CN103706306B - Glass sand high temperature gas-solid reaction unit and reaction method thereof - Google Patents
Glass sand high temperature gas-solid reaction unit and reaction method thereof Download PDFInfo
- Publication number
- CN103706306B CN103706306B CN201310736775.0A CN201310736775A CN103706306B CN 103706306 B CN103706306 B CN 103706306B CN 201310736775 A CN201310736775 A CN 201310736775A CN 103706306 B CN103706306 B CN 103706306B
- Authority
- CN
- China
- Prior art keywords
- gas
- solid reaction
- demarcation strip
- high temperature
- silicon carbide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
Landscapes
- Glass Melting And Manufacturing (AREA)
- Silicon Compounds (AREA)
Abstract
Glass sand high temperature gas-solid reaction unit and reaction method thereof, belong to glass sand preparing technical field. It is characterized in that comprising silicon carbide reactor device and high temperature heater (HTH), described silicon carbide reactor device is made up of porous demarcation strip and separated gas-solid reaction chamber thereof, gas preheating chamber, upper end, gas-solid reaction chamber, top arranges feed pipe, and lower gas preheating chamber arranges air inlet pipe; Quartz sand in reaction unit, under 1200～1400 ° of C with mist generation gas-solid reaction 60～180min, described mist is by HCl, Cl2、N2With Ar gas composition. Above-mentioned glass sand high temperature gas-solid reaction unit and reaction method thereof, the effect of simultaneously removing fluid impurity and metallic element impurity is good, and has greatly improved gas-solid reaction efficiency and reaction effect.
Description
Technical field
The invention belongs to glass sand preparing technical field, be specially glass sand high temperature gas-solid reaction unit and reaction method thereof.
Background technology
Reacting no matter be to be all a kind of more common chemical reaction in laboratory or in industrial production between gaseous feed and solid feed, the efficiency (or speed) of gas-solid reaction and effect thereof except with the internal cause such as the proportioning of feedstock property, reactant mutually outside the Pass, also with reaction temperature, reaction time and raw material mix or the external cause such as exposure level closely related.
Glass sand is unique raw material of current production high-quality quartz glass, quartz glass is with its unique high high-temp stability (as the not explosion of 1200 ° of C direct water-cooling glass), excellent optical property and superpower machinery and chemical property, and is widely used in the high-technology fields such as electronics industry, semiconductor, solar energy, laser and Aero-Space. Along with the continuous increase of high-tech area to high-quality quartz glass demand, the yield and quality of glass sand has been proposed to more and more higher requirement, unremitting research and development are carried out in the production technology to glass sand and equipment in countries in the world always, develop the demand to glass sand to meet national high-technology field.
High temperature gas-solid reaction is the technique of most critical in glass sand production process, and gas-solid reaction effect directly affects the quality of glass sand. Quartz sand is carried out to high temperature gas-solid reaction, and object is in order to remove the quartz fluid impurity (being fluid inclusion) that crystals wraps up in crystalline growth process and the metallic element impurity of intracell; Be generally high temperature decrepitation method for the method for removing quartz fluid inclusion, heating-up temperature and heat time directly affect the removal degree of fluid impurity; Be generally under high temperature quartz and high activity gas are reacted (gas-solid reaction) for the method for removing quartzy lattice metallic element impurity, the factor such as exposure level, reaction time of the kind of heating-up temperature, active gases and proportioning, throughput, gas and quartz (sand) all affects the removal degree of metallic element impurity; Quartz sand is not carried out to high temperature gas-solid reaction, is impossible obtain stable glass sand product certainly. In order to obtain glass sand product qualified, stay in grade, scientific research personnel carries out unremitting research in the best approach to quartz sand high temperature gas-solid reaction and device always, and to the research and development achievement patent protection obtaining.
(Germany of Heraeus Quarzglas GmbH, co-applicant Shin-etsu Quartz Co., Ltd) process patent of CN1146429A continuous refining of quartz powder of application, under hot conditions, make silica flour contact and refine with chlorine-containing gas in the reaction chamber of horizontal revolving drum quartz glass tube, it is 20kg/h that the method maximum is carried out speed, and suggestion speed is 10kg/h.
The method and apparatus patent that the CN200910262856.5 of Nanjing University's application produces glass sand, be utilize the vertical gasification reaction kettle of quartz glass, under 1000-1200 ° of C by quartz sand and mixed gas reaction 30-120min, remove fluid impurity and element impurity in quartz sand, mist is by HCl and Cl simultaneously2Gas composition.
The CN200620169077.2 quartz sand high-heating calcining evaporated purification apparatus patent of Chen Shibin application, is to utilize vertical response still at high temperature quartz sand to be reacted with reacting gas generating gasification, removes fluid impurity and element impurity in quartz sand.
Foregoing invention patent or utility model patent, although be all the method and apparatus of the high-temperature gasification reaction carried out for glass sand, but the reactor using in all patents or reaction vessels are all that adopting quartz glass material is (in the CN200620169077.2 patent of Chen Shibin application, although there is no clear reaction still is quartz glass material, but be provided with at reactor top the water tank wrapping in outside escape pipe and feed pipe in patent, this labyrinth only has and can just may complete by the glassware of welding processing), the greatest drawback of quartz glass product is to experience for a long time 1150 ° of high temperature more than C, under the long-term condition of high temperature, quartz glass is not only easy to occur crystallization or devitrification phenomenon, also may cause that quartz glass product produces creep, thereby cause the damage of quartz glass reaction still or reaction vessels.
Summary of the invention
For the above-mentioned problems in the prior art, the object of the invention is to design provides the technical scheme of a kind of glass sand high temperature gas-solid reaction unit and reaction method thereof, can be under hot conditions steady in a long-term, trouble free service, remove fluid impurity and metallic element impurity effect in quartz sand good.
