CN102674462B - Ultrasonic microwave hydro-thermal cooperative reinforcing prepares the method and apparatus of high-purity ammonium paratungstate - Google Patents
Ultrasonic microwave hydro-thermal cooperative reinforcing prepares the method and apparatus of high-purity ammonium paratungstate Download PDFInfo
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Abstract
Ultrasonic microwave hydro-thermal cooperative reinforcing prepares the method and apparatus of high-purity ammonium paratungstate.Described equipment comprises magnetic stirring apparatus, microwave generator, ultrasonic generator, there-necked flask, temperature sensor etc.The concrete steps of described method are: by WO
3the ammonium tungstate solution that concentration is not less than 220g/l is placed in there-necked flask, and opens magnetic stirring apparatus, stirs with the stirring velocity of 70-300rpm; Open microwave generator and ultrasonic generator, be 1-3KW with power, microwave frequency is 0.5-1.5Hz, and ultrasonic frequency is the ultrasonic wave of 100-200KHz, microwave hydrothermal mode heats ammonium tungstate solution; Open camera and temperature sensor simultaneously; When Heating temperature reaches 80 DEG C, start hydro-thermal evaporative crystallization, and control temperature is more than 80 DEG C; Crystallization control rate within 65%, i.e. high purity ammonium paratungstate product.Ammonium paratungstate purity prepared by the present invention is high.
Description
Technical field
The present invention relates to the field of preparing ammonium paratungstate, be specially a kind of method and apparatus utilizing ultrasonic microwave hydro-thermal cooperative reinforcing to prepare high-purity ammonium paratungstate.
Background technology
Ammonium paratungstate (APT) is the important intermediate compound producing tungsten powder, tungsten filament, tungsten-bast alloy and all tungsten materials, large exporting of Ye Shi China.Due to genetic affinity, the crystal property of APT is as very big in the material property impact on follow-up powder metallurgy product tungsten powder, tungsten filament and tungstenalloy of crystal morphology, lattice parameter, mean particle size and size-grade distribution, loose specific weight and mobility, thus the exploitation of High Performance W material, proposes more and more higher requirement to the granularity of crystalline product from solution and APT, characteristic such as pine ratio, mobility, crystal morphology and lattice parameter etc.Specific value obtain it is noted that the tungsten powder produced of high homogeneity monocrystalline APT powder due to the defect of material few, compacted density is high, is the excellent material producing high temperature resistance, anti-sagging, Resisting fractre, shock resistance tungsten filament.Main application fields is the products such as high-performance, heavy metal and antidetonation tungsten filament, and miniature drill.In APT micro crystal mass crystallization process, react along with very complicated polymeric chemical, because grain-size is little, quantity is large, Van der Waals force and salt bridge effect remarkable, crystal is very easily reunited, the APT produced both at home and abroad is compound crystal intergrowth, and granularity performance is also difficult to control, the larger production difficulty adding high quality tungsten material.Thus study the preparation technique of high-bed bus, to prepare high performance tungsten powder, Wimet, heavy metal, belong in national economy and social development and need Scientific And Technical Problems in the urgent need to address, have a wide range of applications.
At present, the common traditional technology producing APT by tungsten mineral material is:
1. sheelite and Scheelite-Wolframite Mixed Mine → basic pressure digestion → ion-exchange → evaporative crystallization produce APT.
2. sheelite and Scheelite-Wolframite Mixed Mine → basic pressure digestion → magnesium salts purification → abstraction and type-reverting → evaporative crystallization produce APT.
Its process flow sheet is shown in accompanying drawing 1.In figure, containing the dilution water of inhibitor, described inhibitor is calcium salt, because in low-grade tungsten ore raw material NaOH decomposition course, P, As, Si etc. in raw material are leaching in varying degrees, therefore needs interpolation inhibitor to suppress the leaching of above-mentioned impurity.And after adding the inhibitor of calcium salt, can effectively the form of the impurity such as P, As, Si insoluble calcium salts be suppressed in slag.Parsing agent is NH
4cl+NH
4oH.
