CN102674462A - Method and device for preparing high-purity ammonium paratungstate by ultrasonic and microwave hydrothermal collaborative strengthening - Google Patents
Method and device for preparing high-purity ammonium paratungstate by ultrasonic and microwave hydrothermal collaborative strengthening Download PDFInfo
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Abstract
Disclosed are a method and a device for preparing high-purity ammonium paratungstate by ultrasonic and microwave hydrothermal collaborative strengthening. The device comprises a magnetic stirrer, a microwave generator, an ultrasonic generator, a three-neck flask, a temperature sensor and the like. The method includes the steps that an ammonium tungstate solution with tungsten trioxide which has a concentration of no less than 220g/l is placed in the three-neck flask, the magnetic stirrer is opened, stirring is performed at a stirring speed of 70-300rpm, the microwave generator and the ultrasonic generator are opened, the powers of both the microwave generator and the ultrasonic generator are set to 1-3KW, the microwave frequency is 0.5-1.5Hz, the ultrasonic frequency is 100-200KHz, the ammonium tungstate solution is heated in an ultrasonic and microwave hydrothermal mode, a camera and the temperature sensor are simultaneously opened, when the heating temperature reaches to 80 DEG C, hydrothermal evaporation and crystallization are performed, the temperature is controlled above 80 DEG C, and the crystallization rate is controlled within 65% to obtain a high-purity ammonium paratungstate product. The prepared ammonium paratungstate by the method is high in purity.
Description
Technical field
The present invention relates to prepare the field of ammonium paratungstate, be specially a kind of method and apparatus that utilizes UW microwave hydrothermal cooperative reinforcing to prepare high-purity ammonium paratungstate.
Background technology
Ammonium paratungstate (APT) is an important intermediate compound of producing tungsten powder, tungsten filament, tungsten-bast alloy and all tungsten materials, also is large exporting of China.Because genetic affinity; The crystal property of APT such as crystal morphology, lattice parameter, mean particle size and size-grade distribution, loose specific weight and flowability are very big to the material property influence of follow-up powder metallurgy product tungsten powder, tungsten filament and tungstenalloy; Thereby the exploitation of high-performance tungsten material, be that characteristics such as the granularity of APT, loose ratio, flowability, crystal morphology and lattice parameter have proposed increasingly high requirement to crystalline product from solution.It is worthy of note that especially the tungsten powder that high homogeneity monocrystalline APT powder is produced is because the defective of material is few, compacted density is high, is the excellent material of producing high temperature resistance, anti-sagging, anti-fracture, shock resistance tungsten filament.Main application fields is products such as high-performance, heavy metal and antidetonation tungsten filament, and miniature brill.In APT micro crystal mass crystallization process; Be accompanied by very complicated polymeric chemical reaction, because grain-size is little, quantity is big, Van der Waals force and salt bridge effect are remarkable; Crystal is reunited very easily; The APT that produces both at home and abroad is the compound crystal intergrowth, the granularity performance also be difficult to control, bigger increase the production difficulty of high quality tungsten material.Thereby study the preparation technique of high-purity APT, and to prepare high performance tungsten powder, wimet, heavy metal, belong to the scientific and technological problem that need press for solution in the national economy and social development, have a wide range of applications.
At present, the common traditional technology of producing APT by tungsten mineral material is:
1. sheelite and Scheelite-Wolframite Mixed Mine → basic pressure digestion → IX → evaporative crystallization is produced APT.
2. sheelite and Scheelite-Wolframite Mixed Mine → basic pressure digestion → magnesium salts purification → abstraction and type-reverting → evaporative crystallization is produced APT.
Its process flow sheet is seen accompanying drawing 1.Among the figure, contain the dilution water of suppressor factor, described suppressor factor is a calcium salt, because in low-grade tungsten ore raw material NaOH decomposition course, the P in the raw material, As, Si etc. are leaching in varying degrees, therefore need to add the leaching that suppressor factor suppresses above-mentioned impurity.And after adding the suppressor factor of calcium salt, can effectively impurity such as P, As, the Si form of insoluble calcium salts be suppressed in the slag.The parsing agent is NH
4Cl+NH
4OH.
