CN103288086A - Recovery method of silicon carbide, silicon powder and polyethylene glycol from cutting fluid of silicon chips - Google Patents
Recovery method of silicon carbide, silicon powder and polyethylene glycol from cutting fluid of silicon chips Download PDFInfo
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Abstract
The invention discloses a recovery method of silicon carbide, silicon powder and polyethylene glycol from cutting fluid of silicon chips. The recovery method comprises the following steps: step 1, stirring and filtering the cutting fluid to separate the cutting fluid into solid compounds and liquid compounds; step 2, adding water into the solid compounds, and then stirring uniformly and filtering to get liquid and solid; step 3, precipitating the liquid of step 2 to get precipitates, washing the precipitates by water and then by acid, drying, so as to obtain the silicon powder; step 4, separating the solid of step 2 into solid-phase material and liquid-phase material, rinsing the solid-phase material, washing by alkali and then by acid, drying, screening, so as to obtain the silicon carbide finished product; step 5, separating the liquid of step 2 into solid-phase material and liquid-phase material, adding decolorising agents and filter aids into the liquid-phase material, subjecting the liquid-phase material to ion exchange treatment, distilling, so as to obtain the polyethylene glycol. The method is easy to operate. Recovering processes of the method is clean and safe, and of no pollution to the environment. Recovery rates of the silicon carbide, the polyethylene glycol and the silicon powder can reach 80% or more, 90% or more and 75% or more respectively.
Description
Technical field
The present invention relates to a kind of recovery method, particularly a kind of method of from silicon chip cutting liquid, extracting silicon carbide, silicon powder and polyoxyethylene glycol.
Background technology
Silicon chip is semi-conductor, is the base mateiral of sun power, liquid-crystal display.Along with the development of sun power, the use of silicon chip is more and more.Because silicon chip belongs to hard material, its cutting technique occupies very important position in complete processing.The mode of steel disc cutting is adopted in the cutting of traditional silicon chip, defectives such as this cutting mode exists that joint-cutting is wideer, volume recovery is low, surface figure accuracy difference and surface damage layer depth.In order to address the above problem, the line cutting has appearred recently, the mortar that has abrasive material by the line of cut supply, realize the cutting of silicon chip by the abrasive wear principle between abrasive material, line of cut and the silicon crystal, this mode can realize the cutting of multi-disc silicon chip, the cutting efficiency height, and the silicon chip surface quality is good, but can produce a large amount of mortar waste materials.Because main component is polyoxyethylene glycol and silicon carbide in the mortar, therefore, in the mortar waste material also content a large amount of polyoxyethylene glycol and silicon carbide are arranged, simultaneously, also have a spot of metallic iron and silicon bits.In order to carry out recycling, can reclaim the polyoxyethylene glycol in the mortar, silicon carbide and silicon material.
Chinese patent literature, the patent No. 201010528153.5 discloses a kind of method that reclaims silicon carbide and polyoxyethylene glycol cutting fluid from silicon chip dicing waste mortar, comprises the steps:
A, with mortar after stirring under the normal temperature, carry out solid-liquid separation, obtaining down, liquid stream and last liquid flow;
B, down liquid flows to into band filter, obtains the silicon carbide through cleaning, and uses the alkali lye rinsing, squeeze into separating centrifuge after, after band filter cleans, use the oxalic acid rinsing again, squeeze into three grades of waterpower cyclone separator again, the silicon carbide that obtains;
C, following liquid flow to into the 3rd band filter, and the silicon carbide that cleaned enters dryer through travelling belt, and dried silicon carbide screens out large granular impurity through air classification classification, vibratory screening apparatus and can pack;
The liquid portion that D, mortar obtain after separating carries out solid-liquid separation, adds discoloring agent and flocculating aids in the liquid, enter pressure filter, isolated liquid enters ion exchange system through behind the deep bed filter, slough moisture through evaporation unit again, namely obtain polyoxyethylene glycol.
Though the recyclable silicon carbide of this method and polyoxyethylene glycol, the rate of recovery of silicon carbide and polyoxyethylene glycol purity lower and silicon carbide is also lower.
Chinese patent literature, the patent No. 2009102330039 discloses a kind of method of extracting silicon, silicon carbide and polyoxyethylene glycol from the silicon chip cutting mortar, and mortar obtains efflux of solids and liquid flow by physical sepn after stirring under the normal temperature.Efflux of solids enters settling separation device, after the reaction, obtains silicon liquid stream and silicon carbide liquid stream.Silicon liquid stream obtains solid silicon and liquid through mechanical separation.Silicon carbide liquid stream is through mechanical separation, and again through a rinsing, oven dry is packed.The solid silicon that reclaims is the basic raw material of silicon chip, and the silicon carbide of recovery is the auxilliary material of silicon chip cutting.The liquid flow part adds discoloring agent and flocculating aids, enters mechanical separation, adds ion adsorbent and flocculating aids in the isolated liquid, carries out mechanical separation, through behind the membrane filtration, sloughs moisture, namely obtains polyoxyethylene glycol.The present invention can avoid the generation of polluting, and accomplish the close friendization to environment fully, but the rate of recovery of silicon carbide and polyoxyethylene glycol is lower, have only 50% the rate of recovery, and the purity of silicon carbide is also lower, and the silicon-carbide particle granularity is inhomogeneous in addition, particle size distribution range value D
50It is big that value becomes, if directly be used for silicon chip cutting again, will influence the quality of silicon chip cutting face, and the water yield of using in the recovery is big, and the sewage effluent amount is more.
