CN105693120A - Preparation and application of conductivity-controllable fly ash-based geopolymer material - Google Patents

Preparation and application of conductivity-controllable fly ash-based geopolymer material Download PDF

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CN105693120A
CN105693120A CN201610065412.2A CN201610065412A CN105693120A CN 105693120 A CN105693120 A CN 105693120A CN 201610065412 A CN201610065412 A CN 201610065412A CN 105693120 A CN105693120 A CN 105693120A
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fly ash
flyash
polymer
electrical conductivity
geo
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CN105693120B (en
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张耀君
张科
张力
张懿鑫
余淼
康乐
杨梦阳
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Xian University of Architecture and Technology
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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
    • 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
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention discloses a preparation method of a conductivity-controllable fly ash-based geopolymer semiconductor material. The preparation method comprises the following steps: putting fly ash, carbon black, sodium silicate nonahydrate and an aqueous solution of potassium hydroxide into a stirring device and mixing; and forming with a mould and curing to obtain the conductivity-controllable fly ash-based geopolymer semiconductor material, wherein the dosage of the sodium silicate nonahydrate, potassium hydroxide, carbon black and water accounts for 15%, 7%, 0.5-4.5% and 30-40% of the fly ash mass respectively; the stable conductivity of the prepared fly ash-based geopolymer semiconductor material can be controlled in a range from 0.00025 to 0.65 (S/m) in a curing age of 28 days; and when the prepared conductivity-controllable fly ash-based geopolymer semiconductor material is used as a novel photocatalyst for degrading malachite green organic dye, a change law that the conductivity of the material is directly proportional to the degradation rate of the dye is discovered. The preparation technology is simple, the cost is low, the discharge of three wastes is avoided in the preparation process, and the conductivity-controllable fly ash-based geopolymer semiconductor material can be used as a dye degrading high-activity catalyst.

Description

The preparation of electrical conductivity controllable fly ash base geology polymer material and application
Technical field
The invention belongs to the preparation of silicate catalyst and solid waste resource recovery utilizes field, be specifically related to a kind of electrical conductivity controllable fly ash base geo-polymer method for preparing semi-conducting material and the application in dyestuff is degraded thereof。
Background technology
The country that China is is main energy sources with coal, substantial amounts of coal is used for thermal power generation, and thermal power output accounts for the 76% of whole nation 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 about Chinese Resources in 2014 and shows, the flyash discharge capacity of China in 2013 is about 5.8 hundred million tons [1], accumulation volume of cargo in storage about 2,700,000,000 tons, land occupation 270,000 mu。The huge volume of cargo in storage of flyash causes huge pressure to the development of the national economy and the improvement of the ecological environment of China。Take measures, open up thinking, strengthen and flyash is comprehensively utilized the sustainable development being not only related to the energy, simultaneously significant to realizing recycling economy。
At present, total utilization of PCA is 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], the agricultural field such as [11], wastewater treatment [12-14]；Flyash has potential pozzolanic activity, utilizes coal ash for manufacturing to become the study hotspot of Chinese scholars for geo-polymer。The mechanical property of fly ash base geo-polymer, reaction mechanism are studied by Liao Minghui [15-17] etc.；Liao Minghui [15] examines the conservation system impact on fly ash base geo-polymer comprcssive strength；Cao Wa [16] etc., with flyash and slag for raw material, adopt waterglass and sodium hydroxide as alkali-activator, prepare strong geo-polymer a kind of morning；Zhang Yunshengs [17] etc. adopt electrodeless resistivity method, have studied the condensation of fly ash base geo-polymer hardening, analyze the reaction mechanism between flyash and alkali-activator。