Described glass sand high temperature gas-solid reaction unit, it is characterized in that comprising silicon carbide reactor device and high temperature heater (HTH), described silicon carbide reactor device is made up of porous demarcation strip and separated gas-solid reaction chamber thereof, gas preheating chamber, upper end, gas-solid reaction chamber, top arranges feed pipe, and lower gas preheating chamber arranges air inlet pipe; Described high temperature heater (HTH) comprises the cuboid burner hearth of being made up of insulation material, cuboid burner hearth up and down four sides hearth wall in one group of heater is all set, cuboid burner hearth arranges fire door, rear wall arranges aperture A, aperture B, silicon carbide reactor device is placed in burner hearth through the fire door of high temperature heater (HTH), the feed pipe of silicon carbide reactor device extends high temperature heater (HTH) through aperture A, and the air inlet pipe of silicon carbide reactor device is extended high temperature heater (HTH) through aperture B.
Described glass sand high temperature gas-solid reaction unit, it is characterized in that being equipped with under porous demarcation strip porous demarcation strip bracket, porous demarcation strip bracket is the carborundum tube of a hollow, porous demarcation strip bracket one end is fixed in the circular groove arranging in gas preheating chamber, the porous demarcation strip bracket other end is by thickening outer wall, make its card holder in air inlet pipe, on porous demarcation strip bracket, be provided with the pallet for fixing porous demarcation strip, porous demarcation strip card holder is in pallet, tray bottom arranges hole, hole is communicated with the through hole of porous demarcation strip, the hole of mid portion is communicated with porous demarcation strip bracket hollow tube, the hole of other parts is communicated with gas preheating chamber.
Described glass sand high temperature gas-solid reaction unit, is characterized in that bottom, gas-solid reaction chamber is pyramidal structure.
Described glass sand high temperature gas-solid reaction unit, is characterized in that described heater is Elema or Si-Mo rod.
Described glass sand high temperature gas-solid reaction unit, is characterized in that the diameter of porous demarcation strip is greater than the circular hole between gas-solid reaction chamber and gas preheating chamber, and porous demarcation strip thickness is 5-20mm.
The reaction method of described glass sand high temperature gas-solid reaction unit, is characterized in that comprising the following steps:
1) first quartz sand is joined in gas-solid reaction chamber through the feed pipe of silicon carbide reactor device, quartz sand is subject to stopping of porous demarcation strip and is placed on porous demarcation strip;
2) start high temperature heater (HTH), set 1200-1400 ° of C of gas-solid reaction temperature, when fire box temperature reaches after set reaction temperature, open mist feeder, the gas preheating chamber that mist is passed into silicon carbide reactor device through air inlet pipe, described mist is HCl, the Cl that 500-5000ml/min flow, pressure are 0.05-0.8MPa2、N2With Ar mixed gas flow, HCl, Cl2、N2, Ar volume ratio be 20-1:1-20:2:2;
3) described mist sees through porous demarcation strip and is penetrated into gas-solid reaction chamber, and by diffusion along the taper surface Upward Migration of gas-solid reaction chamber, run through quartz sand layer, make the abundant haptoreaction of mist and quartz sand, quartz sand under 1200-1400 ° of C with mist generation gas-solid reaction 60-180min; Reacted waste gas is discharged silicon carbide reactor device through feed pipe;
4) reaction is closed high temperature heater (HTH) after finishing, is closed mist feeder, after temperature is reduced to room temperature, silicon carbide reactor device is taken out from burner hearth through fire door, and the quartz sand from feed pipe is poured out gas-solid reaction, completes whole gas-solid reaction flow process.
The reaction method of described glass sand high temperature gas-solid reaction unit, is characterized in that comprising the following steps:
1) first porous demarcation strip is placed in the pallet of porous demarcation strip bracket, by porous demarcation strip bracket in the air inlet pipe of silicon carbide reactor device is placed in gas preheating chamber, porous demarcation strip is placed between gas-solid reaction chamber and gas preheating chamber and plays compartmentation, quartz sand is joined in gas-solid reaction chamber through the feed pipe of silicon carbide reactor device, quartz sand is subject to stopping of porous demarcation strip and is placed on porous demarcation strip again; Then silicon carbide reactor device is placed in burner hearth through the fire door of high temperature heater (HTH), the feed pipe of silicon carbide reactor device extends high temperature heater (HTH) through aperture A, and the air inlet pipe of silicon carbide reactor device is extended high temperature heater (HTH) through aperture B;
2) start high temperature heater (HTH), set 1200-1400 ° of C of gas-solid reaction temperature, when fire box temperature reaches after set reaction temperature, open mist feeder, by mist in air inlet pipe, porous demarcation strip bracket pass into gas preheating chamber and porous demarcation strip bracket, mist after preheating is under the double action of stream pressure and heat energy, through the hole of porous demarcation strip bracket top tray bottom, see through porous demarcation strip and be penetrated into gas-solid reaction chamber, described mist is HCl, the Cl that 500-5000ml/min flow, pressure are 0.05-0.8MPa2、N2With Ar mixed gas flow, HCl, Cl2、N2, Ar volume ratio be 20-1:1-20:2:2;
3) described mist by diffusion along the taper surface Upward Migration of gas-solid reaction chamber, run through quartz sand layer, make the abundant haptoreaction of mist and quartz sand, quartz sand under 1200-1400 ° of C with mist generation gas-solid reaction 60-180min; Reacted waste gas is discharged silicon carbide reactor device through feed pipe;
4) reaction is closed high temperature heater (HTH) after finishing, is closed mist feeder, after temperature is reduced to room temperature, silicon carbide reactor device is taken out from burner hearth through fire door, and the quartz sand from feed pipe is poured out gas-solid reaction, completes whole gas-solid reaction flow process.
The reaction method of described glass sand high temperature gas-solid reaction unit, is characterized in that comprising the following steps 2) in: described mixed gas flow is 1000-4000ml/min, preferably 2000-3000ml/min, more preferably 2500-3000ml/min; Mixture pressure is 0.08-0.7Mpa, preferably 0.1-0.5Mpa, more preferably 0.2-0.3Mpa; HCl, Cl2、N2, Ar volume ratio be 15-1:1-15:2:2, preferably 10-1:1-10:2:2.
