicated with lautertuns, has bake out temperature controller and drying time controller;
Cerium hydroxide product container, its upstream is communicated with baking oven, baking oven and cerium hydroxide product container itBetween be provided with cribellum and blender.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410134846.4A CN103910373B (en) | 2014-04-04 | 2014-04-04 | A kind of preparation method of cerium hydroxide and system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410134846.4A CN103910373B (en) | 2014-04-04 | 2014-04-04 | A kind of preparation method of cerium hydroxide and system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103910373A CN103910373A (en) | 2014-07-09 |
| CN103910373B true CN103910373B (en) | 2016-05-18 |
Family
ID=51036429
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410134846.4A Active CN103910373B (en) | 2014-04-04 | 2014-04-04 | A kind of preparation method of cerium hydroxide and system |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103910373B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104925844B (en) * | 2015-06-11 | 2016-08-17 | 乐山沃耐稀电子材料有限公司 | A kind of process for purification of high-purity cerous carbonate |
| CN104961149A (en) * | 2015-07-01 | 2015-10-07 | 乐山沃耐稀电子材料有限公司 | Preparation method of electron-grade ceric ammonium nitrate |
| CN106277022A (en) * | 2016-07-28 | 2017-01-04 | 乐山沃耐稀电子材料有限公司 | A kind of production method of electronic-grade sulfuric acid cerium ammonium |
| CN107043122A (en) * | 2017-05-18 | 2017-08-15 | 赣州晨光稀土新材料股份有限公司 | A kind of continuous method for producing rare earth compound precipitation |
| CN107919482A (en) * | 2017-11-24 | 2018-04-17 | 内蒙古大学 | A kind of directly alcohol fuel battery anode catalyst and preparation method thereof |
| CN110745855A (en) * | 2018-07-04 | 2020-02-04 | 乐山东承新材料有限公司 | Preparation method of high-purity cerium hydroxide |
| CN109234549B (en) * | 2018-10-19 | 2021-09-03 | 包头华美稀土高科有限公司 | Method for separating cerium from water leaching solution |
| CN109761259B (en) * | 2019-03-27 | 2021-04-02 | 淄博加华新材料有限公司 | Preparation method of cerium glue with high gelling property |
| CN109928420B (en) * | 2019-04-11 | 2020-06-16 | 四川沃耐稀新材料科技有限公司 | Production process of electronic grade ammonium ceric nitrate |
| CN114368773B (en) * | 2021-12-09 | 2023-06-02 | 江西师范大学 | Method for preparing cerium oxide nano particles by two-step method |
| CN115367782B (en) * | 2022-08-22 | 2023-08-18 | 吉水金诚新材料加工有限公司 | Method for preparing low-chloride rare earth carbonate |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62191422A (en) * | 1986-02-18 | 1987-08-21 | Mitsubishi Chem Ind Ltd | Production of cerium hydroxide |
| KR20030055505A (en) * | 2001-12-26 | 2003-07-04 | 한국지질자원연구원 | A method for manufacturing of cerium carbonate from the cerium hydroxide |
| CN1635169A (en) * | 2003-12-30 | 2005-07-06 | 北京方正稀土科技研究所有限公司 | Process for preparing cerous hydroxide |
| CN101633516A (en) * | 2008-07-23 | 2010-01-27 | 甘肃稀土新材料股份有限公司 | Preparation method of high-purity cerium hydroxide |
| CN101898780A (en) * | 2009-05-25 | 2010-12-01 | 甘肃稀土新材料股份有限公司 | Production technique of granular crystal cerous nitrate products |
| CN203855423U (en) * | 2014-04-04 | 2014-10-01 | 江西稀有金属钨业控股集团有限公司 | System for preparing cerium hydroxide |
-
2014
- 2014-04-04 CN CN201410134846.4A patent/CN103910373B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62191422A (en) * | 1986-02-18 | 1987-08-21 | Mitsubishi Chem Ind Ltd | Production of cerium hydroxide |
| KR20030055505A (en) * | 2001-12-26 | 2003-07-04 | 한국지질자원연구원 | A method for manufacturing of cerium carbonate from the cerium hydroxide |
