CN101113029B - Treatment recovery method for monocrystalline silicon cutting waste liquor - Google Patents
Treatment recovery method for monocrystalline silicon cutting waste liquor Download PDFInfo
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Abstract
A treatment and reclaim method of single crystal silicon cutting waste liquid comprises the steps: (1). the waste liquid is treated with diluted hydrochloric acid then is stirred and mixed to enable the liquid to become a flowable mixture; (2). the mixed material is heated to separate solid and liquid, by which water and polyethylene glycol are extracted. The polyethylene glycol is obtained by the process of condensation, dehydration and recovery. The solid after being separated is a crude solid mixture of silicon carbide and silicon; (3). the quadratic-cleaning solid mixture of silicon diluted and silicon is obtained after quadratic cleaning to the crude solid mixture obtained in step 2; (4). the mixture is treated by mixed acid liquid comprising HNO3+HF to recover and get silicon diluted and silicon. The method has easy operation, simple equipment, low cost, high efficiency in treatment and recovery. The allover recovery rate calculated based on the weight of waste liquid can reach 26-46 percent and the recovering material can reach or close to the standard index, and can be directly used in solar energy battery production, so the invented method has good economic benefit and also can greatly contribute to environment protective, thereby having large exploration prospect.
Description
Technical field
The invention relates to a kind of processing recovery method of monocrystalline silicon cutting waste liquor.
Background technology
Along with the growing tension of the energy and increasing the weight of of pollution, cause the attention that various countries use clean energy.The whole world all starts solar cell and builds agitation, and China's development solar cell development in recent years is very fast, and solar cell is used the also fast development of production that has impelled as the main raw material silicon single crystal of solar cell widely.The monocrystalline silicon piece that solar cell uses is to be formed by the silicon single crystal rod cutting processing, and silicon single crystal rod must use the cutting liquid of lubricated cooling effect in cutting process, therefore just produces a large amount of cutting waste liquors in cutting process.At present the cutting liquid that adopts usually at home is one and comprises polyoxyethylene glycol, silicon carbide, and trolamine, saponification liquor, the mixture of kerosene etc., so the COD value of cutting waste liquor substantially exceeds wastewater discharge standard, forbids discharging by environmental requirement.And do not find suitable liquid waste disposal recovery method at present, so domestic production factory can only stack a large amount of waste liquids, along with producing constantly development, also pile up like a mountain for the cutting waste liquor of Dui Jiing year in year out, become the Land Rover of pulling that enterprise continues production.Therefore urgently to seek the processing recovery method of a simple and effective monocrystalline silicon cutting waste liquor, main polyoxyethylene glycol, silicon carbide and the silicon of reclaiming from cutting waste liquor.Not only the processing of waste liquid is reclaimed and has been solved environmental issue, and very big economic benefit is arranged again.
Summary of the invention
The invention provides a kind of processing recovery method of monocrystalline silicon cutting waste liquor, the technical process of method is referring to Fig. 1, and this method comprises the following steps:
1. will remove the monocrystalline silicon cutting waste liquor of kerosene and put into the spraying agitator, adding dilute hydrochloric acid handles, the concentration of hydrochloric acid is 0.0001-0.4mol, and the per kilogram waste liquid adds the 100-500ml hydrochloric acid soln, and the circulation spraying was stirred 10-30 minute, get preliminary compound, discharge enters the spray mixing device, and recirculation spray mixing 10-30 minute, temperature rise to 30-50 ℃, get the secondary compound, discharge;
Factory will leave waste liquid in the bucket in and repeatedly incline and strain recovery, and kerosene is removed substantially in the therefore pending waste liquid.
Monocrystalline silicon cutting waste liquor is a thickness material that has solid powder/particle that viscosity is very big, is difficult for flowing carrying the art breading difficulty.The inventive method is handled waste liquid with dilute hydrochloric acid, generating salt by neutralizing effect removes the alkaline matter trolamine and the saponification liquor that contain in the waste liquid, the viscosity of waste liquid obviously reduces simultaneously, mix by the spraying of the circulation in spraying agitator and spray mixing device, make waste liquid become a uniform mixing material that easily flows and carry, be beneficial to art breading.
The spraying agitator is to stir by circulation spraying, the acid solution of adding is stirred evenly with the heavy-gravity waste liquid as far as possible and reacts.Compound is by first spray channel ejection in the spraying agitator, form a circulation on a large scale and mix, owing to form negative pressure in nozzle chambers, compound enters nozzle chambers by liquid flow hole again, form one again and mix among a small circle, can increase greatly like this and mix and reaction effect.
The constructional feature of spray mixing device is to be provided with spray channel and guide plate in its spraying plant, be provided with the turbulent flow road in the spray channel, the reynolds number Re (ratio of mass force during liquid-flow and internal friction is called Reynolds number) of liquid stream is greater than 3000, therefore liquid stream is turbulent flows, molecules strike and friction take place in compound in the turbulent flow road, compound is mixed and more refinement of particle, again because the setting of guide plate, make compound form and flee among a small circle, make mixing and reaction effect better.
2. the secondary compound of discharging from the spray mixing device enters solid-liquid separator, and compound is 50-80 ℃ electric heating panel heating by Heating temperature, and water vapor and polyoxyethylene glycol steam together, by the cooling of first condenser, the mixed solution of water and polyoxyethylene glycol.Enter and pass through circulation spraying dehydration 15-40 minute in the spraying water trap, temperature rises to 40-80 ℃, and moisture is by discharging in the spraying water trap, with regard to the recyclable polyoxyethylene glycol that gets.The solid-liquid separator bottom emits the thick solid mixture of silicon carbide and silicon;
The principle of work of spraying water trap is, the liquid stream of water and poly-second dimerization is turbulent flows in the turbulent flow road, molecules strike and friction take place in the turbulent flow road, make the more refinement of molecule particle of water and polyoxyethylene glycol, in the circulation spray mixing process, temperature rises gradually, and low-boiling water molecules just evaporation is discharged, thereby reaches the purpose of polyoxyethylene glycol dehydration.