Summary of the invention
Technical problem to be solved by this invention provides the recovery method of silicon carbide, silicon powder and polyoxyethylene glycol in a kind of silicon chip cutting liquid, this method is easy to operate, removal process, technology cleaning, safety do not have dirt to environment, in addition, the standard that the silicon carbide that reclaims and polyoxyethylene glycol quality product can reach product innovation fully, rate of recovery height: the rate of recovery of silicon carbide can reach more than 80%, and the rate of recovery of polyoxyethylene glycol can reach more than 90%, and the rate of recovery of silicon can reach more than 75%.
A kind of method of extracting silicon, silicon carbide and polyoxyethylene glycol from the silicon chip cutting mortar comprises the following step:
A, cutting fluid is stirred, for behind the 10-100 purpose screen filtration, isolate solid ingredient and liquid ingredient through whizzer through the number of looking over so as to check again;
Add water the formation solidliquid mixture that stirs in B, the solid ingredient, water: solid composition=1-5: 1 (calculating with mass parts); By fixing solid and the liquid separation in the mixture of pressure filter, make the water content of solid reach 3-5%;
C, step B is filtered the solid obtain separate and obtain silicon carbide material and silicon feed liquid;
D, extract silicon powder, precipitate and obtain the silicon material collecting the silicon feed liquid that obtains among the step C, again the silicon material is carried out pickling, filtration, the solid matter after filtering is dried, obtain silicon powder;
E, extraction silicon carbide:
E1, the silicon carbide material that obtains among the step C is entered hydraulic vortex flow devices, carry out solid-liquid separation, solid part is entered vacuum band-type filter machine filters and rinsing, the solid part after the rinsing carries out alkali cleaning, pickling, the refining purification and obtains the silicon carbide work in-process;
E2, the silicon carbide work in-process are dewatered, obtaining water content is the silicon carbide filter body of 5-20% (by mass percentage), and further oven dry makes the silicon carbide water content less than 0.1%, screen out large particulate matter after, obtain finished silicon carbide product;
F, extraction polyoxyethylene glycol,
F1, the steps A liquid ingredient is separated, obtain solid and liquid, add 0.1-2% discoloring agent and 0.1-0.5% flocculating aids in the liquid, continuously stirring under the 40-80 degree, churning time are 0.2-2 hour, and stirring velocity is 60-120 commentaries on classics/min;
F2, will filter through the liquid that step F 1 obtains;
F3, the liquid after filtering through step F 2 is entered ion exchange system, feeding temperature is controlled at the 0-40 degree;
F4, will behind the liquid filtering after the ion-exchange, distill, get water content less than 0.5% polyoxyethylene glycol distillation body;
F5, polyoxyethylene glycol is distilled body cooling, form the polyoxyethylene glycol product.
The above-mentioned method of from the silicon chip cutting mortar, extracting silicon, silicon carbide and polyoxyethylene glycol, wherein, the method separation by precipitation among the step C obtains silicon carbide material and silicon feed liquid, and precipitation comprises the steps:
C1, solid and water that step B filtration is obtained stir water: solid=2-10: 1 by mass parts; Under the normal temperature state, left standstill 1-4 hour, heavy precipitation be the silicon carbide material, lightweight suspension be the silicon feed liquid, collection respectively;
C2, the silicon carbide material is carried out repeated washing 2-5 time, and collect each silicon feed liquid and silicon carbide material that obtains that clean.
The above-mentioned method of extracting silicon, silicon carbide and polyoxyethylene glycol from the silicon chip cutting mortar, wherein, step D comprises the steps:
D1, the silicon feed liquid is carried out pre-treatment, make the liquid phase in the silicon feed liquid: solid phase=1-3: 1 (by mass);
D2, add hydrochloric acid in pretreated silicon feed liquid, and stirred 0.5-2 hour, form silicon solution, concentration of hydrochloric acid is 1-10% (densitometer by mass percentage) in the silicon solution;
D3, pickling after-filtration also clean the silicon powder filter body that obtains, and silicon powder is filtered body in the oven dry of 100-150 degree, continuous discharging during oven dry, and discharging speed is 1.5hr.