As can be seen from Figure, domestic most producer is that the technical process of waste APT exists following problem with tungsten ore:
Remaining alkali l () most producer decomposes after is not recycled, and just adopt the way of simple sour neutralizing treatment when handing over waste liquid discharge after replacement, being both unfavorable for saves production cost turn increases inorganic salt refuse.Only have minority producer by evaporation concentration coarse sodium tungstate, after crystallization sodium wolframate crystal, alkali liquor is returned leaching ore, the base excess of about 80-90% can be recycled.Most producers select the reason not recycling remaining alkali mainly contain following some:
1. the cost reclaiming alkali is high.The general direct energy consumption cost often reclaiming lt alkali is l-1.5 times that alkali itself is worth, and during process low grade ore, the production cost of unit product also can rise at double, and most producer is difficult to accept.
2., when processing low grade ore or complicated ore, bubbling because the beneficiation reagent brought in raw material can cause during evaporation concentration, production can be caused time serious to carry out, add the difficulty of operation.
3. the sodium wolframate crystal of crystallization and alkali separation difficulty, higher to the requirement of equipment, adds the maintenance of more facility investment and equipment, running cost simultaneously.
4. add treatment process, the labour intensity of workman increases.
(2) precipitation except aluminium process employ costly containing α-benzoinoxime, when processing high aluminium ore, production cost is high.The aluminium of association in tungsten ore more than 90% to be leached when decomposing simultaneously, general industry produce in by the precipitator method except aluminium time, often precipitate 1kgMO and need consume metallic copper 2-3kg.
In sum, there is remaining alkali and be difficult to reclaim in the current Tungsten smelting flow process generally adopted, and removes phase cost high deficiency when processing high aluminium ore, needs to be improved.
In addition, the high-purity ammonium paratungstate foreign matter content that the existing method and apparatus preparing high-purity ammonium paratungstate is produced is all higher, produces the requirement not reaching high-purity ammonium paratungstate, and therefore needing provides a kind of better preparation method and equipment.
Summary of the invention
Technical problem solved by the invention is to provide a kind of ultrasonic microwave hydro-thermal cooperative reinforcing to prepare the method and apparatus of high-purity ammonium paratungstate, to solve the problem in above-mentioned background technology.
Technical problem solved by the invention realizes by the following technical solutions:
Ultrasonic microwave hydro-thermal cooperative reinforcing prepares the equipment of high-purity ammonium paratungstate, i.e. crystallizer, it comprises microwave oven, described microwave oven comprises fire door, body of heater and door open button, magnetic stirring apparatus, microwave generator and fault detection module is provided with in described body of heater, be provided with pallet in the inner chamber of body of heater, there-necked flask placed by the pressure transmitter that pallet is arranged, the sensor socket on described intracavity sidewall connects temperature sensor; The mount pad at described body of heater top is provided with ultrasonic generator and two-way Glass tubing, described ultrasonic generator upper end connects water inlet pipe and rising pipe respectively, and lower end connects titanium alloy probe; Titanium alloy probe and temperature sensor are all fixed on there-necked flask inside, and two-way Glass tubing lower end connects a side mouth of there-necked flask; Described temperature sensor is connected rly. with pressure transmitter by transmitter, and rly. connects ultrasonic generator and microwave generator respectively, and described microwave generator connects fault detection module, and the fault detection module the other end connects rly..
Described body of heater is also provided with USB interface and liquid crystal display.
Described intracavity sidewall is provided with camera, and camera connects rly..
Described temperature sensor is fixedly connected with another side mouth of there-necked flask by silica gel bottle stopper.
Described titanium alloy probe is fixedly connected with the intermediate openings of there-necked flask by tetrafluoroethylene bottle stopper.
