CN106467312A - A kind of purification process of beryllium oxide and its product - Google Patents
A kind of purification process of beryllium oxide and its product Download PDFInfo
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Abstract
The invention discloses a kind of purification process of beryllium oxide and its product, this purification process includes dissolving oxalic acid beryllium oxide, Ba (OH)2Solution processes and is passed through N2And H2The steps such as gaseous mixture calcining.This purification process is conducive to carrying out the protection of beryllium, the healthy of operator and environment will not be threatened, will not introduce new foreign ion.Employ twice desulfurization process simultaneously in this purification process, effectively the sulphur impurity being most difficult in industrial beryllium oxide remove is removed, also have simple to operate, be easier to realize the advantage of industrialized production.The beryllium oxide product that the present invention prepares gained meets core pure level beryllium oxide standard, has wide range of applications.
Description
Technical field
The invention belongs to chemical field is and in particular to a kind of purification process of beryllium oxide and its product.
Background technology
Due to beryllium oxide have the core of uniqueness, heat, electricity, machinery and physicochemical property so that beryllium oxide not
Only can as metallic beryllium, beallon and beryllium oxide ceramics produce raw material, more reactor engineering,
The field such as Aero-Space and electronics industry has and is widely applied.Beryllium in the application of these high-tech sectors,
Only core pure level beryllium oxide can meet technical requirements, therefore the purification of beryllium oxide just become very urgent,
The difficult problem that must solve.
The smelting process of industrial beryllium has two kinds, and one kind is that beryllium ore deposit extracts beryllium after sulfuric acid dissolution, another kind of
It is sodium silicofluoride, sodium carbonate and ferrum fluoric acid sodium to be mixed, sinters, generate the fluorine sodium beryllate of solubility, from
And extract beryllium.The latter is all poisonous due to fluorine, beryllium, and product quality is also worse than sulfuric acid process, therefore leads at present
The beryllium smelting process of stream is sulfuric acid process.Sulfuric acid process smelt beryllium produce beryllium oxide in often contain Al, S,
The impurity such as Si, Fe, Cu.Inherently affected with the downstream product that the beryllium oxide containing these impurity produces containing beryllium
Fusing point containing beryllium components and parts, thermal conductivity, electrical conductivity and mechanical performance.When beryllium is used in reactor, also
The neutron economy of reactor can be affected and strengthen the corrosion to piping material for the MSR.Pure in order to prepare core
The beryllium oxide of level, Bradley Shi Pi industry company of the U.S. (ASFM, 1955) adopts sulfuric acid dissolution beryllium oxide, then
Add excessive ammonium sulfate to make aluminum vitriol ammonium repeat to crystallize, so that very pure beryllium sulfate is crystallized out, will
Beryllium sulfate calcining obtains purer beryllium oxide.The shortcoming of this method is the side using beryllium sulfate calcining
Method, just inevitably has sulfur to remain in beryllium oxide.Be used as smelt beryllium intermediate product,
Wherein there is a certain amount of sulphur impurity residual.Mill Fu Dehawen factory (the Inst.of Min.and of Britain
Metallurgy, 1957) propose to dissolve beryllium hydroxide using caustic soda, then make beryllium hydroxide hydrolysis obtain hydrogen
Beryllium oxide precipitates, and subsequent beryllium hydroxide calcining obtains beryllium oxide.The shortcoming of this method is the purification obtaining
More sodium is contained in product.Therefore, how to remove the impurity in beryllium oxide and have and do not introduce new impurity,
Become the key of purification beryllium oxide.
Content of the invention
The technical problem to be solved is to overcome existing beryllium oxide purification process gained oxygen
The purity changing beryllium is not high, and containing plurality of impurities particularly sulphur impurity, the environmental pollution of purification process is larger,
It is unsuitable for the defects such as industrialized production, there is provided a kind of new beryllium oxide purification process, the method gained oxygen
Change the purity height of beryllium, operating procedure is simple and environmentally-friendly, be suitable to industrialized production.
The inventors discovered that, due to source and the preparation method complex process of beryllium oxide, in beryllium oxide preparation
During impurity, the method for purification preparation being difficult to use for reference existing beryllium oxide meets the beryllium oxide of the pure level of core.
