CN101691217B - Method for preparing white carbon black and simultaneously recycling silicon carbide from waste mortar for wire cutting - Google Patents
Method for preparing white carbon black and simultaneously recycling silicon carbide from waste mortar for wire cutting Download PDFInfo
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- CN101691217B CN101691217B CN 200910204543 CN200910204543A CN101691217B CN 101691217 B CN101691217 B CN 101691217B CN 200910204543 CN200910204543 CN 200910204543 CN 200910204543 A CN200910204543 A CN 200910204543A CN 101691217 B CN101691217 B CN 101691217B
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- silicon carbide
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- white carbon
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Abstract
The invention discloses a process method for preparing white carbon black and simultaneously recycling silicon carbide powder from waste mortar produced in the process of cutting or grinding monocrystalline silicon or polysilicon into silicon wafers, which comprises the following steps: adding ammonium fluoride into the pre-treated waste mortar so that the added ammonium fluoride reacts with silicon in the waste mortar to produce ammonium fluorosilicate and ammonia gas, and adding water for filtering to obtain the pure silicon carbide; and adding ammonia water dropwise into the aqueous solution of the produced ammonium fluorosilicate to produce the white carbon black and the ammonium fluoride which is recycled after being condensed. The method in the invention can effectively utilize the silicon in the waste mortar to prepare the white carbon black, simultaneously recycle the silicon carbide and effectively reduce the cost on recycling the waste mortar and preparing the white carbon black by recycling the ammonium fluoride, is the practicable technology which can make waste profitable, greatly reduce the discharge of the wastewater and create remarkable economic and social benefits.
Description
Technical field
Produce the method for white carbon black and simultaneously recycling silicon carbide in the waste mortar that the present invention relates to produce a kind of cutting from silicon single crystal or polycrystalline silicon rod or the ground finish silicon wafer process.Concrete, the waste mortar for wire cutting utilization silicon wherein that produces in the silicon wafer complete processing is produced white carbon black, recovery silicon carbide solid micro-powder wherein is to realize being used for again the purpose of silicon rod slicing process simultaneously.
Background technology
The formal name used at school of white carbon black is hydrated SiO 2 (mSiO
2NH
2O), similar because of its microtexture and aggregate form and carbon black, reinforcing property and carbon black compare favourably, so be called as white carbon black.White carbon black has features such as particle diameter is little, specific surface area is big, chemical purity is high, dispersing property is good, be used widely at many industrial circles such as rubber, coating, medicine, papermaking with its superior stability, reinforcement, thickening property and thixotropy, and for the development in its related industries field provides novel material basis and technical guarantee, be widely used in every field.Add Nano carbon white in the coating, functions such as anti-caking, sag prevention, thickening delustring can be provided; In plastics, add white carbon black, can improve transparency, toughness, the intensity of film, water resistance etc.Add white carbon black in binding agent and the seal gum, can form network-like masonry structure rapidly, suppress colloid and flow, solidification rate is accelerated, and improves bond effect.In medicine, agricultural chemicals, can play the effect of thickening, suspension, carrier.Newest research results shows: introduce white carbon black and can demonstrate a series of praiseworthy optical properties and mechanical property in polymeric system.Enjoy the good reputation of " industrial monosodium glutamate ", " initial point of Materials science ".Since coming out, become and can adapt to one of requirements of the times and kind with fastest developing speed in world today's Materials science, developed country the fine inorganic material of high-performance, high added value as next century novel material emphasis developed.