Ultrasonic microwave hydro-thermal cooperative reinforcing prepares the method for high-purity ammonium paratungstate, and concrete steps are as follows:
(1) by WO
3the ammonium tungstate solution that concentration is not less than 220g/l is placed in there-necked flask, and opens magnetic stirring apparatus, stirs with the stirring velocity of 70-300rpm;
(2) open microwave generator and ultrasonic generator, be 1-3KW with power, microwave frequency is 0.5-1.5Hz, and ultrasonic frequency is the ultrasonic wave of 100-200KHz, microwave hydrothermal mode heats ammonium tungstate solution;
(3) open camera and temperature sensor simultaneously;
(4) when Heating temperature reaches 80 DEG C, start hydro-thermal evaporative crystallization, and control temperature is more than 80 DEG C;
(5) crystallization control rate is within 65%, i.e. high purity ammonium paratungstate product.
In the preparation technology of the middle ammonium tungstate solution of step (1), the method for caustic digestion and remaining alkali collection is: the slip after leaching is not diluted direct filtration and first reclaims alkali lye, residue and sodium wolframate are all stayed in solid phase, then realizes being separated of slag and tungsten by dissolving sodium wolframate with the wash water containing calcium salt inhibitor.
The method that in the preparation technology of the middle ammonium tungstate solution of step (1), tungsten is separated is: first soak molybdenum slag ammonia, refilter recovery copper ashes, then by copper ashes with containing adding precipitation together with α-benzoinoxime except in the technique of molybdenum, the percentage composition wherein accounting for gross weight containing α-benzoinoxime is 1% ~ 3%.
beneficial effect:the invention solves the problem that the current remaining alkali of Tungsten smelting flow process existence generally adopted is difficult to reclaim, and remove phase cost high deficiency when processing high aluminium ore.Provide a kind of method and apparatus preparing high-purity ammonium paratungstate completely newly, make use of the effect of ultrasonic microwave hydro-thermal cooperative reinforcing, the ammonium paratungstate purity of preparation is high.Because ultrasonic wave cavatition in the solution produces high temperature, high pressure effect, obviously, this local pole high pressure forms the reason of the shockwave outwards propagated with bubble center just in a liquid.Cavitation bubble is closed also produces discharge effect instantaneously, just because of these effects, ultrasonic wave has possessed the condition changing chemical reaction velocity.And crystallisation process and general chemical similar process, all need certain impellent, namely need enough energy, and hyperacoustic cavitation effect provides condition for accelerating ammonium tungstate solution crystallization.Microwave is easy to polar liquid is heated, and temperature rise rate is fast, and heating efficiency is high, can be very easy to, accurately keep constant temperature.Micro-wave energy produces heat at solution inner homogeneous timely and effectively, and this causes crystal size inequality to provide a kind of novel method for solving in conventional heating methods because being heated inequality.
Accompanying drawing explanation
Fig. 1 is take tungsten ore as waste APT typical process flow figure.
Fig. 2 for shown in Fig. 1 typical process improve after process flow sheet.
Fig. 3 is the equipment that ultrasonic microwave hydro-thermal cooperative reinforcing prepares high-purity ammonium paratungstate, the i.e. structural representation of crystallizer.
Fig. 4 be crystallizer by the system chart of Control part.
Fig. 5 is the system chart of the feed control of crystallizer.
Fig. 6 is the grain size distribution of ammonium para-tungstate crystal.
Fig. 7 is not for open ultrasonic microwave cooperative reinforcing ammonium para-tungstate crystal pattern.
Fig. 8 is for opening ultrasonic microwave cooperative reinforcing ammonium para-tungstate crystal pattern.
Fig. 9 is not for open ultrasonic microwave cooperative reinforcing X-diffracting spectrum.
Figure 10 is for opening ultrasonic microwave cooperative reinforcing X-diffracting spectrum.
Embodiment
Reaching object to make technique means of the present invention, creation characteristic, workflow, using method and effect is easy to understand, below in conjunction with concrete diagram, setting forth the present invention further.