In addition, being also possible to introduce new impurity in the purge process of beryllium oxide.As described in the background art
The purification of existing beryllium oxide, complicated process of preparation are it is difficult to meet the needs of large-scale industrial production.For
Reduce the content of impurity in beryllium oxide, inventor finds can not according to conventional thinking, that is, only from beryllium oxide
Method of purification carry out screening improvement, also need acidic leach condition and follow-up alkali cleaning and calcine technology knot
Unify and consider.A series of technical parameters in beryllium oxide purge process are carried out by the specifically present invention
Analysis and screening：Including to the species of bronsted lowry acids and bases bronsted lowry and the selection of consumption, mixed gas in calcination process
When species, the restriction of the pressure of mixed gas and the mol ratio of gas with various, calcining heat and calcining
Between restriction, and the combination to various technical parameters has carried out meticulous screening, finally achieves gained oxidation
Beryllium purity increases substantially, and impurity content is remarkably decreased, and meets the technique effect of core pure level beryllium oxide standard.
For solving above-mentioned technical problem, one of technical scheme that the present invention takes is：A kind of beryllium oxide pure
Change method, described purification process comprises the following steps：
(1) beryllium oxide is dissolved in oxalic acid solution, is filtrated to get beryllium oxalate solution；By gained oxalic acid
Beryllium solution is mixed with barium hydroxide solution, is filtrated to get beryllium hydroxide precipitation and oxalic acid precipitated barium；
(2) step (1) gained beryllium hydroxide precipitation and barium oxalate are precipitated and dissolved in oxalic acid solution, mistake
Filter obtains beryllium oxalate solution；
(3) by step (2) gained beryllium oxalate solution, evaporative crystallization obtains containing crystallization under vacuum
The beryllium oxalate of water, the beryllium oxalate that gained is contained water of crystallization heats under vacuum, in N2And H2Mixed
Close in gas and calcine, obtain final product.
Wherein step (1) is that beryllium oxide is dissolved in oxalic acid solution, is filtrated to get beryllium oxalate solution；
Gained beryllium oxalate solution is mixed with barium hydroxide solution, is filtrated to get beryllium hydroxide precipitation and barium oxalate sinks
Form sediment.
Wherein said beryllium oxide is preferably 1 with the mol ratio of oxalic acid solution mesoxalic acid:1～1:1.4, more preferably
For 1:1.2～1:1.3 it is therefore preferable to 1:1.2.5, the time of dissolving preferably 25～35 minutes, more preferably
For 28～32 minutes it is therefore preferable to 30 minutes.When described beryllium oxide and oxalic acid solution mesoxalic acid mole
Work as described beryllium oxide than the time of dissolving with the mol ratio of oxalic acid solution mesoxalic acid more than 1:When 1, can lead to
Beryllium oxide excess is it is impossible to reach completely by dissolving oxalic acid；When mol ratio is less than 1:When 1.4, then can lead to grass
Excessive acid is too many, uneconomical.When mol ratio is 1:Both can guarantee that beryllium oxide is fully molten when between 1～1.4
Solution, is unlikely to waste oxalic acid again.
In the production process of beryllium oxide, this area is usually used sulfuric acid dissolution beryllium, the sulphuric acid of generation
Beryllium is calcined through evaporative crystallization again and is obtained beryllium oxide, and the beryllium oxide so obtaining contains more sulphur impurity.For
Purifying beryllium oxide further must select suitably acid to dissolve beryllium oxide.For dissolving oxidation beryllium
The selection one of sour species be that this sour corresponding beryllium salt solubility of requirement is big and evaporative crystallization after beryllium salt
Acid ion can be removed by calcining, and oxalic acid of the present invention can meet this two conditions simultaneously.As
Fruit uses sulphuric acid, then be easily further introduced into sulfur impurity in beryllium oxide, thus cannot purification to prepare core pure
The beryllium oxide of level.
The mol ratio of barium hydroxide in beryllium oxalate in wherein said beryllium oxalate solution and barium hydroxide solution
Preferably 1:1～1:1.5, more preferably for 1:1.2～1:1.4 it is therefore preferable to 1:1.3, the time of described dissolving
Preferably 25～35 minutes, more preferably for 28～32 minutes it is therefore preferable to 30 minutes.The present invention selects
Alkali obtains after inventor carefully selects, and inventor finds can be effective using barium hydroxide
Remove free sulfate ion in beryllium oxide solution, play the technique effect removing sulfate pollution, such as
Fruit is then difficult to remove sulfate ion it is impossible to prepare core pure level beryllium oxide from other alkaline solutions.Work as institute
State the mol ratio of beryllium hydroxide and oxalic acid solution mesoxalic acid and dissolution time is claimed beyond the present invention
It is impossible to the technique effect obtained by obtaining the present invention is it is impossible to prepare core pure level beryllium oxide during scope.
