CN102167563A - Method for producing ceramic chips by using calcium fluoride sludge and abandoned serpentine mine tailing - Google Patents

Method for producing ceramic chips by using calcium fluoride sludge and abandoned serpentine mine tailing Download PDF

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Publication number
CN102167563A
CN102167563A CN 201110000569 CN201110000569A CN102167563A CN 102167563 A CN102167563 A CN 102167563A CN 201110000569 CN201110000569 CN 201110000569 CN 201110000569 A CN201110000569 A CN 201110000569A CN 102167563 A CN102167563 A CN 102167563A
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China
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dry powder
caf
serpentine
abandoned
mine tailing
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朱萍
洪岱
周鸣
范泽云
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University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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Abstract

The present invention relates to a method for producing ceramic chips by using calcium fluoride sludge and abandoned serpentine mine tailing. The method comprises: placing CaF<2> sludge taken from a sludge processing factory in a temperature below 150 DEG C for drying, crushing and sieving into CaF<2> dry powder; crushing the abandoned serpentine mine tailing taken form a mine factory, carrying out ball milling by a ball mill, and drying into abandoned serpentine mine tailing dry powder; mixing the CaF<2> dry powder and the abandoned serpentine mine tailing dry powder in a mass ratio of 3:1 to 1:2, and carrying out the ball milling and blending by the ball mill for 1 to 2 hours; adding 5wt% to 15wt% of clay, 3wt% to 8wt% of adhesive and 1wt% to 3wt% of other auxiliary additives; adding a proper amount of water into raw materials and stirring into even mixture, which is placed into a disk-shaped ceramic pressing die for carrying out tabletting processing, with intensity of pressure being controlled within from 6 to 12 M Pa; and placing ceramics formed by tabletting into a high-temperature furnace for sintering, with the sintering temperature being from 1000 to 1300 DEG C. The method has the characteristics that all of the raw materials are wastes, cost is low, and processing technology is simple, thus the aim of solid wastes recycling is achieved.