3. the thick solid mixture of silicon carbide and silicon is sent in the first spraying cleanser, be incorporated as the water of the 10-20% amount of thick solid mixture weight, the spraying that circulates was together cleaned 10-30 minute, temperature rises to 40-80 ℃, clean the back mixture and put into first shaking table, separate " the shell residue " of removing light specific gravity, get the once cleaning solid mixture of silicon carbide and silicon.Send in the second spraying cleanser, after solid mixture equally heavily covered once circulation spraying cleaning again, mixture was put into second shaking table, separates and removes " shell residue ", obtains the secondary cleaning solid mixture of silicon carbide and silicon again;
The salt that the neutralization that contains in the thick solid mixture of silicon carbide and silicon generates and other impurity are wrapped in the outside of silicon carbide powder and silica flour grain closely with the form of " shell ", are difficult to remove.By spraying cleanser seconary water use clean, mix stirring and washing by circulating repeatedly, material molecule and water molecules bump and friction in the mixture, the material particles refinement, " shell " pine is split and comes off, played cleanup action, separate by shaking table again, because the difference of proportion makes silicon carbide separate with " shell residue " with silicon, after " the shell residue " told reclaims, might be used to as fertilizer sources and use.
4. the secondary cleaning solid mixture of silicon carbide and silicon is sent in the reactor, mat silicon generates the reaction of silicofluoric acid and makes silicon carbide and silicon Separation and Recovery in the solid mixture.Adding concentration is 5%HNO
3With concentration be the mix acid liquor that 30% HF forms, volume ratio is HNO
3: HF=1: 5, the solid mixture of per 1 kilogram of silicon carbide and silicon adds 1-1.5 kilogram mix acid liquor, circulation spraying stirring reaction 10-30 minute, temperature rises to reflux temperature, silicate fluoride solution steams, by second condenser cooling, reclaim water white silicate fluoride solution.Silicate fluoride solution is operated routinely, after its oven dry, can be processed into silicon single crystal and reclaim silicon.Residuum silicon carbide and acid solution in the reactor are filtered, and with the washing of 5-10wt% alkaline solution, washing is 7-7.5 to pH, drying, reclaim silicon carbide.Described alkaline solution can be selected NaOH for use, KOH or Na
3CO
3Prepare.
Be used to realize the device of the processing recovery method of monocrystalline silicon cutting waste liquor of the present invention, this device comprises:
Spray mixing device 50, by the spraying agitator 49 first drainage conduit 64 link to each other the structure of spray mixing device 50 (this equipment has been applied for utility model patent, and application number is 200620039272.3) with spray mixing device 50.See Fig. 4-6, mainly comprise mixing kettle 3, charging stock tank 6, spraying plant 5, surge pump 1, hot resistance temperature measuring head 2, three-way valve 7 and drainage conduit 4.The filling tube 9 of described charging stock tank 6 bottoms be installed in mixing kettle 3 on cover, and stretch in the mixing kettle 3.Described spraying plant 5 comprises spray channel 19 and guide plate 15.Spray channel 19 comprises the nozzle entrance 10 that communicates successively, turbulent flow road 11, hybrid chamber 12 and jet exit 13.Nozzle entrance 10 is doline, and the diameter in turbulent flow road 11 is 1.2-3mm, and two sides of hybrid chamber 12 walls respectively are provided with a liquid conductance mouth 14.Guide plate 15 is vertically to being arranged on the spray channel 19, and between liquid conductance mouth 14 and jet exit 13, is covered with aperture 16 on the guide plate 15, and the aperture of aperture 16 is 1-3mm, and the percentage of open area on the guide plate 15 is 60-80%.Described surge pump places on the connecting tube 8 between three-way valve 7 and the mixing kettle 3 bottom discharge mouths 18, and drainage conduit 4 links to each other with three-way valve 7.Described hot resistance temperature measuring head 2 is fixedly set in the mixing kettle 3, and the loam cake that passes mixing kettle 3 by lead links to each other with temperature indicator 17;
Solid-liquid separator 30, its structure is seen Fig. 7 and Fig. 8, mainly comprises spray header 31, steam outlet pipe 33, conical plate 42, doline plate 41 and solid outlet 37 etc.The drainage conduit 4 of spray mixing device links to each other with the spray header 31 that solid-liquid separator 30 top cover centers are provided with, be provided with symmetrical up and down two unitary electric heating panels that are fixed on the outer wall 36 in the solid-liquid separator 30, each unitary electric heating panel structure is: the top is a conical plate 42, the below is a doline plate 41 and hole 40, and the diameter of doline plate 41 is greater than the diameter of conical plate 42.Conical plate 42 is fixed on the locating pin 32 of 120 ℃ of arrangements of three one-tenth, and three locating pins 32 are fixed on the outer wall 36.Doline plate 41 is fixed on the pallet 35, and pallet 35 mat retaining screws 34 are fixed on the outer wall 36.Top cover is provided with steam outlet pipe 33, and the bottom is provided with solid outlet 37, is provided with baffle plate 39 around solid outlet 37, also is provided with a liquid exit 38 in the bottom;
Spraying water trap 51 (is seen Fig. 9, spraying plant 5 among Fig. 9 ' referring to Fig. 5-6), its structure is basic identical with spray mixing device 50, and the change in the structure is that top cover is provided with a water shoot 21, and solid-liquid separator 30 links to each other with spraying water trap 51 by first condenser in device.
The structure of spraying water trap 51 mainly comprise mixing kettle 3 ', charging stock tank 6 ', spraying plant 5 ', surge pump 1 ', hot resistance temperature measuring head 2 ', three-way valve 7 ', drainage conduit 4 ' and water shoot 21.The filling tube 9 of described charging stock tank 6 ' bottom ' be installed in mixing kettle 3 ' on cover, and stretch into mixing kettle 3 ' in.Mixing kettle 3 ' on cover and also be provided with a water shoot 21.Described spraying plant 5 ' comprise spray channel 19 ' and guide plate 15 '.The nozzle entrance 10 that spray channel 19 ' comprise communicates successively ', turbulent flow road 11 ', hybrid chamber 12 ' with jet exit 13 '.Nozzle entrance 10 ' be doline, turbulent flow road 11 ' diameter be 1.2-3mm, two sides of hybrid chamber 12 ' wall respectively be provided with a liquid conductance mouth 14 '.Guide plate 15 ' vertically to be arranged on spray channel 19 ' on, and liquid conductance mouth 14 ' and jet exit 13 ' between, guide plate 15 ' on be covered with aperture 16 ', aperture 16 ' the aperture be 1-3mm, guide plate 15 ' on percentage of open area be 60-80%.Described surge pump 1 ' place three-way valve 7 ' and mixing kettle 3 ' bottom discharge mouth 18 ' between connecting tube 8 ' on, drainage conduit 4 ' with three-way valve 7 ' link to each other.Described hot resistance temperature measuring head 2 ' be fixedly set in mixing kettle 3 ' in, and by lead pass mixing kettle 3 ' loam cake and temperature indicator 17 ' link to each other;
The first spraying cleanser (figure does not draw) links to each other with the solid outlet 37 of solid-liquid separator 30.The structure of the first spraying cleanser is identical with the structure of spray mixing device 50.The first spraying cleanser successively with first shaking table, the second spraying cleanser, second shaking table links to each other, the second spraying cleaner structure is identical with the structure of the first spraying cleanser, second cleanser of spraying links to each other with reactor 52 again;
Reactor 52 (see Figure 10, spray channel 66 ' enlarged view is referring to Fig. 3 among Figure 10), its structure are identical with spraying agitator 49 substantially, and the change in the structure is that top cover is provided with a steaming liquid pipe 22, steams liquid pipe 22 and link to each other with second condenser in device.