The reaction method of described glass sand high temperature gas-solid reaction unit, is characterized in that comprising the following steps 3) in: 1250-1350 ° of C of gas-solid reaction temperature, preferably 1300-1320 ° of C; Reaction time is 80-150min, preferably 100-140min, more preferably 120-130min.
Above-mentioned glass sand high temperature gas-solid reaction unit and reaction method thereof, glass sand gas-solid reaction temperature can be brought up to 1400 ° of C, the effect of removing fluid impurity and metallic element impurity is better, fully contact because gaseous state material runs through the solid bed of material in addition, thereby greatly improved gas-solid reaction efficiency and reaction effect thereof.
Brief description of the drawings
Fig. 1 is the structural representation of gas-solid reaction device of the present invention;
Fig. 2 is gas preheating chamber cross section schematic diagram;
Fig. 3 is porous demarcation strip generalized section;
Fig. 4 is porous demarcation strip floor map;
Fig. 5 is the bracket generalized section of porous demarcation strip;
Fig. 6 is the bracket schematic top plan view of porous demarcation strip;
Fig. 7 be infrared spectrometer to quartz sand fluid impurity test result comparison diagram, figure Raw A is quartz sand raw material A;
Fig. 8 be infrared spectrometer to quartz sand fluid impurity test result comparison diagram, figure Raw B is quartz sand raw material B;
In figure: 1-gas-solid reaction chamber, 2-gas preheating chamber, 3-porous demarcation strip, 4-porous demarcation strip bracket, 5-feed pipe, 6-air inlet pipe, 7-support, 8-burner hearth, 9-heater, 10-insulation material, 11-fire door, 12-aperture A, 12a-aperture B.
Detailed description of the invention
The present invention relates generally to the chemical reaction of gaseous state material and solid material (quartz sand), the efficiency of gas-solid reaction and effect, except with reaction raw materials nature and raw material proportioning (internal cause) mutually outside the Pass, also be limited by mixing or the exposure level (external cause) of reaction temperature, reaction time and material, in order to obtain best gas-solid reaction effect, must consider various possible influence factors simultaneously; In above-mentioned influence factor, except obtaining the primary raw material of required product, all the other factors can be by selecting different reaction methods to affect gas-solid reaction effect, and the mixing of material or exposure level are except outside the Pass having with reaction method, also relevant with the structure of reaction unit; Applicant is considering, after the various influence factors of glass sand gas-solid reaction, to have invented glass sand high temperature gas-solid reaction unit and reaction method thereof. Below in conjunction with Figure of description, the invention will be further described.
As shown in the figure, this glass sand high temperature gas-solid reaction unit, comprise silicon carbide reactor device and high temperature heater (HTH), described silicon carbide reactor device is made up of porous demarcation strip 3 and separated gas-solid reaction chamber 1 thereof, gas preheating chamber 2,1 upper end, gas-solid reaction chamber, top arranges feed pipe 5, and lower gas preheating chamber 2 arranges air inlet pipe 6, described high temperature heater (HTH) comprises the cuboid burner hearth 8 of being made up of insulation material 10, cuboid burner hearth 8 up and down four sides hearth wall in one group of heater 9 is all set, cuboid burner hearth 8 arranges fire door 11, rear wall arranges aperture A12, aperture B12a, silicon carbide reactor device is through the fire door 11 of high temperature heater (HTH), be placed in burner hearth 8 by support 7, the feed pipe 5 of silicon carbide reactor device extends high temperature heater (HTH) through aperture A12, and the air inlet pipe 6 of silicon carbide reactor device is extended high temperature heater (HTH) through aperture B12a. feed pipe 5 is double solid material discharge nozzle and exhaust pipe simultaneously. aperture A12, aperture B12a configure supporting insulation material, in the time not carrying out gas-solid reaction experiment, produce, utilize aperture in insulation material shutoff, make heater can be used as common high-temperature electric resistance furnace and use. solid powder material (quartz sand) is positioned on porous demarcation strip, gaseous state material enters gas preheating chamber by air inlet pipe, gaseous state material after preheating is under fluid pressure action, through the upwards gas-solid reaction chamber infiltration of portion of trickle hole of porous demarcation strip, and run through solid powder material (quartz sand) on porous demarcation strip layer, reacted waste gas is discharged reactor from the exhaust pipe (feed pipe) of reative cell upper end, thereby realize fully contacting of gaseous state material and solid material, simultaneously, due to hot diffusion, convection action, under heat energy effect, gaseous state material also can Upward Migration, solid material (quartz sand) layer that forces gaseous state material to pass through to be positioned on porous demarcation strip 3, visible heat energy has also become to make gas, Gu the power that material fully contacts, be that gas solid reactor structure of the present invention makes fluid pressure and heat energy become the dual guarantee that gaseous state material fully contacts with solid material. in the time selecting carborundum as gas solid reactor material, the greatest problem running into can not be carried out post-production or secondary operations exactly, this just causes a lot of complicated structures owing to being subject to the impact of processing technology, can not make by later stage welding processing like that by image-stone quartz glass article, show as in the present invention porous demarcation strip 3 and can not directly process between gas-solid reaction chamber 1 and gas preheating chamber 2, porous demarcation strip 3 can not connect into an entirety with gas-solid reaction chamber 1 and gas preheating chamber 2, for the ease of settling, fix porous demarcation strip 3,1 bottom, gas-solid reaction chamber is designed to taper by the present invention, to reduce the size of porous demarcation strip 3, the diameter of porous demarcation strip 3 is greater than the circular hole between gas-solid reaction chamber 1 and gas preheating chamber 2, thickness 5-20mm, aperture so that solid powder material can not by and gaseous state material can be smooth and easy flows and is advisable, be generally the particle diameter that is slightly less than solid powder material. porous demarcation strip is equipped with porous demarcation strip bracket 4 for 3 times, porous demarcation strip bracket 4 is the carborundum tube of a hollow, porous demarcation strip bracket 4 one end are fixed in the circular groove 2a of gas preheating chamber 2 interior settings, porous demarcation strip bracket 4 other ends are by thickening outer wall, make its card holder in air inlet pipe 6, on porous demarcation strip bracket 4, be provided with the pallet 4a for fixing porous demarcation strip 3, porous demarcation strip 3 card holders are on the pallet 4a of the porous demarcation strip bracket 4 of hollow, and bracket 4 is settled from air inlet pipe 6, compartmentation is played at the circular hole place being fixed between reative cell 1 and gas preheating chamber 2. pallet 4a bottom arranges hole 4a-1, and hole 4a-1 is communicated with the through hole of porous demarcation strip 3, and the hole 4a-1 of mid portion is communicated with porous demarcation strip bracket 4 hollow tubes, and the hole 4a-1 of other parts is communicated with gas preheating chamber 2. gaseous state material just mainly enters gas preheating chamber 2 by the porous demarcation strip bracket 4 of hollow, and the part hole 4a-1 being communicated with carborundum tube through pallet 4a bottom, be penetrated into gas-solid reaction chamber 1 through porous demarcation strip 3, and by diffusion along taper surface Upward Migration, run through solid powder material (quartz sand) layer, all solid materials can fully be contacted with gaseous state material, due to not sealing between porous demarcation strip bracket 4 and air inlet pipe 6, a small amount of gaseous state material can enter gas preheating chamber 2 by the gap between porous demarcation strip bracket 4 and air inlet pipe 6, part hole 4a-1 that this part gaseous state material just can be by not being communicated with porous demarcation strip bracket 4 carborundum tubes bottom porous demarcation strip bracket 4 top tray 4a, is penetrated into gas-solid reaction chamber 1 through porous demarcation strip 3.