Can find out that by figure domestic most producers are that the technical process that raw material is produced APT exists following problem with the tungsten ore:
(l) the surplus alkali after most producers decompose is not recycled, and adopts the way of simple sour neutralizing treatment when just liquid discharges after friendship, not only is unfavorable for saving production cost but also increased the inorganic salt refuse.Have only minority producer through the evaporation concentration coarse sodium tungstate, crystallization returns alkali liquor to the leaching ore after separating out the sodium wolframate crystal, can recycle the base excess of about 80-90%.The reason that surplus alkali is selected not recycle by most producers mainly contain following some:
1. the cost that reclaims alkali is high.The direct energy consumption cost of general every recovery lt alkali is l-1.5 times that alkali itself is worth, and the production cost of unit product also can rise at double during the processing low-grade ore deposit, and most producers are difficult to accept.
2. when processing low-grade ore deposit or complicated ore, bubble in the time of can causing evaporation concentration owing to the beneficiation reagent that brings in the raw material, can cause when serious producing and to carry out, increased the difficulty of operation.
3. sodium wolframate crystal and the alkali separation difficulty separated out of crystallization to having relatively high expectations of equipment, increased maintenance, the running cost of more facility investment and equipment simultaneously.
4. increased treatment process, working strength of workers increases.
(2) deposition is removed the aluminium process and has been used the expensive Tong Shiji that contains, and when handling high aluminium ore, production cost is high.The aluminium of association is leached 90% or more when decomposing simultaneously in the tungsten ore, and with the precipitator method during except that aluminium, every deposition 1kgMO need consume metallic copper 2-3kg during general industry was produced.
In sum, the current tungsten that generally adopts is smelted flow process and is existed surplus alkali to be difficult to reclaim, and removes the high deficiency of phase cost when handling high aluminium ore, need improve.
In addition, the high-purity ammonium paratungstate foreign matter content that the method and apparatus of existing preparation high-purity ammonium paratungstate is produced is produced the requirement that does not reach high-purity ammonium paratungstate all than higher, therefore a kind of better preparation method and equipment need be provided.
Summary of the invention
The technical problem that the present invention solved is to provide a kind of UW microwave hydrothermal cooperative reinforcing to prepare the method and apparatus of high-purity ammonium paratungstate, to solve the problem in the above-mentioned background technology.
The technical problem that the present invention solved adopts following technical scheme to realize:
UW microwave hydrothermal cooperative reinforcing prepares the equipment of high-purity ammonium paratungstate; Be mold, it comprises microwave oven, and said microwave oven comprises fire door, body of heater and door open button; Be provided with magnetic stirring apparatus, microwave generator and fault detection module in the said body of heater; Be provided with pallet in the inner chamber of body of heater, place there-necked flask on the pressure transmitter that is provided with on the pallet, the sensor socket on the said intracavity sidewall connects TP; Ultrasonic generator and two logical Glass tubings are installed on the mount pad at said body of heater top, and said ultrasonic generator upper end connects water inlet pipe and rising pipe respectively, and the lower end connects the titanium alloy probe; Titanium alloy probe and TP all are fixed on there-necked flask inside, and two logical Glass tubing lower ends connect a side mouth of there-necked flask; Said TP is connected rly. with pressure transmitter through transmitter, and rly. connects ultrasonic generator and microwave generator respectively, and said microwave generator connects fault detection module, and the fault detection module the other end connects rly..
Also be provided with USB interface and liquid crystal display on the said body of heater.
Said intracavity sidewall is provided with camera, and camera connects rly..
Said TP is fixedly connected another side mouth of there-necked flask through the silica gel bottle stopper.
Said titanium alloy probe is fixedly connected the intermediate openings of there-necked flask through the tetrafluoroethylene bottle stopper.
UW microwave hydrothermal cooperative reinforcing prepares the method for high-purity ammonium paratungstate, and concrete steps are following:
(1) with WO
3The ammonium tungstate solution that concentration is not less than 220 g/l places in the 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 that UW, the microwave hydrothermal mode of 100-200KHz heats ammonium tungstate solution;
(3) open camera and TP simultaneously;
(4) when Heating temperature reaches 80 ℃, beginning hydro-thermal evaporative crystallization, and controlled temperature is more than 80 ℃;
(5) the crystallization control rate is promptly produced the high-purity ammonium paratungstate product in 65%.