The structure of reactor 52 mainly comprise second mixing kettle 65 ', second charging stock tank 63 ', second spray channel 66 ', second surge pump 61 ', second three-way valve 62 ', second drainage conduit 64 ' and steam liquid pipe 22.Second filling tube 69 of described second charging stock tank 63 ' bottom ' be installed in, second mixing kettle 65 ' on cover, and stretch into second mixing kettle 65 ' in.Second mixing kettle 65 ' on cover and also be provided with one and steam liquid pipe 22.Second nozzle 70 that described second spray channel 66 ' comprise communicates successively ', second nozzle chambers 72 ' with second jet exit 73 '.Two sides of nozzle chambers 72 ' wall respectively be provided with a liquid flow hole 71 ', second nozzle diameter is 3-4mm.Described second surge pump 61 ' place second three-way valve 62 ' and second mixing kettle, 65 ' bottom, second discharge port 67 ' between second connecting tube 68 ' on, second drainage conduit 64 ' with second three-way valve 62 ' link to each other.
The processing recovery method of monocrystalline silicon cutting waste liquor of the present invention, show through implementation and operation: method is easy, equipment is simple, easy to control, cost is low, handles rate of recovery height, the total yield that calculates based on cutting waste liquor weight can reach 26-46%, wherein polyoxyethylene glycol accounts for 20-30%, and silicon carbide accounts for 5-15%, and silicon accounts for 1-2%.And reclaim the quality product obtain can both reach or the be near the mark index of product, can directly in manufacture of solar cells, use or other industrial circle in use.Therefore the inventive method has very big economic benefit, has also done very big contribution for environmental protection, is a processing recovery method that the monocrystalline silicon cutting waste liquor of DEVELOPMENT PROSPECT is arranged very much.
Description of drawings
Fig. 1 is the process flow sheet that monocrystalline silicon cutting waste liquor of the present invention is handled recovery method.
Fig. 2 is a structure iron of realizing the spraying agitator in the device of the inventive method.
Fig. 3 is an A place enlarged view among Fig. 2.
Fig. 4 is a structure iron of realizing the spray mixing device in the device of the inventive method.
Fig. 5 is the longitudinal sectional drawing of spraying plant among Fig. 4.
Fig. 6 is the left view of guide plate among Fig. 5.
Fig. 7 is a structure iron of realizing the solid-liquid separator in the device of the inventive method.
Fig. 8 be among Fig. 7 A-A to vertical view.
Fig. 9 is a structure iron of realizing the spraying water trap in the device of the inventive method.
Figure 10 is a structure iron of realizing the reactor in the device of the inventive method.
Embodiment
Embodiment 1
Referring to accompanying drawing Fig. 1-Fig. 6.Enter in first mixing kettle 65 of spraying agitator 49 by first charging stock tank 63 and first filling tube 69 thereof removing 50 kilograms of the monocrystalline silicon cutting waste liquors of kerosene and 10 liters of dilute hydrochloric acid that concentration is 0.01mol.The passage of first three-way valve 62 and first nozzle passage 66 is opened, and closed passage with first drainage conduit 64, start first surge pump 61 (pneumatic diaphragm pump type QBY-40, Shanghai Changquan Pump Manufacture Co., Ltd. produces), air pressure is 3kg/cm
2Compound is flowed out through first surge pump 61 by first mixing kettle, 65 bottoms, first discharge port 67, first pipeline 68 and first three-way valve 62, the nozzle diameter that enters first spray channel 66 is the nozzle 70 of 3mm, compound fast by 73 ejections of first jet exit, forms a circulation mixing on a large scale by nozzle chambers 72.Because of form negative pressure in nozzle chambers 72, produce pressure difference inside and outside nozzle chambers 72 walls again, the outer compound of wall enters nozzle chambers 72 by liquid flow hole 71, forms one again and mixes among a small circle, makes mixing and reaction effect better.Make compound pass through first mixing kettle, 65 bottom first discharge port, 67, the first surge pumps 61 and circulation loop of first nozzle passage, 66 formations like this, circulation nozzle mixed 25 minutes so repeatedly.With the pathway closure of first three-way valve 62 and first nozzle passage 66, and open passage with first drainage conduit 64, the preliminary compound of gained is discharged from first drainage conduit 64, mix again and enter spray mixing device 50.By the spraying agitator mix preliminary compound, its viscosity descends to some extent than waste liquid, but still has liquid and the uneven phenomenon of the thick material of solid powder/particle.