The above-mentioned method of from the silicon chip cutting mortar, extracting silicon, silicon carbide and polyoxyethylene glycol, wherein, the silicon feed liquid is carried out pre-treatment to be referred to by leaving standstill the silicon feed liquid of step C, after the upper water solution of silicon feed liquid is limpid, discharge supernatant liquid, reservation surplus water is 1-3 times of precipitated solid amount, leaves standstill under the normal temperature 4-12 hour.
The above-mentioned method of from the silicon chip cutting mortar, extracting silicon, silicon carbide and polyoxyethylene glycol, wherein, adopting mass percent concentration in the described step e 1 during alkali cleaning is that the alkaline solution of 1-10% carries out continuously stirring and cleans, and churning time is 0.5-4 hour, and stirring velocity is 60-120r/min; Adopting mass percent concentration during pickling is that the acid solution of 1-10% carries out continuously stirring and cleans, and churning time is 0.5-4 hour, and stirring velocity is 60-120r/min.
The above-mentioned method of extracting silicon, silicon carbide and polyoxyethylene glycol from the silicon chip cutting mortar, wherein, cooling adopts chilling technique to cool off in the described step F 5, namely in 1-5 minute, is cooled to 40 degree from the 40-130 degree.
Beneficial effect of the present invention is as follows:
1. comprehensive, the system, complete of production technique has reclaimed most valuable ingredients in the cutting fluid, at utmost realizes resource reutilization
2. stable processing technique, maturation, the standard that the silicon carbide that reclaims and polyoxyethylene glycol quality product can reach product innovation fully, rate of recovery height: the rate of recovery of silicon carbide can reach more than 80%, and the rate of recovery of polyoxyethylene glycol can reach more than 90%, and the rate of recovery of silicon can reach more than 75%
3. the production technique advanced design can realize increasingly automated continuous production, enhances productivity
4. the whole recovery process is pure physics removal process, technology cleaning, safety, environmentally safe
5. the silicon carbide micro-powder centralized particle diameter of Hui Shouing, foreign matter content is few, the purity height, moisture and polyoxyethylene glycol residual quantity are low
6. the polyoxyethylene glycol of Hui Shouing does not contain any other chemical ingredients, and moisture content is low.
Description of drawings
Fig. 1 is process flow sheet of the present invention.
Embodiment
The invention will be further described below in conjunction with specific embodiment.
A kind of method of extracting silicon, silicon carbide and polyoxyethylene glycol from the silicon chip cutting mortar comprises the steps:
A, cutting fluid is stirred, be that 800-1500r/min carries out continuously stirring with the stirring velocity under the normal temperature, churning time 60-120min, again after the number of looking over so as to check is for 10-100 purpose screen filtration, isolate solid ingredient and liquid ingredient through whizzer again, during separation under normal pressure the speed with 2500-3500r/min separate; By used cutting liquid is carried out sub-sieve, can earlier the big particle in the mortar be screened out processing, solid becomes cake to be difficult for pulverizing in the time of can preventing subsequent disposal, improve subsequent disposal efficient, alleviate the subsequent disposal workload, reduce the amount of disposing waste liquid, alleviate environmental pollution;
Adding water in B, the solid ingredient stirs forms fixedly mixture, water: solid composition=1-5: 1 (calculating with mass parts); By fixing solid and the liquid separation in the mixture of pressure filter, pressure is 3.5-4.5bar, and the time is 1-3hr, makes the water content of solid reach 3-5%; Standby in the liquid components of liquid collecting in the steps A; Reclaim again at polyoxyethylene glycol remaining in the solid ingredient, compared to existing technology, the polyoxyethylene glycol rate of recovery improves, and can reach more than 90%; Water consumption is few in the solid phase separating treatment, only is 30% of prior art water consumption, can reduce sewage output, alleviates environmental pollution;
C, step B is filtered the solid obtain separate and obtain silicon carbide material and silicon feed liquid; Separation obtains the silicon carbide material and the silicon feed liquid can be separated by sedimentation device, also can separate by other means;
D, extract silicon powder, precipitate and obtain the silicon material collecting the silicon feed liquid that obtains among the step C, again the silicon material is carried out pickling, filtration, the solid matter after filtering is dried, obtain silicon powder;
E, extraction silicon carbide: during silicon carbide reclaims, the technology that the present invention adopts multistage swirling flow to separate, Automatic sieve is selected high-quality, highly purified silicon carbide, being evenly distributed of particle diameter is concentrated, the silicon-carbide particle that reclaims meets the requirement of new mortar fully, the purity of silicon carbide reaches more than 99.5%, can unlimitedly recycle
E1, the silicon carbide material that obtains among the step C is entered hydraulic vortex flow devices, carry out solid-liquid separation, solid part enters that vacuum band-type filter machine filters and rinsing, and the solid part after the rinsing carries out alkali cleaning, pickling, the refining purification and obtains the silicon carbide work in-process; Adopting mass percent concentration in the described step e 1 during alkali cleaning is that the alkaline solution (alkaline solution is sodium hydroxide) of 1-10% carries out stirring and washing, churning time is 0.5-4 hour, stirring velocity is 60-120 commentaries on classics/min, adopting mass percent concentration during pickling is that (acid solution can be oxalic acid for the acid solution of 1-10%, also can be hydrochloric acid) carry out stirring and washing, continuously stirring is 0.5-4 hour, stirring velocity is 60-120r/min, make silicon carbide material and acid solution hybrid reaction even, prevent silicon carbide material precipitation; In order to reduce pollution, acid solution is preferably weak acid, can adopt oxalic acid.