The method that alkali decomposes and surplus alkali reclaims among the preparation technology of ammonium tungstate solution in the step (1) is: the slip after will leaching does not dilute direct filtration and reclaims alkali lye earlier; Residue and sodium wolframate are all stayed in the solid phase, realized separating of slag and tungsten through dissolving sodium wolframate again with the wash water that contains the calcium salt suppressor factor.
The isolating method of tungsten is among the preparation technology of the middle ammonium tungstate solution of step (1): at first molybdenum slag ammonia is soaked; Refilter the recovery copper ashes; Then with copper ashes with contain Tong Shiji and add deposition together and remove in the technology of molybdenum, wherein containing the percentage composition that Tong Shiji accounts for gross weight is 1%～3%.
Beneficial effect:The invention solves the current tungsten that generally adopts and smelt the problem that flow process exists surplus alkali to be difficult to reclaim, and remove the high deficiency of phase cost when handling high aluminium ore.A kind of method and apparatus of brand-new preparation high-purity ammonium paratungstate is provided, has utilized the effect of UW microwave hydrothermal cooperative reinforcing, the ammonium paratungstate purity of preparation is high.Because the cavatition of UW in solution produces high temperature, high pressure effect, obviously, this local pole high pressure forms the reason of the shockwave of outwards propagating with bubble center just in liquid.Cavitation bubble closed moment also produces discharge effect, just because of these effects, UW has possessed the condition that changes chemical reaction velocity.And crystallisation process and general chemical similar process all need certain impellent, promptly need enough energy, and hyperacoustic cavitation effect provides condition for quickening the ammonium tungstate solution crystallization.Microwave is easy to make the polar liquid heating, and temperature rise rate is fast, and heating efficiency is high, can be very easy to, accurately keep constant temperature.At the inner heat that evenly produces of solution, this provides a kind of novel method for solving in the traditional heating method because of the inequality of being heated causes the crystal size inequality to micro-wave energy timely and effectively.
Description of drawings
Fig. 1 is for being that raw material is produced APT typical process flow figure with the tungsten ore.
Fig. 2 is the process flow sheet after typical process shown in Figure 1 is improved.
Fig. 3 is the equipment that UW microwave hydrothermal cooperative reinforcing prepares high-purity ammonium paratungstate, i.e. structure of mould synoptic diagram.
Fig. 4 is the system chart by the rly. control section of mold.
Fig. 5 is the system chart of the feed control of mold.
Fig. 6 is the size distribution figure of ammonium para-tungstate crystal.
Fig. 7 does not strengthen the ammonium para-tungstate crystal pattern for opening the UW microwave cooperating.
Fig. 8 strengthens the ammonium para-tungstate crystal pattern for opening the UW microwave cooperating.
Fig. 9 does not strengthen the X-diffracting spectrum for opening the UW microwave cooperating.
Figure 10 strengthens the X-diffracting spectrum for opening the UW microwave cooperating.
Embodiment
Be easy to understand and understand in order to make technique means of the present invention, creation characteristic, workflow, method of use reach purpose and effect,, further set forth the present invention below in conjunction with concrete diagram.
As shown in Figure 3, UW microwave hydrothermal cooperative reinforcing prepares the equipment of high-purity ammonium paratungstate, i.e. mold; It comprises microwave oven; Said microwave oven comprises fire door 7 and body of heater 20, is provided with magnetic stirring apparatus, microwave generator 25 and fault detection module 24 in the said body of heater 20, is provided with pallet 10 in the inner chamber of body of heater 20; Place there-necked flask 8 on the pressure transmitter 21 that is provided with on the pallet 10; Said intracavity sidewall is provided with sensor socket 4 and camera 6, and sensor socket 4 connects TP 8, and TP 8 is fixedly connected a side mouth of there-necked flask 9 through silica gel bottle stopper 5; The top of said body of heater 20 is provided with mount pad 19; Ultrasonic generator 17 and two logical Glass tubings 18 are installed on the mount pad 19; Said ultrasonic generator 17 upper ends connect water inlet pipe 1 and rising pipe 2 respectively; The lower end connects titanium alloy probe 16, and titanium alloy probe 16 is fixedly connected there-necked flask 9 intermediate openingss through tetrafluoroethylene bottle stopper 3, and said two logical Glass tubing 18 lower ends connect another side mouth of there-necked flask 9; Also be provided with magnetic agitation switch 11, door open button 12, usb 13, power switch 14 and liquid crystal display 15 on the said body of heater 20.