In the cutting preparation process of unicircuit with the thin sheet products of substrate (semi-conductor and liquid crystal display etc.) and solar cell substrate, adopt multi-thread incision principle, drive a kind of mobile mixed-abrasive-mortar that has with steel wire, utilize silicon carbide micro-powder particle wherein to impact silicon single crystal and polycrystalline silicon rod surface continuously and healthily, utilize the rigid characteristic of silicon-carbide particle and the sharp water caltrop of particle surface that silicon rod is progressively blocked, this mixed-abrasive-mortar is to be mixed by silicon carbide and a certain proportion of polyoxyethylene glycol (PEG), polyoxyethylene glycol plays the effect of dispersion agent, silicon carbide is evenly distributed in cutting process, and polyoxyethylene glycol possesses certain thermal capacitance, can take away the frictional heat that produces in cutting process in a large number, the good aqueous solubility of polyoxyethylene glycol also is convenient to the cleaning of later stage silicon chip simultaneously.Though this mortar can recycle, but the carrying out along with cutting process, be mixed with the steel wire smear metal of silicon bits and trace in the mortar, and invalid particle in small, broken bits significantly increases, the mortar cutting property is reduced, the silicon wafer precision that causes obtaining worsens, and therefore needs constantly to discharge the old sand slurry in cutting process, and constantly replenishes new mortar.Common treating method is to discharge landfill as industrial residue, and wherein valuable high-purity silicon powder also can lose along with the discarded of mill nitre mortar.Liquid organic suspension liquid also must carry out could reaching environmental emission standard reluctantly after necessary biological degradation is handled, otherwise may cause the secondary pollution (according to [People's Republic of China's integrated wastewater discharge standard (GB8978-1996)] of State Bureau of Technical Supervision's issue on October 4th, 1996) to water source and soil.Therefore will use useless slicing slurry once to handle the significant wastage of being not only social resources as trade waste, and cause the increase of silicon chip production cost simultaneously, and environment is caused certain pollution.
Chinese patent CN 101032806A (200610058747.8) discloses a kind of method of cutting useless suspension recovery, it is characterized in that the cutting of the line in silicon wafer complete processing waste mortar is carried out multiple-stage treatment, comprise the steps: the primary filter of solid-liquid separation, suspension, the essence filter of suspension, the concentrate drying of suspension.Chinese patent CN 101033066A (200610058746.3) discloses the method that a kind of silicon carbide micro-powder reclaims, it is characterized in that the cutting of the line in silicon wafer complete processing waste mortar is carried out multiple-stage treatment, comprise the steps: solid-liquid separation, carborundum granularity classification, the purification of silicon carbide basic acid formula, micro mist drying, disperse the sieve pine.Chinese patent CN 101327622A (200710117665.0) discloses by a membrane filtration isolation technique, makes the waste mortar solid-liquid separation once finish, and obtains qualified PEG and reclaims liquid, and keep its physical properties constant; Then to the filter residue after the above-mentioned solid-liquid separation clean, processing such as classification, drying, obtain qualified SiC and reclaim powder, and after removing impurity, reduce its initial particle size normal distribution.Exhausting line cutting waste mortar technical process: waste mortar stoste-one time membrane filtration-PEG liquid; Waste mortar stoste-one time membrane filtration-alkali cleaning cleanup acid treatment-filtration-powder for drying-powder classification-SiC powder.Chinese patent CN 101474511A (200810232782.6) discloses the method that polyoxyethylene glycol and silicon carbide are recycled in a kind of Silicon Wafer waste mortar for wire cutting, it adds visbreaking agent earlier with the waste mortar for wire cutting in the monocrystalline silicon piece complete processing, carries out solid-liquid separation and obtains suspension part and solid particulate part.Partly add flocculating aids for suspension, filter press, millipore filtration, Hollow Fiber Ultrafiltration, ion-exchange then at last with suspension vacuum distilling, is reclaimed polyoxyethylene glycol.Carry out alkali reaction cleaning, water wash column washing, centrifugation, acid-respons cleaning, water wash column washing again, centrifugation, acid-respons cleaning, drying and dry classification successively for solid particulate, obtain the silicon-carbide particle that can be recycled at last.More than each patent and domestic most of producer be not very high according to the content of the silicon in the waste mortar, adopt the silicon in the molten waste mortar of hydrofluoric acid or the sodium hydroxide molten alkali of acid only to reclaim carborundum, cause the loss of a large amount of hydrofluoric acid or water glass and silicon, and bring pollution to environment.