Description

Utilize calcium fluoride sludge and discarded serpentine tailing to produce the method for ceramic plate
Technical field
The present invention relates to a kind of method of utilizing calcium fluoride sludge and discarded serpentine tailing to produce ceramic plate, belong to the inorganic materials field.This method is to be main raw material with calcium fluoride sludge and discarded serpentine, and adds a small amount of clay, tackiness agent and other supplementary additives, by the press mold moulding, prepares building ceramic brick and ceramic plate under high temperature sintering.
Background technology
The IC industry of China develops rapidly, and the Foundry technology is near advanced international standard.The waste that is produced in the productive consumption process, accumulating silently influences environment damage.
Comprise at ic manufacturing process: work flows such as diffusion, ion implantation, gold-tinted development, dry-and wet-type etching, chemical vapor deposition and film generation.Above-mentioned production technique all can relate to the cleaning at the chip front surface and the back side, will produce hydrofluoric acid waste water in cleaning process, passes through CaCl 2Or Ca (OH) 2Chemical settling is handled, and adds the PAC flocculation agent simultaneously and improves sedimentation, the CaF of generation 2Throw out is collected with pressure filter (Filter Press) dehydration back again, with it landfill.Generally with CaF 2Be soaked in the water, the stripping quantity of fluorion can reach 8.1 mg/L, if do TCLP toxicity leaching experiment, the leaching concentration that then can draw fluorion can be up to 33.78mg/L, and content of fluoride ion safety recommendation value is 1 mg/L in the GB regulation water, so during as ultimate disposal, should avoid groundwater pollution and water source to take with landfill calcium fluoride sludge.Current China is exactly landfill to the calcium fluoride sludge processing mode that integrated circuit manufacturing industry produces, and calcium fluoride sludge runs into water and can make the soluble in water and polluted underground water resource of fluorion.Therefore, exploration calcium fluoride sludge New Method for Processing is extremely urgent.
Because CaF 2Be in high temperature SiO 4When being material, can effectively reduce SiO 4Be the fusing point (Melting Point) of material and the liquid viscosity that reduces high temp glass phase material, this is because of SiO 4Oxonium ion in the crystal very easily with fluorion in high temperature displacement (because of the ionic radius of fluorion and oxonium ion similar), and destruction SiO 4Due to the lattice of system.Event is used for pottery and glass industry can promote the high-temperature liquid-phase sintering, reduces the glass high-temperature viscosity; Being used for metallurgy industry then is to reduce the slag fusing point and increase its temperature flowing, makes slag be easy to separate with high-temperature molten metal.Chinese patent ZL01109444.3 mentions calcium fluoride sludge and utilizes the preparation ceramic again, and it will take from the CaF of sludge treatment factory 2Mud places that temperature drying, pulverizing, screening become CaF below 150 ℃ 2Dry powder; Puddle and be a granulated into A soil with binding agent and mineralizer dry type then; Just feldspar, kaolin, quartz and clay give the ball milling wet type and puddle again, mist projection granulating, and ageing becomes basic earth material; At last A soil, binding agent, basic earth material, calcined kaolin, pottery stone grain and ceramic pigment dry type are puddled, granulation, screening, ageing, high-pressure molding, body drying, high temperature sintering forms the finished product.
The folding strength of the prepared ceramic body of this technology can reach 33.1 kg/cm 2, water-intake rate＜1.0%, and ceramic tile is after acidproof, alkali resistance test, and product surface does not have any appearance change, can meet CNS 13431 China national quality codes and standards.The ceramic tile villiaumite again stripping quantity less than the EPA limit value.
According to the characteristics of foregoing invention patent, my design is that main raw material prepares ceramic plate and brick with depleted serpentine tailing and calcium fluoride sludge.The molecular composition of discarded serpentine minerals is Mg 6[Si 4O 10] (OH) 8, wherein MgO accounts for 43%, SiO 2Account for 44.1%, H 2O accounts for 12.9%.Fe is often contained in the snake ore deposit of occurring in nature, elements such as Mn, Ni, F, Cu, Cr.Serpentine belongs to moisture layer silicate mineral, is the main raw material of making magnesia porcelain, also can add on a small quantity to improve performance in the blank of conventional ceramic.The present invention, oxonium ion can be replaced by fluorion in the interior contained siloxane bond of expectation serpentine Magnesium Silicate q-agent structure, plays solid fluorine effect.The characteristics of this method be raw materials used all be waste, cost is low, treatment process is simple, thereby reach admittedly the purpose of useless resource utilization.
Summary of the invention
It is the stupalith that basic raw material prepares construction applications that the present invention is intended to calcium fluoride sludge and discarded serpentine tailing, finally can reach the effect of useless resource utilization admittedly.