As shown in Figure 3, ultrasonic microwave hydro-thermal cooperative reinforcing prepares the equipment of high-purity ammonium paratungstate, i.e. crystallizer, it comprises microwave oven, described microwave oven comprises fire door 7 and body of heater 20, magnetic stirring apparatus is provided with in described body of heater 20, microwave generator 25 and fault detection module 24, pallet 10 is provided with in the inner chamber of body of heater 20, there-necked flask 8 placed by the pressure transmitter 21 that pallet 10 is arranged, described intracavity sidewall is provided with sensor socket 4 and camera 6, sensor socket 4 connects temperature sensor 8, temperature sensor 8 is fixedly connected with a side mouth of there-necked flask 9 by silica gel bottle stopper 5, the top of described body of heater 20 is provided with mount pad 19, mount pad 19 is installed ultrasonic generator 17 and two-way Glass tubing 18, described ultrasonic generator 17 upper end connects water inlet pipe 1 and rising pipe 2 respectively, lower end connects titanium alloy probe 16, titanium alloy probe 16 is fixedly connected with there-necked flask 9 intermediate openings by tetrafluoroethylene bottle stopper 3, and described two-way Glass tubing 18 lower end connects another side mouth of there-necked flask 9, described body of heater 20 is also provided with magnetic agitation switch 11, door open button 12, usb 13, power switch 14 and liquid crystal display 15.
As shown in Figure 4, crystallizer by the system chart of Control part.Described temperature sensor 8 is connected transmitter 22 with pressure transmitter 21, transmitter 22 can convert switching value to the temperature of reaction recorded and reaction pressure, described transmitter 22 connects rly. 23, rly. 23 connects camera 6, ultrasonic generator 17 and microwave generator 25 respectively, described microwave generator 25 connects fault detection module 24, and fault detection module 24 connects rly. 23.
As shown in Figure 5, the system chart of the feed control of crystallizer.Speed Setting power supply 27 connects potentiometer 26, and potentiometer 26 the other end connects touch down point GND30, and Speed Setting power supply 27 provides electric energy for frequency transformer 28, and frequency transformer 28 connects feed control module 29, controls input speed by speed control by frequency variation.
High-purity ammonium paratungstate prepare: adopt from the ammonium tungstate solution of the production low grade wolfram be raw material, with ultrasonic wave, microwave hydrothermal mode evaporative crystallization in homemade specific crystallizer i.e. outstanding cylinder, control each influence factor, produce high all ammonium paratungstate (APT) products.According to ammonium tungstate solution crystallization, the cooperative reinforcing effect of ultrasonic microwave hydro-thermal and the feature to solution crystallization process influence, crystallization process is adopted to prepare order of ammoniumparatungstate crystal, by initial for difference WO
3the ammonium tungstate solution of concentration is placed in water bath with thermostatic control, selects different temperature, stirring velocity and percent crystallization in massecuite to carry out evaporative crystallization.By the content of the impurity such as P, Mo, S, Fe in analysed preparation APT, investigate different technology conditions to the effect of APT crystallization removal of impurities.In addition and compare with the ammonium paratungstate (APT) without crystallization under the outer field actions such as ultrasonic microwave.
Ultrasonic microwave hydro-thermal cooperative reinforcing prepares the method for high-purity ammonium paratungstate, first prepares ammonium tungstate solution, and as shown in Figure 2, mix tungsten ore for the high-purity ammonium tungstate process flow sheet of waste with low-grade height, it is the improvement to traditional technology, and improvements are as follows:
(1) caustic digestion and remaining alkali collection
Adopt caustic alkali to decompose low-grade height in suitability for industrialized production flow process to mix sheelite, the conclusion that key process parameter draws with reference to experimental study, i.e. solid-to-liquid ratio 1.0, remaining alkali concn 350g/L, decomposition temperature 170 DEG C.Slip after decomposition is mainly containing three kinds of compositions, be respectively alkali lye, sodium wolframate solid and residue, need the separation realizing three kinds of compositions, conventional method first dilutes slip to make sodium wolframate dissolution of solid to liquid phase, by filtering first separating tungsten slag, then be separated sodium wolframate and alkali lye by the way of condensing crystal.