Preliminary compound enters in the mixing kettle 3 of spray mixing device 50 by charging stock tank 6 and filling tube 9 thereof, the three-way valve 7 and the passage of nozzle entrance 10 are opened, and close passage with drainage conduit 4, start surge pump 1, compound is flowed out through surge pump 1 by mixing kettle 3 bottom discharge mouths 18, pipeline 8 and three-way valve 7 enter the nozzle entrance 10 of spraying plant 5, enter turbulent flow road 11 (when pumping capacity is 3 cubic metres/hour, turbulent flow road diameter 2.4mm, when the compound kinetic viscosity is 33.2Pas, Reynolds number=8326), compound is the turbulent flow attitude, therefore molecules strike and friction take place in compound in turbulent flow road 11, compound is mixed and more refinement of particle, compound goes out the vaporific liquid of turbulent flow road 11 to the even fine particle of hybrid chamber 12 ejections, and go out at a high speed by jet exit 13, the anti-phase aperture 16 that passes on the guide plate 15 of partially mixed material enters outside hybrid chamber 12 walls, thereby make the inside and outside generation pressure difference of hybrid chamber 12 walls, compound is formed by liquid conductance mouth 14 again flee among a small circle, make mixing and reaction effect better.Make compound pass through mixing kettle 3 bottom discharge mouths 18 like this, surge pump 1 constitutes a circulation loop with spraying plant 5, the spray mixing that circulates so repeatedly 20 minutes, temperature rise to 35 ℃ (measure by hot resistance temperature measuring head 2, demonstrate the situation of temperature on temperature guiding instrument 17).With three-way valve 7 pathway closure with nozzle entrance 10, and open passage with drainage conduit 4, the secondary compound is discharged from drainage conduit 4, the viscosity by the secondary compound after the spray mixing obviously descends, and has become the runny compound that mixes.
Enter solid-liquid separator 30 by the mixed secondary compound of spray mixing device, its structure mainly comprises spray header 31 as shown in Figure 7 and Figure 8, steam outlet pipe 33, conical plate 42, doline plate 41 and solid outlet 37 etc.Be provided with symmetrical up and down two unitary electric heating panels that are fixed on the outer wall 36 in the solid-liquid separator 30.Compound sprays in the solid-liquid separator 30 by the spray header 31 that the top cover center is provided with, and compound drops on the skin of a conical plate 42 in the unitary top of electric heating panel, again along heating on the internal layer that falls into below doline plate 41 all around.Hole 40 by doline plate 41 bottoms falls on the next unitary electric heating panel again, heats by the same manner, and the temperature of electric heating panel keeps 70 ℃.After the compound heating, water vapor and polyoxyethylene glycol are steamed by steam outlet pipe 33 rapidly together, by the cooling of first condenser, promptly get the mixed solution of water and polyoxyethylene glycol.The drop that may occur a little condensation on solid-liquid separator 30 inwalls descends along wall, is then flowed out by liquid exit 38.The solid that heating and separating gets is emitted by the solid outlet 37 of the bottom setting of solid-liquid separator 30, emits the thick solid mixture that thing is silicon carbide and silicon, promptly is salt and the silicon carbide of all the other impurity and the solid mixture of silicon that contains generation.Do not discharge for the thick solid mixture that makes silicon carbide and silicon does not spatter to perisporium but directly falls by solid outlet 37, prevent that simultaneously the drop of inwall drippage is splashed in the solid outlet 37, around it, be provided with baffle plate 39.
The water of gained and the mixed solution of polyoxyethylene glycol enter spraying water trap 51.Referring to Fig. 9, the structure of spraying water trap 51 is basic identical with spray mixing device 50, and the change in the structure is to be provided with a water shoot 21 on top cover.The mixing kettle 3 of the mixed solution of water and polyoxyethylene glycol by charging stock tank 6 ' and filling tube 9 ' enter spraying water trap 51 ' in, startup surge pump 1 ', spraying dehydration repeatedly circulates, operation is with the spray mixing device, liquid stream turbulent flow road 11 ' in be turbulent flows, beat round-robin surge pump 1 ' flow be 2.5 cubic metres/hour, turbulent flow road diameter is 2.0mm, when the kinetic viscosity of water and polyoxyethylene glycol mixed solution is 19.2Pas, Reynolds number=7319.Circulation spraying dewatering time is 20 minutes, temperature rises to 70 ℃, after moisture is discharged by water shoot 21, with three-way valve 7 ' with nozzle entrance 10 ' pathway closure, and open with drainage conduit 4 ' passage, polyoxyethylene glycol promptly reclaims from drainage conduit 4 ' discharge, obtain 15 kilograms of water white polyoxyethylene glycol, recording molecular weight is 205, pH=6.5, (molecular weight of polyoxyethylene glycol standard product is 300 to water content＜0.3wt%, pH=4-7, water content≤0.5wt%) reaches 30% based on the polyoxyethylene glycol rate of recovery of 50 kilograms of calculating of cutting waste liquor weight.
The silicon carbide that to be discharged by the solid outlet 37 of solid separator 30 and the thick solid mixture of silicon are sent in the first spraying cleanser, the structure of the first spraying cleanser (figure does not draw) is identical with the structure of spray mixing device 50, the thick solid mixture of silicon carbide and silicon enters in the mixing kettle 3 by charging stock tank and filling tube thereof equally, is incorporated as the water of 15% amount of thick solid mixture weight again.Start surge pump, the spray mixing that circulates is repeatedly cleaned, operation is with spray mixing device 50, mixture is turbulent flows in the turbulent flow road, the flow of making the round-robin surge pump is 2.1 cubic metres/hour, turbulent flow road diameter is 2.6mm, when the kinetic viscosity of the compound of solid mixture and water is 13.5Pas, and Reynolds number 3979.Circulation mixed scavenging period 30 minutes; temperature rises to 70 ℃; cleaning back mixture is put into first shaking table, and (Shanghai Hua Yan plant and instrument company limited provides; model HWY-211); separate " the shell residue " of removing light specific gravity; the concentrated flow that water is provided with on shaking table goes out; get the once cleaning solid mixture of silicon carbide and silicon, send into the second spraying cleanser again, its structure is identical with the first spraying cleanser; the solid mixture spray mixing that repeats again once to circulate is cleaned; beating round-robin surge pump flow is 3 cubic metres/hour, and turbulent flow road diameter is 2.1mm, the Reynolds number when kinetic viscosity of compound is 16.8Pas=8670; all the other operations are identical.Clean the back mixture and put into second shaking table (Shanghai Hua Yan plant and instrument company limited provides model 350R), separate again and remove " shell residue " and water, obtain the secondary cleaning solid mixture of silicon carbide and silicon.After " the shell residue " separated reclaims, might be used to as fertilizer sources and use.
