CN105693120B - Electrical conductivity controllable fly ash base geology polymer material is prepared and applied - Google Patents
Electrical conductivity controllable fly ash base geology polymer material is prepared and applied Download PDFInfo
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- CN105693120B CN105693120B CN201610065412.2A CN201610065412A CN105693120B CN 105693120 B CN105693120 B CN 105693120B CN 201610065412 A CN201610065412 A CN 201610065412A CN 105693120 B CN105693120 B CN 105693120B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/24—Cements from oil shales, residues or waste other than slag
- C04B7/243—Mixtures thereof with activators or composition-correcting additives, e.g. mixtures of fly ash and alkali activators
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
- C04B12/005—Geopolymer cements, e.g. reaction products of aluminosilicates with alkali metal hydroxides or silicates
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a kind of electrical conductivity controllable fly ash base geo-polymer method for preparing semi-conducting material, the aqueous solution of flyash, carbon black, nine water sodium metasilicate and potassium hydroxide is put into agitating device and carries out mix, by mould molding, maintenance, electrical conductivity controllable fly ash base geo-polymer semi-conducting material is obtained.Wherein, nine water sodium metasilicate, potassium hydroxide, carbon black and water volume are 15%, 7%, 0.5%~4.5% and the 30%~40% of flyash quality respectively；The stable electrical conductivity controllable of the fly ash base geo-polymer semi-conducting material 28d curing ages of preparation is in the range of 0.00025~0.65 (S/m)；When the obtained electrical conductivity controllable fly ash base geo-polymer semi-conducting material is used for into malachite green degradation of organic dyes as novel photocatalyst, it was found that the changing rule that the electrical conductivity of the material is directly proportional to the degradation rate of dyestuff.Its preparation technology is simple, with low cost, preparation process three-waste free discharge, and the high activated catalyst that can be degraded as dyestuff.
Description
Technical field
Field is utilized the invention belongs to the preparation of silicate catalyst and its solid waste resource recovery, and in particular to a kind of
Electrical conductivity controllable fly ash base geo-polymer method for preparing semi-conducting material and its application in dyestuff degraded.
Background technology
China is the country using coal as main energy sources, and substantial amounts of coal is used for thermal power generation, and thermal power output accounts for the whole nation
The 76% of gross generation.Flyash is the tiny flying dust after coal-fired flue-gas removing dust device is collected；
The National Development and Reform Commission comprehensively utilizes annual report on Chinese Resources in 2014 and shown, China in 2013
Flyash discharge capacity be about 5.8 hundred million tons [1], about 2,700,000,000 tons of accumulation volume of cargo in storage, 270,000 mu of land occupation.The huge heap of flyash
Storage causes huge pressure to the development of the national economy and improvement of the ecological environment of China.Take measures, open up thinking, increasing pair
Flyash is comprehensively utilized the sustainable development for being not only related to the energy, while to realizing that recycling economy is significant.
At present, total utilization of PCA be concentrated mainly on construction material [2-4], road construction work [5], concrete fill [6],
Heat-preserving heat-insulating wall material [7], coal fly ash hollow micro bead [8], soil improvement [9-10], agriculture [11], wastewater treatment [12-14]
Deng field；Flyash has potential pozzolanic activity, and domestic and foreign scholars are turned into for geo-polymer using coal ash for manufacturing
Study hotspot.Liao Minghui [15-17] etc. is studied mechanical property, the reaction mechanism of fly ash base geo-polymer；Liao Ming
Brightness [15] examines influence of the conservation system to fly ash base geo-polymer compression strength；Cao Wa [16] etc. is with flyash and steel
Slag is raw material, using waterglass and sodium hydroxide as alkali-activator, prepares a kind of strong geo-polymer of morning；Zhang Yunsheng
[17] etc. electrodeless resistivity method is used, the condensation hardening of fly ash base geo-polymer is have studied, analyzes flyash and alkali
Reaction mechanism between exciting agent.
People to the acid-alkali salt corrosivity of fly ash base geo-polymer, freeze thawing resistance, chloride permeability, etc. endurance quality open
Substantial amounts of research work [18,19] is opened up；Liu Long [18] etc. is using flyash, red mud, slag as primary raw material, and sodium metasilicate swashs for alkali
Send out agent, the binder materials prepared using steaming pressuring curing system have certain acid and alkali resistance, salt corrosion performance, resistance to elevated temperatures and
Good freezing and thawing performance；Find fly ash base geo-polymer geo-polymer to chlorion in Zhang Chenghao [19] et al. researchs
With excellent ability to cure.