People to the acid-alkali salt corrosivity of fly ash base geo-polymer, freeze thawing resistance, chloride permeability, etc. endurance quality carried out substantial amounts of research work [18,19]；Liu Long [18] etc. are with flyash, red mud, slag for primary raw material, and sodium silicate is alkali-activator, adopt the Binder Materials prepared of steaming pressuring curing system to have certain acid and alkali resistance, salt corrosion performance, resistance to elevated temperatures and good freezing and thawing performance；Zhang Chenghao [19] et al. research finds that chloride ion is had excellent ability to cure by fly ash base geo-polymer geo-polymer。
For the feature that fly ash base geo-polymer fragility is big, some authors have carried out the research work of geo-polymer reinforcing and toughening, Wang Yachao [20] research shows that flyash geo-polymer is had reinforcing and toughening effect by basalt fibre, increases substantially the rupture strength of flyash geo-polymer；The Chinese patent application (publication number: CN104108903A) of Zhu Zhiduo [21] etc. discloses corn stalk fiber and strengthens flyash base polymer gelled material and preparation method thereof, this preparation method is with flyash for raw material, adopting sodium hydroxide and waterglass is alkali-activator, adding the corn stalk fiber of the moisture content 5～10% eliminating surface pectin in the compound of alkali-activator and flyash, it is that 1～3% pair of fly ash base geo-polymer has reinforcing and toughening effect that its corn stalk fiber accounts for the mass percent of compound。
Relevant fly ash base geo-polymer prepares foamed concrete and foaming self-insulation wall material also reports [22,23] to some extent。Ren Zhiqiang [22] etc., with hydrogen peroxide for foaming agent, are prepared for fly ash base geo-polymer geo-polymer base foam concrete, and preparation technology are optimized；The Chinese patent application (publication number: CN1032244350A) of Zhang Shuyuan [23] etc. discloses a kind of flyash geo-polymer heat insulation building block and manufacturing process thereof, the method is to utilize the pozzolanic activity of flyash and breeze, under the exciting of alkali-activator, foamed, a kind of flyash geo-polymer heat insulation building block is made in maintenance, wherein flyash 60-95%, mixed base exciting agent 4-30%, slag micropowder 0.01-25%, foam stabilizer 0.3-5%, it is strong that obtained building block has freeze-thaw resistance, heat conductivity is low, with the building same life-span, good waterproof performance, the feature that intensity is high。In like manner, the Chinese patent application (publication number: CN105152184A) of Liu Yi [24] etc. discloses a kind of method being prepared faujasite molecular sieve by flyash geo-polymer, the method is divided into two steps, and the first step is to prepare flyash geo-polymer；Second step is to put in hydrothermal reaction kettle by this geo-polymer, adds sodium hydroxide solution, and reaction dry obtains faujasite molecular sieve material through washing after terminating。
Fly ash base geo-polymer have certain absorption property can as adsorbent [25], there is the curable nuke rubbish of pore structure [26], can as photocatalyst [27] containing oxide semiconductor；Jie Luo [25] et al. reports flyash geo-polymer to Cs+There is certain characterization of adsorption。The Chinese patent (publication number: CN104200862A) of Li Qin [26] etc. discloses a kind of method utilizing fly ash base geo-polymer to solidify radioactive spent resin。The Chinese patent (publication number: CN102430419A) of Zhang Yaojun [27] etc. discloses a kind of Ni2+The preparation of doping geo-polymer catalyst and the application in organic matter degradation thereof, this preparation method, with flyash for raw material, prepares geo-polymer under chemical activator effect, and adulterate Ni2+As catalyst for industrial wastewater Methylene Blue degradation reaction, its degradation rate is 77.29%。
In sum, inventor passes through system reviews substantial amounts of domestic and foreign literature data and patent, do not have to find the preparation method about any white carbon black modulation alkali-activated carbonatite flyash geo-polymer semi-conducting material, and be applied to any relevant report of degradation of organic dyes。