The Japanese Patent spy opens the recovery method that 2001-278612 discloses a silicon, the technology that adopts is with after the waste mortar dehydration, remove dispersion agent and binding agent with organic solvent, carry out pickling again and remove metal and silicon-dioxide, adopt the way divided silicon of pneumatic separation and silicon carbide to obtain silica flour at last.Adopt pneumatic separation technology in the technology, the terminal velocity of particle is the principal element that influences pneumatic separation, in stable the rising, can't realize the separation of taking as the leading factor by pellet density in theory.Therefore the silica flour purity that reclaims of this invention has only 98% (weight), is mixed with the carborundum of 2% (weight); And air-flow can be taken away the superfine silica flour of particle, causes the loss of silica flour.Chinese patent CN 101130237A (200710018636.9) is bigger according to the proportion of carborundum and steel, and after the flotation of advanced promoting the circulation of qi stream, the Si powder of acquisition can be separated fully with carborundum and steel, can be mingled with 2-10% (weight) carborundum.Further adopt density between Si (2.33g/cm to this low pure silicon powder again
3) and SiC (3.21g/cm
3) solution carry out liquid floatation and gravitational segregation because the difference of specific gravity of silicon and carborundum, the carborundum sinking that the silica flour come-up that density is lower and density are higher can sub-elect highly purified silica flour.Because the silicon monomer surface is oxidized easily, form silicon-dioxide, therefore use hydrofluoric acid to carry out pickling the silica flour that obtains again, finally can obtain highly purified silica flour; Simultaneously carborundum and the metal mixture that obtains used the magnetic force sorting, finally can obtain the carborundum powder of certain purity.There is following shortcoming in the above recovery method:
(1) can lose very thin that part of silica flour in the pneumatic separation process, or need separating device efficiently, facility investment is than higher;
(2) in the pneumatic separation process, because the particle diameter ratio of silica flour is less, specific surface area is bigger, and active high, therefore silica flour is easy to oxidation in the pneumatic separation process, is difficult to make the high silica flour of purity;
When (3) using heavy-liquid concentration, the heavy-fluid viscosity ratio is bigger, and the particle of silica flour is smaller, is easy to form suspension, is difficult to realize layering; It is somewhat expensive and poisonous to add major part, is difficult to realize industrialization.
Each patent in sum; number of research projects has been done in recycling to the polyoxyethylene glycol in the waste mortar for wire cutting and silicon carbide, has promoted the reduction of linear cutting mortar cost, has saved the energy; protected environment, had great importance to realizing that resource circulation is recycled.But all the silicon in the waste mortar for wire cutting (quality 10%) is not carried out effectively rationally recycling.Existing waste mortar recovery technology shows, will become emphasis of future research to the recycling of the silicon in the waste mortar.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of processing method of producing white carbon black and simultaneously recycling silicon carbide from the waste mortar that silicon single crystal and polycrystalline silicon rod carry out producing the cutting processing process.
For reaching above purpose, the present invention adopts following technical scheme to be achieved:
A kind ofly produce the method for white carbon black and simultaneously recycling silicon carbide from waste mortar for wire cutting, its feature comprises the steps:
A. with the waste mortar pre-treatment;
B. add Neutral ammonium fluoride in will step a gained sand powder (silicon and silicon carbide), make itself and pasc reaction generate ammonium silicofluoride and ammonia, the ammonia water absorbs stand-by, and the solid material ammonium silicofluoride that is dissolved in water filters and obtains solid silicon carbide, the dry silicon carbide products that gets;
C. step b gained liquid fluorine ammonium silicate is added ammoniacal liquor or gas ammonia, reaction generates Neutral ammonium fluoride and white gelatinous precipitate, filters, and the solid drying gets the white carbon black product.