This research have employed a kind of more energy-conservation method when specifically implementing, slip after leaching is not diluted direct filtration and first reclaims alkali lye, residue and sodium wolframate are all stayed in solid phase, then by realizing being separated of slag and tungsten with dissolving sodium wolframate containing the wash water of inhibitor (calcium salt).
Can find out in conjunction with the feature of raw material and above-mentioned technological line, require higher when large-scale production to supporting equipment and technology, concrete engineering process mainly solves following problem:
1. devise large-scale pressure reaction still, solve the problem of its difficult sealing, and adopt novel type of heating to shorten treatment cycle, to prevent encrustation, thus improve processing efficiency.
2. adopt the alkali lye of recovery to return the way of dilution slip, solve the problem of slurry pipeline transport difficulty when filtering.
3. fully-automatic sealing pressure filter is adopted, and the automatic control technology of supporting development operation process, the various process parameters of accurate controlled filter and washing process, guarantees that tungsten and alkali can obtain the very high rate of recovery.
(2) tungsten is separated
Tungsten separation relation is to end product quality and production cost, although experimental study shows that copper ashes returns except molybdenum has higher feasibility, industrialization specific implementation process encounters a lot of problem equally, mainly contain following some:
1. the molybdenum due to raw material is very high, the amount of the solid precipitation agent recycled in system is large, and main component is wherein sulfide, there is certain colloidal property, therefore filtration capacity is the important factor of restriction output, technique is mainly taked first standing separation supernatant liquor refilter the measure of bed material, novel filtration medium is selected in equipment aspect.
2. find in practice, because sulfide active is higher, store up and can produce caking and reduce the activity of absorption except molybdenum by natural oxidation in atmosphere, the Long contact time with air need be avoided.
3. when the aluminium of raw material changes, the usage quantity of copper ashes needs corresponding adjustment, should add a small amount of α-benzoinoxime that contains for every batch and supplement fresh copper ashes to maintain its activity with the degree of depth ensureing to remove aluminium simultaneously.
4. regeneration produce the process of copper ashes should strict Controlling Technology condition, and adopt suitable activated measure to ensure the activity of copper ashes.
When this research is specifically implemented, first to the leaching of molybdenum slag ammonia, refilter recovery copper ashes, then by copper ashes with containing adding precipitation together with α-benzoinoxime except in the technique of molybdenum, the percentage composition wherein accounting for gross weight containing α-benzoinoxime is 1% ~ 3%.
Then the ammonium tungstate solution of preparation is added in crystallizer, with the ultrasonic wave of certain power (1-3KW) and frequency (microwave frequency 0.5-1.5Hz, ultrasonic frequency 100-200KHz), microwave hydrothermal mode to ammonium tungstate hydro-thermal evaporative crystallization.Concrete steps are as follows:
1. by WO
3the ammonium tungstate solution that concentration is not less than 220g/l is placed in there-necked flask, and opens magnetic stirring apparatus, stirs with certain stirring velocity (70-300rpm).
2. open microwave generator and ultrasonic generator, with the ultrasonic wave of certain power (1-3KW) and frequency (microwave frequency 0.5-1.5Hz, ultrasonic frequency 100-200KHz), microwave hydrothermal mode, ammonium tungstate solution is heated.
3. open camera and temperature sensor, monitoring reactor temperature and other situation simultaneously.
4., when Heating temperature reaches 80 DEG C, start hydro-thermal evaporative crystallization, and control temperature is more than 80 DEG C.
5. crystallization control rate is within 65%, high purity ammonium paratungstate (APT) product.
Research shows: percent crystallization in massecuite is higher, and in APT crystallization, foreign matter content is higher; Improve the WO in ammonium tungstate solution
3concentration is conducive to the purity improving APT, WO
3starting point concentration is higher, then in APT crystal, foreign matter content is fewer; Raise with Tc, in APT, foreign matter content reduces.Therefore, percent crystallization in massecuite 60%, WO is got
3concentration 220g/l, at Tc 80 DEG C in crystallizer, with the ultrasonic wave of certain power and frequency, microwave hydrothermal mode to ammonium tungstate hydro-thermal evaporative crystallization.