As shown in Figure 4, the system chart by the rly. control section of mold.Said TP 8 is connected transmitter 22 with pressure transmitter 21; Transmitter 22 can convert temperature of reaction that records and reaction pressure to switching value; Said transmitter 22 connects rly. 23; Rly. 23 connects camera 6, ultrasonic generator 17 and microwave generator 25 respectively, and said 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 mold.Speed setting connects potentiometer 26 with power supply 27, and potentiometer 26 the other ends connect touch down point GND 30, and speed setting uses power supply 27 as frequency transformer 28 electric energy to be provided, and frequency transformer 28 connects feed control module 29, controls input speed through speed control by frequency variation.
The high-purity ammonium paratungstate preparation: adopting the ammonium tungstate solution of the production from low grade wolfram is raw material; Promptly hang in the tube with UW, microwave hydrothermal mode evaporative crystallization at homemade specific mold; Control each influence factor, produce high all ammonium paratungstate (APT) products.Reach characteristics according to ammonium tungstate solution crystallization, the effect of UW microwave hydrothermal cooperative reinforcing, adopt crystallization process to prepare order of ammoniumparatungstate crystal, the initial WO of difference to the solution crystallization process influence
3The ammonium tungstate solution of concentration places water bath with thermostatic control, selects different temperature, stirring velocity and percent crystallization in massecuite to carry out evaporative crystallization.Through the content of impurity such as P, Mo, S, Fe among the analysed preparation APT, investigate the effect of different technology conditions to APT crystallization removal of impurities.In addition and with outer field actions such as no UW microwave under crystalline ammonium paratungstate (APT) compare.
UW microwave hydrothermal cooperative reinforcing prepares the method for high-purity ammonium paratungstate, at first prepares ammonium tungstate solution, and is as shown in Figure 2, is that raw material is produced high-purity ammonium tungstate process flow sheet with the assorted tungsten ore of low-grade height, and it is the improvement to traditional technology, and improvements are following:
(1) alkali decomposes and the recovery of surplus alkali
Adopt caustic alkali to decompose the assorted sheelite of low-grade height in the suitability for industrialized production flow process, the conclusion that key process parameter draws with reference to experimental study, promptly solid-to-liquid ratio 1.0, surplus alkali concn 350g/L, decomposition temperature are 170 ℃.Slip after the decomposition mainly contains three kinds of compositions; Be respectively alkali lye, sodium wolframate solid and residue; Need to realize the separation of three kinds of compositions; Conventional method is that the dilution slip makes the sodium wolframate solid be dissolved into liquid phase earlier, through filtering first separating tungsten slag, separates sodium wolframate and alkali lye through the way of condensing crystal again.
Adopted a kind of method for saving energy more during this research practical implementation; Slip after leaching is not diluted direct filtration reclaim alkali lye earlier; Residue and sodium wolframate are all stayed in the solid phase, realized separating of slag and tungsten through dissolving sodium wolframate again with the wash water that contains suppressor factor (calcium salt).
Characteristics and above-mentioned technological line in conjunction with raw material can be found out, when large-scale production, supporting equipment and technology are had relatively high expectations, and concrete through engineering approaches process has mainly solved following problem:
1. design large-scale pressure reaction still, solved the problem of its difficult sealing, and adopted novel type of heating shortening the processing cycle, to prevent encrustation, thereby improved processing efficiency.
2. adopt the alkali lye that reclaims to return the way of diluting slip, solve the problem of slip difficulty of transportation when filtering.