The silicon carbide that obtains and the secondary cleaning solid mixture of silicon are sent into reactor 52, and referring to Figure 10, the structure of reactor 52 is basic identical with spraying agitator 49, and the change in the structure is to be provided with a steaming liquid pipe 22 on top cover.With second mixing kettle 65 by second charging stock tank 63 ' and second filling tube 69 ' enter reactor 52 of the secondary cleaning solid mixture of silicon carbide and silicon ' in, adding concentration again is 5%HNO
3With concentration be 30%HF that form with mix acid liquor (volume HNO solid mixture equivalent
3: HF=1: 5), start second surge pump 61 ', spraying stirring reaction 10 minutes repeatedly circulates, second nozzle diameter is 3.5mm, and temperature reaches reflux temperature, and silicate fluoride solution steams by steaming liquid pipe 22, by second condenser cooling, reclaim water white silicate fluoride solution.Silicate fluoride solution concentration is 30wt%.Silicate fluoride solution is operated routinely, after its oven dry, put into the single crystal growing furnace crucible and be processed into silicon single crystal.In the single crystal growing furnace crucible, vacuumize; feed the shielding gas argon gas; electrically heated makes it fusing; use spacer cooling water control temperature again; keep about 1420 ℃ of furnace temperature, the beginning crystallization, with a fritter single crystal ingot as introduction pull out silicon single crystal rod; obtaining silicon 0.6kg, is 1.2% based on the rate of recovery of 50 kilograms of calculating of cutting waste liquor weight.Carried out fermi level mensuration to reclaiming product silicon: show C on the fermi level diagram
B=10
15Centimetre
-3Be equivalent to the p=5.0 ohmcm, 0.86 ev than low 0.24 ev at the bottom of the conduction band, risen than valence band than band gap height of center 0.31 ev in the position of fermi level.Measure and show that above index belongs to polysilicon near silicon single crystal.Residuum silicon carbide and acid solution are by second drainage conduit 64 in the reactor 52, and " discharge, filter, use the 5wt%NaOH solution washing, washing is 7.5 to pH, and drying reclaims and obtains 7.5 kilograms in glaucous fine powder product silicon carbide.By analysis, purity is 94%, Mohs' hardness 9.5, it is that (silicon carbide standard degree of purity of production is 94-99% to α-SiC hexagonal system that electron microscope detects the crystalline crystalline form, Mohs' hardness is 9.2-9.6, α-SiC hexagonal system), be 15% based on the rate of recovery of 50 kilograms of calculating of cutting waste liquor weight.
To remove in first mixing kettle 65 of 50 kilograms of the monocrystalline silicon cutting waste liquors of kerosene and 15 liters of dilute hydrochloric acid adding spraying agitators 49 that concentration is 0.001mol, circulation repeatedly spraying is stirred and was reacted 20 minutes.The preliminary compound that obtains enter spray mixing device 50 circulate repeatedly spray mixing and the reaction 20 minutes, temperature rises to 50 ℃, compound enters turbulent flow road 11 and is the turbulent flow attitude, pumping capacity is 3 cubic metres/hour, turbulent flow road diameter 1.5mm, when the compound kinetic viscosity was 40.6Pas, Reynolds number was 9845.Enter solid-liquid separator 30 by the mixed secondary compound of spray mixing device, compound keeps two unitary electric heating panels of 60 ℃ to heat by temperature, and water vapor and polyoxyethylene glycol steam together, and condensation gets the mixed solution of water and polyoxyethylene glycol.Solid-liquid separator 30 bottom solid outlets 37 are emitted the thick solid mixture of silicon carbide and silicon.Gained water and polyoxyethylene glycol mixed solution enter spraying water trap 51, the spraying dehydration that circulates repeatedly, and the time is 15 minutes, temperature rises to 40 ℃.Liquid stream turbulent flow road 11 ' in be turbulent flows, when the round-robin flow is 2.5 cubic metres/hour, turbulent flow road diameter 2.5mm, when the kinetic viscosity of water and polyoxyethylene glycol mixed solution was 14.0Pas, Reynolds number was 5139.After the dehydration, 11.9 kilograms of water white polyoxyethylene glycol, reach 23.8% based on the rate of recovery of cutting waste liquor weight.The thick solid mixture of silicon carbide and silicon is sent in the first spraying cleanser, be incorporated as the water of 10% amount of thick solid mixture weight again, the spray mixing that circulates is repeatedly cleaned, liquid stream is turbulent flows in the turbulent flow road, when circular flow is 2.1 cubic metres/hour, turbulent flow road diameter 2.5mm, when the kinetic viscosity of the compound of solid mixture and water is 10.2Pas, Reynolds number=5925.Circulation mixed scavenging period 10 minutes, and temperature rises to 80 ℃.After mixture is put into the separation of first shaking table after cleaning, this is once cleaned solid mixture send into the second spraying cleanser, the solid mixture spray mixing that repeats equally more once to circulate is cleaned, when circular flow is 3 cubic metres/hour, turbulent flow road diameter 1.8mm, when the mixture kinetic viscosity was 20.6Pas, Reynolds number was 11229.Put into second shaking table after the cleaning and separate, promptly obtain the secondary cleaning solid mixture of silicon carbide and silicon.The silicon carbide that obtains and the secondary cleaning solids of silicon are sent into reactor 52, be incorporated as the HNO of 1.2 times of amounts of solid mixture again
3With the mix acid liquor of HF, the spraying stirring reaction 10 minutes that circulates repeatedly, from the silicofluoric acid liquid that obtains reclaim silicon 0.8kg, the rate of recovery of calculating based on cutting waste liquor 1.6%.Residuum in the reactor filters, and uses the 5wt%KOH solution washing, and washing is 7.2 to pH, gets light gray green fine powder silicon carbide product 5.1kg, and the rate of recovery of calculating based on cutting waste liquor weight 50kg is 10.2%, and all the other operations of present embodiment are with embodiment 1.
