CN105749857A - Bentonite composite material for treating high-zinc and copper cyaniding wastewater and application of bentonite composite material - Google Patents
Bentonite composite material for treating high-zinc and copper cyaniding wastewater and application of bentonite composite material Download PDFInfo
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- CN105749857A CN105749857A CN201610243250.7A CN201610243250A CN105749857A CN 105749857 A CN105749857 A CN 105749857A CN 201610243250 A CN201610243250 A CN 201610243250A CN 105749857 A CN105749857 A CN 105749857A
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- 229910000278 bentonite Inorganic materials 0.000 title claims abstract description 70
- 239000000440 bentonite Substances 0.000 title claims abstract description 70
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 239000002351 wastewater Substances 0.000 title claims abstract description 34
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 21
- 239000011701 zinc Substances 0.000 title claims abstract description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title abstract description 9
- 229910052802 copper Inorganic materials 0.000 title abstract description 9
- 239000010949 copper Substances 0.000 title abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 75
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000008367 deionised water Substances 0.000 claims abstract description 25
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 21
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 20
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 13
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 21
- 229910052719 titanium Inorganic materials 0.000 claims description 20
- 239000010936 titanium Substances 0.000 claims description 20
- 229910052746 lanthanum Inorganic materials 0.000 claims description 19
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 7
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052753 mercury Inorganic materials 0.000 claims description 5
- 238000004062 sedimentation Methods 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- 238000005286 illumination Methods 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 32
- 239000004408 titanium dioxide Substances 0.000 abstract description 15
- 150000002500 ions Chemical class 0.000 abstract description 7
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052737 gold Inorganic materials 0.000 abstract description 5
- 239000010931 gold Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 238000007873 sieving Methods 0.000 abstract 1
- 238000004065 wastewater treatment Methods 0.000 abstract 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 16
- 230000001699 photocatalysis Effects 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- DRIUWMIAOYIBGN-UHFFFAOYSA-N lanthanum titanium Chemical compound [Ti][La] DRIUWMIAOYIBGN-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- -1 meanwhile Chemical compound 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- B01J2220/00—Aspects relating to sorbent materials
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- B01J2220/42—Materials comprising a mixture of inorganic materials
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
The invention relates to a bentonite composite material for treating high-zinc and copper cyaniding wastewater and application of the bentonite composite material, and belongs to the technical field of wastewater treatment.The preparation method of the bentonite composite material comprises the following steps: mixing butyl titanate, absolute ethyl alcohol and concentrated nitric acid to obtain a mixture A; dissolving lanthanum nitrate hexahydrate in deionized water, adding the concentrated nitric acid, and then adding the absolute ethyl alcohol to obtain a mixture B; dropwise adding the mixture B in the mixture A to obtain a mixture C, and after dropwise adding is finished, continuing stirring to obtain milky liquid; adding bentonite and the deionized water in the milky liquid to obtain a mixture D; and settling, evaporating to dryness, grinding, sieving, roasting, and cooling to room temperature to obtain the bentonite composite material.The titanium dioxide is generated in a reaction process, the generated titanium dioxide is loaded on the bentonite, high-zinc and copper cyaniding wastewater in the gold industry is treated through modification, cyanogens in the cyanide-containing wastewater can be degraded and heavy metal ions are effectively adsorbed.
Description
Technical field
The present invention relates to and a kind of administer high zinc, the bentonite composite material of copper cyanide wastewater and application thereof, belong to technical field of waste water processing.
Background technology
The cyanide wastewater of gold industry mainly contains cyanide, the difference according to composition of ores, also can contain zinc, copper heavy metal ion, and these heavy metal ion and cyanide can form complex ion.Owing to cyanide has severe toxicity, it is impossible to directly discharged.The method having a lot of Treatment of Cyanide-containing Wastewater, for instance chlor-alkali oxidizing process, sulfur dioxide air oxidation process, hydrogen peroxide oxidation process, biochemical breakdown method, the method such as acidization and ion exchange.But these method Treatment of Cyanide-containing Wastewater effects are unsatisfactory.