3. adopt the fully-automatic sealing pressure filter, and the automatic control technology of supporting development operation process, accurately each item processing parameter of controlled filter and washing process guarantees that tungsten and alkali can both obtain the very high recovery.
(2) tungsten separates
The tungsten separation relation is to end product quality and production cost, returns except that molybdenum and has higher feasibility although experimental study shows copper ashes, and industriallization practical implementation process has run into a lot of problems equally, mainly contain following some:
1. because the molybdenum of raw material is very high; The amount of the solid precipitation agent that recycles in the system is big; And staple wherein is a sulfide, has certain colloidal property, so filtration capacity is the important factor of restriction output; Mainly take first standing separation supernatant to refilter the measure of bed material on the technology, novel filtration medium is selected in the equipment aspect.
2. find in the practice, higher owing to the sulfide activity, store up in air and can produce caking and reduce the activity of absorption by natural oxidation except that molybdenum, need avoid Long contact time with air.
When 3. the aluminium of raw material changed, the usage quantity of copper ashes needed corresponding adjustment, should add a spot of Tong Shiji that contains for every batch and replenish fresh copper ashes simultaneously to keep its activity to guarantee the degree of depth of removing aluminium.
4. the process of producing copper ashes of regenerating is answered strict CONTROL PROCESS condition, and adopts suitable activated measure to guarantee the activity of copper ashes.
During this research practical implementation, at first molybdenum slag ammonia is soaked, refilters the recovery copper ashes, then with copper ashes with contain Tong Shiji and add deposition together and remove in the technology of molybdenum, wherein containing the percentage composition that Tong Shiji accounts for gross weight is 1%～3%.
Ammonium tungstate solution with preparation adds in the mold then, with the UW 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 following:
1. with WO
3The ammonium tungstate solution that concentration is not less than 220 g/l places in the there-necked flask, and opens magnetic stirring apparatus, and (70-300rpm) stirs with certain stirring velocity.
2. open microwave generator and ultrasonic generator, ammonium tungstate solution is heated with UW, the microwave hydrothermal mode of certain power (1-3KW) and frequency (microwave frequency 0.5-1.5Hz, ultrasonic frequency 100-200KHz).
3. open camera and TP simultaneously, monitoring reactor temperature and other situation.
4. when Heating temperature reaches 80 ℃, begin the hydro-thermal evaporative crystallization, and controlled temperature is more than 80 ℃.
5. the crystallization control rate is produced high-purity ammonium paratungstate (APT) product in 65%.
Research shows: percent crystallization in massecuite is high more, and foreign matter content is high more in the APT crystallization; Improve the WO in the ammonium tungstate solution
3Concentration helps improving the purity of APT, WO
3Starting point concentration is high more, and then foreign matter content is few more in the APT crystal; Raise with Tc, foreign matter content reduces among the APT.Therefore, get percent crystallization in massecuite 60%, WO
3Concentration 220 g/l, under 80 ℃ of the Tcs in mold, with the UW of certain power and frequency, microwave hydrothermal mode to ammonium tungstate hydro-thermal evaporative crystallization.
Below through verifying the effect of UW, microwave hydrothermal mode to ammonium tungstate hydro-thermal evaporative crystallization.
1, UW microwave hydrothermal cooperative reinforcing is to the influence of ammonium para-tungstate crystal speed
Prepare in the process of order of ammoniumparatungstate crystal at ammonium tungstate solution; With a branch of converging light irradiation solution, from observing solution with the vertical direction of light beam, solution begins not have Tyndall phenomenon; When evaporation proceeds to certain hour; Tyndall phenomenon has appearred in the discovery system, though it is so remarkable to be not so good as colloidal sol, and can be to observe this phenomenon.And then produced a small amount of tiny shining point in the system, shining point increases sharply and becomes big, and Tyndall effect weakens rapidly until disappearance, and whole process duration is short especially.Obviously when Tyndall effect occurring, the fine particle less than visible wavelength has appearred in system, has promptly produced small nucleus.Along with growing up of small nucleus, Tyndall phenomenon weakens.When its radius was arrived in nuclei growth greater than visible wavelength, Tyndall effect disappeared.The time that occurs Tyndall phenomenon when promptly preparing order of ammoniumparatungstate crystal is for the time of small nucleus occurring.The time that nucleus appears in the solution of no UW effect is 36 min, is 25 min and the time of nucleus appears in UW microwave hydrothermal cooperative reinforcing.Explain that UW microwave hydrothermal cooperative reinforcing can accelerate the crystallization velocity of ammonium tungstate solution, obviously improve the formation speed of ammonium paratungstate nucleus.