| CN1635169A (en) * | 2003-12-30 | 2005-07-06 | 北京方正稀土科技研究所有限公司 | Process for preparing cerous hydroxide |
| CN101633516A (en) * | 2008-07-23 | 2010-01-27 | 甘肃稀土新材料股份有限公司 | Preparation method of high-purity cerium hydroxide |
| CN101898780A (en) * | 2009-05-25 | 2010-12-01 | 甘肃稀土新材料股份有限公司 | Production technique of granular crystal cerous nitrate products |
| CN203855423U (en) * | 2014-04-04 | 2014-10-01 | 江西稀有金属钨业控股集团有限公司 | System for preparing cerium hydroxide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103910373A (en) | 2014-07-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103910373B (en) | A kind of preparation method of cerium hydroxide and system | |
| JP5406386B2 (en) | Method for producing manganese sulfate monohydrate | |
| CN203855423U (en) | System for preparing cerium hydroxide | |
| CN102139927B (en) | High-purity iron oxide black pigment and production method thereof | |
| US3159452A (en) | Process for recovering thorium and rare earth values | |
| CN108423704A (en) | The production method of basic copper chloride | |
| CN105016371B (en) | A kind of preparation method of electronic-grade sulfuric acid height cerium | |
| CN103864099B (en) | The method of comprehensive utilization of a kind of cyanuric acid industrial gaseous waste and waste water | |
| CN106029270A (en) | Method for producing nickel powder | |
| RU2367606C1 (en) | Method for preparation of basic bismuth gallate | |
| CN205709874U (en) | Iron phosphate production system | |
| CN103804172B (en) | A kind of method improving organic acid production quality | |
| CN208032572U (en) | A kind of manganese chloride solution exclusion device | |
| CN107324409A (en) | A kind of method for preparing platinum nitrate solution | |
| CN102633640B (en) | Integrated production technique of acetyl tributyl citrate (ATBC) | |
| CN103012217A (en) | Method for preparing high-purity aminoguanidine bicarbonate | |
| CN106430278B (en) | A kind of preparation method of high-pure anhydrous acetic acid scandium and High-purity Sc Oxide | |
| CN105110353A (en) | Method for carbonizing by-product soda solution used for water treatment by using micro-silicon powder as raw material | |
| CN106478405A (en) | A kind of preparation method of acylate | |
| CN104341289A (en) | Preparation method and system of cerium acetate | |
| CN105648227A (en) | Method for separating antimony and arsenic from antimony and arsenic-containing ash through oxidation and alkaline leaching | |
| CN104928403B (en) | A kind of compound lime emulsifier and its preparation method and application | |
| CN108823410A (en) | A method of feed grade manganese sulfate and recycling lead are prepared with electrolytic zinc anode mud | |
| CN101767837A (en) | Titanium removal method for titanium white byproduct ferrous sulfate | |
| CN104355327A (en) | Preparation method for high-purity lithium carbonate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 330046 No. 118 West Beijing Road, Jiangxi, Nanchang Patentee after: JIANGXI TUNGSTEN HOLDING GROUP CO.,LTD. Address before: 330046 No. 118 West Beijing Road, Jiangxi, Nanchang Patentee before: JIANGXI RARE EARTH & RARE METALS TUNGSTEN GROUP HOLDING Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220215 Address after: 330013 No. 1089, Jingkai Avenue, economic development zone, Nanchang City, Jiangxi Province Patentee after: JIANGXI GOLDEN CENTURY ADVANCED MATERIALS Co.,Ltd. Address before: 330046 No. 118 West Beijing Road, Jiangxi, Nanchang Patentee before: JIANGXI TUNGSTEN HOLDING GROUP CO.,LTD. |