E2, the silicon carbide work in-process are dewatered, obtaining water content is the silicon carbide filter body of 5-20% (by mass percentage), and further oven dry makes the silicon carbide water content less than 0.1%, screen out large particulate matter after, obtain finished silicon carbide product;
F, extraction polyoxyethylene glycol, during polyoxyethylene glycol reclaims, liquid phase component is not carried out any pickling process, do not add any pH regulator agent, guarantee the original physics of polyoxyethylene glycol, chemical property, adopt secondary filter technology in the recovery, can reduce environmental pollution, can keep reclaiming the whole knot of workshop condition, clean.
F1, the steps A liquid ingredient is separated, obtain solid and liquid, add the 0.1-2% discoloring agent in the liquid (as gac, adsorb bamboo property fiber) and 0.1-0.5% flocculating aids (as diatomite, perlite), under the 40-80 degree, stir, the continuously stirring time is 0.2-2 hour, and stirring velocity is 60-120r/min;
F2, will filter through the liquid that step F 1 obtains; Filtration requires filtrate as clear as crystal, can not contain any solid impurity in the filtrate, adopts the full-automatic accurate strainer to filter, and filtering accuracy can reach 0.1 micron
F3, the liquid after filtering through step F 2 is entered ion exchange system, feeding temperature is controlled at the 0-40 degree; Ion-exchange can make various metals and the (nonmetallic ion that contained originally in the liquid, as calcium ion, magnesium ion, iron ion, chlorion, sulfate ion etc., absorb these ions of removal by ion exchange resin, improve the purity of polyoxyethylene glycol, these ions are dissolved in the water, if do not remove, when the water in the polyoxyethylene glycol distills, these ions can be separated out from solution, cause equipment scaling.Ion exchange resin after the use uses hydrochloric acid and sodium hydroxide regeneration, can use repeatedly;
F4, the liquid after ion-exchange is distilled, get water content less than 0.5% polyoxyethylene glycol.The distillation parameter: vaporization temperature scope 50-130 degree, vacuum tightness-0.03～-0.1MPa;
F5, polyoxyethylene glycol is distilled body cooling, form the polyoxyethylene glycol product.Cooling adopts chilling technique to cool off in the described step F 5, namely in 1-5 minute, is cooled to 40 degree from the 40-130 degree.Be chilled to colourity, viscosity, pH and the chemical stability that can keep polyoxyethylene glycol behind the normal temperature, keep high temperature can cause above product performance to change for a long time and the chemical stability of product.Heat exchange can use various interchanger to carry out, and uses water coolant and material heat exchange to cool off, and generally uses plate-type heat exchanger.Processing parameter: as long as can in 1-5 minute, reach the purpose that is cooled to 40 degree.
Method separation by precipitation among the step C obtains silicon carbide material and silicon feed liquid, and precipitation comprises the steps:
C1, solid and water that step B filtration is obtained stir water: solid=2-10: 1 by mass parts; Under the normal temperature state, left standstill 1-4 hour, heavy precipitation be the silicon carbide material, lightweight suspension be silicon liquid material, collection respectively;
C2, the silicon carbide material is carried out repeated washing 2-5 time, and collect each silicon liquid material and silicon carbide material that obtains that clean; The silica flour purity height that precipitate and separate obtains, settling separation device is the process of dynamic separation, the settling velocity of silicon and silicon carbide is close, dynamic separation is complete inadequately, generally about 80%, precipitate and separate is the static separation process to the silica flour purity that obtains, by adjusting sedimentation time, separating of silicon and silicon carbide is more complete, and therefore the silica flour purity that obtains is higher.
Step D extracts silicon powder and comprises the steps:
D1: the silicon material is precipitation earlier, and the part of draining water purpose is concentrated solution, reduces the amount of solution, can reduce later stage hydrochloric acid consumption.D2: adding the hydrochloric acid purpose is the insoluble impurities of removing in the silicon, improves the purity of silicon.D3: cleaning is that flush away remains in the hydrochloric acid in the silicon, obtains product after the oven dry.