For achieving the above object, pottery proposed by the invention adopts following technical process preparation:
A. will take from the CaF of sludge treatment factory 2Mud places that temperature drying, pulverizing, screening become CaF below 150 ℃ 2Dry powder;
B. will take from the discarded serpentine tailing jaw crushing crusher machine of ore deposit factory, and cross 120 orders with the ball mill ball milling, oven dry becomes discarded serpentine tailing dry powder;
C. with CaF 2Dry powder mixes according to the ratio of mass ratio 3:1～1:2 with discarded serpentine tailing dry powder, with ball mill ball milling mixing 1～2h, crosses 120 mesh sieves then, is designated as raw material A;
D. add the clay of 5 wt%～15 wt%, the tackiness agent of 3 wt%～8 wt%, and other supplementary additives of 1 wt%～3 wt% mix with raw material A, and 120 orders that sieve behind the ball milling are designated as raw material B, give over to standby;
E. raw material B adds an amount of water, and stirs and put into the flaky ceramic pressing mold of circle and carry out compressing tablet and handle, and control pressure is 6～12MPa, pressurize 1～2min;
F. the pottery behind the compression molding is put into High Temperature Furnaces Heating Apparatus and carry out sintering, sintering temperature is 1000 ℃～1300 ℃, and heat-up rate is 10 ℃/min.
This method prepares the ceramic plate of gained, and surface luster is careful, and pore is few.XRD shows that (Fig. 2) generated new thing phase, Ca in pyroreaction 1.92Mg 5.08(Si 8O 22) F 2, therefrom as can be seen, fluorion be attached to effectively new thing mutually in, formed hornblende, the main expression formula of amphibole be (Ca, Na) 2-3(Mg 2+, Fe 2+, Fe 3+, Al 3+) 5[(Al, Si) 4O 11] (OH) 2, wherein the calcium sodium ion can the phase double replacement, and ferrous ion, magnesium ion and trivalent aluminium ion be double replacement mutually also, and hydroxyl wherein can be replaced by fluorion, plays the effect of solid fluorine.
The thermogravimetric GC-MS shows (Fig. 3), and in high-temperature sintering process, the effusion of fluoro-gas does not cause second environmental pollution.Illustrate that the material that fluorion at high temperature reacts generation has high-temperature stability preferably.
TCLP toxicity leaches in addition and fluorion leaching (Fig. 4) draws, and the heavy metal leaching amount of sintering gained pottery reaches GB and EPA standard, and fluorinion concentration is also far below emission standard.
Adopt calcium fluoride sludge and depleted serpentine tailing to prepare the stupalith of fluorinated calcium mud, Calcium Fluoride (Fluorspan) can be solidificated in the stupalith, avoid fluorion to run into water and leach, the polluted underground water environment, and its preparation technology is simple, the raw materials used solid waste that mostly is greatly can reduce cost to a certain extent.
Description of drawings
Fig. 1 is ceramic preparation technology's schema.
Fig. 2 is the XRD spectra of sintered ceramic sheet.
Fig. 3 is the TC-MS spectrogram of ceramic raw material.
Fig. 4 is the TCLP toxicity leaching test and the fluorinion concentration test of sintered ceramic sheet.
Embodiment
To take from the CaF of sludge treatment factory 2Mud 1000 gram places that temperature drying, pulverizing, screening become CaF below 150 ℃ 2Dry powder; In addition, will take from discarded serpentine tailing 600 grams of ore deposit factory and use the jaw crushing crusher machine, and cross 120 orders with the ball mill ball milling, oven dry becomes discarded serpentine tailing dry powder; Above-mentioned two sample mix are put into ball mill, and rotating speed is controlled at 200 rpm, and the ball milling time is 2 hours.The sample that ball milling is crossed is crossed 120 mesh sieves.
Take by weighing sample 1000 grams that ball milling sieves, get clay 90 grams, adding concentration is PVA solution 50ml and aluminum oxide supplementary additive 20 grams of 5wt%, carries out ball milling and stirs, and rotating speed is controlled at 200 rpm, and the time is 1 hour, and 120 orders sieve behind the ball milling.
Take by weighing sample 500 grams that above-mentioned ball milling stirs, add a spot of water and stir, put into ceramic die and carry out the compressing tablet processing, control pressure is 10MPa, pressurize 2min.The stove of the ceramic plate that presses being put into temperature programming carries out high temperature sintering, and heat-up rate is 10 ℃/min, and temperature is controlled at 1100 ℃, and the time is 5 hours.
The ceramic plate that burns till is carried out the test of ultimate compression strength and water-intake rate, record its folding strength and can reach 30 kg/cm 2, water-intake rate＜1.25%.After pottery put into pure water and soak 24 hours, record its villiaumite again stripping quantity be 0.8 mg/L, far below the limit value of the water 15mg/L that releases.
In addition, at 15%KOH(W/V) soak after 24 hours in the basic solution, its fluorion stripping quantity is 3mg/L only, at 15%H 2SO 4(V/V) soak after 24 hours in the acidic solution, its fluorion also only is 130mg/L.
The invention is not restricted to the embodiment here, those skilled in the art should be within protection scope of the present invention to improvement and modification that the present invention makes according to announcement of the present invention.