Titanium dioxide is widely used in the process of liquid debris or toxic wastewater, and it has Heat stability is good, efficiency is high, nontoxic and will not produce the advantageous properties such as secondary pollution.But the application for titanium dioxide is but not as extensive, and this is relatively wide mainly due to the band gap of titanium dioxide, light as longer in ultraviolet equiwavelength can only be absorbed, the utilization rate of solar energy is relatively low.The photocatalytic activity of titanium dioxide can be improved by doped with rare-earth elements.The titanium dioxide of doped with rare-earth elements accelerates electronics and the separation in cavity, and improves the scope of its absorption spectrum, thus accelerating redox reaction process.When temperature is not as high time, Eu, Er and La etc. is rare earth doped can slow down the Anatase transformation to Rutile Type in titanium dioxide, and research shows, the doping of rare earth element can be effectively improved photocatalysis efficiency.
Bentonite is mainly composed of the montmorillonite that specific surface area is bigger, is the clay having good absorption property and ion-exchange performance, and this special crystal structure containing alumina octahedral and silicon-oxy tetrahedron with it has close relationship.Bentonite is widely used in field of environment protection, for instance paper-making industry, electroplating industry and petroleum refining industry etc., other industrial waste water containing heavy metal ion produced or solid refuses, it is also possible to use bentonite in treatment.By studying bentonitic character, Many researchers has set about the photocatalytic activity by effectively utilizing titanium dioxide on titanium dichloride load to bentonite, meanwhile, titanium dioxide also is able to effectively utilize bentonitic layer structure and microporous properties, and is well dispersed in bentonitic surface.
The patent of application titanium dioxide process waste water aspect mainly has following several at present, is shown in Table 1.
Table 1 cyanide wastewater processes patent list
Summary of the invention
It is an object of the invention to provide a kind of bentonite composite material administering high zinc, copper cyanide wastewater, it is achieved to the active adsorption of effectively degraded and the heavy metal ion of cyanogen in cyanide wastewater；Present invention simultaneously provides its application.
The bentonite composite material of improvement gold industry cyanide wastewater of the present invention, its preparation method comprises the following steps:
(1) by butyl titanate, dehydrated alcohol and concentrated nitric acid mixing and stirring, mixture A is obtained；
(2) lanthanum nitrate hexahydrate is dissolved in deionized water, adds concentrated nitric acid mix homogeneously, add dehydrated alcohol mix homogeneously, obtain mixture B；
(3) mixture B is added drop-wise in mixture A, obtains mixture C, after being added dropwise to complete, continue mixture C is stirred, obtain milky white liquid；
(4) milky white liquid obtained to step (3) adds bentonite, stir, be eventually adding deionized water, continue to stir, obtain mixture D；
(5) mixture D is settled, be evaporated, grind, sieve, roasting, it is cooled to room temperature, obtains bentonite composite material.
Butyl titanate in step (1), dehydrated alcohol, concentrated nitric acid volume ratio be 10～30:30～60:1～5, the mix and blend time is 20～60min.
In step (2), lanthanum is 0.5～1.5:100 with the mol ratio of titanium in step (1), in step (2), the volume ratio of deionized water, concentrated nitric acid and dehydrated alcohol is 3～6:0.3～0.6:12～24, and wherein lanthanum is 12～36:1000 with the mass ratio of deionized water.
In step (3) under the stirring condition of 160～200rpm, mixture B is added drop-wise in mixture A, mixture B rate of addition be every 1 to 3 seconds, continuing time that mixture C is stirred is 20～60min.
In step (4), bentonite is 1:10～15 with the mass ratio of deionized water, and bentonite is 1.6～1.9:1 with the mass ratio of titanium in step (1), and continuing mixing time is 2～6 hours.Titanium in step (1) is the titanium in butyl titanate.