D1, the silicon feed liquid is precipitated pre-treatment, make the liquid phase in the silicon feed liquid: solid phase=2: 1 (by mass);
D2, in pretreated silicon feed liquid, add hydrochloric acid, and stirred 0.5-2 hour, form silicon solution, concentration of hydrochloric acid is that 1-10% adds the amount of hydrochloric acid according to the ratio adding of silicon feed liquid in concentration of hydrochloric acid 1-10% in the silicon solution, if any the silicon feed liquid 1000g that adds hydrochloric acid, concentration of hydrochloric acid is 1%, then wherein contains 10g hydrochloric acid, concentration of hydrochloric acid is 10%, then wherein contains 100g hydrochloric acid.
D3, pickling after-filtration also clean the silicon material that obtains, and the silicon material in the discharging of 100-150 degree continuous drying, are obtained silicon powder, discharging 1.5 hours.
Embodiment one
Extract the method for silicon, silicon carbide and polyoxyethylene glycol in a kind of silicon chip cutting mortar, comprise the steps:
A, cutting fluid is stirred, be that 800r/min carries out continuously stirring with the stirring velocity under the normal temperature, churning time churning time 60 minutes, again through behind the 10 purpose screen filtrations, enter supercentrifuge and isolate solid ingredient 579g and liquid ingredient 420g, isolate solid ingredient and liquid ingredient through whizzer again, during separation under normal pressure the speed with 2600r/min separate; Cutting fluid: carbonization model silicon 1500 orders, poly-second two model alcohol 200,8.01 microns of silicon carbide D50 indexs.Each component content wherein: silicon carbide 44%, silicon 6%, iron and oxide compound 5% thereof, polyoxyethylene glycol 42%, water 2%, other impurity 1%;
Adding water in B, the solid ingredient stirs forms fixedly mixture, water: solid is formed=2: 1 (calculating with mass parts); By fixing solid and the liquid separation in the mixture of pressure filter, pressure is 3.6bar, and the time is 2hr, makes the water content of solid reach 4.5%; Standby in the liquid components of liquid collecting in the steps A;
C, step B is filtered the solid obtain separate and obtain silicon carbide material and silicon feed liquid;
C1, step B is filtered solid and the water obtain stir water: solid=8: 1 is by mass parts; Under the normal temperature state, left standstill 4 hours, heavy precipitation be the silicon carbide material, lightweight suspension be silicon liquid material, collection respectively;
C2, the silicon carbide material is carried out repeated washing 2 times, and collect each silicon liquid material and silicon carbide material that obtains that clean;
D, extract silicon powder, precipitate and obtain the silicon material collecting the silicon feed liquid that obtains among the step C, again the silicon material is carried out pickling, filtration, the solid matter after filtering is dried, obtain silicon powder;
D1, the silicon feed liquid is precipitated pre-treatment, make the liquid phase in the silicon feed liquid: solid phase=2: 1 (by mass);
D2, add hydrochloric acid in pretreated silicon feed liquid, and stirred 2 hours, form silicon solution, concentration of hydrochloric acid is 1% in the silicon solution;
D3, pickling after-filtration also clean the silicon material that obtains, and the silicon material in 120 degree continuous drying dischargings, is obtained silicon powder, discharging 1.5hr
E, extraction silicon carbide
E1, the silicon carbide material that obtains among the step C is entered hydraulic vortex flow devices, carry out solid-liquid separation, the operating pressure 3.5bar of hydraulic vortex flow devices, solid part enters that vacuum band-type filter machine filters and rinsing, and the solid part after the rinsing carries out alkali cleaning, pickling, the refining purification and obtains the silicon carbide work in-process; Adopting mass percent concentration in the described step e 1 during alkali cleaning is that 1% sodium hydroxide carries out stirring and washing, churning time is 4 hours, stirring velocity is 100r/min, adopting mass percent concentration during pickling is that stirring and washing is carried out in 1% acid, continuously stirring is 4 hours, stirring velocity is 100r/min, makes carbonized stock and acid solution hybrid reaction even, prevents the carbonized stock precipitation; In order to reduce pollution, acid solution is preferably weak acid, can adopt oxalic acid.
E2, the silicon carbide work in-process are dewatered, obtaining water content is the silicon carbide filter body of 8% (by mass percentage), and further oven dry makes the silicon carbide water content less than 0.1%, screen out large particulate matter after, finished product behind the silicon carbide;
F, extraction polyoxyethylene glycol,
F1, the steps A liquid ingredient is separated, obtain solid and liquid, add the diatomite perlite of mass percent 0.5% gac and mass percent 0.5% in the liquid, under 40 degree, stir, the continuously stirring time is 1.5 hours, and stirring velocity is 60r/min;
F2, will filter through the liquid that step F 1 obtains;
F3, the liquid after filtering through step F 2 is entered ion exchange system, feeding temperature control is at 0 degree;
F4, will behind the liquid filtering after the ion-exchange, distill, get water content less than 0.5% polyoxyethylene glycol.Distillation parameter: vaporization temperature scope 120 degree, vacuum tightness-0.09MPa;
F5, polyoxyethylene glycol is distilled body cooling, form the polyoxyethylene glycol product.Cooling adopts chilling technique to cool off in the described step F 5, namely in 5 minutes, is cooled to 40 degree from 120 degree.