Step (2) is that to be precipitated and dissolved in oxalic acid molten by step (1) gained beryllium hydroxide precipitation and barium oxalate
Liquid, is filtrated to get beryllium oxalate solution.
Beryllium hydroxide in wherein said beryllium hydroxide precipitation is preferable with the mol ratio of oxalic acid solution mesoxalic acid
Ground is 1:1.4～1:1.6, more preferably for 1:1.5, preferably 28～32 minutes time of described dissolving, more
It is 30 minutes goodly.
Step (3) is that evaporative crystallization is contained under vacuum by step (2) gained beryllium oxalate solution
There is the beryllium oxalate of water of crystallization, the beryllium oxalate that gained is contained water of crystallization heats under vacuum, in N2
And H2Calcine in mixed gas, obtain final product.
Preferably 40 DEG C～70 DEG C of the temperature of evaporative crystallization under wherein said vacuum condition, more preferably for
50 DEG C～60 DEG C it is therefore preferable to 55 DEG C；Preferably 110～130 minutes time of described evaporative crystallization,
It it is more preferably 115～125 minutes it is therefore preferable to 120 minutes；The beryllium oxalate that gained is contained water of crystallization exists
Preferably 300 DEG C～450 DEG C of the temperature of heated under vacuum, more preferably for 350 DEG C～420 DEG C, excellent
Selection of land is 400 DEG C；Preferably 110～130 minutes time of described heating, more preferably for 115～125
Minute it is therefore preferable to 120 minutes.N in described mixed gas2And H2Mol ratio be preferably 1:1～1:4,
It is more preferably 1:1.1～1:3 it is therefore preferable to 1:2, the pressure of mixed gas is preferably
0.1Mpa～0.3Mpa, more preferably for 0.15Mpa～0.28Mpa it is therefore preferable to 0.2Mpa, described calcining
Preferably 600 DEG C～1000 DEG C of temperature, more preferably for 700 DEG C～800 DEG C it is therefore preferable to 750 DEG C,
Preferably 2 hours～5 hours time of calcining, more preferably for 2.5 hours～3.5 hours it is therefore preferable to
3 hours.The described beryllium oxalate containing water of crystallization middle evaporative crystallization and the technology ginseng heating under vacuum
During the scope that number is claimed beyond the present invention it is impossible to technique effect obtained by the acquisition present invention it is impossible to
Prepare core pure level beryllium oxide.N of the present invention2And H2The pressure value unit of mixed gas is Mpa,
Mpa is this area routine pressure unit, and the Chinese of this pressure unit is MPa, and full name is MPa this
Card.1 Pascal is exactly 1N/m2.As described N2And H2The mol ratio of mixed gas, pressure value, with
And calcining temperature and time be claimed beyond the present invention scope when it is impossible to acquisition the present invention acquired in
Technique effect it is impossible to prepare core pure level beryllium oxide.
For solving above-mentioned technical problem, the two of the technical scheme that the present invention takes is：One kind is as institute of the present invention
The purification process stating beryllium oxide prepares the beryllium oxide product of gained.
Wherein said beryllium oxide product is the conventional beryllium oxide product in this area, preferably core pure level oxidation
Beryllium, that is, in described beryllium oxide product, impurity content is extremely low, meets the impurity content standard of core pure level beryllium oxide.
This beryllium oxide product poisonous substance impurity content fully meets application in reactor for the beryllium oxide, particularly molten
The application requirement of salt four generations reactor.Therefore, the present invention prepares the beryllium oxide of gained and can be widely applied to fire
Arrow technology, aeronautical technology, nuclear industry technology and high-end beryllium oxide ceramics manufacture field, and its derived product can
Manufacture for beryllium alloy.
On the basis of meeting common sense in the field, above-mentioned each optimum condition, can combination in any, obtain final product this
Bright each preferred embodiments.