For glass sand high temperature gas-solid reaction is carried out smoothly under desired reaction temperature, the present invention selects the material of carborundum as glass sand gas solid reactor, and the goods of silicon carbide material can tolerate 1400 ° of high temperature more than C. At high temperature, first silicon carbide articles forms one deck quartz glass at surface oxidation, and quartz glass has very high heat endurance and chemical stability, thereby silicon carbide articles is played a very good protection; Make gas solid reactor with respect to direct use quartz glass, silicon carbide material has better temperature tolerance, because quartz glass product is worked for a long time under 1200 ° of C, will there is certain ruckbildung, like this under glass deadweight and solid material extruding, will there is creep, affect the use of gas solid reactor; Quartz glass product uses for a long time under 1200 ° of C simultaneously, is easy to produce crystallization or devitrification phenomenon, destroys the structure of glass, affects heat endurance and the mechanical strength of quartz glass; And the quartz glass layer on silicon carbide articles surface, owing to being subject to the support of internal layer carborundum, even also can not be out of shape under the high temperature of 1400 ° of C, same, even if top layer quartz glass has some crystallizatioies, also can not affect temperature tolerance and the mechanical performance of overall silicon carbide articles. The present invention adopts high temperature heater (HTH) to obtain the required high temperature of glass sand gas-solid reaction; Described heater 9 is Elema or Si-Mo rod, mainly selects according to the temperature range of need heating, and as preferred version, the present invention adopts Elema as heater.
The reaction method that adopts above-mentioned glass sand high temperature gas-solid reaction unit, comprises the following steps:
1) first porous demarcation strip 3 is placed in the pallet 4a of porous demarcation strip bracket 4, porous demarcation strip bracket 4 is placed in gas preheating chamber 2 through the air inlet pipe 6 of silicon carbide reactor device, porous demarcation strip 3 is placed between gas-solid reaction chamber 1 and gas preheating chamber 2 and plays compartmentation, quartz sand is joined in gas-solid reaction chamber 1 through the feed pipe 5 of silicon carbide reactor device, quartz sand is subject to stopping of porous demarcation strip 3 and is placed on porous demarcation strip 3 again; Then by silicon carbide reactor device through the fire door 11 of high temperature heater (HTH), be placed in burner hearth 8 by support 7, the feed pipe 5 of silicon carbide reactor device extends high temperature heater (HTH) through aperture A12, and the air inlet pipe 6 of silicon carbide reactor device is extended high temperature heater (HTH) through aperture B12a;
2) start high temperature heater (HTH), set 1200-1400 ° of C of gas-solid reaction temperature, when burner hearth 8 temperature reach after set reaction temperature, open mist feeder, by mist through air inlet pipe 6, porous demarcation strip bracket 4 passes in gas preheating chamber 2 and porous demarcation strip bracket 4, mist after preheating is under the double action of stream pressure and heat energy, through the hole 4a-1 of porous demarcation strip bracket 4 top tray 4a bottoms, see through porous demarcation strip 3 and be penetrated into gas-solid reaction chamber 1, described mist is 500-5000ml/min flow, pressure is the HCl of 0.05-0.8MPa, Cl2、N2With Ar mixed gas flow, HCl, Cl2、N2, Ar volume ratio be 20-1:1-20:2:2;
3) all mists after preheating, be all under the double action of fluid pressure and heat energy the taper surface Upward Migration along gas-solid reaction chamber 1, run through quartz sand layer, make the abundant haptoreaction of mist and quartz sand, quartz sand under 1200-1400 ° of C with mist generation gas-solid reaction 60-180min; Reacted waste gas is discharged silicon carbide reactor device through feed pipe 5;
4) reaction is closed high temperature heater (HTH) after finishing, is closed mist feeder, after temperature is reduced to room temperature, silicon carbide reactor device is taken out from burner hearth 8 through fire door 11, pours out the quartz sand gas-solid reaction from feed pipe 5, completes whole gas-solid reaction flow process.
Described mixed gas flow is 1000-4000ml/min, preferably 2000-3000ml/min, more preferably 2500-3000ml/min; Mixture pressure is 0.08-0.7Mpa, preferably 0.1-0.5Mpa, more preferably 0.2-0.3Mpa; HCl, Cl2、N2, Ar volume ratio be 20-1:1-20:2:2, preferably 15-1:1-15:2:2, more preferably 10-1:1-10:2:2. 1250-1350 ° of C of gas-solid reaction temperature, preferably 1300-1320 ° of C; Reaction time is 80-150min, preferably 100-140min, more preferably 120-130min.