For the big feature of fly ash base geo-polymer fragility, some authors have carried out geo-polymer reinforcing and toughening
Research work, Wang Yachao [20] researchs show that basalt fibre has reinforcing and toughening effect to flyash geo-polymer, significantly
Degree improves the rupture strength of flyash geo-polymer；Zhu Zhiduo [21] etc. Chinese patent application (publication number：
CN104108903A corn stalk fiber enhancing flyash base polymer gelled material and preparation method thereof) is disclosed, should
Preparation method uses sodium hydroxide and waterglass for alkali-activator using flyash as raw material, in the mixed of alkali-activator and flyash
The corn stalk fiber that addition in material eliminates the moisture content 5~10% of surface pectin is closed, its corn stalk fiber accounts for compound
Mass percent there is reinforcing and toughening effect for 1~3% pair of fly ash base geo-polymer.
Relevant fly ash base geo-polymer prepares foamed concrete and foaming self-insulation wall material has also been reported
[22,23].Ren Zhiqiang [22] etc. is prepared for fly ash base geo-polymer geo-polymer base foam using hydrogen peroxide as foaming agent
Concrete, and preparation technology is optimized；Zhang Shuyuan [23] etc. Chinese patent application (publication number：
CN1032244350A a kind of flyash geo-polymer heat insulation building block and its manufacturing process) are disclosed, this method is to utilize powder
The pozzolanic activity of coal ash and miberal powder, under the exciting of alkali-activator, a kind of flyash geology polymerization is made in foamed, maintenance
Thing heat insulation building block, wherein flyash 60-95%, mix alkali-activator 4-30%, slag micropowder 0.01-25%, foam stabilizer
0.3-5%, obtained building block has that freeze-thaw resistance is strong, thermal conductivity factor is low, the spy high with building same life-span, good waterproof performance, intensity
Point.Similarly, Liu Yi [24] etc. Chinese patent application (publication number：CN105152184A one kind) is disclosed by flyash geology to be gathered
The method that compound prepares faujasite molecular sieve, this method is divided into two steps, and the first step is to prepare flyash geo-polymer；The
Two steps are that the geo-polymer is put into hydrothermal reaction kettle, add sodium hydroxide solution, and reaction is dry through washing after terminating
To faujasite molecular sieve material.
Fly ash base geo-polymer has certain absorption property can be as adsorbent [25], curable with pore structure
Nuke rubbish [26], photochemical catalyst [27] can be used as containing oxide semiconductor；Jie Luo [25] et al. reports flyash geology and gathered
Compound is to Cs+With certain characterization of adsorption.Li Qin [26] etc. Chinese patent (publication number：CN104200862A one) is disclosed
Plant the method for solidifying radioactive spent resin using fly ash base geo-polymer.Zhang Yaojun [27] etc. Chinese patent (publication number：
CN102430419A a kind of Ni) is disclosed2+The preparation and its application in organic matter degradation of doping geo-polymer catalyst,
The preparation method prepares geo-polymer using flyash as raw material under chemical activator effect, and adulterate Ni2+Used as catalyst
In industrial wastewater Methylene Blue degradation reaction, its degradation rate is 77.29%.
In summary, inventor by system reviews substantial amounts of domestic and foreign literature data and patent, do not find relevant
The preparation method of any carbon black modulation alkali-activated carbonatite flyash geo-polymer semi-conducting material, and it is applied to organic dyestuff
Any related report of degraded.
The creative part of the present invention is to be prepared for a kind of regulatable flyash of electrical conductivity degraded available for dyestuff
Base geological polymer semi-conducting material, its method is the volume by controlling carbon black, by fly ash base geo-polymer semiconductor
The electrical conductivity of material regulates and controls in semi-conducting material 10-8~103(S/M) within the scope of, conductive black polymerize with fly ash base geology
Oxide semiconductor in thing matrix is mutually overlapped, and forms the conductive network of connection；The material is under illumination condition, fly ash base
The conduction that the light induced electron for the photo-generate electron-hole centering that oxide semiconductor in geo-polymer is produced is connected by carbon black
Network is able to transmit in time, so that light induced electron is efficiently separated with hole, photohole can efficient oxidation dye molecule make
It is degraded；Creative is found that the changing rule that the electrical conductivity of the material is directly proportional to the degradation rate of dyestuff.
The bibliography provided the following is inventor：
[1] National Development and Reform Commission, Chinese Resources comprehensive utilization annual report (2014).
[2] Han Jinzhou, application of the simple analysis flyash in architectural engineering, science and technology prospect, 11 (2014) 69.