Agents useful for same of the present invention and raw material are all commercially available.
The positive effect of the present invention is：
(1) all steps of this purification process are all to carry out in the solution or carry out in vacuum condition,
Be conducive to carrying out the protection of beryllium, the healthy of operator will not be threatened.
(2) this purification process will not introduce new foreign ion.Although making in the operating procedure of alkali cleaning
With Ba (OH)2But, barium ionss can be removed effectively in subsequent operating procedure.
(3) employ twice desulfurization process in this purification process, that is, utilize Ba (OH)2Alkali cleaning and
It is passed through N2And H2Calcined, effectively the sulphur impurity being most difficult in industrial beryllium hydroxide remove removed,
Improve the purity of beryllium oxide, be prepared for core pure level beryllium oxide.
(4) this purification process is simple to operate, is easier to realize industrialized production.
Brief description
Fig. 1 is the beryllium oxide impurity content of gained and core after beryllium oxide purification process of the present invention process
Pure level beryllium oxide impurity content contrast.
Fig. 2 is the pass that in beryllium oxide purification process of the present invention, hydrogen removes reaction energy and temperature in reaction of Salmon-Saxl
System.
Fig. 3 is that in beryllium oxide purification process of the present invention, hydrogen removes reaction constant and temperature in reaction of Salmon-Saxl
Relation.
Fig. 4 is to pass through after oxalic acid and barium hydroxide are processed in beryllium oxide purification process of the present invention again
Sulphur impurity content in beryllium oxide during hydrogen desulfurization and the relation curve of temperature.
Specific embodiment
Mode below by embodiment further illustrates the present invention, but does not therefore limit the present invention to
Among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, according to normal
Rule method and condition, or select according to catalogue.In the present invention, if no special instructions, described room
About 20 DEG C about of temperature, usually 18～25 DEG C of temperature conditionss.If the reagent used in embodiment is not
Plus explanation, it is analytical reagent, buy from Chinese medicines group.
The purification of embodiment 1 beryllium oxide
Take 2.5g BeO, add (concentration is 0.2mol/L), 20 DEG C of dissolvings 25 in 0.5L oxalic acid solution
Minute, after dissolving completely, gained beryllium oxalate solution is filtered, beryllium oxalate solution adds 0.55L Ba after filtering
(OH)2Solution (concentration is 0.2mol/L), 25 minutes, after reaction completely, filters this solution and obtains
Beryllium hydroxide and the mixture of oxalic acid precipitated barium, gained mixture is added 0.6L oxalic acid solution (concentration
For 0.2mol/L), dissolve 30 minutes, dissolving filters gained beryllium oxalate solution completely afterwards, after filtering
Beryllium oxalate solution is put in vacuum drying oven, 45 DEG C of evaporative crystallizations 130 minutes, obtains the oxalic acid containing water of crystallization
Beryllium, this beryllium oxalate containing water of crystallization is heated to 450 DEG C in a vacuum furnace, reacts 120 minutes, to
It is passed through N in vacuum drying oven2、H2Gaseous mixture (wherein N2/H2Mol ratio be 1:1), keep vacuum furnace pressure
Power is 0.15Mpa, keeps temperature of reaction system to be 800 DEG C, reacts 3 hours, after purge process finishes,
Closing vacuum drying oven is cooled to room temperature and obtains final product.Gained beryllium oxide reaches the standard of core pure level beryllium oxide after testing.
The purification of embodiment 2 beryllium oxide
Take 2.5g BeO, add (concentration is 0.2mol/L), 18 DEG C of dissolvings 35 in 0.55L oxalic acid solution
Minute, after dissolving completely, gained beryllium oxalate solution is filtered, beryllium oxalate solution adds 0.6L Ba after filtering
(OH)2Solution (concentration is 0.2mol/L), 25 minutes, after reaction completely, filters this solution and obtains
Beryllium hydroxide and the mixture of oxalic acid precipitated barium, gained mixture is added 0.65L oxalic acid solution (concentration
For 0.2mol/L), dissolve 30 minutes, dissolving filters gained beryllium oxalate solution completely afterwards, after filtering
Beryllium oxalate solution is put in vacuum drying oven, 40 DEG C of evaporative crystallizations 120 minutes, obtains the oxalic acid containing water of crystallization
Beryllium, this beryllium oxalate containing water of crystallization is heated to 300 DEG C in a vacuum furnace, reacts 120 minutes, to
It is passed through N in vacuum drying oven2、H2Gaseous mixture (wherein N2/H2Mol ratio be 1:2), keep vacuum furnace pressure
Power is 0.25Mpa, keeps temperature of reaction system to be 800 DEG C, reacts 2 hours, after purge process finishes,
Closing vacuum drying oven is cooled to room temperature and obtains final product.Gained beryllium oxide reaches the standard of core pure level beryllium oxide after testing.