D. step c gained Neutral ammonium fluoride dilute liquid after concentrating, negative pressure is recycled.
In the such scheme, described Neutral ammonium fluoride and pasc reaction, 5 ℃～130 ℃ of temperature, time 0.25～8h; The concentration of described ammoniacal liquor is 1～25% (quality), and 5 ℃～110 ℃ of temperature and ammonium silicofluoride are 1～30% (quality); 60 ℃～280 ℃ of drying temperatures; It is in temperature below 80 ℃ and vacuum tightness 0.01～0.1MPa that described Neutral ammonium fluoride concentrates.
The present invention compares with existing technological method, this law adopts the Neutral ammonium fluoride dissolves silicon to make it form solution, filtration obtains silicon carbide, the silicofluoric acid that recycling generates makes white carbon black and Neutral ammonium fluoride, ammonium fluoride aqueous solution concentrates and recycles, finally by the recycling of Neutral ammonium fluoride, realize in same process, producing white carbon black and reclaimed silicon carbide, demonstrated fully the effective recycling to the silicon in the waste mortar.Its advantage is, recycles by Neutral ammonium fluoride, reduced the cost recovery of waste mortar, significantly reduced effluxing of sewage, has tangible economic and social benefit.
Description of drawings
Fig. 1 is process flow sheet of the present invention.
Reaction 1:6NH
4F+Si → (NH
4)
2SiF
6+ 4NH
3↑+2H
2↑ (1)
Reaction 2:(NH
4)
2SiF
6+ 4NH
3+ (n+2) H
2O → 6NH
4F+SiO
2NH
2O ↓ (2)
Total reaction: Si+ (n+2) H
2O → SiO
2NH
2O ↓+2H
2↑ (3)
Embodiment
Embodiment 1
Make the silicon chip of solar cell and unicircuit (semi-conductor and liquid crystal display etc.) usefulness with multi-thread cutting, dispersion agent in the abrasive material mortar that uses (as polyoxyethylene glycol etc.) is oiliness, waste mortar consist of dispersion agent 42% (weight), silicon carbide abrasive 48% (weight), silica flour 8.4% (weight), metal 1.6% (weight).Get pretreated 28 kg sand powder and put into container, and add the water of 36 kilograms of Neutral ammonium fluorides and 20 kilograms, in 40 ℃ of reactions 1 hour down, the reactant ammonium silicofluoride that is dissolved in water, control concentration 10% (quality).Carry out filtering separation, obtain 23.3 kilograms of wet silicon carbide, drying gets finished product silicon carbide; Add 10 kilograms of (10% quality) ammonia precipitation processes in the solution and separate out white gelatinous precipitate, after the filtration, in solution, add ammoniacal liquor again, till the precipitation precipitation is separated out fully, filter, twice white glue is deposited in 120 ℃ of dryings, get the white carbon black product, specific surface area 151m
2/ g; Solution after separating out concentrates under 60 ℃ of temperature and vacuum tightness 0.09Mpa, obtains returning of Neutral ammonium fluoride and recycles.Wherein each rate of recovery of Neutral ammonium fluoride is 98%.
Embodiment 2
Utilize multi-thread cutting to make the silicon chip of solar cell and unicircuit (semi-conductor and liquid crystal display etc.) usefulness, dispersion agent in the abrasive material mortar that uses (as polyoxyethylene glycol etc.) is oiliness, waste mortar consist of dispersion agent 38% (weight), silicon carbide abrasive 47% (weight), silica flour 12.9% (weight), metal 2.1% (weight).Get pretreated 30 kg sand powder and put into container, add the water of 39 kilograms of Neutral ammonium fluorides and 22 kilograms, in 60 ℃ of reactions 1 hour down, the reactant ammonium silicofluoride that is dissolved in water, control concentration 8% (quality).Carry out filtering separation, obtain 22.1 kilograms of wet silicon carbide, drying gets finished product silicon carbide; Add 15 kilograms of (25% quality) ammonia precipitation processes in the solution and separate out white gelatinous precipitate, after the filtration, in solution, add ammoniacal liquor again, till the precipitation precipitation is separated out fully, filter, twice white glue is deposited in 80 ℃ of vacuum-dryings, get the white carbon black product, specific surface area 186m
2/ g; Solution after separating out concentrates under 75 ℃ of temperature and vacuum tightness 0.05Mpa, obtains returning of Neutral ammonium fluoride and recycles.Wherein each rate of recovery of Neutral ammonium fluoride is 95%.