[3] the application problem research of flyash, Jiangxi building materials, 22 (2015) in Lin Shuixiang, construction material.3-5.
[4] Korea Spro Wu, application of the flyash in construction material, Chinese building material science and technology, 04 (2010) 63-67.
[5] Cui Jingqi, flyash roadbed filling Analysis of Construction Technique, value engineering, 07 (2014).122-123.[6]
Rafat.S, Effect of fine aggregate replacement with Class F fly ash on the
Mech-anical properties of concrete, Cem.Concr.Res., 33 (2003) 539-547.
[7] Lu Qingwen, industrial applications flyash production environment friendly wall material engineering, Guangdong chemical industry, 18 (2013) 84-
85。
[8] Li Guijin, Bai Zhimin, horse are loyal, Wen Zhai armies, the preparation of Ni ferrite/coal fly ash hollow micro bead composite granule
And electromagnetic performance, silicate journal, 02 (2015) 231-236.
[9] Zhang Jinai, flyash and farm manure mixing are applied to improvement salt-soda soil effect analysis, agricultural and technology, 08
(2015)11-12。
[10] Jia Yanping, Jiang Xiuping, Jiang Cheng, Zhang Haifeng, Zhang Lanhe, the preparation of modified coal ash and its at phosphorus-containing wastewater
Application progress in reason, silicate circular, 07 (2015) 1921-1925.
[11] Wang Zhanhua, Zhou Bing, Sun Xuejing, Peng Juwei, application present situation flyash modified and its in the treatment of waste water are ground
Study carefully, energy environment protection, 04 (2014) 1-5.
[12] king's Yi Wei, Hou Yingying, Wang Zuwei, progress of the flyash in soil improvement and pollution control, resource
Save and environmental protection, 10 (2014) 142-143.
[13] Yang Xin is beautiful, purposes of the flyash in terms of industry and agricultural, scientific and technological wind, 19 (2011) 163.
[14] Y.J.Zhang, L.C.Liu, Fly ash-based geopolymer as a novel
Photocatalyst for degradation of dye from wastewater, Particulogy, 11 (2013) 353-
358。
[15] Liao Minghui, the strength characteristics of alkali-activated carbonatite high-calcium fly ass geo-polymer, silicate circular, 34 (08)
(2015)2167-2176。
[16] Cao Wa, Yi Yuanrong, Ma Zuo, Wang Long, the compression strength of fly ash base geo-polymer-slag geo-polymer
Experimental study, Environmental science and technology, 37 (12) (2014) 205-208.
[17] Zhang Yunsheng, Jia Yantao, Li Zongjin, Quan Jizhuo, the condensation of resistivity method research fly ash-based geopolymer is hard
Change, Wuhan University of Technology's journal, 07 (2009) 111-114.
[18] Liu Long, Huang Limei, Wang Aizhen, Jia Baoshuan, red mud-flyash-slag alkali excited cementing material property are ground
Study carefully, Luoyang Institute Of Science And Technology's journal (natural science edition), 01 (2012) 13-20.
[19] Zhang Chenghao, Li Yue, Liu great Cheng, tight Jian Hua, fly ash base geo-polymer fix chlorion ability and its machine
The research of reason, Journal of Tangshan College, 03 (2013) 40-42.
[20] Wang Yachao, Xu Yong, Zhang Yaojun, Xu Delong, polyacrylic resin toughness reinforcing fly ash base geo-polymer geology
The performance study of polymer, silicate circular, 30 (02) (2011) 403-406.
[21] Zhu Zhiduo, Chen Wu, Wu Changsheng, corn stalk fiber enhancing flyash geo-polymer binder materials and its system
Preparation Method, Chinese patent application (publication number：CN104108903A).
[22] Ren Zhiqiang, the Study on Preparation of fly ash base geo-polymer foam concrete, Northcentral University (2014).
[23] Zhang Shuyuan, flyash geo-polymer heat insulation building block and manufacturing process, Chinese patent application (publication number：
CN103224350A)。
[24] Liu Yi, Yan Chunjie, a kind of method that faujasite molecular sieve is prepared by flyash geo-polymer, China is specially
Profit application (publication number：CN105152184A).
[25] Jie Luo, Zhang Haijun, Liu's Jing, Yang Jian, Huang Sheng, Deng Shiming, fly ash base geo-polymer is to Cs+Absorption row
For chemical industry environmental protection, 02 (2015) 192-198.