Quartz mineral is in nature crystallization, growth course, surrounding medium can be wrapping to crystals and form inclusion enclave, while selecting glass sand raw materials for production, only may select inclusion enclave is taking fluid inclusion as main ore, fluid composition, taking liquid (water) and gas (CO2) as main, wherein can be dissolved with a small amount of impurity metallic elements; And the Al3+ element of minute quantity can substitute Si4+ element and enters quartzy lattice in crystallization process medium, Na+, K+, Li+ element can enter lattice in the mode of balance electricity price simultaneously, thereby form the metallic element impurity in quartz crystal. Quartz sand is carried out to high temperature gas-solid reaction, be exactly by the fluid inclusion explosion in quartz particles (crystal) by high temperature action, make fluid all with the gaseous state mode particle of overflowing, the reacting gas being passed into is taken reaction unit out of, and reaction gas know from experience by fluid inclusion, dissolve, to remain in a small amount of metallic element gas in parcel body lumen wall after explosion molten in reacting gas, and takes reaction unit out of; Simultaneously, in order to Na+, K+, the Li+ alkali metal of balance electricity price, the high activity reacting gas that is easy to be passed under high temperature action from quartz particles surface active, transfer to gas phase, taken away and remove by gas, the alkali metal of granule interior is because of high temperature action increased activity, can be diffused rapidly to particle surface to reach concentration balance, be diffused into surperficial alkali metal again by the follow-up activation of high activity reacting gas, transfer, the removal passing into, such gas-solid reaction is continued until that the gas-solid reaction time finishes. Theoretically, glass sand gas-solid reaction temperature is more high better, reaction time, the longer the better, the high activity reaction gas flow passing into is the bigger the better, but in actual production, the ability to bear that must consider production cost and reaction unit, it is necessary to formulate rational reaction method and obtains optimum response effect.
Applicant shows the research of fluid inclusion in quartz, and gas liquid inclusion is about 95% the meeting generation of 120min explosion under 1200 ° of C, and extending warm-up time has affected not quite; And under 1300 ° of C 30min, have more than 97% gas liquid inclusion explosion; Along with improving constantly of heating-up temperature, also have tiny gas liquid inclusion explosion, but explosion effect is more and more not remarkable. And the experimental study of quartz sand high-temperature gasification reaction is shown, quartz sand is at 1200 ° of C and high activity mixed gas reaction 120min, and the clearance of alkali metal can reach 80% left and right; And under 1300 ° of C, react 60-180min, and the clearance of alkali metal can arrive 85% left and right, and some samples even can arrive 95%; Along with the raising of reaction temperature, the clearance of alkali metal also can improve constantly, but consider the factors such as the ability to bear of reaction unit, applicant selects quartz sand gas-solid reaction temperature at 1200-1400 ° of C, reaction time 60-180min, just can reach the effect of desirable removal fluid impurity and metallic element impurity.
Described mist is the mixed gas flow that 500-5000ml/min flow, pressure are 0.05-0.8MPa, HCl, Cl2、N2Compare for 20-1:1-20:2:2 with the mixed volume of Ar. The Main Function of high activity mist: at high temperature, by the gaseous impurities after fluid inclusion explosion take out of reaction unit, by remain in impurity metallic elements gas on Fluid inclusions body cavity wall molten to taking reaction unit out of after mist, by the alkali metal Mobilization on quartz particles surface in gas phase (high activity mist) and take reaction unit out of. Mist must be constantly updated in reaction unit, but its flow can not be too large, because the inflow of mist all needs to consume heat energy with outflow in reaction unit, the fluctuation of the temperature that induces reaction, considers used high activity gas (HCl and Cl simultaneously2) be high risk gas, flow is greatly to exhaust-gas treatment meeting mineralization pressure; And every kind of element solubility (or dividing potential drop) at a certain temperature, in a certain gas is certain, in unit volume, gaseous species amount of element more, that dissolve are just larger; Therefore, applicant selects to reach by the kind of increase mist the object that improves glass sand high temperature gas-solid reaction effect, at high activity gas HCl and Cl2Middle increase inert gas N2With Ar, and on experimental study basis, obtain mist HCl, Cl2、N2With the mixed volume proportioning of Ar be 20-1:1-20:2:2.
Embodiment 1
Glass sand high temperature gas-solid reaction is the critical process in glass sand production process, carry out high temperature gas-solid reaction by quartz glass reactor at present, its serviceability temperature is up to 1200 ° of C, and long-term serviceability temperature is no more than 1150 ° of C, and the gaseous state material of use is HCl and Cl2Mist, mixed volume is than for 19:1-3:2; Embodiment contrasts the temperature to high temperature gas-solid reaction and mist, shows gas-solid reaction effect of the present invention, but does not limit therefrom the present invention.