Performance index:
Embodiment two
A kind of method of extracting silicon, silicon carbide and polyoxyethylene glycol from the silicon chip cutting mortar comprises the steps:
A, cutting fluid is stirred, be that 1200r/min carries out continuously stirring with the stirring velocity under the normal temperature, churning time 80min, again through the number of looking over so as to check for after through 50 purpose screen filtrations, enter supercentrifuge and isolate solid ingredient (574g) and liquid ingredient (426g), isolate solid ingredient and liquid ingredient through whizzer again, during separation under normal pressure the speed with 3400r/min separate; Cutting fluid: carbonization model silicon 1500 orders, poly-second two model alcohol 200,8.01 microns of silicon carbide D50 indexs.Each component content wherein: silicon carbide 44%, silicon 6%, iron and oxide compound 5% thereof, polyoxyethylene glycol 42%, water 2%, other impurity 1%;
Adding water in B, the solid ingredient stirs forms fixedly mixture, water: solid is formed=5: 1 (calculating with mass parts); By fixing solid and the liquid separation in the mixture of pressure filter, pressure is 4.2bar, and the time is 3hr, makes the water content of solid reach 3.3%; Standby in the liquid components of liquid collecting in the steps A;
C, step B is filtered the solid obtain separate and obtain silicon carbide material and silicon feed liquid;
C1, step B is filtered solid and the water obtain stir water: solid=2: 1 is by mass parts;
Under the normal temperature state, left standstill 1 hour, heavy precipitation be the silicon carbide material, lightweight suspension be silicon liquid material, collection respectively;
C2, the silicon carbide material is carried out repeated washing 5 times, and collect each silicon liquid material and silicon carbide material that obtains that clean;
D, extract silicon powder, precipitate and obtain the silicon material collecting the silicon feed liquid that obtains among the step C, again the silicon material is carried out pickling, filtration, the solid matter after filtering is dried, obtain silicon powder;
D1, the silicon feed liquid is precipitated pre-treatment, make the liquid phase in the silicon feed liquid: solid phase=2: 1 (by mass);
D2, add hydrochloric acid in pretreated silicon feed liquid, and stirred 1 hour, form silicon solution, concentration of hydrochloric acid is 5% in the silicon solution;
D3, pickling after-filtration also clean the silicon material that obtains, and the silicon material in 140 degree continuous drying dischargings, is obtained silicon powder, discharging 1.5hr
E, extraction silicon carbide
E1, the silicon carbide material that obtains among the step C is entered hydraulic vortex flow devices, carry out solid-liquid separation, hydraulic vortex flow devices operating pressure 3.9bar, solid part enter that vacuum band-type filter machine filters and rinsing, and the solid part after the rinsing carries out alkali cleaning, pickling, the refining purification and obtains the silicon carbide work in-process; Adopting mass percent concentration in the described step e 1 during alkali cleaning is that 5% sodium hydroxide carries out stirring and washing, churning time is 1 hour, stirring velocity is 60r/min, adopting mass percent concentration during pickling is that 5% oxalic acid carries out stirring and washing, continuously stirring is 1 hour, stirring velocity is 60r/min, makes carbonized stock and acid solution hybrid reaction even, prevents the carbonized stock precipitation; In order to reduce pollution, acid solution is preferably weak acid, can adopt oxalic acid.
E2, the silicon carbide work in-process are dewatered, obtaining water content is the silicon carbide filter body of 12.4% (by mass percentage), and further oven dry makes the silicon carbide water content less than 0.1%, screen out large particulate matter after, finished product behind the silicon carbide;
F, extraction polyoxyethylene glycol,
F1, the steps A liquid ingredient is separated, obtain solid and liquid, add the perlite of 1.5% absorption bamboo property fiber and 0.2% in the liquid, stir under 75 degree, the continuously stirring time is 0.5 hour, and stirring velocity is 80r/min;
F2, will filter through the liquid that step F 1 obtains;
F3, the liquid after filtering through step F 2 is entered ion exchange system, feeding temperature control is at 35 degree;
F4, will behind the liquid filtering after the ion-exchange, distill, get water content less than 0.5% polyoxyethylene glycol.Distillation parameter: vaporization temperature scope 90 degree, vacuum tightness-0.098MPa;
F5, polyoxyethylene glycol is distilled body cooling, form the polyoxyethylene glycol product.Cooling adopts chilling technique to cool off in the described step F 5, namely in 2 minutes, is cooled to 40 degree from 90 degree.