[26] Li Qin, Deng Ning, Cui Hao, a kind of method that utilization fly ash base geo-polymer solidifies radioactive spent resin,
Chinese patent application (publication number：CN104200862A).
[27] Zhang Yaojun, Liu Licai, Xu Delong, Wang Yachao, Ni2+Adulterate geo-polymer catalyst preparation and organic
Application in thing degraded, China applies for a patent (publication number:CN102430419A).
The content of the invention
It is an object of the present invention to provide prepared by a kind of electrical conductivity controllable fly ash base geo-polymer semi-conducting material
Method, and it is applied to degradation of organic dyes by the obtained electrical conductivity controllable fly ash base geo-polymer semi-conducting material
Application.
In order to realize above-mentioned task, the present invention takes following technical solution：
A kind of preparation method of electrical conductivity controllable fly ash base geo-polymer semi-conducting material, it is characterised in that should
The aqueous solution of flyash, carbon black, nine water sodium metasilicate and potassium hydroxide is put into agitating device by method carries out mix formation slurry,
By mould molding, maintenance, the regulatable fly ash base geo-polymer of electrical conductivity is prepared into；Wherein, nine water sodium metasilicate, hydrogen-oxygen
The volume of change potassium and carbon black is based on flyash quality；Nine water sodium metasilicate volumes are the 15% of flyash quality, potassium hydroxide
Volume is the 7% of flyash quality, and the volume of carbon black is the 0.5%~4.5% of flyash quality, and the volume of water is fine coal grey matter
The 30%~40% of amount.
Specifically include the following steps：
(1) powdered coal ash is weighed by formula ratio, be placed in the transit mixer of setting program；
(2) carbon black feed stock is weighed by formula ratio, be placed in the transit mixer of setting program dry-mixed uniform with flyash；
(3) nine water sodium metasilicate, potassium hydroxide are weighed by formula ratio；
(4) water is weighed by formula ratio, nine water sodium metasilicate, potassium hydroxide is soluble in water；
(5) aqueous solution of nine water sodium metasilicate and potassium hydroxide is placed in net slurry mixer, adds the uniform charcoal of mix
The black compound with flyash, carries out chemical reaction and forms uniform slurry；
(6) slurry is loaded into three die for molding, the equidistant zinc-plated stainless steel electrode (specification of insertion 4：2cm×
3cm), sealed with plastic sheeting hermetic bag, be placed in 80 DEG C of maintenance 6h in insulating box, then take out, be stripped after room temperature maintenance 18h,
It is put into fog room to continue to conserve, electrical conductivity controllable fly ash base geo-polymer semi-conducting material test block is made, conductance is detected
The 3d compression strength of rate controllable fly ash base geo-polymer semi-conducting material test block, and use four electrode method test material
The electrical conductivity of 3d, 7d, 14d, 28d different larval instar.
Through applicants have found that, the obtained electrical conductivity controllable fly ash base geo-polymer semi-conducting material of the present invention
Application available for malachite green degradation of organic dyes.
Specifically applying is：Wavelength is used at room temperature for 365nm PHILIPS TL-D 18W ACTINIC BL ultraviolets
Fluorescent tube irradiates malachite green dyestuff, carries out photocatalytic degradation, specifically includes the following steps：
(1) electrical conductivity controllable fly ash base geo-polymer semi-conducting material is broken into pieces, crosses the mesh standard sieve of 85 mesh~55,
0.160mm~0.315mm particulate matter is made in granulation；
(2) initial concentration (C is prepared with volumetric flasko) malachite green aqueous dye solutions；Use ultraviolet-visible spectrophotometer
Determine its initial absorbance A0；
(3) by quantitative electrical conductivity controllable fly ash base geo-polymer semi-conducting material particle, it is put into and fills necessarily
Volume, concentration are CoMalachite green dyestuff reactor in, at room temperature with ultraviolet lamp irradiate certain time, carry out centrifugation point
From the supernatant in centrifuge tube being moved in cuvette, with ultraviolet-visible spectrophotometer in λmax=616nm determines the t times
Absorbance At, corresponding dye strength is Ct；
(4) determined after absorbance, all reaction solutions and solid catalyst have been re-poured into reaction unit；
(5) repeat step (3) and step (4), until the absorbance of malachite green does not change with time and changed, are used
Below equation calculates the degradation rate of malachite green dyestuff：
The innovation of the present invention is：
(1) a kind of electrical conductivity controllable fly ash base geo-polymer semi-conducting material is prepared for, its method is by control
The black volume of charcoal processing, by the electricity that electrical conductivity controllable fly ash base geo-polymer semi-conducting material 28d curing ages are stable
Conductance regulates and controls within the scope of 0.00025~0.65 (S/m)；In conductive black and flyash geo-polymer binder materials matrix
Conductor oxidate contact with each other, formed connection conductive network.