2, UW microwave hydrothermal cooperative reinforcing is to the influence of ammonium para-tungstate crystal granularity
Sample is carried out sreen analysis, and the instrument that is adopted is the Mastersizer2000 particle-size analyzer that Britain Malvern company produces, and main particle size analyzer adopts laser diffractometry.As shown in Figure 6, the size distribution figure of ammonium para-tungstate crystal is the sreen analysis curve of sample 1 (not opening the UW microwave cooperating strengthens) with sample 2 (opening the UW microwave cooperating strengthens).The size distribution curve of finding out sample 2 from figure almost be on sample 1 curve to left, the granularity of sample 2 to 1 attenuates, and the particle of the detailed particle of data sheet and 56-70 μ m almost remains unchanged from table 1, mainly is the particle increase about 50 μ m.The above particle of 70 μ m reduces.Distribute from integral particles, during 80 ℃ of evaporations, the particle that the strengthening effect of UW microwave cooperating obtains is than not using the little of UW microwave cooperating strengthening effect.
Table 1 sample 1 and sample 2 size-grade distribution %
3, scanning electron microscope analysis
Fig. 7 and Fig. 8 are respectively the SEM figure of sample 1 and sample 2.Can find out evaporative crystallization under 80 ℃ of constant temperature, the product particle that obtains under the traditional heating method is thick, surface irregularity, and size-grade distribution is uneven.And the product particle that makes under the strengthening effect of UW microwave cooperating is more carefully more even, smooth surface, and corner angle are clearly demarcated, even particle size distribution.
4, X-diffraction analysis
Sample sent do the X-diffraction analysis.Fig. 9 and Figure 10 are 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 peaks.Learn that from table 2 the d value of sample 1 and 2 diffraction peaks and the literature value of five water order of ammoniumparatungstate crystal are consistent, and resulting crystalline d value and document d value are coincide after the strengthening effect of UW microwave cooperating better.Find out that from diffracting spectrum sample 2 lacks than sample 1 assorted peak.This has just explained the five water order of ammoniumparatungstate crystal that obtain 80 ℃ of evaporations, the resulting five water order of ammoniumparatungstate crystal that make than the strengthening effect of no UW microwave cooperating under the strengthening effect of UW microwave cooperating, and the assorted peak of its X-diffracting spectrum is few.
The document d value of table 2 five water ammonium paratungstates and the d value of sample 1 and 2 diffraction peaks
UW microwave cooperating strengthening mechanism
The cavatition of UW in solution produces high temperature, high pressure effect.Obviously, this local pole high pressure forms the reason with the outside shockwave of propagating of bubble center just in liquid.Cavitation bubble closed moment also produces discharge effect, just because of these effects, UW has possessed the condition that changes chemical reaction velocity.And crystallisation process and general chemical similar process all need certain impellent, promptly need enough energy, and hyperacoustic cavitation effect provides condition for quickening the ammonium tungstate solution crystallization.Microwave is easy to make the polar liquid heating, and temperature rise rate is fast, and heating efficiency is high, can be very easy to, accurately keep constant temperature.At the inner heat that evenly produces of solution, this provides a kind of method for solving in the traditional heating method because of the inequality of being heated causes the crystal size inequality to micro-wave energy timely and effectively.
Its concrete mechanism of action is:
(1) heat effect
The heat effect of CW: when UW was propagated in medium, its vibrational energy was constantly absorbed and internal friction by medium, and changes heat energy into, and ultrasonic continuous action within a certain period of time can make sound field zone generation temperature rise in the medium.