The purification of embodiment 3 beryllium oxide
Take 2.5g BeO, add (concentration is 0.2mol/L), 25 DEG C of dissolvings 28 in 0.6L oxalic acid solution
Minute, after dissolving completely, gained beryllium oxalate solution is filtered, beryllium oxalate solution adds 0.9L Ba after filtering
(OH)2Solution (concentration is 0.2mol/L), 25 minutes, after reaction completely, filters this solution and obtains
Beryllium hydroxide and the mixture of oxalic acid precipitated barium, gained mixture is added 0.7L oxalic acid solution (concentration
For 0.2mol/L), dissolve 30 minutes, dissolving filters gained beryllium oxalate solution completely afterwards, after filtering
Beryllium oxalate solution is put in vacuum drying oven, 60 DEG C of evaporative crystallizations 120 minutes, obtains the oxalic acid containing water of crystallization
Beryllium, this beryllium oxalate containing water of crystallization is heated to 400 DEG C in a vacuum furnace, reacts 115 minutes, to
It is passed through N in vacuum drying oven2、H2Gaseous mixture (wherein N2/H2Mol ratio be 1:3), keep vacuum furnace pressure
Power is 0.3Mpa, keeps temperature of reaction system to be 600 DEG C, reacts 2.5 hours, after purge process finishes,
Closing vacuum drying oven is cooled to room temperature and obtains final product.Gained beryllium oxide reaches the standard of core pure level beryllium oxide after testing.
The purification of embodiment 4 beryllium oxide
Take 2.5g BeO, add (concentration is 0.2mol/L), 20 DEG C of dissolvings 32 in 0.65L oxalic acid solution
Minute, after dissolving completely, gained beryllium oxalate solution is filtered, beryllium oxalate solution adds 0.7L Ba after filtering
(OH)2Solution (concentration is 0.2mol/L), 28 minutes, after reaction completely, filters this solution and obtains
Beryllium hydroxide and the mixture of oxalic acid precipitated barium, gained mixture is added 0.75L oxalic acid solution (concentration
For 0.2mol/L), dissolve 30 minutes, dissolving filters gained beryllium oxalate solution completely afterwards, after filtering
Beryllium oxalate solution is put in vacuum drying oven, 55 DEG C of evaporative crystallizations 125 minutes, obtains the oxalic acid containing water of crystallization
Beryllium, this beryllium oxalate containing water of crystallization is heated to 350 DEG C in a vacuum furnace, reacts 130 minutes, to
It is passed through N in vacuum drying oven2、H2Gaseous mixture (wherein N2/H2Mol ratio be 1:4), keep vacuum furnace pressure
Power is 0.28Mpa, keeps temperature of reaction system to be 1000 DEG C, reacts 3.5 hours, purge process finishes
Afterwards, closing vacuum drying oven is cooled to room temperature and obtains final product.Gained beryllium oxide reaches the mark of core pure level beryllium oxide after testing
Accurate.
The purification of embodiment 5 beryllium oxide
Take 2.5g BeO, add (concentration is 0.2mol/L) in 0.7L oxalic acid solution, 20 DEG C dissolve 30 points
Gained beryllium oxalate solution is filtered after dissolving completely by clock, and beryllium oxalate solution adds 0.7L Ba (OH) after filtering2Solution (concentration is 0.2mol/L), 32 minutes, after reaction completely, filters this solution and obtains hydroxide
Beryllium and the mixture of oxalic acid precipitated barium, gained mixture is added 0.85L oxalic acid solution, and (concentration is
0.2mol/L), dissolve 28 minutes, gained beryllium oxalate solution is filtered in dissolving completely afterwards, by the grass after filtering
Sour beryllium solution is put in vacuum drying oven, 65 DEG C of evaporative crystallizations 120 minutes, obtains the oxalic acid containing water of crystallization
Beryllium, this beryllium oxalate containing water of crystallization is heated to 450 DEG C in a vacuum furnace, reacts 110 minutes, to
It is passed through N in vacuum drying oven2、H2Gaseous mixture (wherein N2/H2Mol ratio be 1:1.1), keep vacuum furnace pressure
Power is 0.1Mpa, keeps temperature of reaction system to be 950 DEG C, reacts 4 hours, after purge process finishes,
Closing vacuum drying oven is cooled to room temperature and obtains final product.Gained beryllium oxide reaches the standard of core pure level beryllium oxide after testing.