(2) the electrical conductivity controllable fly ash base geo-polymer semi-conducting material is under illumination condition, flyash base
The conductive mesh that the light induced electron for the photo-generate electron-hole centering that oxide semiconductor in matter polymer is produced is connected by carbon black
Network is able to transmit in time, so that photo-generate electron-hole is to efficiently separating, photohole efficiently oxidation dye molecule can make
It is degraded.
(3) the creative electrical conductivity and dye that are found that electrical conductivity controllable fly ash base geo-polymer semi-conducting material
The changing rule that the degradation rate of material is directly proportional.
Brief description of the drawings
Fig. 1 is preparation and the degradation of organic dyes work of the electrical conductivity controllable alkali-activated carbonatite flyash semi-conducting material of the present invention
Skill flow；
Fig. 2 is the XRD spectrum of flyash；
Fig. 3 is four-electrode method detection electrical conductivity test block；
Fig. 4 is electrical conductivity controllable fly ash base geo-polymer semi-conducting material photocatalytic degradation malachite green dyestuff
Degradation rate versus time curve (amount of samples 0.4g, the concentration 4mg/L, volume 100mL of malachite green dyestuff).
Fig. 5 is electrical conductivity and the hole of electrical conductivity controllable fly ash base geo-polymer semi-conducting material prepared by the present invention
The degradation rate contrast of sparrow malachite green dyestuff.
The following is the present invention is described in further detail in conjunction with the accompanying drawings and embodiments.
Embodiment
Below in an example, applicant provide electrical conductivity controllable fly ash base geo-polymer semi-conducting material and
Its Application Example in degradation of organic dyes.
It should be noted that following embodiment preferably annotates the present invention only for inventor, the invention is not restricted to this
A little embodiments.
Below in an example, the electrical conductivity controllable fly ash base geo-polymer semi-conducting material maintenance 3- of preparation
28d test block, is tested its resistance by UT39A digital multi-purpose electric meters using four electrode method, then changes resistivity
For electrical conductivity.
The preparation of electrical conductivity controllable fly ash base geo-polymer semi-conducting material, the primary raw material of use is by industry
Solid waste coal ash, carbon black, the water sodium metasilicate of solid nine and hydroxide flake potassium composition, wherein, nine water sodium metasilicate, hydrogen-oxygen
The volume of change potassium and carbon black is based on flyash quality；Nine water sodium metasilicate volumes are the 15% of flyash quality, potassium hydroxide
Volume is the 7% of flyash quality, and the volume of carbon black is the 0.5%~4.5% of flyash quality, and the volume of water is fine coal grey matter
The 30%~40% of amount.
It is prepared as follows：
(1) (Conductive Carbon Black, are abbreviated as carbon black:CCB), Tianjin Li Huajin Co., Ltds are purchased from, than
Surface area is in 860~1200m2Between/g, particle diameter 20nm, resistivity<0.50Ω·cm.
(2) (Fly Ash, are abbreviated as flyash：FA), from I grade of ash of Taiyuan power plant, by flyash 105 in baking oven
DEG C drying 2h, through ball milling 2h, measures density for 2.45 × 103kg/m3, Blain specific surface is 505m2/kg.Flyash it is main
Oxide composition (mass percent) is as shown in table 1；The mineral phase composition of flyash as shown in Fig. 2 mainly contain quartz with not
Carry out stone crystalline phase.
Table 1：The oxide composition (wt%) of flyash
| Oxide | SiO2 | Al2O3 | Fe2O3 | CaO | Na2O | MgO | K2O | SO3 | TiO2 | Loss |
| Wt% | 48.88 | 34.59 | 7.46 | 3.85 | 0.41 | 0.58 | 1.73 | 0.48 | 1.31 | 0.71 |
(3) solid potassium hydroxide
It is purchased from Chemical Reagent Co., Ltd., Sinopharm Group, AR.
(4) nine water sodium metasilicate
It is purchased from Chemical Reagent Co., Ltd., Sinopharm Group, AR.
Prepare embodiment 1：
Powdered coal ash 300g accurately is weighed, as measurement basis (100%), using outer doping, solid potassium hydroxide
Volume is the 7% of flyash quality, and nine water sodium metasilicate volumes are the 15% of flyash quality, and the quality of water is flyash quality
30%.