Performance index:
Embodiment three
A kind of method of extracting silicon, silicon carbide and polyoxyethylene glycol from the silicon chip cutting mortar comprises the steps:
A, cutting fluid is stirred, be that 1500r/min carries out continuously stirring with the stirring velocity under the normal temperature, churning time 60min, again through behind the 100 purpose screen filtrations, enter supercentrifuge and isolate solid ingredient 585g and liquid ingredient 415g, isolate solid ingredient and liquid ingredient through whizzer again, during separation under normal pressure the speed with 3100r/min separate; Cutting fluid: carbonization model silicon 1500 orders, poly-second two model alcohol 200,8.01 microns of silicon carbide D50 indexs.Each component content wherein: silicon carbide 44%, silicon 6%, iron and oxide compound 5% thereof, polyoxyethylene glycol 42%, water 2%, other impurity 1%;
Adding water in B, the solid ingredient stirs forms fixedly mixture, water: solid is formed=3: 1 (calculating with mass parts); By fixing solid and the liquid separation in the mixture of pressure filter, pressure is 4.0bar, and the time is 2.5hr, makes the water content of solid reach 4.1%; Standby in the liquid components of liquid collecting in the steps A;
C, step B is filtered the solid obtain separate and obtain silicon carbide material and silicon feed liquid;
C1, step B is filtered solid and the water obtain stir water: solid=5: 1 is by mass parts; Under the normal temperature state, left standstill 3 hours, heavy precipitation be the silicon carbide material, lightweight suspension be silicon liquid material, collection respectively;
C2, the silicon carbide material is carried out repeated washing 3 times, and collect each silicon liquid material and silicon carbide material that obtains that clean;
D, extract silicon powder, precipitate and obtain the silicon material collecting the silicon feed liquid that obtains among the step C, again the silicon material is carried out pickling, filtration, the solid matter after filtering is dried, obtain silicon powder;
D1, the silicon feed liquid is precipitated pre-treatment, make the liquid phase in the silicon feed liquid: solid phase=2: 1 (by mass);
D2, add hydrochloric acid in pretreated silicon feed liquid, and stirred 1.5 hours, form silicon solution, concentration of hydrochloric acid is 3% in the silicon solution;
D3, pickling after-filtration also clean the silicon material that obtains, and the silicon material in 125 degree continuous drying dischargings, is obtained silicon powder, discharging 1.5hr
E, extraction silicon carbide
E1, the silicon carbide material that obtains among the step C is entered hydraulic vortex flow devices, carry out solid-liquid separation, the operating pressure 3.7bar of hydraulic vortex flow devices, solid part carried out vacuum band-type filter machine filters and rinsing, the solid part after the rinsing carries out alkali cleaning, pickling, the refining purification and obtains the silicon carbide work in-process; Adopting mass percent concentration in the described step e 1 during alkali cleaning is that 3% sodium hydroxide carries out stirring and washing, churning time is 2 hours, stirring velocity is 80r/min, adopting mass percent concentration during pickling is that 3% oxalic acid carries out stirring and washing, continuously stirring is 2 hours, stirring velocity is 80r/min, makes carbonized stock and acid solution hybrid reaction even, prevents the carbonized stock precipitation; In order to reduce pollution, acid solution is preferably weak acid, can adopt oxalic acid.
E2, the silicon carbide work in-process are dewatered, obtaining water content is the silicon carbide filter body of 10.3% (by mass percentage), and further oven dry makes the silicon carbide water content less than 0.1%, screen out large particulate matter after, finished product behind the silicon carbide;
F, extraction polyoxyethylene glycol,
F1, the steps A liquid ingredient is separated, obtains solid and liquid, add the perlite of 0.8% gac and 0.3% in the liquid), under 55 degree, stir, the continuously stirring time is 1 hour, stirring velocity is 80r/min;
F2, will filter through the liquid that step F 1 obtains;
F3, the liquid after filtering through step F 2 is entered ion exchange system, feeding temperature control is at 30 degree;
F4, will behind the liquid filtering after the ion-exchange, distill, get water content less than 0.5% polyoxyethylene glycol.Distillation parameter: vaporization temperature scope 110 degree, vacuum tightness-0.096MPa;
F5, polyoxyethylene glycol is distilled body cooling, form the polyoxyethylene glycol product.Cooling adopts chilling technique to cool off in the described step F 5, namely in 4 minutes, is cooled to 40 degree from 110 degree.
Performance index:
The present invention is not limited to above-described embodiment; every on the basis of technical scheme disclosed by the invention; those skilled in the art is according to disclosed technology contents; do not need performing creative labour just can make some replacements and distortion to some technical characterictics wherein, these replacements and distortion are all in the scope of protection of the invention.