Verify that ultrasonic wave, microwave hydrothermal mode are to the effect of ammonium tungstate hydro-thermal evaporative crystallization below by way of testing.
1, ultrasonic microwave hydro-thermal cooperative reinforcing is on the impact of ammonium para-tungstate crystal speed
Prepare in the process of order of ammoniumparatungstate crystal at ammonium tungstate solution, solution is irradiated with a branch of converging light, solution is observed from the direction with beam orthogonal, solution starts without Tyndall phenomenon, when evaporation proceeds to certain hour, there is Tyndall phenomenon in discovery system, though so remarkable not as colloidal sol, and can to observe this phenomenon.And then create shining point tiny on a small quantity in system, shining point increases sharply and becomes large, and Tyndall effect weakens rapidly until disappear, and whole process duration is short especially.Obviously, when there is Tyndall effect, having there is the fine particle being less than visible wavelength in system, namely creates small nucleus.Along with growing up of small nucleus, Tyndall phenomenon weakens.When nuclei growth is greater than visible wavelength to its radius, Tyndall effect disappears.The time of Tyndall phenomenon is there is, for there is the time of small nucleus when namely preparing order of ammoniumparatungstate crystal.Solution without ul-trasonic irradiation occurs that the time of nucleus is 36min, and ultrasonic microwave hydro-thermal cooperative reinforcing occurs that the time of nucleus is 25min.Illustrate that ultrasonic microwave hydro-thermal cooperative reinforcing can accelerate the crystallization velocity of ammonium tungstate solution, significantly improve the synthesis speed of ammonium paratungstate nucleus.
2, ultrasonic microwave hydro-thermal cooperative reinforcing is on the impact of ammonium para-tungstate crystal granularity
Sample is carried out sreen analysis, and the instrument adopted is the Mastersizer2000 particle-size analyzer that Malvern company of Britain produces, and main particle size analyzer adopts laser diffractometry.As shown in Figure 6, the grain size distribution of ammonium para-tungstate crystal, for sample 1(does not open ultrasonic microwave cooperative reinforcing) with sample 2(open ultrasonic microwave cooperative reinforcing) sreen analysis curve.Find out that the size distribution curve of sample 2 is almost that the granularity of sample 2 to 1 attenuates to left on sample 1 curve from figure, and the particle of the detailed particle of data sheet and 56-70 μm almost remains unchanged from table 1, mainly the particle of about 50 μm increases.The particle of more than 70 μm reduces.From integral particles distribution, during 80 DEG C of evaporations, the particle ratio ultrasonic microwave cooperative reinforcing effect that the effect of ultrasonic microwave cooperative reinforcing obtains little.
Table 1 sample 1 and sample 2 size-grade distribution %
3, scanning electron microscope analysis
Fig. 7 and Fig. 8 is respectively the SEM figure of sample 1 and sample 2.Can find out evaporative crystallization under 80 DEG C of constant temperature, the product particle obtained under conventional heating methods is thick, surface irregularity, and size-grade distribution is uneven.And product particle obtained under the effect of ultrasonic microwave cooperative reinforcing thinner evenly, smooth surface, corner angle are clearly demarcated, even particle size distribution.
4, X-diffraction analysis
Sample is sent and does X-diffraction analysis.Fig. 9 and Figure 10 is respectively the XRD diffracting spectrum of sample 1 and 2.Table 2 is the document d value of five water ammonium paratungstates (APT-4) and the d value of sample 1 and 2 diffraction peak.Learn from table 2, sample 1 is consistent with the d value of 2 diffraction peaks and the literature value of five water order of ammoniumparatungstate crystal, and the d value of the crystal obtained after the effect of ultrasonic microwave cooperative reinforcing and document d value are coincide better.Find out that sample 2 is fewer than sample 1 peak of mixing from diffracting spectrum.This illustrates the five water order of ammoniumparatungstate crystal obtained 80 DEG C of evaporations, the ratio obtained under the effect of ultrasonic microwave cooperative reinforcing is without the obtained five water order of ammoniumparatungstate crystal of ultrasonic microwave cooperative reinforcing effect, and its X-diffracting spectrum peak of mixing is few.