Water, the water sodium metasilicate of solid nine, solid potassium hydroxide is soluble in water, the potassium hydroxide configured are weighed by formula ratio
Solution and nine water sodium silicate solutions pour into it is double turn double speed and starch only in mixer, add flyash and be stirred, through chemical reaction
Form uniform slurry；Slurry is fitted into 3cm (width) × 4cm (height) × 5cm (length) three gang moulds tool, on glue sand plain bumper
Jolt ramming, it is then equidistant to insert 4 zinc-plated stainless steel electrode [specifications：2cm (width) × 3cm (length)], use plastic sheeting hermetic bag
Sealing, is placed in insulating box after 80 DEG C of thermal curing 6h and takes out, room temperature conserves to 18h form removal, and test block is placed in into fog room maintenance
2d, obtaining electrical conductivity controllable fly ash base geo-polymer, (Fly Ash Geopolymer, are abbreviated as：FAG) semiconductor material
Material test block (is labeled as：0.0CCB/FAG) as shown in Figure 3.It is 63MPa to detect that it conserves 3d compression strength, using four electrode method
Detect electrical conductivity controllable fly ash base geo-polymer semi-conducting material test block 3d, 7d, 14d and 28d different larval instar prepared
Electrical conductivity, survey its result as shown in table 2.
Prepare embodiment 2：
Powdered coal ash 300g accurately is weighed, as measurement basis (100%), using outer doping, the volume of carbon black is
For the 0.5% of flyash quality, solid potassium hydroxide volume is the 7% of flyash quality, and the water sodium metasilicate volume of solid nine is powder
The 15% of coal ash quality, the quality of water is the 32% of flyash quality.
Water, the water sodium metasilicate of solid nine, solid potassium hydroxide is soluble in water, the potassium hydroxide configured are weighed by formula ratio
Solution and nine water sodium silicate solutions.
Flyash and carbon black are poured into mixer and be thoroughly mixed uniformly；By potassium hydroxide and nine water sodium metasilicate
Mixed ammonium/alkali solutions pour into it is double turn double speed and starch only in mixer to be sufficiently mixed with carbon black with flyash, remaining step and implementation
Example 1 is identical, and obtaining electrical conductivity controllable fly ash base geo-polymer, (Fly Ash Geopolymer, are abbreviated as：FAG) partly lead
Body material test block (is labeled as：0.5CCB/FAG) as shown in Figure 3.It is 57MPa to detect that it conserves 3d compression strength, using four electricity
Pole method detection electrical conductivity controllable fly ash base geo-polymer semi-conducting material test block 3d, 7d, 14d and 28d different larval instar
Electrical conductivity, surveys its result as shown in table 2.
Prepare embodiment 3：
All operating procedures are same as Example 2, and simply the volume of carbon black is the 1.5% of flyash quality, the matter of water
Amount is the 35% of flyash quality, obtains electrical conductivity controllable fly ash base geo-polymer (Fly Ash Geopolymer, letter
It is written as：FAG) semi-conducting material test block (is labeled as：1.5CCB/FAG), as shown in Figure 3.Its 3d compression strength is surveyed for 44.3MPa,
Using four electrode method detect prepare electrical conductivity controllable fly ash base geo-polymer semi-conducting material test block 3d, 7d, 14d and
The electrical conductivity of 28d different larval instars, its result is as shown in table 2.
Prepare embodiment 4：
All operations step is same as Example 2, and simply the volume of carbon black is the 3.5% of flyash quality, the quality of water
It is the 41% of flyash quality, obtaining electrical conductivity controllable fly ash base geo-polymer, (Fly Ash Geopolymer, write a Chinese character in simplified form
For：FAG) semi-conducting material test block (is labeled as：3.5CCB/FAG), as shown in Figure 3.Its 3d compression strength is surveyed for 27.8MPa, is adopted
With four electrode method detect prepare electrical conductivity controllable fly ash base geo-polymer semi-conducting material test block 3d, 7d, 14d and
The electrical conductivity of 28d different larval instars, its result is as shown in table 2.
Prepare embodiment 5：
All operations step is same as Example 2, and simply the volume of carbon black is the 4.5% of flyash quality, the quality of water
It is the 44% of flyash quality, obtains the regulatable fly ash base geo-polymer of electrical conductivity (Fly Ash Geopolymer, letter
It is written as：FAG) semi-conducting material test block (is labeled as：4.5CCB/FAG), as shown in Figure 3.Its 3d compression strength is surveyed for 18MPa, is adopted
With four electrode method detect prepare electrical conductivity controllable fly ash base geo-polymer semi-conducting material test block 3d, 7d, 14d and
The electrical conductivity of 28d different larval instars, its result is as shown in table 2.