In step (5), the sedimentation time is 3～5 hours, and the process that is evaporated keeps temperature to be 60～90 DEG C, and screen-aperture is 100～200 orders, and sintering temperature is 300～600 DEG C, and roasting time is 0.5～5 hour.
The bentonite composite material of improvement gold industry cyanide wastewater of the present invention comprises the following steps for the process of cyanide wastewater: is mixed with cyanide wastewater by bentonite composite material under room temperature, carries out lucifuge vibration so that it is mix homogeneously obtains mixed solution；Mixed solution is carried out magnetic agitation, and being maintained with of magnetic agitation blasts air in mixed solution and keeps high voltage mercury lamp to carry out illumination in mixed solution vertical direction.
Wherein, the preferred 150W of the power of high voltage mercury lamp.
Water used by the present invention is deionized water, and dehydrated alcohol used, butyl titanate, lanthanum nitrate hexahydrate are analytical pure, and bentonite used all crosses 200 mesh sieves.
Beneficial effects of the present invention is as follows:
The present invention generates titanium dioxide in course of reaction, and by the titanium dichloride load of generation on bentonite, by modifiying high zinc, the copper cyanide wastewater administered gold industry and produce, it utilizes the photocatalysis of titanium dioxide and bentonitic adsorption that cyanide is decomposed effectively, adsorbs with realizing heavy metal ion simultaneously.
Materials kind of the present invention is less, and equipment is simple, easy and simple to handle, and reaction condition requires loose；In bentonite composite material used, bentonitic consumption is maximum, and bentonite is widely distributed in China, cheap and easy to get, saves cost；Bentonite has special layer structure and bigger specific surface area, and titanium dioxide utilizes this characteristic of bentonite, and distribution is more uniform, greatly increases light-catalyzed reaction efficiency；While utilizing optically catalytic TiO 2 performance, there is again bentonitic adsorption, be effectively improved the utilization rate of bentonite composite material；The doping of rare-earth elements La so that photocatalytic activity is further enhanced.
Compared with tradition absorption method, cyanogen can be decomposed by the present invention, effectively removes the harm of cyanogen, and polluted by copper amount reaches 12.11～15.64mg/g, and the decomposition amount of cyanogen reaches 22.36～36.4mg/g, and zinc adsorbance reaches 18.11～29.51mg/g.
Accompanying drawing explanation
Fig. 1 is the SEM figure of bentonite composite material in embodiment 1；
Fig. 2 is the TG-DTG image of bentonite composite material in embodiment 1；
Fig. 3 is the XRD figure of bentonite original soil and bentonite composite material；
Wherein: a, bentonite original soil；B, the non-impurity-doped bentonite composite material of roasting at 400 DEG C；C, 300 DEG C of roastings the bentonite composite material of La and Ti mol ratio 1:100；D, 400 DEG C of roastings the bentonite composite material of La and Ti mol ratio 1:100；E, 500 DEG C of roastings the bentonite composite material of La and Ti mol ratio 1:100；F, 600 DEG C of roastings the bentonite composite material of La and Ti mol ratio 1:100；A, titanium dioxide；B, bentonite；
Fig. 4 is the EDS spectrogram of different La doped amount bentonite composite materials in embodiment 4；
Wherein: a, La and Ti mol ratio 0.5:100；B, La and Ti mol ratio 1:100；C, La and Ti mol ratio 1.5:100.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
(1) butyl titanate, dehydrated alcohol and concentrated nitric acid are added in there-necked flask, stir 30min, mix homogeneously, obtain mixture A；Wherein butyl titanate, dehydrated alcohol, concentrated nitric acid three's volume ratio are 20:40:1；
(2) lanthanum nitrate hexahydrate is dissolved in deionized water, adds concentrated nitric acid mix homogeneously, add dehydrated alcohol mix homogeneously, obtain mixture B；Deionized water, concentrated nitric acid, dehydrated alcohol three's volume ratio are 5:0.5:20；In step (2), the mol ratio of La and Ti is 1:100；The mass ratio of lanthanum and deionized water is 24:1000.