The creative part of the present invention is in that to be prepared for a kind of regulatable fly ash base geo-polymer semi-conducting material of electrical conductivity that can be used for dyestuff degraded, its method is the volume by controlling white carbon black, regulates and controls the electrical conductivity of fly ash base geo-polymer semi-conducting material at semi-conducting material 10-8～103(S/M) within scope, conductive black overlaps mutually with the oxide semiconductor in fly ash base geo-polymer matrix, forms the conductive network of connection；This material is under illumination condition, the light induced electron of the photo-generate electron-hole centering that the oxide semiconductor in fly ash base geo-polymer produces is able to timely transmission by the conductive network that white carbon black connects, so that light induced electron efficiently separates with hole, photohole can make it degrade by efficient oxidation dye molecule；The creationary Changing Pattern being found that the electrical conductivity of this material is directly proportional to the degradation rate of dyestuff。
The following is the list of references that inventor provides:
[1] National Development and Reform Commission, Chinese Resources comprehensive utilization annual report (2014)。
[2] Han Jinzhou, simply analyses flyash application in architectural engineering, and science and technology is looked forward to, and 11 (2014) 69。
[3] Lin Shuixiang, the application problem research of flyash in construction material, Jiangxi building materials, 22 (2015)。3-5。
[4] Korea Spro Wu, flyash application 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, EffectoffineaggregatereplacementwithClassFflyashonthemec h-anicalpropertiesofconcrete, Cem.Concr.Res., 33 (2003) 539-547。
[7] Lu Qingwen, industrial applications flyash produces environment friendly wall material engineering, Guangdong chemical industry, 18 (2013) 84-85。
[8] Li Guijin, Bai Zhimin, horse loyalty, Wen Zhai army, 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 used 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 the application progress in treatment of Phosphorus Containing Waste Water thereof, silicate is circulated a notice of, 07 (2015) 1921-1925。
[11] Wang Zhanhua, Zhou Bing, Sun Xuejing, Peng Juwei, flyash modified and application present studies in the treatment of waste water, energy environment is protected, 04 (2014) 1-5。
[12] Wang Wei, Hou Yingying, Wang Zuwei, flyash progress in soil improvement and pollution control, resources conservation and environmental protection, 10 (2014) 142-143。
[13] Yang Xin is beautiful, flyash purposes in industrial and agriculture, science and technology wind, and 19 (2011) 163。
[14] Y.J.Zhang, L.C.Liu, Flyash-basedgeopolymerasanovelphotocatalystfordegradatio nofdyefromwastewater, Particulogy, 11 (2013) 353-358。
[15] Liao Minghui, the strength characteristics of alkali-activated carbonatite high-calcium fly ass geo-polymer, silicate is circulated a notice of, 34 (08) (2015) 2167-2176。
[16] Cao Wa, Yi Yuanrong, Ma Zuo, Wang Long, the comprcssive strength experimentation of fly ash base geo-polymer-slag geo-polymer, Environmental science and technology, 37 (12) (2014) 205-208。
[17] Zhang Yunsheng, Jia Yantao, Li Zongjin, Quan Jizhuo, the condensation hardening of resistivity method research fly ash-based geopolymer, 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 Quality Research, 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, the research of the fixing chloride ion ability of fly ash base geo-polymer and mechanism thereof, Journal of Tangshan College, 03 (2013) 40-42。
[20] Wang Yachao, Xu Yong, Zhang Yaojun, Xu Delong, the performance study of the toughness reinforcing fly ash base geo-polymer geo-polymer of polyacrylic resin, silicate is circulated a notice of, 30 (02) (2011) 403-406。
[21] Zhu Zhiduo, Chen Wu, Wu Changsheng, corn stalk fiber strengthens flyash geo-polymer Binder Materials and preparation method thereof, 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 being prepared faujasite molecular sieve by flyash geo-polymer, Chinese patent application (publication number: CN105152184A)。
[25] Jie Luo, Zhang Haijun, Liu, Yang Jian, Huang Sheng, Deng Shiming, fly ash base geo-polymer is to Cs+Absorption behavior, chemical industry environmental protection, 02 (2015) 192-198。
[26] Li Qin, Deng Ning, Cui Hao, a kind of method utilizing fly ash base geo-polymer to solidify radioactive spent resin, Chinese patent application (publication number: CN104200862A)。