First porous demarcation strip 3 is placed in the pallet 4a of porous demarcation strip bracket 4, porous demarcation strip bracket 4 is placed in gas preheating chamber 2 through the gaseous state material air inlet pipe 6 of silicon carbide reactor device, porous demarcation strip 3 is placed between gas-solid reaction chamber 1 and gas preheating chamber 2 and plays compartmentation; Then the 100g quartz sand raw material A that is 0.1-0.25mm by particle diameter joins in gas-solid reaction chamber 1 through the feed pipe 5 of carborundum gas solid reactor, quartz sand is subject to stopping of porous demarcation strip 3 and is placed in the gas-solid reaction chamber 1 on demarcation strip 3, by gas solid reactor heater via fire door 11, be placed in burner hearth 8 by support 7, feed pipe 5 and air inlet pipe 6 respectively the aperture A12 on burner hearth 8 rear walls and aperture B12a are extended heater; Select HCl and Cl2Mist do reacting gas, HCl and Cl2Mixed volume than for 10:1, mist feeder is connected with the air inlet pipe 6 on silicon carbide reactor device, gas sampling, treating apparatus are connected with the double discharge nozzle 5 of feed pipe 5 and exhaust pipe 5 on silicon carbide reactor device; Start high temperature heater (HTH), set 1200 ° of C of gas-solid reaction temperature, when fire box temperature reaches after set reaction temperature, open mist feeder, set pressure 0.2MPa, the flow 1100ml/min of mist, silicon carbide reactor device is carried to mist; Mist adds the gas preheating chamber 2 of gas solid reactor through air inlet pipe 6, mist after preheating is under the double action of stream pressure and heat energy, through the hole 4a-1 of porous demarcation strip bracket 4 top tray 4a bottoms, see through porous demarcation strip 3 and be penetrated into gas-solid reaction chamber 1, and by diffusion along the taper surface Upward Migration of gas-solid reaction chamber 1, run through quartz sand layer, make quartz sand fully contact, react with mist under 1200 ° of C; Reacted waste gas, continues to rise, arrive 1 top, gas-solid reaction chamber, discharges reactor through the double exhaust pipe 5 of solid material feed pipe 5, and through neutralisation treatment; Be set under 1200 ° of C high temperature, quartz sand and mixed gas reaction 120min, reach after the reaction time, close high temperature heater (HTH), close mist feeder, after temperature is reduced to room temperature, take off mist feeder and gas sampling, treating apparatus from silicon carbide reactor device, open fire door 11, reactor is taken out from burner hearth 8 through fire door 11, pour out the quartz sand (finished product) gas-solid reaction from the double discharge nozzle 5 of solid material charging material pipe 5 and exhaust pipe 5, complete whole gas-solid reaction flow process. The finished product quartz sand of learning from else's experience after gas-solid reaction, utilize ICP-MS and infrared spectrometer to carry out glass sand the key technical indexes---the test of metallic element impurity and fluid impurity content, with the impurity-eliminating effect of inspection quartz sand high temperature gas-solid reaction, ICP-MS is to quartz sand metallic element impurity test result in table 1, and infrared spectrometer is shown in Fig. 7 to quartz sand fluid impurity test result; Fluid impurity in Fig. 7 (water comprises hydroxyl) test peak position: 2800-3800cm-1, the darker fluid impurity of peak valley is more.
Embodiment 2
Select quartz sand raw material A and the gas-solid reaction temperature identical with embodiment 1, except mist is adjusted into HCl, Cl2、N2Mix with Ar, the mixed volume ratio of mist is that 10:1:2:2(mixture pressure and flow are constant) outside, adopt with the identical method and apparatus of embodiment 1 and carry out gas-solid reaction, wherein gas-solid reaction temperature is 1200 ° of C. Get reacted finished product quartz sand, carry out the test of metallic element impurity and fluid impurity content, with the impurity-eliminating effect of inspection quartz sand high temperature gas-solid reaction, ICP-MS is to quartz sand metallic element impurity test result in table 1, and infrared spectrometer is shown in Fig. 7 to quartz sand fluid impurity test result.
Embodiment 3
Select quartz sand raw material A and the mist feature identical with embodiment 2, except gas-solid reaction temperature setting being set to 1300 ° of C, adopt with the identical method and apparatus of embodiment 2 and carry out gas-solid reaction, wherein mist HCl, Cl2、N2Compare for 10:1:2:2 pressure 0.2MPa, the flow 1100ml/min of mist with the mixed volume of Ar. Get reacted finished product quartz sand, carry out the test of metallic element impurity and fluid impurity content, with the impurity-eliminating effect of inspection quartz sand high temperature gas-solid reaction, ICP-MS is to quartz sand metallic element impurity test result in table 1, and infrared spectrometer is shown in Fig. 7 to quartz sand fluid impurity test result.
Embodiment 4
Select the 100g quartz sand raw material B that particle diameter is 0.1-0.25mm, its metallic element impurity content, apparently higher than quartz sand raw material A (in table 1), is adjusted mist HCl, Cl2、N2Than being 1:10:2:2, the pressure that mist is set is 0.3MPa, flow 3000ml/min with the mixed volume of Ar; Adopt with the identical method and apparatus of embodiment 3 and carry out gas-solid reaction, wherein gas-solid reaction temperature is 1300 ° of C. Get reacted finished product quartz sand, carry out the test of metallic element impurity and fluid impurity content, with the impurity-eliminating effect of inspection quartz sand high temperature gas-solid reaction, ICP-MS is to quartz sand metallic element impurity test result in table 1, and infrared spectrometer is shown in Fig. 8 to quartz sand fluid impurity test result.
Embodiment 5
Select quartz sand raw material B and the mist feature identical with embodiment 4, except gas-solid reaction temperature being adjusted into 1350 ° of C, adopt with the identical method and apparatus of embodiment 4 and carry out gas-solid reaction, wherein mist HCl, Cl2、N2Than being 1:10:2:2, pressure is 0.3MPa, flow 3000ml/min with the mixed volume of Ar. Get reacted finished product quartz sand, carry out the test of metallic element impurity and fluid impurity content, with the impurity-eliminating effect of inspection quartz sand high temperature gas-solid reaction, ICP-MS is to quartz sand metallic element impurity test result in table 1, and infrared spectrometer is shown in Fig. 8 to quartz sand fluid impurity test result.