The document d value of table 2 five water ammonium paratungstate and the d value of sample 1 and 2 diffraction peak
Ultrasonic microwave cooperative reinforcing mechanism
Ultrasonic wave cavatition in the solution produces high temperature, high pressure effect.Obviously, this local pole high pressure forms the reason of the shockwave outwards propagated with bubble center just in a liquid.Cavitation bubble is closed also produces discharge effect instantaneously, just because of these effects, ultrasonic wave has possessed the condition changing chemical reaction velocity.And crystallisation process and general chemical similar process, all need certain impellent, namely need enough energy, and hyperacoustic cavitation effect provides condition for accelerating ammonium tungstate solution crystallization.Microwave is easy to polar liquid is heated, and temperature rise rate is fast, and heating efficiency is high, can be very easy to, accurately keep constant temperature.Micro-wave energy produces heat at solution inner homogeneous timely and effectively, and this causes crystal size inequality to provide a kind of method for solving in conventional heating methods because being heated inequality.
Its concrete mechanism of action is:
(1) heat effect
The heat effect of continuous wave: when ultrasonic wave is propagated in medium, its vibrational energy is constantly absorbed and internal friction by medium, and changes heat energy into, ultrasonic continuous action within a certain period of time, and sound field region in medium can be made to produce temperature rise.
(2) mechanical effect
Effective stirring and flowing during ultrasonic high-frequency vibration and radiation pressure can be formed in gas, liquid.Cavitation bubble vibration, to the strong jet of solid surface generation and local micro slipstream, all significantly can weaken surface tension and the frictional force of liquid, and destroys the boundary layer at a solid liquid interface, thus reaches common Low-Frequency Mechanical and stirs the effect do not reached.
(3) cavatition
Due to eddy current or hyperacoustic physical action in liquid medium, in liquid, a certain region can form the temporary transient negative pressuren zone of local, so produce cavitation bubble in liquid medium, referred to as hole or bubble.There is the alternating cycles of a positive and negative pressure in ultrasonic wave, liquid medium is ruptured in Medium Propagation process, and produce microvesicle, microvesicle grows up into cavitation bubble further.These bubbles continue along with the change of sound field to grow up until negative pressure reaches maximum value.In back to back compression process, these cavitation bubbles are compressed, its volume-diminished, the even completely dissolve had, when exceeding the resonance phase place of ultrasonic field, cavitation bubble is just no longer stable, at this moment the pressure in cavitation bubble can not support himself size, namely starts collapse.
Ultrasonic and microwave cavatition in the solution produces high pressure high temperature dependence and makes adiabatic closed speed formula according to bubble, and to utilize gas adiabatic equation to derive gas temperature T when bubble is closed into minimum radius be 10000K, and the temperature on sun surface is approximately only also 7000K.Rate of temperature change reaches 109K/s, and pressure can up to hundreds of and even thousands of normal atmosphere.Rayleigh is derived pressure formula when bubbles of vacuum closes in liquid, and to demonstrate when bubble closes near bubble producible instantaneous pressure in liquid be 1300atm.Obviously, this local pole high pressure in a liquid, forms the reason of the shockwave outwards propagated with bubble center just.Cavitation bubble is closed also produces discharge effect instantaneously: when gas closes, and because bubble wall movement velocity is exceedingly fast, exceedes the gas velocity of sound in bubble, thus create micronucleus ripple in bubble, and to centre convergence.Because positive ion is different from mass of the electron, there is electric core and be separated, form very strong internal electric field, cause photoelectricity radiation.Just because of these effects, ultrasonic possessed the condition changing chemical reaction velocity.And crystallisation process is similar to general chemical reaction process, all need certain impellent, namely need enough energy, and cavitation effect that is ultrasonic and microwave cooperating strengthening provides condition for accelerating ammonium tungstate solution crystallization.Crystallisation process is the process producing cenotype, and this process comprises two stages, i.e. nucleating process and nuclei growth process.In nucleating process, be first that solute molecule in solution or ion collide with each other, agglomerated together and form crystallite, i.e. nucleus.And the vibration of ultrasonic and microwave cooperating Tsing-Hua University can increase the chance that in gas, liquid, particle collides mutually, formed made certain contribution for accelerating ammonium paratungstate nucleus.