Claims (1)
1. produce the method for white carbon black and simultaneously recycling silicon carbide from waste mortar for wire cutting for one kind, its feature comprises the steps:
A. with the waste mortar pre-treatment;
B. will add Neutral ammonium fluoride in step a gained sand powder silicon and the silicon carbide, make itself and pasc reaction generate ammonium silicofluoride and ammonia, the ammonia water absorbs stand-by, and the solid material ammonium silicofluoride that is dissolved in water filters and obtains solid silicon carbide, dry silicon carbide products;
C. step b gained liquid fluorine ammonium silicate is added ammoniacal liquor or gas ammonia, reaction generates Neutral ammonium fluoride and white gelatinous precipitate, filters, and the solid drying gets the white carbon black product;
D. step c gained Neutral ammonium fluoride dilute liquid after concentrating, negative pressure is recycled;
Neutral ammonium fluoride described in the above-mentioned steps b and pasc reaction, 5 ℃～130 ℃ of temperature, time 0.25～8h;
Ammoniacal liquor mass percent concentration described in the above-mentioned steps c is 1～25%, 5 ℃～110 ℃ of temperature; The ammonium silicofluoride mass percent concentration is 1～30%; 60 ℃～280 ℃ of drying temperatures;
It is in temperature below 80 ℃ and vacuum tightness 0.01～0.1MPa that Neutral ammonium fluoride described in the above-mentioned steps d concentrates.
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| CN101691217B true CN101691217B (en) | 2013-07-17 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102079520A (en) * | 2011-01-12 | 2011-06-01 | 虹京环保有限公司 | Recycling method of silicon carbide |
| CN102167322A (en) * | 2011-01-15 | 2011-08-31 | 塔里木大学 | Method for recovering silicon carbide in waste cutting mortar by using ammonium bifluoride |
| CN102491369A (en) * | 2011-12-02 | 2012-06-13 | 瓮福（集团）有限责任公司 | Method for producing ammonium fluoride by recovering fluorine resources |
| CN102491352B (en) * | 2011-12-14 | 2013-07-10 | 江苏佳宇资源利用股份有限公司 | Method for preparing white carbon black by silicon powder component acquired by cyclone separation of waste motar |
| CN102530948B (en) * | 2012-01-04 | 2013-07-10 | 浙江大学 | Method for recycling silicon from filings obtained through silicon wafer cutting |
| CN107324349B (en) * | 2017-07-21 | 2019-06-11 | 淄博飞源化工有限公司 | A method of high-specific area nano grade white carbon black is prepared using fluosilicic acid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1319561A (en) * | 2001-04-10 | 2001-10-31 | 夏克立 | Method for producing fluoride and silicon dioxide |
| CN101033066A (en) * | 2006-03-06 | 2007-09-12 | 张捷平 | Method of recovering silicon carbide micro-powder |
| CN101269816A (en) * | 2008-05-16 | 2008-09-24 | 夏克立 | Method for producing fluorine series compounds and white carbon black |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1319561A (en) * | 2001-04-10 | 2001-10-31 | 夏克立 | Method for producing fluoride and silicon dioxide |
| CN101033066A (en) * | 2006-03-06 | 2007-09-12 | 张捷平 | Method of recovering silicon carbide micro-powder |
| CN101269816A (en) * | 2008-05-16 | 2008-09-24 | 夏克立 | Method for producing fluorine series compounds and white carbon black |
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Effective date of registration: 20210105 Address after: No. 1501, Beixin West Road, Tengzhou City, Shandong Province 277599 Patentee after: TENGZHOU INSTITUTE OF PRODUCT QUALITY SUPERVISION AND INSPECTION Address before: 266510 No. 579, Bay Road, Huangdao District, Shandong, Qingdao Patentee before: Shandong University of Science and Technology |