(3) under the stirring condition of 200rpm, mixture B is added drop-wise in mixture A with the rate of addition of 1 drop/sec, obtains mixture C, after being added dropwise to complete, continue mixture C is stirred 30min, obtain milky white liquid；
(4) milky white liquid obtained to step (3) adds bentonite, stir, be eventually adding deionized water, continue stirring 5h, obtain mixture D；Bentonite, both water mass ratio are 1:12；Bentonite is 1.8:1 with the mass ratio of titanium in step (1)；
(5) mixture D carries out sedimentation in 5 hours, and 80 DEG C are evaporated, grind, and cross 200 mesh sieves, 400 DEG C of roastings 2 hours, are cooled to room temperature, obtain bentonite composite material, standby.
The bentonite composite material obtained in embodiment 1 is carried out respectively SEM detection, TG-DTG detection, as shown in Figure 1 and Figure 2.
Photocatalytic is tested:
Under room temperature, the bentonite composite material of embodiment 1 is mixed with cyanide wastewater, carry out lucifuge vibration in 2 hours so that it is mix homogeneously obtains mixed solution；Mixed solution carries out magnetic agitation, and magnetic agitation rotating speed is 120rpm, and mixing time is 4 hours；Magnetic agitation be maintained with blasting air in mixed solution, air velocity is 2～3 bubbles per second, and mixed solution vertical direction keep 150W high voltage mercury lamp carry out 4 h light Catalysis experiments.
Its catalytic adsorption effect is as shown in table 2:
Table 2 embodiment 1 catalytic adsorption effect table
| Cyanogen decomposition amount (mg/g) | Polluted by copper amount (mg/g) | Zinc adsorbance (mg/g) |
| 36.4mg/g | 15.64mg/g | 29.51mg/g |
Embodiment 2
Testing by changing different sintering temperatures, sintering temperature respectively 300 DEG C, 400 DEG C, 500 DEG C and 600 DEG C, obtain 4 different samples, more respectively cyanide wastewater is carried out photocatalytic experiment with the sample prepared, result is table 3 such as.All the other are such as embodiment 1.4 bentonite composite materials obtained in bentonite original soil and embodiment 2 are carried out XRD detection respectively, as shown in Figure 3.
Table 3 embodiment 2 catalytic adsorption effect table
| Sintering temperature/DEG C | 300 | 400 | 500 | 600 |
| Cyanogen decomposition amount (mg/g) | 28.61 | 36.4 | 25.97 | 22.36 |
| Polluted by copper amount (mg/g) | 15.64 | 15.28 | 12.85 | 12.11 |
| Zinc adsorbance (mg/g) | 27.35 | 27.37 | 23.06 | 20.98 |
Embodiment 3
Testing by changing different roasting time, roasting time respectively 30min, 60min, 90min, 120min, 150min and 180min, obtain different samples, more respectively cyanide wastewater is carried out photocatalytic experiment with the sample prepared, result is table 4 such as.All the other are such as embodiment 1.
Table 4 embodiment 3 catalytic adsorption effect table
| Roasting time/min | 30 | 60 | 90 | 120 | 150 | 180 |
| Cyanogen decomposition amount (mg/g) | 34.39 | 35.19 | 35.35 | 36.4 | 31.59 | 29.89 |
| Polluted by copper amount (mg/g) | 15.25 | 15.51 | 15.63 | 15.22 | 13.65 | 12.75 |
| Zinc adsorbance (mg/g) | 18.11 | 24.2 | 27.34 | 26.48 | 26.1 | 22.45 |
Embodiment 4
Testing by changing different La dopings, doping is mol ratio respectively 0.5:100,1.0:100,1.5:100 of La and Ti, obtains different samples, more respectively cyanide wastewater is carried out photocatalytic experiment with the sample prepared, and result is table 5 such as.All the other are such as embodiment 1.