More than show and describe ultimate principle of the present invention, principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Application claims protection domain is defined by appending claims and equivalent thereof.
Claims (2)
1. ultrasonic microwave hydro-thermal cooperative reinforcing prepares the method for high-purity ammonium paratungstate, and concrete steps are as follows:
(1) by WO
3the ammonium tungstate solution that concentration is not less than 220g/l is placed in there-necked flask, and opens magnetic stirring apparatus, stirs with the stirring velocity of 70-300rpm;
(2) open microwave generator and ultrasonic generator, be 1-3KW with power, microwave frequency is 0.5-1.5Hz, and ultrasonic frequency is the ultrasonic wave of 100-200KHz, microwave hydrothermal mode heats ammonium tungstate solution;
(3) open camera and temperature sensor simultaneously;
(4) when Heating temperature reaches 80 DEG C, start hydro-thermal evaporative crystallization, and control temperature is more than 80 DEG C;
(5) crystallization control rate is within 65%, i.e. high purity ammonium paratungstate product;
It is characterized in that, in the preparation technology of the middle ammonium tungstate solution of step (1), the method for caustic digestion and remaining alkali collection is: the slip after leaching is not diluted direct filtration and first reclaims alkali lye, residue and sodium wolframate are all stayed in solid phase, then realizes being separated of slag and tungsten by dissolving sodium wolframate with the wash water containing calcium salt inhibitor.
2. ultrasonic microwave hydro-thermal cooperative reinforcing according to claim 1 prepares the method for high-purity ammonium paratungstate, it is characterized in that, the method that in the preparation technology of the middle ammonium tungstate solution of step (1), tungsten is separated is: first soak molybdenum slag ammonia, refilter recovery copper ashes, then by copper ashes with containing adding precipitation together with α-benzoinoxime except in the technique of molybdenum, the percentage composition wherein accounting for gross weight containing α-benzoinoxime is 1% ~ 3%.
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| CN87101927A (en) * | 1987-03-11 | 1988-09-21 | 中南工业大学 | Select low grade wolfram to produce ammonium paratungstate with tungsten slurry and difficulty |
| CN1203279A (en) * | 1997-06-19 | 1998-12-30 | 中南工业大学 | Process for removing Mo, As, Sb and Sn by precipitating of tungstate solution |
| CN201186171Y (en) * | 2008-03-20 | 2009-01-28 | 北京祥鹄科技发展有限公司 | Microwave ultrasonic wave combined instrument for catalysis, synthesis and extraction |
-
2012
- 2012-05-28 CN CN201210168360.3A patent/CN102674462B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87101927A (en) * | 1987-03-11 | 1988-09-21 | 中南工业大学 | Select low grade wolfram to produce ammonium paratungstate with tungsten slurry and difficulty |
| CN1203279A (en) * | 1997-06-19 | 1998-12-30 | 中南工业大学 | Process for removing Mo, As, Sb and Sn by precipitating of tungstate solution |
| CN201186171Y (en) * | 2008-03-20 | 2009-01-28 | 北京祥鹄科技发展有限公司 | Microwave ultrasonic wave combined instrument for catalysis, synthesis and extraction |
Non-Patent Citations (1)
| Title |
|---|
| 微波超声波法对仲钨酸铵蒸发结晶的影响;孟凡伟等;《有色金属(冶炼部分)》;20101231;第43-45页 * |
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