Table 2：The electrical conductivity of electrical conductivity controllable fly ash base geo-polymer semi-conducting material different larval instar test block
Through inventor it is demonstrated experimentally that electrical conductivity controllable fly ash base geo-polymer semi-conducting material prepared by the present invention
Degradation of organic dyes can be efficiently applied to, is specifically carried out by following experimental procedure：
(1) initial concentration (C is prepared with volumetric flasko) malachite green aqueous dye solutions；Use ultraviolet-visible spectrophotometer
Determine its initial absorbance A0；
(2) by quantitative electrical conductivity controllable fly ash base geo-polymer semi-conducting material particle, it is put into and fills necessarily
Volume, concentration are CoMalachite green dyestuff reactor in, at room temperature with ultraviolet lamp irradiate certain time, carry out centrifugation point
From the supernatant in centrifuge tube being moved in cuvette, with ultraviolet-visible spectrophotometer in λmax=616nm determines the t times
Absorbance At, corresponding dye strength is Ct；
(3) determined after absorbance, all reaction solutions and solid catalyst have been re-poured into reaction unit；
(4) (2), (3) step are repeated, until the absorbance of malachite green does not change with time and changed, using formula
(1) degradation rate of malachite green dyestuff is calculated；
Formula (1)
Application Example 1：
It is accurate to weigh the sample 0.4g (0.160mm~0.315mm particle is made in granulation) for preparing embodiment 1 and marking, put
Enter in the malachite green dye solution that 100mL concentration is 4mg/L, after placing 15min in darkroom, be placed on magnetic stirring apparatus, use
Wavelength is 365nm PHILIPS TL-D 18W ACTINIC BL ultraviolet lamp tubes irradiation 10min, stands, takes supernatant in beaker
Centrifuge, supernatant in centrifuge tube is moved into cuvette, determining malachite green dyestuff with ultraviolet-visible spectrophotometer exists
λmaxAbsorbance at=616nm, calculated successively using formula (1) catalyst 10min, 20min, 30min, 40min,
Degradation rate when 50min, 60min, 70min is as shown in Fig. 4 and table 3, and from Fig. 4 and table 3, dyestuff is in 60min and 70min
Degradation rate it is identical, show that degradation rate of the dyestuff in 60min has reached stable state；Degradation rate during dyestuff 60min with
The conductivity relation of 0.0CCB/FAG test blocks is as shown in Figure 5.
Table 3：Degradation rate of the 0.0CCB/FAG samples to dyestuff
| Light application time (min) | 0 | 10 | 20 | 30 | 40 | 50 | 60 | 70 |
| Degradation rate (%) | 0 | 25.21 | 34.56 | 42.91 | 49.82 | 54.73 | 59.46 | 59.46 |
Application Example 2：
It is accurate to weigh the sample 0.4g (0.160mm~0.315mm particle is made in granulation) for preparing embodiment 2 and marking, put
Enter in the malachite green dye solution that 100mL concentration is 4mg/L, remaining experimental procedure is identical with Application Example 1, utilizes formula
(1) degradation rate of the catalyst in 10min, 20min, 30min, 40min, 50min, 60min, 70min, such as Fig. 4 and table 4 are calculated
Shown, from Fig. 4 and table 4, degradation rate of the dyestuff when 60min is with 70min is identical, shows degraded of the dyestuff in 60min
Rate has reached stable state；Degradation rate and the conductivity relation of 0.5CCB/FAG test blocks during dyestuff 60min is as shown in Figure 5.
Table 4：Degradation rate of the 0.5CCB/FAG samples to dyestuff
| Light application time (min) | 0 | 10 | 20 | 30 | 40 | 50 | 60 | 70 |
| Degradation rate (%) | 0 | 20.89 | 29.54 | 37.67 | 44.34 | 49.17 | 53.26 | 53.26 |
Application Example 3：
It is accurate to weigh the sample 0.4g (0.160mm~0.315mm particle is made in granulation) for preparing embodiment 5 and marking, put
Enter in the malachite green simulation industrial wastewater that 100mL concentration is 4mg/L, remaining experimental procedure is identical with Application Example 1, utilizes
Formula (1) calculates degradation rate of the catalyst in 10min, 20min, 30min, 40min, 50min, 60min, 70min, such as Fig. 4
With shown in table 5, from Fig. 4 and table 5, degradation rate of the dyestuff when 60min is with 70min is identical, shows dyestuff in 60min
Degradation rate has reached stable state；Degradation rate and conductivity relation such as Fig. 5 institutes of 4.5CCB/FAG test blocks during dyestuff 60min
Show.