The purification of embodiment 6 beryllium oxide
Take 2.5g BeO, add (concentration is 0.2mol/L), 20 DEG C of dissolvings 30 in 0.65L oxalic acid solution
Minute, after dissolving completely, gained beryllium oxalate solution is filtered, beryllium oxalate solution adds 0.7L Ba after filtering
(OH)2Solution (concentration is 0.2mol/L), 30 minutes, after reaction completely, filters this solution and obtains
Beryllium hydroxide and the mixture of oxalic acid precipitated barium, gained mixture is added 0.8L oxalic acid solution (concentration
For 0.2mol/L), dissolve 32 minutes, dissolving filters gained beryllium oxalate solution completely afterwards, after filtering
Beryllium oxalate solution is put in vacuum drying oven, 50 DEG C of evaporative crystallizations 125 minutes, obtains the grass containing water of crystallization
Sour beryllium, this beryllium oxalate containing water of crystallization is heated to 420 DEG C in a vacuum furnace, reacts 125 minutes,
It is passed through N in vacuum drying oven2、H2Gaseous mixture (wherein N2/H2Mol ratio be 1:2), keep vacuum drying oven
Pressure is 0.18Mpa, keeps temperature of reaction system to be 700 DEG C, reacts 3 hours, purge process finishes
Afterwards, closing vacuum drying oven is cooled to room temperature and obtains final product.Gained beryllium oxide reaches the mark of core pure level beryllium oxide after testing
Accurate.
The purification of embodiment 7 beryllium oxide
Take 2.5g BeO, add (concentration is 0.2mol/L), 20 DEG C of dissolvings 35 in 0.6L oxalic acid solution
Minute, after dissolving completely, gained beryllium oxalate solution is filtered, beryllium oxalate solution adds 0.65L Ba after filtering
(OH)2Solution (concentration is 0.2mol/L), 35 minutes, after reaction completely, filters this solution and obtains
Beryllium hydroxide and the mixture of oxalic acid precipitated barium, gained mixture is added 0.75L oxalic acid solution (concentration
For 0.2mol/L), dissolve 30 minutes, dissolving filters gained beryllium oxalate solution completely afterwards, after filtering
Beryllium oxalate solution is put in vacuum drying oven, 70 DEG C of evaporative crystallizations 110 minutes, obtains the oxalic acid containing water of crystallization
Beryllium, this beryllium oxalate containing water of crystallization is heated to 380 DEG C in a vacuum furnace, reacts 120 minutes, to
It is passed through N in vacuum drying oven2、H2Gaseous mixture (wherein N2/H2Mol ratio be 1:3), keep vacuum furnace pressure
Power is 0.2Mpa, keeps temperature of reaction system to be 880 DEG C, reacts 5 hours, after purge process finishes,
Closing vacuum drying oven is cooled to room temperature and obtains final product.Gained beryllium oxide reaches the standard of core pure level beryllium oxide after testing.
Effect example 1
Example 1 gained beryllium oxide utilizes ICP-OES method to analyze, and result shows, gained beryllium oxide
In impurity content be fully achieved the impurity content standard of core pure level beryllium oxide.Analysis test result such as table 1
With shown in Fig. 1：
The BeO impurity content of table 1 beryllium oxide purification process gained and the contrast of core pure level BeO impurity content
Table 1 and Fig. 1 result show, prepare gained beryllium oxide through beryllium oxide purification process of the present invention
Impurity content be fully achieved the standard of core pure level beryllium oxide, the content of some of them impurity is substantially less than core
The content impurity of pure level beryllium oxide requires, the therefore sub- poisonous substance of the beryllium oxide through gained after this purification process impurity
Content fully meets application in reactor for the beryllium oxide, the particularly application requirement of fused salt four generations reactor.