[27] Zhang Yaojun, Liu Licai, Xu Delong, Wang Yachao, Ni2+The preparation of doping geo-polymer catalyst and the application in organic matter degradation, China applies for a patent (publication number: CN102430419A)。
Summary of the invention
It is an object of the invention to, it is provided that a kind of electrical conductivity controllable fly ash base geo-polymer method for preparing semi-conducting material, and it is applied to the application of degradation of organic dyes by this prepared electrical conductivity controllable fly ash base geo-polymer semi-conducting material。
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 characterized in that, the aqueous solution of flyash, white carbon black, nine water sodium silicate and potassium hydroxide is put into and is carried out mix formation slurry in agitating device by the method, through mould molding, maintenance, prepare into the regulatable fly ash base geo-polymer of electrical conductivity；Wherein, the volume of nine water sodium silicate, potassium hydroxide and white carbon black is based on flyash quality；Nine water sodium silicate volumes are the 15% of flyash qualities, and potassium hydroxide volume is the 7% of flyash quality, and the volume of white carbon black is the 0.5%～4.5% of flyash quality, and the volume of water is the 30%～40% of flyash quality。
Specifically include the following step:
(1) weigh powdered coal ash by formula ratio, be placed in the transit mixer of setting program；
(2) weigh carbon black feed stock by formula ratio, be placed in the transit mixer of setting program and flyash is dry mixed uniformly；
(3) nine water sodium silicate, potassium hydroxide are weighed by formula ratio；
(4) water is weighed by formula ratio, by soluble in water to nine water sodium silicate, potassium hydroxide；
(5) aqueous solution of nine water sodium silicate Yu potassium hydroxide is placed in clean slurry blender, adds the compound of the uniform white carbon black of mix and flyash, carry out chemical reaction and form uniform slurry；
(6) slurry is loaded three die for molding, 4 zinc-plated stainless steel electrodes of equidistant insertion (specification: 2cm × 3cm), seal bag with plastic sheeting to seal, it is placed in calorstat 80 DEG C of maintenance 6h, then take out, the demoulding after room temperature maintenance 18h, put into fog room and continue maintenance, prepare electrical conductivity controllable fly ash base geo-polymer semi-conducting material test block, the 3d comprcssive strength of detection electrical conductivity controllable fly ash base geo-polymer semi-conducting material test block, and adopt the electrical conductivity of four electrode method test material 3d, 7d, 14d, 28d different larval instar。
Studying discovery through applicant, the electrical conductivity controllable fly ash base geo-polymer semi-conducting material that the present invention obtains can be used for the application of malachite green oxalate degradation of organic dyes。
Concrete application is: the PHILIPSTL-D18WACTINICBL quartz burner adopting wavelength to be 365nm under room temperature irradiates malachite green oxalate dyestuff, carries out photocatalytic degradation, specifically includes the following step:
(1) being broken into pieces by electrical conductivity controllable fly ash base geo-polymer semi-conducting material, cross 85 order～55 mesh standard sieves, pelletize prepares the particulate matter of 0.160mm～0.315mm；
(2) initial concentration (C is prepared with volumetric flasko) malachite green oxalate aqueous dye solutions；Its initial absorbance A is measured with ultraviolet-visible spectrophotometer0；
(3) by quantitative electrical conductivity controllable fly ash base geo-polymer semi-conducting material granule, put into and fill certain volume, concentration is CoMalachite green oxalate dyestuff reactor in, irradiate certain time with Burdick lamp under room temperature, be centrifuged separate, the supernatant in centrifuge tube is moved in cuvette, with ultraviolet-visible spectrophotometer at λmax=616nm measures the absorbance A of t timet, corresponding dye strength is Ct；
(4), after having measured absorbance, all reactant liquors and solid catalyst are re-poured in reaction unit；
(5) repeat step (3) and step (4), until the absorbance of malachite green oxalate does not change over time, adopt below equation to calculate the degradation rate of malachite green oxalate dyestuff:
η = A 0 - A t A 0 = C 0 - C t C 0 × 100 % .