To remove in first mixing kettle 65 of 50 kilograms of the monocrystalline silicon cutting waste liquors of kerosene and 25 liters of dilute hydrochloric acid adding spraying agitators 49 that concentration is 0.0001mol, circulation repeatedly spraying is stirred and was reacted 30 minutes.The preliminary compound that obtains enter spray mixing device 50 circulate repeatedly spray mixing and the reaction 10 minutes, temperature rises to 40 ℃, compound enters turbulent flow road 11 and is the turbulent flow attitude, pumping capacity is 3 cubic metres/hour, turbulent flow road diameter 2.5mm, when the compound kinetic viscosity was 28.4Pas, Reynolds number was 3040.Enter solid-liquid separator 30 by the mixed secondary compound of spray mixing device, compound keeps two unitary electric heating panels of 80 ℃ to heat by temperature, and water vapor and polyoxyethylene glycol steam together, and condensation gets the mixed solution of water and polyoxyethylene glycol.Solid-liquid separator 30 bottom solid outlets 37 are emitted the thick solid mixture of silicon carbide and silicon.Gained water and polyoxyethylene glycol mixed solution enter spraying water trap 51, the spraying dehydration that circulates repeatedly, and the time is 40 minutes, temperature rises to 80 ℃.Liquid stream turbulent flow road 11 ' in be turbulent flows, when the round-robin flow is 2.5 cubic metres/hour, turbulent flow road diameter 1.8mm, when the kinetic viscosity of water and polyoxyethylene glycol mixed solution was 21.4Pas, Reynolds number was 9007.After the dehydration, 10.2 kilograms of water white polyoxyethylene glycol, reach 20.4% based on the rate of recovery of cutting waste liquor weight.The thick solid mixture of silicon carbide and silicon is sent in the first spraying cleanser, be incorporated as the water of 15% amount of thick solid mixture weight again, the spray mixing that circulates is repeatedly cleaned, liquid stream is turbulent flows in the turbulent flow road, when circular flow is 2.1 cubic metres/hour, turbulent flow road diameter 3.0mm, when the kinetic viscosity of the compound of solid mixture and water is 9.6Pas, Reynolds number=3643.Circulation mixed scavenging period 30 minutes, and temperature rises to 70 ℃.After mixture is put into the separation of first shaking table after cleaning, this is once cleaned solid mixture send into the second spraying cleanser, the solid mixture spray mixing that repeats equally more once to circulate is cleaned, when circular flow is 3 cubic metres/hour, turbulent flow road diameter 2.4mm, when the compound kinetic viscosity was 14.0Pas, Reynolds number was 6970.Put into second shaking table after the cleaning and separate, promptly obtain the secondary cleaning solid mixture of silicon carbide and silicon.The silicon carbide that obtains and the secondary cleaning solids of silicon are sent into reactor 52, be incorporated as the HNO of 1.5 times of amounts of solid mixture again
3With the mix acid liquor of HF, the spraying stirring reaction 20 minutes that circulates repeatedly, from the silicofluoric acid liquid that obtains reclaim silicon 1kg, the rate of recovery of calculating based on cutting waste liquor is 2%.Residuum in the reactor 52 filters, and uses the 10wt%NaOH solution washing, and washing is 7.3 to pH, gets light gray green fine powder silicon carbide product 2.9kg, and the rate of recovery of calculating based on cutting waste liquor weight 50kg is 5.8%, and all the other operations of present embodiment are with embodiment 1.
To remove in first mixing kettle 65 of 50 kilograms of the monocrystalline silicon cutting waste liquors of kerosene and 7.5 liters of dilute hydrochloric acid adding spraying agitators 49 that concentration is 0.2mol, circulation repeatedly spraying is stirred and was reacted 15 minutes.The preliminary compound that obtains enter spray mixing device 50 circulate repeatedly spray mixing and the reaction 20 minutes, temperature rises to 30 ℃, compound enters turbulent flow road 11 and is the turbulent flow attitude, pumping capacity is 3 cubic metres/hour, turbulent flow road diameter 2.0mm, when the compound kinetic viscosity was 35.6Pas, Reynolds number was 4736.Enter solid-liquid separator 30 by the mixed secondary compound of spray mixing device, compound keeps two unitary electric heating panels of 50 ℃ to heat by temperature, and water vapor and polyoxyethylene glycol steam together, and condensation gets the mixed solution of water and polyoxyethylene glycol.Solid-liquid separator 30 bottom solid outlets 37 are emitted the thick solid mixture of silicon carbide and silicon.Gained water and polyoxyethylene glycol mixed solution enter spraying water trap 51, the spraying dehydration that circulates repeatedly, and the time is 15 minutes, temperature rises to 50 ℃.Liquid stream turbulent flow road 11 ' in be turbulent flows, when the round-robin flow is 2.5 cubic metres/hour, turbulent flow road diameter 3.0mm, when the kinetic viscosity of water and polyoxyethylene glycol mixed solution was 11.5Pas, Reynolds number was 3620.After the dehydration, get 13.7 kilograms of water white polyoxyethylene glycol, the rate of recovery of calculating based on cutting waste liquor weight reaches 27.4%.The thick solid mixture of silicon carbide and silicon is sent in the first spraying cleanser, be incorporated as the water of 20% amount of thick solid mixture weight again, the spray mixing that circulates is repeatedly cleaned, liquid stream is turbulent flows in the turbulent flow road, when circular flow is 2.1 cubic metres/hour, turbulent flow road diameter 2.7mm, when the kinetic viscosity of the compound of solid mixture and water is 11.2Pas, Reynolds number=4283.Circulation mixed scavenging period 20 minutes, and temperature rises to 50 ℃.After mixture is put into the separation of first shaking table after cleaning, this is once cleaned solid mixture send into the second spraying cleanser, the solid mixture spray mixing that repeats equally more once to circulate is cleaned, when circular flow is 3 cubic metres/hour, turbulent flow road diameter 3.0mm, when the compound kinetic viscosity was 16.8Pas, Reynolds number was 4626.Put into second shaking table after the cleaning and separate, promptly obtain the secondary cleaning solid mixture of silicon carbide and silicon.The silicon carbide that obtains and the secondary cleaning solids of silicon are sent into reactor 52, be incorporated as the HNO of 1.1 times of amounts of solid mixture again
3With the mix acid liquor of HF, the spraying stirring reaction 30 minutes that circulates repeatedly, from the silicofluoric acid liquid that obtains reclaim silicon 0.5kg, the rate of recovery of calculating based on cutting waste liquor is 1%.Residuum in the reactor filters, and uses the 7wt%KOH solution washing, and washing is 7 to pH, gets light gray green fine powder silicon carbide product 6.3kg, and the rate of recovery of calculating based on cutting waste liquor weight 50kg is 12.6%, and all the other operations of present embodiment are with embodiment 1.