Table 5 embodiment 4 catalytic adsorption effect table
| La doped amount (lanthanum titanium mol ratio/%) | 0.5 | 1.0 | 1.5 |
| Cyanogen decomposition amount (mg/g) | 31.2 | 36.4 | 33.79 |
| Polluted by copper amount (mg/g) | 15.25 | 15.53 | 15.57 |
| Zinc adsorbance (mg/g) | 28.63 | 28.52 | 28.6 |
Embodiment 5
(1) butyl titanate, dehydrated alcohol and concentrated nitric acid are added in there-necked flask, stir 40min, mix homogeneously, obtain mixture A；Wherein butyl titanate, dehydrated alcohol, concentrated nitric acid three's volume ratio are 10:30:3；
(2) lanthanum nitrate hexahydrate is dissolved in deionized water, adds concentrated nitric acid mix homogeneously, add dehydrated alcohol mix homogeneously, obtain mixture B；Deionized water, concentrated nitric acid, dehydrated alcohol three's volume ratio are 3:0.6:24；In step (2), the mol ratio of La and Ti is 1:100；The mass ratio of lanthanum and deionized water is 12:1000.
(3) under the stirring condition of 160rpm, mixture B is added drop-wise in mixture A with the rate of addition of 1 drop/sec, obtains mixture C, after being added dropwise to complete, continue mixture C is stirred 20min, obtain milky white liquid；
(4) milky white liquid obtained to step (3) adds bentonite, stir, be eventually adding deionized water, continue stirring 3h, obtain mixture D；Bentonite, both water mass ratio are 1:10；Bentonite is 1.6:1 with the mass ratio of titanium in step (1)；
(5) mixture D carries out sedimentation in 3 hours, and 60 DEG C are evaporated, grind, and cross 200 mesh sieves, 300 DEG C of roastings 5 hours, are cooled to room temperature, obtain bentonite composite material, standby.
Embodiment 6
(1) butyl titanate, dehydrated alcohol and concentrated nitric acid are added in there-necked flask, stir 50min, mix homogeneously, obtain mixture A；Wherein butyl titanate, dehydrated alcohol, concentrated nitric acid three's volume ratio are 30:60:5；
(2) lanthanum nitrate hexahydrate is dissolved in deionized water, adds concentrated nitric acid mix homogeneously, add dehydrated alcohol mix homogeneously, obtain mixture B；Deionized water, concentrated nitric acid, dehydrated alcohol three's volume ratio are 6:0.3:12；In step (2), the mol ratio of La and Ti is 1:100；The mass ratio of lanthanum and deionized water is 36:1000.
(3) under the stirring condition of 180rpm, mixture B is added drop-wise in mixture A with the rate of addition of 1 drop/sec, obtains mixture C, after being added dropwise to complete, continue mixture C is stirred 50min, obtain milky white liquid；
(4) milky white liquid obtained to step (3) adds bentonite, stir, be eventually adding deionized water, continue stirring 6h, obtain mixture D；Bentonite, both water mass ratio are 1:15；Bentonite is 1.9:1 with the mass ratio of titanium in step (1)；
(5) mixture D carries out sedimentation in 4 hours, and 90 DEG C are evaporated, grind, and cross 200 mesh sieves, 600 DEG C of roastings 1 hour, are cooled to room temperature, obtain bentonite composite material, standby.