Table 1 quartz sand metallic element impurity test result (unit: ppm)
| Sample number | Al | Ti | Fe | Mn | Mg | Ca | Na | K | Li |
| Raw material A | 20.66 | 3.67 | 1.76 | 0.60 | 0.66 | 1.15 | 4.54 | 1.91 | 1.07 |
| Embodiment 1 | 18.76 | 2.18 | 0.30 | 0.33 | 0.44 | 0.77 | 0.96 | 0.78 | 0.86 |
| Embodiment 2 | 18.15 | 2.03 | 0.34 | 0.30 | 0.24 | 0.55 | 0.74 | 0.61 | 0.70 |
| Embodiment 3 | 17.12 | 1.51 | 0.07 | 0.01 | 0.07 | 0.50 | 0.37 | 0.29 | 0.42 |
| Raw material B | 20.97 | 2.42 | 2.63 | 0.72 | 0.98 | 1.90 | 12.15 | 5.18 | 1.64 |
| Embodiment 4 | 16.43 | 1.36 | 0.12 | 0.03 | 0.11 | 0.49 | 0.47 | 0.37 | 0.51 |
| Embodiment 5 | 15.92 | 1.05 | 0.03 | 0.01 | 0.09 | 0.28 | 0.27 | 0.25 | 0.26 |
Claims (10)
1. glass sand high temperature gas-solid reaction unit, it is characterized in that comprising silicon carbide reactor device and high temperature heater (HTH), described silicon carbide reactor device is made up of porous demarcation strip (3) and separated gas-solid reaction chamber (1) thereof, gas preheating chamber (2), upper end, gas-solid reaction chamber, top (1) arranges feed pipe (5), and lower gas preheating chamber (2) arranges air inlet pipe (6), described high temperature heater (HTH) comprises the cuboid burner hearth (8) of being made up of insulation material (10), cuboid burner hearth (8) up and down four sides hearth wall in one group of heater (9) is all set, cuboid burner hearth (8) arranges fire door (11), rear wall arranges aperture A(12), aperture B(12a), silicon carbide reactor device is placed in burner hearth (8) through the fire door (11) of high temperature heater (HTH), the feed pipe (5) of silicon carbide reactor device is through aperture A(12) extend high temperature heater (HTH), the air inlet pipe (6) of silicon carbide reactor device is through aperture B(12a) extend high temperature heater (HTH).
2. glass sand high temperature gas-solid reaction unit as claimed in claim 1, it is characterized in that being equipped with under porous demarcation strip (3) porous demarcation strip bracket (4), porous demarcation strip bracket (4) is the carborundum tube of a hollow, porous demarcation strip bracket (4) one end is fixed in the circular groove (2a) arranging in gas preheating chamber (2), porous demarcation strip bracket (4) other end is by thickening outer wall, make its card holder in air inlet pipe (6), on porous demarcation strip bracket (4), be provided with the pallet (4a) for fixing porous demarcation strip (3), porous demarcation strip (3) card holder is in pallet (4a), pallet (4a) bottom arranges hole (4a-1), hole (4a-1) is communicated with the through hole of porous demarcation strip (3), the hole (4a-1) of mid portion is communicated with porous demarcation strip bracket (4) hollow tube, the hole (4a-1) of other parts is communicated with gas preheating chamber (2).
3. glass sand high temperature gas-solid reaction unit as claimed in claim 1, is characterized in that bottom, gas-solid reaction chamber (1) is pyramidal structure.
4. glass sand high temperature gas-solid reaction unit as claimed in claim 1, is characterized in that described heater (9) is Elema or Si-Mo rod.
5. glass sand high temperature gas-solid reaction unit as claimed in claim 1, is characterized in that the diameter of porous demarcation strip (3) is greater than the circular hole between gas-solid reaction chamber (1) and gas preheating chamber (2), and porous demarcation strip (3) thickness is 5-20mm.
6. the reaction method that adopts glass sand high temperature gas-solid reaction unit claimed in claim 1, is characterized in that comprising the following steps:
1) first quartz sand is joined in gas-solid reaction chamber (1) through the feed pipe (5) of silicon carbide reactor device, quartz sand is subject to stopping of porous demarcation strip (3) and is placed on porous demarcation strip (3);
2) start high temperature heater (HTH), set 1200-1400 ° of C of gas-solid reaction temperature, when burner hearth (8) temperature reaches after set reaction temperature, open mist feeder, the gas preheating chamber (2) that mist is passed into silicon carbide reactor device through air inlet pipe (6), described mist is HCl, the Cl that 500-5000ml/min flow, pressure are 0.05-0.8MPa2、N2With Ar mixed gas flow, HCl, Cl2、N2, Ar volume ratio be 20-1:1-20:2:2;
3) described mist sees through porous demarcation strip (3) and is penetrated into gas-solid reaction chamber (1), and by diffusion along the taper surface Upward Migration of gas-solid reaction chamber (1), run through quartz sand layer, make the abundant haptoreaction of mist and quartz sand, quartz sand under 1200-1400 ° of C with mist generation gas-solid reaction 60-180min; Reacted waste gas is discharged silicon carbide reactor device through feed pipe (5);
4) reaction is closed high temperature heater (HTH) after finishing, is closed mist feeder, after temperature is reduced to room temperature, silicon carbide reactor device is taken out from burner hearth (8) through fire door (11), pour out the quartz sand gas-solid reaction from feed pipe (5), complete whole gas-solid reaction flow process.
7. the reaction method that adopts glass sand high temperature gas-solid reaction unit claimed in claim 1, is characterized in that comprising the following steps:
1) first porous demarcation strip (3) is placed in the pallet (4a) of porous demarcation strip bracket (4), porous demarcation strip bracket (4) is placed in gas preheating chamber (2) through the air inlet pipe (6) of silicon carbide reactor device, porous demarcation strip (3) is placed between gas-solid reaction chamber (1) and gas preheating chamber (2) and plays compartmentation, quartz sand is joined in gas-solid reaction chamber (1) through the feed pipe (5) of silicon carbide reactor device, quartz sand is subject to stopping of porous demarcation strip (3) and is placed on porous demarcation strip (3) again; Then silicon carbide reactor device is placed in burner hearth (8) through the fire door (11) of high temperature heater (HTH), the feed pipe (5) of silicon carbide reactor device is through aperture A(12) extend high temperature heater (HTH), the air inlet pipe (6) of silicon carbide reactor device is through aperture B(12a) extend high temperature heater (HTH);
2) start high temperature heater (HTH), set 1200-1400 ° of C of gas-solid reaction temperature, when burner hearth (8) temperature reaches after set reaction temperature, open mist feeder, by mist through air inlet pipe (6), porous demarcation strip bracket (4) passes in gas preheating chamber (2) and porous demarcation strip bracket (4), mist after preheating is under the double action of stream pressure and heat energy, through the hole (4a-1) of porous demarcation strip bracket (4) top tray (4a) bottom, see through porous demarcation strip (3) and be penetrated into gas-solid reaction chamber (1), described mist is 500-5000ml/min flow, pressure is the HCl of 0.05-0.8MPa, Cl2、N2With Ar mixed gas flow, HCl, Cl2、N2, Ar volume ratio be 20-1:1-20:2:2;
3) described mist by diffusion along the taper surface Upward Migration of gas-solid reaction chamber (1), run through quartz sand layer, make the abundant haptoreaction of mist and quartz sand, quartz sand under 1200-1400 ° of C with mist generation gas-solid reaction 60-180min; Reacted waste gas is discharged silicon carbide reactor device through feed pipe (5);
4) reaction is closed high temperature heater (HTH) after finishing, is closed mist feeder, after temperature is reduced to room temperature, silicon carbide reactor device is taken out from burner hearth (8) through fire door (11), pour out the quartz sand gas-solid reaction from feed pipe (5), complete whole gas-solid reaction flow process.