In addition, gained beryllium oxide also can apply rocketry, aeronautical technology and high-end beryllium oxide ceramics to manufacture field,
Its derived product can be used for the manufacture of beryllium alloy.
Detect that in embodiment of the present invention, hydrogen removes reaction energy and temperature in reaction of Salmon-Saxl, by acquired results profit
Processed with ORIGIN mapping software, show both relations as shown in Fig. 2 as shown in Figure 2, calcining
Temperature is more high more carrying out that be conducive to hydrogen desulphurization reaction.Detection embodiment of the present invention hydrogen removes reaction of Salmon-Saxl
In reaction constant and temperature, by acquired results utilize ORIGIN mapping software process, show the present invention
The relation of neutral temperature as shown in figure 3, as shown in Figure 3 calcining heat raise and often react to a certain extent afterwards
Number tends to constant, and the too high economy being also unfavorable for hydrogen desulfurization of calcining heat, the therefore temperature of calcining
Degree only can be only achieved optimal desulfurized effect in the framework of the present definition.
Detect S impurity content and temperature in embodiment hydrogen desulfurization of the present invention, gained is tied
Fruit utilizes ORIGIN mapping software to process, and the relation obtaining is as shown in figure 4, as shown in Figure 4 at other
In the case of condition identical, calcining heat is higher, is more conducive to the removal of sulphur impurity in beryllium oxide.In conjunction with
The subsequent applications scope of the economy of beryllium oxide purification process and gained beryllium oxide is it was determined that the present invention limits
Fixed calcination temperature range is more suitable hydrogen de-sulfurization temperature range.
Comparative example 1
Take 2.5g BeO, add (concentration is 0.2mol/L) in 2L oxalic acid solution, 40 DEG C dissolve 50 points
Gained beryllium oxalate solution is filtered after dissolving completely by clock, and beryllium oxalate solution adds 0.65L Ba (OH) after filtering2Solution (concentration is 0.2mol/L), 30 minutes, after reaction completely, filters this solution and obtains beryllium hydroxide
With the mixture of oxalic acid precipitated barium, gained mixture is added 0.75L oxalic acid solution, and (concentration is
0.2mol/L), dissolve 30 minutes, gained beryllium oxalate solution is filtered in dissolving completely afterwards, by the grass after filtering
Sour beryllium solution is put in vacuum drying oven, 100 DEG C of evaporative crystallizations 200 minutes, obtains the oxalic acid containing water of crystallization
Beryllium, this beryllium oxalate containing water of crystallization is heated to 380 DEG C in a vacuum furnace, reacts 120 minutes, to
It is passed through N in vacuum drying oven2、H2Gaseous mixture (wherein N2/H2Mol ratio be 1:5), keep vacuum furnace pressure
Power is 0.28Mpa, keeps temperature of reaction system to be 880 DEG C, reacts 4 hours, after purge process finishes,
Closing vacuum drying oven is cooled to room temperature and obtains final product.Gained beryllium oxide does not meet the pure level beryllium oxide of table 1 center after testing
Impurity content standard.Comparative example result shows, when the parameter value of beryllium oxide purification process is not in the present invention
When within the scope of being claimed, the purity of gained beryllium oxide can significantly reduce, and is not inconsistent the oxidation of synkaryon pure level
The impurity content standard of beryllium.
It should be understood that after the above having read the present invention, those skilled in the art can be to this
Bright make various changes or modifications, these equivalent form of values equally fall within the application appended claims and are limited
Scope.
Claims (10)
1. a kind of purification process of beryllium oxide is it is characterised in that described purification process comprises the following steps：
(1) beryllium oxide is dissolved in oxalic acid solution, is filtrated to get beryllium oxalate solution；By gained oxalic acid
Beryllium solution is mixed with barium hydroxide solution, is filtrated to get beryllium hydroxide precipitation and oxalic acid precipitated barium；
(2) step (1) gained beryllium hydroxide precipitation and barium oxalate are precipitated and dissolved in oxalic acid solution, mistake
Filter obtains beryllium oxalate solution；
(3) by step (2) gained beryllium oxalate solution, evaporative crystallization obtains containing crystallization under vacuum
The beryllium oxalate of water, the beryllium oxalate that gained is contained water of crystallization heats under vacuum, in N2And H2Mixed
Close in gas and calcine, obtain final product.