Claims (6)
1. the recovery method of silicon carbide, silicon powder and the polyoxyethylene glycol in the silicon chip cutting liquid is characterized in that, comprises the steps:
A, cutting fluid is stirred, for behind the 10-100 purpose screen filtration, isolate solid ingredient and liquid ingredient through whizzer through the number of looking over so as to check again;
Add water the formation solidliquid mixture that stirs in B, the solid ingredient, water: solid composition=1-5: 1 (calculating with mass parts); By fixing solid and the liquid separation in the mixture of pressure filter, make the water content of solid reach 3-5%;
C, step B is filtered the solid obtain separate and obtain silicon carbide material and silicon feed liquid;
D, extract silicon powder, precipitate and obtain the silicon material collecting the silicon feed liquid that obtains among the step C, again the silicon material is carried out pickling, filtration, the solid matter after filtering is dried, obtain silicon powder;
E, extraction silicon carbide:
E1, the silicon carbide material that obtains among the step C is entered hydraulic vortex flow devices, carry out solid-liquid separation, solid part is entered vacuum band-type filter machine filters and rinsing, the solid part after the rinsing carries out alkali cleaning, pickling, the refining purification and obtains the silicon carbide work in-process;
E2, the silicon carbide work in-process are dewatered, obtaining water content is the silicon carbide filter body of 5-20% (by mass percentage), and further oven dry makes the silicon carbide water content less than 0.1%, screen out large particulate matter after, finished product behind the silicon carbide;
F, extraction polyoxyethylene glycol,
F1, with the steps A liquid ingredient from, obtain solid and liquid, add 0.1-2% discoloring agent and 0.1-0.5% flocculating aids in the liquid, continuously stirring under the 40-80 degree, churning time are 0.2-2 hour, stirring velocity is 60-120 commentaries on classics/min;
F2, will filter through the liquid that step F 1 obtains;
F3, the liquid after filtering through step F 2 is entered ion exchange system, feeding temperature is controlled at the 0-40 degree;
F4, will behind the liquid filtering after the ion-exchange, distill, get water content less than 0.5% polyoxyethylene glycol distillation body;
F5, polyoxyethylene glycol is distilled body cooling, form the polyoxyethylene glycol product.
2. the recovery method of silicon carbide, silicon powder and the polyoxyethylene glycol in the silicon chip cutting liquid as claimed in claim 1 is characterized in that, the method separation by precipitation among the described step C obtains silicon carbide material and silicon feed liquid, and precipitation comprises the steps:
C1, solid and water that step B filtration is obtained stir water: solid=2-10: 1 by mass parts; Under the normal temperature state, left standstill 1-4 hour, heavy precipitation be the silicon carbide material, lightweight suspension be the silicon feed liquid, collection respectively;
C2, the silicon carbide material is carried out repeated washing 2-5 time, and collect each silicon feed liquid and silicon carbide material that obtains that clean.
3. the recovery method of silicon carbide, silicon powder and the polyoxyethylene glycol in the silicon chip cutting liquid as claimed in claim 1 or 2 is characterized in that described step D comprises the steps:
D1, the silicon feed liquid is carried out pre-treatment, make the liquid phase in the silicon feed liquid: solid phase=1-3: 1 (by mass);
D2, add hydrochloric acid in pretreated silicon feed liquid, and stirred 0.5-2 hour, form silicon solution, concentration of hydrochloric acid is 1-10% (densitometer by mass percentage) in the silicon solution;
D3, pickling after-filtration also clean the silicon powder filter body that obtains, and silicon powder is filtered body in the oven dry of 100-150 degree, continuous discharging during oven dry, and discharging speed is 1.5hr.
4. as the recovery method of silicon carbide, silicon powder and polyoxyethylene glycol in the silicon chip cutting liquid as described in the claim 3, it is characterized in that, the silicon feed liquid is carried out pre-treatment to be referred to by leaving standstill the silicon feed liquid of step C, after the upper water solution of silicon feed liquid is limpid, discharge supernatant liquid, reservation surplus water is 1-3 times of precipitated solid amount, leaves standstill under the normal temperature 4-12 hour.
5. the recovery method of silicon carbide, silicon powder and the polyoxyethylene glycol in the silicon chip cutting liquid as claimed in claim 1, it is characterized in that, adopting mass percent concentration in the described step e 1 during alkali cleaning is that the alkaline solution of 1-10% carries out continuously stirring and cleans, churning time is 0.5-4 hour, and stirring velocity is 60-120r/min; Adopting mass percent concentration during pickling is that the acid solution of 1-10% carries out continuously stirring and cleans, and churning time is 0.5-4 hour, and stirring velocity is 60-120r/min.
6. the recovery method of silicon carbide, silicon powder and the polyoxyethylene glycol in the silicon chip cutting liquid as claimed in claim 1 is characterized in that, cooling adopts chilling technique to cool off in the described step F 5, namely in 1-5 minute, is cooled to 40 degree from the 40-130 degree.
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| CN107487773A (en) * | 2017-08-09 | 2017-12-19 | 中国恩菲工程技术有限公司 | Handle the method and system of silicon materials cutting disposed slurry |
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