Claims (1)

1. method of utilizing calcium fluoride sludge and discarded serpentine tailing to produce ceramic plate is characterized in that the concrete steps of this method are as follows:
A. will take from the CaF of sludge treatment factory 2Mud places that temperature drying, pulverizing, screening become CaF below 150 ℃ 2Dry powder;
B. will take from the discarded serpentine tailing jaw crushing crusher machine of ore deposit factory, and cross 120 orders with the ball mill ball milling, oven dry becomes discarded serpentine tailing dry powder;
C. with CaF 2Dry powder mixes according to the ratio of mass ratio 3:1～1:2 with discarded serpentine tailing dry powder, with ball mill ball milling mixing 1～2h, crosses 120 mesh sieves then, is designated as raw material A;
D. add the clay of 5 wt%～15 wt%, the tackiness agent of 3 wt%～8 wt%, and other supplementary additives of 1 wt%～3 wt% mix with raw material A, and 120 orders that sieve behind the ball milling are designated as raw material B, give over to standby;
E. raw material B adds an amount of water, and stirs and put into the flaky ceramic pressing mold of circle and carry out compressing tablet and handle, and control pressure is 6～12MPa, pressurize 1～2min;
F. the pottery behind the compression molding is put into High Temperature Furnaces Heating Apparatus and carry out sintering, sintering temperature is 1000～1300 ℃, and heat-up rate is 10 ℃/min.
CN 201110000569 2011-01-05 2011-01-05 Method for producing ceramic chips by using calcium fluoride sludge and abandoned serpentine mine tailing Pending CN102167563A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102432276A (en) * 2011-09-13 2012-05-02 苏州市亨文环保水业有限公司 Application of CaF2 sludge in ceramics
CN102557444A (en) * 2012-01-04 2012-07-11 上海大学 Method for preparing glass ceramic from serpentine tailings
CN102807360A (en) * 2012-08-28 2012-12-05 黄靖宇 Preparation of novel ceramic particle by adopting calcium fluoride sludge
CN105669209A (en) * 2015-12-30 2016-06-15 刘操 Silicon nitride ceramic material, and preparation method and application thereof
CN106365610A (en) * 2016-10-26 2017-02-01 长沙聚优能环保科技有限公司 Method for making shale bricks with calcium fluoride sludge and treatment method of fluorine-containing wastewater
CN107827471A (en) * 2017-11-27 2018-03-23 柳州市闽贵砖厂 A kind of Fire-resistant ceramic tile and preparation method thereof
CN113213939A (en) * 2021-04-26 2021-08-06 湖北垚冶环保科技有限公司 Method for producing calcium fluoride product by using calcium fluoride sludge

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1041740A (en) * 1988-10-08 1990-05-02 张天中 With the serpentine is the method for raw material production magnesiumcarbonate and/or magnesium oxide and porous silica
CN1172087A (en) * 1997-07-11 1998-02-04 西南工学院 Cement mixed material
CN1374270A (en) * 2001-03-08 2002-10-16 全盛兴资源科技股份有限公司 Calcium fluoride sludge reusing method and product
CN101235440A (en) * 2008-03-14 2008-08-06 大悟华龙吕王石材有限公司 Method of comprehensively utilizing serpentine

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1041740A (en) * 1988-10-08 1990-05-02 张天中 With the serpentine is the method for raw material production magnesiumcarbonate and/or magnesium oxide and porous silica
CN1172087A (en) * 1997-07-11 1998-02-04 西南工学院 Cement mixed material
CN1374270A (en) * 2001-03-08 2002-10-16 全盛兴资源科技股份有限公司 Calcium fluoride sludge reusing method and product
CN101235440A (en) * 2008-03-14 2008-08-06 大悟华龙吕王石材有限公司 Method of comprehensively utilizing serpentine

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102432276A (en) * 2011-09-13 2012-05-02 苏州市亨文环保水业有限公司 Application of CaF2 sludge in ceramics
CN102432276B (en) * 2011-09-13 2013-08-14 苏州市亨文环保水业有限公司 Application of CaF2 sludge in ceramics
CN102557444A (en) * 2012-01-04 2012-07-11 上海大学 Method for preparing glass ceramic from serpentine tailings
CN102807360A (en) * 2012-08-28 2012-12-05 黄靖宇 Preparation of novel ceramic particle by adopting calcium fluoride sludge
CN102807360B (en) * 2012-08-28 2014-05-14 苏州伟宇天诚环保科技有限公司 Preparation of ceramic particle by adopting calcium fluoride sludge
CN105669209A (en) * 2015-12-30 2016-06-15 刘操 Silicon nitride ceramic material, and preparation method and application thereof
CN106365610A (en) * 2016-10-26 2017-02-01 长沙聚优能环保科技有限公司 Method for making shale bricks with calcium fluoride sludge and treatment method of fluorine-containing wastewater
CN107827471A (en) * 2017-11-27 2018-03-23 柳州市闽贵砖厂 A kind of Fire-resistant ceramic tile and preparation method thereof
CN113213939A (en) * 2021-04-26 2021-08-06 湖北垚冶环保科技有限公司 Method for producing calcium fluoride product by using calcium fluoride sludge

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Application publication date: 20110831