(2) mechanical effect
During can forming in gas, liquid, ultransonic high-frequency vibration and radiation pressure effectively stir with mobile.The cavitation bubble vibration all can significantly weaken the surface tension and the frictional force of liquid to strong jet and local micro slipstream that solid surface produces, and destroys the boundary layer at a solid liquid interface, thereby reaches the inaccessible effect of common low frequency mechanical agitation.
(3) cavatition
Owing to eddy current or hyperacoustic physical action, a certain zone can form partial temporary transient negative pressuren zone in the liquid, so in liquid medium, produce cavitation bubble, abbreviates hole or bubble as in liquid medium.There is the alternating cycles of a positive negative pressure in UW in the medium communication process, liquid medium is ruptured, and produces microvesicle, and microvesicle is further grown up into cavitation bubble.These bubbles continue along with change of sound field to grow up to reach peak until negative pressure.In back to back compression process, these cavitation bubbles are compressed, its volume-diminished; That have even completely dissolve, when exceeding the resonance phase place of ultrasonic field, cavitation bubble is just no longer stable; At this moment the pressure in the cavitation bubble can not support the size of himself, promptly begins collapse.
Ultrasonic and the cavatition of microwave in solution produces high pressure high temperature dependence and makes adiabatic closed speed formula according to bubble; And utilize the gas adiabatic equation derive bubble when being closed into minimum radius gas temperature T be 10000K, and the temperature on sun surface is 7000K approximately only also.Rate of temperature change reaches 109K/s, and pressure can be up to hundreds of and even thousands of normal atmosphere.Rayleigh has been derived bubbles of vacuum pressure formula in liquid when closed, and has proved when the bubble closure that near bubble producible instantaneous pressure is 1300atm in the liquid.Obviously, this local pole high pressure in liquid forms the reason with the outside shockwave of propagating of bubble center just.Cavitation bubble closed moment also produces discharge effect: when gas is closed,, surpasses the gas velocity of sound in the bubble, thereby in bubble, produced the micronucleus ripple because bubble wall movement velocity is exceedingly fast, and to centre convergence.Because positive ion is different with mass of the electron, electricity nuclear takes place to be separated, form very strong internal electric field, cause photoelectricity radiation.Just because of these effects, the ultrasonic condition that has possessed the change chemical reaction velocity.And crystallisation process is similar with general chemical reaction process, all needs certain impellent, promptly needs enough energy, and cavitation effect ultrasonic and that microwave cooperating is strengthened provides condition for quickening the ammonium tungstate solution crystallization.Crystallisation process is the process that produces cenotype, and this process comprises two stages, i.e. nucleating process and nuclei growth process.In the nucleating process, at first be that solute molecule or the ion in the solution runs foul of 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 particle collides each other in gas, the liquid, forms and has made certain contribution for quickening the ammonium paratungstate nucleus.
More than show and described 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; That describes in the foregoing description and the specification sheets just explains principle of the present invention; Under the prerequisite that does not break away from spirit and scope of the invention, the present invention also has various changes and modifications, and these variations and improvement all fall in the scope of the invention that requires protection.The present invention requires protection domain to be defined by appending claims and equivalent thereof.
Claims (8)
1. UW microwave hydrothermal cooperative reinforcing prepares the equipment of high-purity ammonium paratungstate; It comprises microwave oven, and said microwave oven comprises fire door, body of heater and door open button, it is characterized in that; Be provided with magnetic stirring apparatus, microwave generator and fault detection module in the said body of heater; Be provided with pallet in the inner chamber of body of heater, place there-necked flask on the pressure transmitter that is provided with on the pallet, the sensor socket on the said intracavity sidewall connects TP; Ultrasonic generator and two logical Glass tubings are installed on the mount pad at said body of heater top, and said ultrasonic generator upper end connects water inlet pipe and rising pipe respectively, and the lower end connects the titanium alloy probe; Titanium alloy probe and TP all are fixed on there-necked flask inside, and two logical Glass tubing lower ends connect a side mouth of there-necked flask; Said TP is connected rly. with pressure transmitter through transmitter, and rly. connects ultrasonic generator and microwave generator respectively, and said microwave generator connects fault detection module, and the fault detection module the other end connects rly..