The innovation of the present invention is in that:
(1) it is prepared for a kind of electrical conductivity controllable fly ash base geo-polymer semi-conducting material, its method is the volume by controlling white carbon black, electrical conductivity stable for this electrical conductivity controllable fly ash base geo-polymer semi-conducting material 28d curing age is regulated and controled within 0.00025～0.65 (S/m) scope；Conductive black contacts with each other with the conductor oxidate in flyash geo-polymer Binder Materials matrix, forms the conductive network of connection。
(2) this electrical conductivity controllable fly ash base geo-polymer semi-conducting material is under illumination condition, the light induced electron of the photo-generate electron-hole centering that the oxide semiconductor in fly ash base geo-polymer produces is able to timely transmission by the conductive network that white carbon black connects, so that photo-generate electron-hole is to high efficiency separation, photohole can make it degrade by oxidation dye molecule efficiently。
(3) Changing Pattern that the creationary electrical conductivity being found that electrical conductivity controllable fly ash base geo-polymer semi-conducting material is directly proportional to the degradation rate of dyestuff。
Accompanying drawing explanation
Fig. 1 is preparation and the degradation of organic dyes technological process of the electrical conductivity controllable alkali-activated carbonatite flyash semi-conducting material of the present invention；
Fig. 2 is the XRD figure spectrum of flyash；
Fig. 3 is four-electrode method detection electrical conductivity test block；
Fig. 4 is the degradation rate versus time curve (amount of samples 0.4g, the concentration 4mg/L of malachite green oxalate dyestuff, volume 100mL) of electrical conductivity controllable fly ash base geo-polymer semi-conducting material photocatalytic degradation malachite green oxalate dyestuff。
Fig. 5 is that the electrical conductivity of electrical conductivity controllable fly ash base geo-polymer semi-conducting material prepared by the present invention contrasts with the degradation rate of malachite green oxalate dyestuff。
The following is in conjunction with the accompanying drawings and embodiments that the present invention is described in further detail。
Detailed description of the invention
Below in an example, applicant provides electrical conductivity controllable fly ash base geo-polymer semi-conducting material and the Application Example in degradation of organic dyes thereof。
It should be noted that below example better annotates the present invention only for inventor, the invention is not restricted to these embodiments。
Below in an example, the test block of the electrical conductivity controllable fly ash base geo-polymer semi-conducting material maintenance 3-28d of preparation, adopt four electrode method by UT39A digital multi-purpose electric meter, its resistance to be tested, then resistivity is converted to electrical conductivity。
The preparation of electrical conductivity controllable fly ash base geo-polymer semi-conducting material, the primary raw material adopted is made up of industrial solid castoff flyash, white carbon black, solid nine water sodium silicate and hydroxide flake potassium, wherein, the volume of nine water sodium silicate, potassium hydroxide and white carbon black is based on flyash quality；Nine water sodium silicate volumes are the 15% of flyash qualities, and potassium hydroxide volume is the 7% of flyash quality, and the volume of white carbon black is the 0.5%～4.5% of flyash quality, and the volume of water is the 30%～40% of flyash quality。
It is prepared as follows:
(1) white carbon black (ConductiveCarbonBlack, is abbreviated as: CCB), is purchased from Tianjin Li Huajin company limited, and specific surface area scope is at 860～1200m2Between/g, particle diameter 20nm, resistivity < 0.50 Ω cm。
(2) flyash (FlyAsh, is abbreviated as: FA), selects I grade of ash of Taiyuan power plant, and by flyash 105 DEG C of drying 2h in baking oven, through ball milling 2h, recording density is 2.45 × 103kg/m3, Blain specific surface is 505m2/ kg。Main oxides composition (mass percent) of flyash is as shown in table 1；The mineral facies composition of flyash is as in figure 2 it is shown, mainly contain quartz and mullite crystalline phase。
Table 1: 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, analytical reagent。
(4) nine water sodium silicate
It is purchased from Chemical Reagent Co., Ltd., Sinopharm Group, analytical reagent。
Preparation embodiment 1:
Accurately weighing powdered coal ash 300g, as measurement basis (100%), adopt outer doping, solid potassium hydroxide volume is the 7% of flyash quality, and nine water sodium silicate volumes are the 15% of flyash quality, and the quality of water is the 30% of flyash quality。
Water is weighed by formula ratio, by soluble in water to solid nine water sodium silicate, solid potassium hydroxide, the potassium hydroxide solution configured and nine water sodium silicate solutions are poured into and double; two turned double speed and only starch in blender, add flyash and are stirred, form uniform slurry through chemical reaction；Slurry is loaded in the three gang mould tools of 3cm (width) × 4cm (height) × 5cm (length), jolt ramming on glue sand plain bumper, then 4 zinc-plated stainless steel electrodes of equidistant insertion [specification: 2cm (width) × 3cm (length)], seal bag with plastic sheeting to seal, take out after being placed in calorstat 80 DEG C of thermal curing 6h, room temperature maintenance is to form removal after 18h, test block is placed in fog room maintenance 2d, obtain electrical conductivity controllable fly ash base geo-polymer (FlyAshGeopolymer, it being abbreviated as: FAG) semi-conducting material test block (being labeled as: 0.0CCB/FAG) is as shown in Figure 3。The comprcssive strength detecting its maintenance 3d is 63MPa, adopts the electrical conductivity of the electrical conductivity controllable fly ash base geo-polymer semi-conducting material test block 3d of four electrode method detection preparation, 7d, 14d and 28d different larval instar, surveys its result as shown in table 2。
Preparation embodiment 2:
Accurately weigh powdered coal ash 300g, as measurement basis (100%), adopt outer doping, 0.5% that the volume of white carbon black is flyash quality, solid potassium hydroxide volume is the 7% of flyash quality, solid nine water sodium silicate volume is the 15% of flyash quality, and the quality of water is the 32% of flyash quality。
Water is weighed by formula ratio, by soluble in water to solid nine water sodium silicate, solid potassium hydroxide, the potassium hydroxide solution configured and nine water sodium silicate solutions。
Flyash is poured into white carbon black in blender and carries out being sufficiently stirred for mixing homogeneously；The mixed ammonium/alkali solutions of potassium hydroxide and nine water sodium silicate is poured into double; two double speed that turns only starch in blender and be sufficiently mixed with flyash and white carbon black, all the other steps are identical with embodiment 1, obtain electrical conductivity controllable fly ash base geo-polymer (FlyAshGeopolymer, is abbreviated as: FAG) semi-conducting material test block (being labeled as: 0.5CCB/FAG) as shown in Figure 3。The comprcssive strength detecting its maintenance 3d is 57MPa, adopts the electrical conductivity of four electrode method detection electrical conductivity controllable fly ash base geo-polymer semi-conducting material test block 3d, 7d, 14d and 28d different larval instar, surveys its result as shown in table 2。
Preparation embodiment 3:
All of operating procedure is identical with embodiment 2, simply volume is flyash quality the 1.5% of white carbon black, the quality of water is the 35% of flyash quality, obtain electrical conductivity controllable fly ash base geo-polymer (FlyAshGeopolymer, it is abbreviated as: FAG) semi-conducting material test block (being labeled as: 1.5CCB/FAG), as shown in Figure 3。Surveying its 3d comprcssive strength is 44.3MPa, adopts the electrical conductivity of the electrical conductivity controllable fly ash base geo-polymer semi-conducting material test block 3d of four electrode method detection preparation, 7d, 14d and 28d different larval instar, and its result is as shown in table 2。
Preparation embodiment 4:
All operations step is identical with embodiment 2, simply volume is flyash quality the 3.5% of white carbon black, the quality of water is the 41% of flyash quality, obtain electrical conductivity controllable fly ash base geo-polymer (FlyAshGeopolymer, it is abbreviated as: FAG) semi-conducting material test block (being labeled as: 3.5CCB/FAG), as shown in Figure 3。Surveying its 3d comprcssive strength is 27.8MPa, adopts the electrical conductivity of the electrical conductivity controllable fly ash base geo-polymer semi-conducting material test block 3d of four electrode method detection preparation, 7d, 14d and 28d different larval instar, and its result is as shown in table 2。
Preparation embodiment 5:
All operations step is identical with embodiment 2, simply volume is flyash quality the 4.5% of white carbon black, the quality of water is the 44% of flyash quality, obtain the regulatable fly ash base geo-polymer (FlyAshGeopolymer of electrical conductivity, it is abbreviated as: FAG) semi-conducting material test block (being labeled as: 4.5CCB/FAG), as shown in Figure 3。Surveying its 3d comprcssive strength is 18MPa, adopts the electrical conductivity of the electrical conductivity controllable fly ash base geo-polymer semi-conducting material test block 3d of four electrode method detection preparation, 7d, 14d and 28d different larval instar, and 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 can be applied to degradation of organic dyes efficiently, specifically undertaken by following experimental procedure:
(1) initial concentration (C is prepared with volumetric flasko) malachite green oxalate aqueous dye solutions；Its initial absorbance A is measured with ultraviolet-visible spectrophotometer0；
(2) by quantitative electrical conductivity controllable fly ash base geo-polymer semi-conducting material granule, put into and fill certain volume, concentration is CoMalachite green oxalate dyestuff reactor in, irradiate certain time with Burdick lamp under room temperature, be centrifuged separate, the supernatant in centrifuge tube is moved in cuvette, with ultraviolet-visible spectrophotometer at λmax=616nm measures the absorbance A of t timet, corresponding dye strength is Ct；
(3), after having measured absorbance, all reactant liquors and solid catalyst are re-poured in reaction unit；
(4) repeat (2), (3) step, until the absorbance of malachite green oxalate does not change over time, adopt formula (1) to calculate the degradation rate of malachite green oxalate dyestuff；
&eta; = A 0 - A t A 0 = C 0 - C t C 0 &times; 100 % Formula (1)
Application Example 1:
Accurately weigh the sample 0.4g granule of 0.160mm～0.315mm (pelletize prepare) of preparation embodiment 1 labelling, put in the malachite green oxalate dye solution that 100mL concentration is 4mg/L, after 15min is placed in darkroom, it is placed on magnetic stirring apparatus, 10min is irradiated with the PHILIPSTL-D18WACTINICBL ultraviolet lamp tube that wavelength is 365nm, stand, take supernatant centrifugation in beaker, supernatant in centrifuge tube is moved in cuvette, measure malachite green oxalate dyestuff at λ with ultraviolet-visible spectrophotometermaxThe absorbance at=616nm place, formula (1) is utilized to calculate the catalyst degradation rate when 10min, 20min, 30min, 40min, 50min, 60min, 70min successively such as shown in Fig. 4 and Biao 3, from Fig. 4 and Biao 3, the dyestuff degradation rate when 60min and 70min is identical, it was shown that the dyestuff degradation rate when 60min has reached steady statue；The conductivity relation of degradation rate during dyestuff 60min and 0.0CCB/FAG test block is as shown in Figure 5。
The table 3:0.0CCB/FAG sample degradation rate 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:
Accurately weigh the sample 0.4g granule of 0.160mm～0.315mm (pelletize prepare) of preparation embodiment 2 labelling, put in the malachite green oxalate dye solution that 100mL concentration is 4mg/L, all the other experimental procedures are identical with Application Example 1, formula (1) is utilized to calculate the catalyst degradation rate when 10min, 20min, 30min, 40min, 50min, 60min, 70min, as shown in Fig. 4 and Biao 4, from Fig. 4 and Biao 4, the dyestuff degradation rate when 60min and 70min is identical, it was shown that the dyestuff degradation rate when 60min has reached steady statue；The conductivity relation of degradation rate during dyestuff 60min and 0.5CCB/FAG test block is as shown in Figure 5。
The table 4:0.5CCB/FAG sample degradation rate 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:
Accurately weigh the sample 0.4g granule of 0.160mm～0.315mm (pelletize prepare) of preparation embodiment 5 labelling, put in the malachite green oxalate simulation industrial wastewater that 100mL concentration is 4mg/L, all the other experimental procedures are identical with Application Example 1, formula (1) is utilized to calculate the catalyst degradation rate when 10min, 20min, 30min, 40min, 50min, 60min, 70min, as shown in Fig. 4 and Biao 5, from Fig. 4 and Biao 5, the dyestuff degradation rate when 60min and 70min is identical, it was shown that the dyestuff degradation rate when 60min has reached steady statue；The conductivity relation of degradation rate during dyestuff 60min and 4.5CCB/FAG test block is as shown in Figure 5。
The table 5:4.5CCB/FAG sample degradation rate 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 is proportional with the degradation rate of dye molecule, electrical conductivity is higher, then the degradation rate of dyestuff is higher；Therefore, by regulating and controlling white carbon black volume, it is possible to prepare the fly ash base geo-polymer that electrical conductivity is controlled, and become the high activated catalyst of malachite green oxalate degradation of organic dyes。