2. the purification process of beryllium oxide as claimed in claim 1 is it is characterised in that step (1) is described
Beryllium oxide is 1 with the mol ratio of oxalic acid solution mesoxalic acid:1～1:1.4, the time of dissolving is 25～35 minutes,
Described beryllium oxalate solution mesoxalic acid beryllium is 1 with the mol ratio of barium hydroxide in barium hydroxide solution:1～1:1.5,
The time of described mixing is 25～35 minutes.
3. the purification process of beryllium oxide as claimed in claim 1 is it is characterised in that step (1) is described
Beryllium oxide is 1 with the mol ratio of oxalic acid solution mesoxalic acid:1.2～1:1.3, the time of dissolving is 28～32 minutes,
Described beryllium oxalate solution mesoxalic acid beryllium is 1 with the mol ratio of barium hydroxide in barium hydroxide solution:1.2～1:1.4,
The time of described mixing is 28～32 minutes.
4. the purification process of beryllium oxide as claimed in claim 2 is it is characterised in that described beryllium oxide one
The mol ratio of oxalic acid solution mesoxalic acid is 1:1.25, the time of dissolving is 30 minutes, described beryllium oxalate solution
Mesoxalic acid beryllium is 1 with the mol ratio of barium hydroxide in barium hydroxide solution:1.3, the time of described mixing is
30 minutes.
5. the purification process of beryllium oxide as claimed in claim 1 is it is characterised in that step (1) is described
Beryllium oxalate solution mesoxalic acid beryllium is 1 with the mol ratio of barium hydroxide in barium hydroxide solution:1～1:1.5, described
The time of mixing is 25～35 minutes.
6. the purification process of beryllium oxide as claimed in claim 1 is it is characterised in that step (2) is described
Beryllium hydroxide in beryllium hydroxide precipitation is 1 with the mol ratio of oxalic acid solution mesoxalic acid:1.4～1:1.6, described
The time of dissolving is 28～32 minutes.
7. the purification process of beryllium oxide as claimed in claim 6 is it is characterised in that described beryllium hydroxide
Beryllium hydroxide in precipitation is 1 with the mol ratio of oxalic acid solution mesoxalic acid:1.5, described dissolution time is 30
Minute.
8. the purification process of beryllium oxide as claimed in claim 1 is it is characterised in that step (3) is described
The temperature of evaporative crystallization is 40 DEG C～70 DEG C, and the time of evaporative crystallization is 110～130 minutes, and gained is contained
The temperature that the beryllium oxalate having water of crystallization heats under vacuum is 300 DEG C～450 DEG C, and the time of heating is
110～130 minutes；N in described mixed gas2And H2Mol ratio be 1:1～1:4, the pressure of mixed gas
Power is 0.1Mpa～0.3Mpa, and the temperature of described calcining is 600 DEG C～1000 DEG C, and the time of calcining is 2
Hour～5 hours.
9. the purification process of beryllium oxide as claimed in claim 1 is it is characterised in that step (3) is described
The temperature of evaporative crystallization is 50 DEG C～60 DEG C, and the time of evaporative crystallization is 115～125 minutes, and gained is contained
The temperature that the beryllium oxalate having water of crystallization heats under vacuum is 350 DEG C～420 DEG C, and the time of heating is
115～125 minutes；N in described mixed gas2And H2Mol ratio be 1:1.1～1:3, mixed gas
Pressure is 0.15Mpa～0.28Mpa, and the temperature of described calcining is 650 DEG C～800 DEG C, and the time of calcining is
2.5 hours～3.5 hours.
10. as described in a kind of any one as claim 1～9, the purification process of beryllium oxide prepares the oxidation of gained
Beryllium product.
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| CN114671444A (en) * | 2022-04-08 | 2022-06-28 | 上海太洋科技有限公司 | Beryllium oxide and preparation method thereof |
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| CN114671444A (en) * | 2022-04-08 | 2022-06-28 | 上海太洋科技有限公司 | Beryllium oxide and preparation method thereof |
| CN114671444B (en) * | 2022-04-08 | 2023-11-07 | 上海太洋科技有限公司 | Beryllium oxide and preparation method thereof |
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