2. UW microwave hydrothermal cooperative reinforcing according to claim 1 prepares the equipment of high-purity ammonium paratungstate, it is characterized in that, also is provided with USB interface and liquid crystal display on the said body of heater.
3. UW microwave hydrothermal cooperative reinforcing according to claim 1 prepares the equipment of high-purity ammonium paratungstate, it is characterized in that, said intracavity sidewall is provided with camera, and camera connects rly..
4. UW microwave hydrothermal cooperative reinforcing according to claim 1 prepares the equipment of high-purity ammonium paratungstate, it is characterized in that, said TP is fixedly connected another side mouth of there-necked flask through the silica gel bottle stopper.
5. UW microwave hydrothermal cooperative reinforcing according to claim 1 prepares the equipment of high-purity ammonium paratungstate, it is characterized in that, said titanium alloy probe is fixedly connected the intermediate openings of there-necked flask through the tetrafluoroethylene bottle stopper.
6. UW microwave hydrothermal cooperative reinforcing prepares the method for high-purity ammonium paratungstate, it is characterized in that, concrete steps are following:
(1) with WO
3The ammonium tungstate solution that concentration is not less than 220 g/l places in the 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 that UW, the microwave hydrothermal mode of 100-200KHz heats ammonium tungstate solution;
(3) open camera and TP simultaneously;
(4) when Heating temperature reaches 80 ℃, beginning hydro-thermal evaporative crystallization, and controlled temperature is more than 80 ℃;
(5) the crystallization control rate is promptly produced the high-purity ammonium paratungstate product in 65%.
7. UW microwave hydrothermal cooperative reinforcing according to claim 6 prepares the method for high-purity ammonium paratungstate; It is characterized in that; The method that alkali decomposes and surplus alkali reclaims among the preparation technology of ammonium tungstate solution in the step (1) is: the slip after will leaching does not dilute direct filtration and reclaims alkali lye earlier; Residue and sodium wolframate are all stayed in the solid phase, realized separating of slag and tungsten through dissolving sodium wolframate again with the wash water that contains the calcium salt suppressor factor.
8. UW microwave hydrothermal cooperative reinforcing according to claim 6 prepares the method for high-purity ammonium paratungstate; It is characterized in that; The isolating method of tungsten is among the preparation technology of the middle ammonium tungstate solution of step (1): at first molybdenum slag ammonia is soaked; Refilter the recovery copper ashes, then with copper ashes with contain Tong Shiji and add deposition together and remove in the technology of molybdenum, wherein containing the percentage composition that Tong Shiji accounts for gross weight is 1%～3%.
Priority Applications (1)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102942222A (en) * | 2012-10-28 | 2013-02-27 | 孙世凡 | Method for preparing ammonium tungstate by treating waste tungsten oxide |
| CN103602807A (en) * | 2013-09-18 | 2014-02-26 | 崇义章源钨业股份有限公司 | Treating method of removed molybdenum slag produced from tungsten smelting processes |
| CN106867620A (en) * | 2017-04-12 | 2017-06-20 | 太原科技大学 | For the microwave desulfurization intelligent integrated experimental system of sulphur coal |
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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 |
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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 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942222A (en) * | 2012-10-28 | 2013-02-27 | 孙世凡 | Method for preparing ammonium tungstate by treating waste tungsten oxide |
| CN103602807A (en) * | 2013-09-18 | 2014-02-26 | 崇义章源钨业股份有限公司 | Treating method of removed molybdenum slag produced from tungsten smelting processes |
| CN103602807B (en) * | 2013-09-18 | 2015-06-03 | 崇义章源钨业股份有限公司 | Treating method of removed molybdenum slag produced from tungsten smelting processes |
| CN106867620A (en) * | 2017-04-12 | 2017-06-20 | 太原科技大学 | For the microwave desulfurization intelligent integrated experimental system of sulphur coal |
| CN106867620B (en) * | 2017-04-12 | 2023-03-24 | 太原科技大学 | Microwave desulfurization intelligent integrated experimental system for high-sulfur coal |
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