8. reaction method as claimed in claim 6, is characterized in that comprising the following steps 2) in: described mixed gas flow is 1000-4000ml/min, and mixture pressure is 0.08-0.7MPa, HCl, Cl2、N2, Ar volume ratio be 15-1:1-15:2:2.
9. reaction method as claimed in claim 6, is characterized in that comprising the following steps 2) middle HCl, Cl2、N2, Ar volume ratio be 10-1:1-10:2:2.
10. reaction method as claimed in claim 6, is characterized in that comprising the following steps 3) in: 1250-1350 ° of C of gas-solid reaction temperature, the reaction time is 80-150min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310736775.0A CN103706306B (en) | 2013-12-27 | 2013-12-27 | Glass sand high temperature gas-solid reaction unit and reaction method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310736775.0A CN103706306B (en) | 2013-12-27 | 2013-12-27 | Glass sand high temperature gas-solid reaction unit and reaction method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103706306A CN103706306A (en) | 2014-04-09 |
| CN103706306B true CN103706306B (en) | 2016-05-04 |
Family
ID=50399866
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310736775.0A Expired - Fee Related CN103706306B (en) | 2013-12-27 | 2013-12-27 | Glass sand high temperature gas-solid reaction unit and reaction method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103706306B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1146429A (en) * | 1995-04-10 | 1997-04-02 | 赫罗伊斯石英玻璃有限公司 | Method for continuous refining of quartz powder |
| CN200999203Y (en) * | 2006-12-31 | 2008-01-02 | 陈士斌 | Quartz sand high-heating calcining evaporated purification apparatus |
| CN101723387A (en) * | 2009-12-11 | 2010-06-09 | 南京大学 | Method and device for producing high purity quartz sand |
| CN203678355U (en) * | 2013-12-27 | 2014-07-02 | 浙江永强石英科技发展股份有限公司 | High-temperature gas-solid reaction device for high-purity quartz sand |
-
2013
- 2013-12-27 CN CN201310736775.0A patent/CN103706306B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1146429A (en) * | 1995-04-10 | 1997-04-02 | 赫罗伊斯石英玻璃有限公司 | Method for continuous refining of quartz powder |
| CN200999203Y (en) * | 2006-12-31 | 2008-01-02 | 陈士斌 | Quartz sand high-heating calcining evaporated purification apparatus |
| CN101723387A (en) * | 2009-12-11 | 2010-06-09 | 南京大学 | Method and device for producing high purity quartz sand |
| CN203678355U (en) * | 2013-12-27 | 2014-07-02 | 浙江永强石英科技发展股份有限公司 | High-temperature gas-solid reaction device for high-purity quartz sand |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103706306A (en) | 2014-04-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102432022B (en) | Method for producing ultra-pure quartz sand by vein quartz and high-temperature chlorination device | |
| CN101585536B (en) | Device and method for purifying solar energy level polysilicon | |
| CN105463506B (en) | A kind of method for separating and recovering electrolyte and carbon in aluminium electrolyte anodic carbon residue | |
| TW201033123A (en) | Method for manufacturing a silicon material with high purity | |
| CN101353167A (en) | Preparation of hyperpure metallurgy silicon | |
| CN104370438A (en) | Molten glass clarifying and homogenizing device and method | |
| CN109665528A (en) | Method containing corundum type quartzite preparation use for electronic products high purity quartz emery dust | |
| CN111153409A (en) | Method for purifying quartz sand by removing iron through microwave heating and ultrasonic-assisted acid leaching | |
| CN103395787A (en) | Apparatus and preparation method for high purity silicon from silicon ore | |
| CN106957061A (en) | The boron chloride process units and method of a kind of low phosgene content | |
| CN106219488B (en) | A kind of method and device preparing hydrochloric acid and purifying quartz sand | |
| CN101426740A (en) | Manufacture of large articles in synthetic vitreous silica | |
| CN203678355U (en) | High-temperature gas-solid reaction device for high-purity quartz sand | |
| CN103708474A (en) | Device and method for continuous high-temperature gas-solid reaction of high purity quartz sand | |
| CN201125165Y (en) | Polysilicon reducing furnace having double cooling system | |
| CN103706306B (en) | Glass sand high temperature gas-solid reaction unit and reaction method thereof | |
| CN107098351A (en) | A kind of horizontal quartz sand high-temperature gasification purifying plant | |
| CN103172381A (en) | Preparation method and applications of cold-wall fluidized bed | |
| CN102328929A (en) | Purifying process of silicon carbide micropowder | |
| CN102432020B (en) | Manufacturing method of solar grade polysilicon | |
| CN203683101U (en) | High purity quartz sand continuous high temperature gas-solid reaction device | |
| CN106430939A (en) | Production process of basalt scales | |
| CN201525754U (en) | Polysilicon experiment reduction furnace | |
| CN101066762A (en) | High purity silicon preparing oxygen and chlorine refining process and apparatus | |
| CN110079361A (en) | The method and its equipment of the non-slag gasification production hydrogen-rich synthetic gas of petroleum coke |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160504 Termination date: 20181227 |