Claims (5)

1. an electrical conductivity controllable fly ash base geo-polymer method for preparing semi-conducting material, it is characterized in that, the aqueous solution of flyash, white carbon black, nine water sodium silicate and potassium hydroxide is put into mix in agitating device, form the slurry of mix homogeneously, the regulatable fly ash base geo-polymer semi-conducting material of electrical conductivity is obtained, wherein: the volume of nine water sodium silicate, potassium hydroxide and white carbon black is based on flyash quality through molding, maintenance；Nine water sodium silicate volumes are the 15% of flyash qualities, and potassium hydroxide volume is the 7% of flyash quality, and the volume of white carbon black is the 0.5%～4.5% of flyash quality, and the volume of water is the 30%～40% of flyash quality。
2. the method for claim 1, it is characterised in that specifically include following steps:
(1) weigh flyash by formula ratio, be placed in the transit mixer of setting program；
(2) weigh white carbon black by formula ratio, be placed in the transit mixer of setting program and be fully dry mixed uniformly with flyash；
(3) solid nine water sodium silicate and solid potassium hydroxide are weighed by formula ratio；
(4) water is weighed by formula ratio, by soluble in water to solid nine water sodium silicate, solid potassium hydroxide；
(5) aqueous solution of nine water sodium silicate Yu potassium hydroxide is placed in clean slurry blender, adds the compound of the uniform white carbon black of mix and flyash, carry out chemical reaction and form uniform slurry；
(6) slurry is loaded three die for molding, 4 zinc-plated stainless steel electrodes of equidistant insertion, seal bag with plastic sheeting to seal, it is placed in calorstat under 80 DEG C of conditions maintenance 6 hours, then takes out, the demoulding after room temperature maintenance 18 hours, put into fog room and continue maintenance, prepare electrical conductivity controllable flyash geo-polymer test block, the 3d comprcssive strength of detection test block, and adopt the electrical conductivity of four electrode method test material 3d, 7d, 14d, 28d different larval instar。
3. claim 1 or 2 prepares electrical conductivity controllable fly ash base geo-polymer semi-conducting material。
4. one of them described electrical conductivity controllable fly ash base geo-polymer semi-conducting material of claims 1 to 3 is for the application of malachite green oxalate degradation of organic dyes。
5. the application described in claim 4, it is characterised in that the PHILIPSTL-D18WACTINICBL quartz burner adopting wavelength to be 365nm under room temperature irradiates malachite green oxalate dyestuff, carries out photocatalytic degradation, specifically includes the following step:
(1) being broken into pieces by electrical conductivity controllable fly ash base geo-polymer semi-conducting material, cross 85 order～55 mesh standard sieves, pelletize prepares the particulate matter of 0.160mm～0.315mm；
(2) initial concentration (C is prepared with volumetric flasko) malachite green oxalate aqueous dye solutions；Its initial absorbance A is measured with ultraviolet-visible spectrophotometer0；
(3) by quantitative electrical conductivity controllable fly ash base geo-polymer semi-conducting material granule, put into and fill certain volume, concentration is CoMalachite green oxalate dyestuff reactor in, irradiate certain time with Burdick lamp under room temperature, be centrifuged separate, the supernatant in centrifuge tube is moved in cuvette, with ultraviolet-visible spectrophotometer at λmax=616nm measures the absorbance A of t timet, corresponding dye strength is Ct；
(4), after having measured absorbance, all reactant liquors and solid catalyst are re-poured in reaction unit；
(5) repeat step (3) and step (4), until the absorbance of malachite green oxalate does not change over time, adopt below equation to calculate the degradation rate of malachite green oxalate dyestuff:
&eta; = A 0 - A t A 0 = C 0 - C t C 0 &times; 100 % .
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CN104628330A (en) * 2013-11-11 2015-05-20 北京华宇新奥科技有限责任公司 Electromagnetic wave-absorbing ceramsite concrete
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CN108117365B (en) * 2017-12-27 2020-09-25 广州大学 Method for producing conductive material and conductive material
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