Table 5：Degradation rate of the 4.5CCB/FAG samples to dyestuff
| Light application time (min) | 0 | 10 | 20 | 30 | 40 | 50 | 60 | 70 |
| Degradation rate (%) | 0 | 52.41 | 65.36 | 73.22 | 82.38 | 88.45 | 92.82 | 92.82 |
From fig. 5, it can be seen that the electrical conductivity of material and the degradation rate of dye molecule are proportional, electrical conductivity is higher, then
The degradation rate of dyestuff is higher；Therefore, by regulating and controlling carbon black volume, the controllable fly ash base geology polymerization of electrical conductivity can be prepared
Thing, and the high activated catalyst as malachite green degradation of organic dyes.
Claims (2)
1. a kind of electrical conductivity controllable fly ash base geo-polymer semi-conducting material is used for malachite green degradation of organic dyes
It is using, it is characterised in that the preparation method of the electrical conductivity controllable fly ash base geo-polymer semi-conducting material：By powder
Coal ash, carbon black, the aqueous solution of nine water sodium metasilicate and potassium hydroxide are put into mix in agitating device, form well mixed slurry,
The regulatable fly ash base geo-polymer semi-conducting material of electrical conductivity is obtained through shaping, maintenance, wherein：Nine water sodium metasilicate, hydrogen
The volume of potassium oxide and carbon black is based on flyash quality；Nine water sodium metasilicate volumes are the 15% of flyash quality, potassium hydroxide
Volume is the 7% of flyash quality, and the volume of carbon black is the 0.5%~4.5% of flyash quality, and the volume of water is flyash quality
30%~40%；
Wavelength is used to irradiate malachite green for 365nm PHILIPS TL-D 18W ACTINIC BL quartz burners at room temperature
Dyestuff, carries out photocatalytic degradation, specifically includes the following steps：
（1）Electrical conductivity controllable fly ash base geo-polymer semi-conducting material is broken into pieces, the mesh standard sieve of 85 mesh~55, granulation is crossed
0.160mm~0.315mm particulate matter is made；
（2）Initial concentration is prepared with volumetric flask（Co）Malachite green aqueous dye solutions；Determined with ultraviolet-visible spectrophotometer
Its initial absorbance A0；
（3）By quantitative electrical conductivity controllable fly ash base geo-polymer semi-conducting material particle, be put into fill certain volume,
Concentration is CoMalachite green dyestuff reactor in, irradiate certain time with ultraviolet lamp at room temperature, be centrifuged, will be from
Supernatant in heart pipe is moved in cuvette, is existed with ultraviolet-visible spectrophotometer=616 nm determine the absorbance of t times
At, corresponding dye strength is Ct；
（4）Determine after absorbance, all reaction solutions and solid catalyst have been re-poured into reaction unit；
（5）Repeat step（3）And step（4）, until the absorbance of malachite green does not change with time and changed, using following
Formula calculates the degradation rate of malachite green dyestuff：
。
2. application as claimed in claim 1, it is characterised in that the electrical conductivity controllable fly ash base geo-polymer is partly led
The preparation method of body material specifically includes following steps：
（1）Flyash is weighed by formula ratio, is placed in the transit mixer of setting program；
（2）Carbon black is weighed by formula ratio, is placed in transit mixer fully dry-mixed uniform；
（3）The water sodium metasilicate of solid nine and solid potassium hydroxide are weighed by formula ratio；
（4）Water is weighed by formula ratio, the water sodium metasilicate of solid nine, solid potassium hydroxide is soluble in water；
（5）The aqueous solution of nine water sodium metasilicate and potassium hydroxide is placed in net slurry mixer, add the uniform carbon black of mix with
The compound of flyash, carries out chemical reaction and forms uniform slurry；
（6）Slurry is loaded into three die for molding, equidistant 4 zinc-plated stainless steel electrodes of insertion use plastic sheeting hermetic bag
Sealing, is placed in insulating box and is conserved 6 hours under the conditions of 80 DEG C, then taken out, and room temperature is stripped after conserving 18 hours, is put into maintenance
Room continues to conserve, and electrical conductivity controllable flyash geo-polymer test block is made, and detects the 3d compression strength of test block, and uses four
Electrode method test material 3d, 7d, 14d, the electrical conductivity of 28 d different larval instars.
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