Claims (5)
1. the processing recovery method of a monocrystalline silicon cutting waste liquor is characterized in that this method comprises the following steps:
(1). the monocrystalline silicon cutting waste liquor that will remove kerosene is put into the spraying agitator, adding concentration is the hydrochloric acid of 0.0001-0.4mol, the per kilogram waste liquid adds the 100-500ml hydrochloric acid soln, churning time 10-30 minute, get preliminary compound, discharge and enter the spray mixing device, remix 10-30 minute, temperature rises to 30-50 ℃, gets the secondary compound, discharges;
(2). the secondary compound of discharging from the spray mixing device enters solid-liquid separator, compound is 50-80 ℃ electric heating panel heating by Heating temperature, water vapor and polyoxyethylene glycol steam together, condensation, the mixed solution of water and polyoxyethylene glycol, entered in the spraying water trap dehydration again 15-40 minute, temperature rises to 40-80 ℃, moisture is discharged, promptly reclaim polyoxyethylene glycol, the solid-liquid separator bottom emits the thick solid mixture of silicon carbide and silicon;
(3). the thick solid mixture of silicon carbide and silicon is sent in the first spraying cleanser, be incorporated as the water of the 10-20% amount of thick solid mixture weight, cleaned together 10-30 minute, temperature rises to 40-80 ℃, clean the back mixture and put into first shaking table, separate and remove " shell residue ", get the once cleaning solid mixture of silicon carbide and silicon, send into again in the second spraying cleanser, after solid mixture heavily covers and once cleans, mixture is put into second shaking table, separates and removes " shell residue ", obtains the secondary cleaning solid mixture of silicon carbide and silicon;
(4). the secondary cleaning solid mixture of silicon carbide and silicon is sent in the reactor, and adding concentration is 5%HNO
3With concentration be the mix acid liquor that 30% HF forms, both volume ratios are HNO
3: HF=1: 5, the secondary cleaning solid mixture of per 1 kilogram of silicon carbide and silicon adds 1-1.5 kilogram mix acid liquor, stirring reaction 10-30 minute, temperature rises to reflux temperature, and silicate fluoride solution steams, condensation, water white silicate fluoride solution, reprocessing reclaim silicon, residuum silicon carbide and acid solution in the reactor, filter, the alkaline solution washing, washing is 7-7.5 to pH, drying, reclaim silicon carbide.
2. device that is used to realize the described method of claim 1, this device comprises:
Spraying agitator (49), its structure mainly comprises first mixing kettle (65), first charging stock tank (63), first spray channel (66), first surge pump (61), first three-way valve (62) and first drainage conduit (64), first filling tube (69) of described first charging stock tank (63) bottom be installed in first mixing kettle (65) on cover, and stretch in first mixing kettle (65), described first spray channel (66) comprises the nozzle (70) that communicates successively, nozzle chambers (72) and first jet exit (73), two sides at nozzle chambers (72) wall respectively are provided with a liquid flow hole (71), nozzle diameter is 3-4mm, described first surge pump (61) places on first connecting tube (68) between first three-way valve (62) and first mixing kettle (65) bottom first discharge port (67), and first drainage conduit (64) links to each other with first three-way valve (62);
Spray mixing device (50), first drainage conduit (64) by spraying agitator (49) links to each other with spray mixing device (50), the structure of spray mixing device (50) mainly comprises the 3rd mixing kettle (3), the 3rd charging stock tank (6), the 3rd spraying plant (5), the 3rd surge pump (1), the first hot resistance temperature measuring head (2), the 3rd three-way valve (7) and the 3rd drainage conduit (4), the 3rd filling tube (9) of described the 3rd charging stock tank (6) bottom be installed in the 3rd mixing kettle (3) on cover, and stretch in the 3rd mixing kettle (3), described the 3rd spraying plant (5) comprises the 3rd spray channel (19) and first guide plate (15), the 3rd spray channel (19) comprises the 3rd nozzle entrance (10) that communicates successively, the first turbulent flow road (11), first hybrid chamber (12) and the 3rd jet exit (13), the 3rd nozzle entrance (10) is doline, the diameter in the first turbulent flow road (11) is 1.2-3mm, two sides of first hybrid chamber (12) wall respectively are provided with liquid stream first and lead mouthful (14), first guide plate (15) is vertically to being arranged on the 3rd spray channel (19), and be positioned at liquid stream first and lead between mouthful (14) and the 3rd jet exit (13), be covered with aperture (16) on first guide plate (15), described the 3rd surge pump places on the 3rd connecting tube (8) between the 3rd three-way valve (7) and the 3rd mixing kettle (3) bottom the 3rd discharge port (18), the 3rd drainage conduit (4) links to each other with the 3rd three-way valve (7), the described first hot resistance temperature measuring head (2) is fixedly set in the 3rd mixing kettle (3), and the loam cake that passes the 3rd mixing kettle (3) by lead links to each other with the first temperature indicator (17);
Solid-liquid separator (30), its structure mainly comprises spray header (31), steam outlet pipe (33), conical plate (42), doline plate (41) and solid outlet (37), the 3rd drainage conduit (4) of spray mixing device links to each other with the spray header (31) that solid-liquid separator (30) top cover center is provided with, symmetry is fixed on two unitary electric heating panels on the outer wall (36) about being provided with in the solid-liquid separator (30), each unitary electric heating panel structure is: the top is a conical plate (42), the below is a doline plate (41) and hole (40), and the diameter of doline plate (41) is greater than the diameter of conical plate (42), conical plate (42) is fixed on the locating pin (32) of 120 ° of arrangements of three one-tenth, three locating pins (32) are fixed on the outer wall (36), doline plate (41) is fixed on the pallet (35), pallet (35) mat retaining screw (34) is fixed on the outer wall (36), top cover is provided with steam outlet pipe (33), the bottom is provided with solid outlet (37), be provided with baffle plate (39) all around at solid outlet (37), also be provided with a liquid exit (38) in the bottom;
Spraying water trap (51), its structure is basic identical with spray mixing device (50), and the change in the structure is that top cover is provided with a water shoot (21), and solid-liquid separator in device (30) links to each other with spraying water trap (51) by first condenser;