Claims (8)
1. the bentonite composite material administering high zinc, copper cyanide wastewater, it is characterised in that: its preparation method comprises the following steps:
(1) by butyl titanate, dehydrated alcohol and concentrated nitric acid mixing and stirring, mixture A is obtained；
(2) lanthanum nitrate hexahydrate is dissolved in deionized water, adds concentrated nitric acid mix homogeneously, add dehydrated alcohol mix homogeneously, obtain mixture B；
(3) mixture B is added drop-wise in mixture A, obtains mixture C, after being added dropwise to complete, continue mixture C is stirred, obtain milky white liquid；
(4) milky white liquid obtained to step (3) adds bentonite, stir, be eventually adding deionized water, continue to stir, obtain mixture D；
(5) mixture D is settled, be evaporated, grind, sieve, roasting, it is cooled to room temperature, obtains bentonite composite material.
2. the bentonite composite material of the high zinc of improvement according to claim 1, copper cyanide wastewater, it is characterized in that: butyl titanate in step (1), dehydrated alcohol, concentrated nitric acid volume ratio be 10～30:30～60:1～5, the mix and blend time is 20～60min.
3. the bentonite composite material of the high zinc of improvement according to claim 1, copper cyanide wastewater, it is characterized in that: in step (2), lanthanum is 0.5～1.5:100 with the mol ratio of titanium in step (1), in step (2), the volume ratio of deionized water, concentrated nitric acid and dehydrated alcohol is 3～6:0.3～0.6:12～24, and wherein lanthanum is 12～36:1000 with the mass ratio of deionized water.
4. the bentonite composite material of the high zinc of improvement according to claim 1, copper cyanide wastewater, it is characterized in that: in step (3) under the stirring condition of 160～200rpm, mixture B is added drop-wise in mixture A, mixture B rate of addition be every 1 to 3 seconds, continuing time that mixture C is stirred is 20～60min.
5. the bentonite composite material of the high zinc of improvement according to claim 1, copper cyanide wastewater, it is characterized in that: in step (4), bentonite is 1:10～15 with the mass ratio of deionized water, bentonite is 1.6～1.9:1 with the mass ratio of titanium in step (1), and continuing mixing time is 2～6 hours.
6. the bentonite composite material of the high zinc of improvement according to claim 1, copper cyanide wastewater, it is characterized in that: in step (5), the sedimentation time is 3～5 hours, the process that is evaporated keeps temperature to be 60～90 DEG C, screen-aperture is 100～200 orders, sintering temperature is 300～600 DEG C, and roasting time is 0.5～5 hour.
7. the application of the arbitrary described bentonite composite material administering high zinc, copper cyanide wastewater of claim 1～6, it is characterized in that: the process for cyanide wastewater comprises the following steps: mixed with cyanide wastewater by bentonite composite material under room temperature, carry out lucifuge vibration so that it is mix homogeneously obtains mixed solution；Mixed solution is carried out magnetic agitation, and being maintained with of magnetic agitation blasts air in mixed solution and keeps high voltage mercury lamp to carry out illumination in mixed solution vertical direction.
8. the application of the bentonite composite material of the high zinc of improvement according to claim 7, copper cyanide wastewater, it is characterised in that: the power of high voltage mercury lamp is 150W.
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| CN107159210A (en) * | 2017-05-22 | 2017-09-15 | 句容康泰膨润土有限公司 | A kind of Novel Titanium dioxide bentonite composite material and preparation method thereof |
| CN107469767A (en) * | 2017-09-14 | 2017-12-15 | 山东理工大学 | Silica/nano titanium oxide/silicone zeolite composite of Treatment of Cyanide-containing Wastewater and its application |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107159210A (en) * | 2017-05-22 | 2017-09-15 | 句容康泰膨润土有限公司 | A kind of Novel Titanium dioxide bentonite composite material and preparation method thereof |
| CN107469767A (en) * | 2017-09-14 | 2017-12-15 | 山东理工大学 | Silica/nano titanium oxide/silicone zeolite composite of Treatment of Cyanide-containing Wastewater and its application |
| CN107469767B (en) * | 2017-09-14 | 2019-10-25 | 山东理工大学 | Silica/nano-titanium dioxide/silicone zeolite composite material of Treatment of Cyanide-containing Wastewater and its application |
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