The structure of spraying water trap (51) mainly comprises the 4th mixing kettle (3 '), the 4th charging stock tank (6 '), the 4th spraying plant (5 '), the 4th surge pump (1 '), the second hot resistance temperature measuring head (2 '), the 4th three-way valve (7 '), the 4th drainage conduit (4 ') and water shoot (21), the 4th filling tube (9 ') of described the 4th charging stock tank (6 ') bottom be installed in the 4th mixing kettle (3 ') on cover, and stretch in the 4th mixing kettle (3 '), on the 4th mixing kettle (3 '), cover and also be provided with a water shoot (21), described the 4th spraying plant (5 ') comprises the 4th spray channel (19 ') and second guide plate (15 '), the 4th spray channel (19 ') comprises the 4th nozzle entrance (10 ') that communicates successively, the second turbulent flow road (11 '), second hybrid chamber (12 ') and the 4th jet exit (13 '), the 4th nozzle entrance (10 ') is doline, the diameter in the second turbulent flow road (11 ') is 1.2-3mm, two sides of second hybrid chamber (12 ') wall respectively are provided with liquid stream second and lead mouthful (14 '), second guide plate (15 ') is vertically to being arranged on the 4th spray channel (19 '), and be positioned at liquid stream second and lead between mouthful (14 ') and the 4th jet exit (13 '), second guide plate (15 ') is gone up the full aperture (16 ') of row, described the 4th surge pump (1 ') places on the 4th connecting tube (8 ') between the 4th three-way valve (7 ') and the 4th mixing kettle (3 ') bottom the 4th discharge port (18 '), the 4th drainage conduit (4 ') links to each other with the 4th three-way valve (7 '), the described second hot resistance temperature measuring head (2 ') is fixedly set in the 4th mixing kettle (3 '), and the loam cake that passes the 4th mixing kettle (3 ') by lead links to each other with the second temperature indicator (17 ');
The first spraying cleanser, link to each other with the solid outlet (37) of solid-liquid separator (30), the structure of the first spraying cleanser is identical with the structure of the second spray mixing device (50), first the spraying cleanser successively with first shaking table, the second spraying cleanser, second shaking table links to each other, and the second spraying cleaner structure is identical with the structure of the first spraying cleanser, and the second spraying cleanser links to each other with reactor (52) again;
Reactor (52), its structure are identical with spraying agitator (49) substantially, and the change in the structure is that top cover is provided with a steaming liquid pipe (22), and in device, steam liquid pipe (22) and link to each other with second condenser,
The structure of reactor (52) mainly comprises second mixing kettle (65 '), second charging stock tank (63 '), second spray channel (66 '), second surge pump (61 '), second three-way valve (62 '), second drainage conduit (64 ') and steaming liquid pipe (22), second filling tube (69 ') of described second charging stock tank (63 ') bottom be installed in second mixing kettle (65 ') on cover, and stretch in second mixing kettle (65 '), on second mixing kettle (65 '), cover and also be provided with a steaming liquid pipe (22), described second spray channel (66 ') comprises second nozzle (70 ') that communicates successively, second nozzle chambers (72 ') and second jet exit (73 '), two sides at nozzle chambers (72 ') wall respectively are provided with a liquid flow hole (71 '), second nozzle diameter is 3-4mm, described second surge pump (61 ') places on second connecting tube (68 ') between second three-way valve (62 ') and second mixing kettle (65 ') bottom second discharge port (67 '), and second drainage conduit (64 ') links to each other with second three-way valve (62 ').
3. the method for claim 1 is characterized in that selecting NaOH, KOH or Na for use in the washing of alkaline solution described in the 4th step
2CO
3Be mixed with the alkaline solution washing of 5-10wt%.
4. device as claimed in claim 2, the aperture that it is characterized in that being covered with on first guide plate (15) in the described spray mixing device (50) aperture (16) is 1-3mm, the percentage of open area on first guide plate (15) is 60-80%.
5. device as claimed in claim 2, the aperture that it is characterized in that being covered with on second guide plate (15 ') in the described spraying water trap (51) aperture (16 ') is 1-3mm, the percentage of open area on second guide plate (15 ') is 60-80%.
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| CN101244823B (en) * | 2008-02-20 | 2010-06-23 | 江南大学 | Method for recycling silicon carbide from by-product in silicon slice cutting process |
| CN101654250B (en) * | 2008-08-21 | 2011-08-17 | 北京有色金属研究总院 | Method for extracting silicon powder from grinding waste liquid |
| CN101684028B (en) * | 2008-09-28 | 2012-07-18 | 张伟民 | Method and device for disposing cutting waste of silicon crystal board |
| CN101623898B (en) * | 2009-04-28 | 2012-02-15 | 江西赛维Ldk太阳能高科技有限公司 | Chemical recovery method for mortar in wire cutting technology |
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| CN101941699B (en) * | 2010-09-14 | 2012-08-22 | 东北大学 | Method for reclaiming silicon and silicon carbide from cutting waste materials of monocrystalline silicon and polycrystalline silicon |
| CN101983919B (en) * | 2010-11-15 | 2012-06-27 | 桂劲宁 | Method for producing white carbon black by polycrystalline silicon cut waste alkali-wash waste water |
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| CN103030144A (en) * | 2011-09-28 | 2013-04-10 | 汇隆科技有限公司 | Method for recovering silicon carbide in waste liquid |
| CN102530948B (en) * | 2012-01-04 | 2013-07-10 | 浙江大学 | Method for recycling silicon from filings obtained through silicon wafer cutting |
| CN102746936A (en) * | 2012-08-08 | 2012-10-24 | 铁生年 | Recycling purification method for carborundum powder in silicon slice cutting waste liquid |
| CN102925276B (en) * | 2012-11-15 | 2014-05-07 | 晶科能源有限公司 | Recovery method of slurry |
| CN103060518A (en) * | 2013-01-12 | 2013-04-24 | 铁生年 | Method for preparing steelmaking deoxidization pellets by sliced chip silicon carbide liquid waste |
| CN103387307B (en) * | 2013-08-08 | 2014-12-17 | 王岚 | Method for processing organic waste liquor in electronic manufacturing industry |
| CN105417546A (en) * | 2015-11-10 | 2016-03-23 | 晶科能源有限公司 | Cleaning fluid used for polycrystalline silicon material and cleaning process of polycrystalline silicon material |
| CN108910887A (en) * | 2018-07-25 | 2018-11-30 | 成都斯力康科技股份有限公司 | A kind of monocrystalline silicon cuts the recovery and treatment method of slag and cutting waste liquor |
| CN112390259B (en) * | 2020-11-17 | 2022-01-28 | 江苏鑫华半导体材料科技有限公司 | Electronic grade polysilicon cleaning method |
| CN112441588A (en) * | 2020-12-31 | 2021-03-05 | 重庆大学 | Deoxidation method for diamond wire cutting silicon waste |
| CN114621756B (en) * | 2022-03-28 | 2023-04-07 | 南昌大学 | Method for preparing Mn4+ activated fluoride red fluorescent powder by using recycled silicon sawdust powder |
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