CN106693943A - Mesoporous activated carbon/titanium dioxide photocatalyst for degrading colored sewage and preparation method and application thereof - Google Patents
Mesoporous activated carbon/titanium dioxide photocatalyst for degrading colored sewage and preparation method and application thereof Download PDFInfo
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- CN106693943A CN106693943A CN201611149133.0A CN201611149133A CN106693943A CN 106693943 A CN106693943 A CN 106693943A CN 201611149133 A CN201611149133 A CN 201611149133A CN 106693943 A CN106693943 A CN 106693943A
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- activated carbon
- titanium dioxide
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- photochemical catalyst
- sewage
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 123
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 38
- 239000010865 sewage Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000011941 photocatalyst Substances 0.000 title abstract description 12
- 230000000593 degrading effect Effects 0.000 title abstract 3
- 239000003054 catalyst Substances 0.000 claims abstract description 57
- 238000001354 calcination Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000003610 charcoal Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 238000011282 treatment Methods 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 10
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 238000000643 oven drying Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 15
- 230000015556 catabolic process Effects 0.000 abstract description 14
- 238000006731 degradation reaction Methods 0.000 abstract description 14
- 239000011148 porous material Substances 0.000 abstract description 11
- 238000007146 photocatalysis Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- 238000011160 research Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000002028 Biomass Substances 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000010276 construction Methods 0.000 abstract description 2
- 238000005457 optimization Methods 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 6
- 235000017491 Bambusa tulda Nutrition 0.000 description 6
- 241001330002 Bambuseae Species 0.000 description 6
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 6
- 239000011425 bamboo Substances 0.000 description 6
- 239000002250 absorbent Substances 0.000 description 5
- 230000002745 absorbent Effects 0.000 description 5
- 230000005587 bubbling Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000001994 activation Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
- 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
-
- 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
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/32—Details relating to UV-irradiation devices
- C02F2201/322—Lamp arrangement
- C02F2201/3227—Units with two or more lamps
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a mesoporous activated carbon/titanium dioxide photocatalyst for degrading colored sewage and a preparation method and application thereof and belongs to the techcnial field of colored sewage degrading photocatalysts. The photocatalyst is obtained through activated carbon pretreatment, sol liquid preparation, photocatalyst preparation and the like. A mesoporous pore structure facilitates improvement of absorption effect and degradation efficiency of the photocatalysis process. The recovery problem of the titanium dioxide photocatalyst is solved by adopting the method, and the photocatalytic efficiency of the photocatalyst is improved. The preparation method researching biomass AC/TiO2 is conductive to photocatalyst optimization and makes the photocatalyst adapt to practical application. By applying a research result to actual life for production, life and environment protection, economical efficiency and construction of environmentally friendly society are improved to the most degree. The researched photocatalytic performance influence on the specific surface, calcination temperature and catalyst usage amount can provide valuable experience for production, life and follow-up research.
Description
Technical field
The invention belongs to coloured sewage photocatalytic degradation agent technical field, and in particular to a kind of mesoporous activated carbon/titanium dioxide
Photochemical catalyst of the coloured sewage of titanium degraded and preparation method and application.
Background technology
Titanium dioxide is a kind of more typical photochemical catalyst, is also a kind of semi-conducting material of broad stopband, because of its stability
The property such as good, low cost, photocatalytic activity be strong, harmless and have good application prospect.Titanium dioxide generally has three kinds
Crystal habit, respectively：Detitanium-ore-type, rutile-type and brookite type.Three kinds of atoms of crystal form titanium dioxide crystal are all rows
6 O atom coordinations are arranged into, tundish is containing a common summit structure of the octahedron of Ti atoms.But, in the elementary cell of crystal
In, rutile-type has 2 TiO of chemical unit2, anatase titanium dioxide has 4, and plate titanium-type has 8；This just determines that three kinds of crystal formations have
Different physics and chemical property.Plate titanium-type is unstable crystal formation, without actual industrial utility value, simply academicly
Studied.Rutile-type and anatase titanium dioxide are same crystal formation, belong to tetragonal crystal system, but penetrate with different lattices, thus X
Line image is also different, and the angle of diffraction of anatase titanium dioxide is located at 25.5 °, rutile positioned at 27.5 °.In TiO2Crystal structure in, it is sharp
The octahedra distortion of titanium ore is maximum, and energy gap is relatively low, is usually used in light degradation.
Photochemical catalyst is widely used in the neighborhoods such as dye wastewater treatment, purification of air, deodorization and sterilization；Light-catalyzed reaction is logical
Cross catalyst and absorb luminous energy, the process for producing oxidizing species to degrade organic matter and some inorganic matters, reaction condition
It is more gentle, clean-up effect thoroughly, the features such as photochemical catalyst long service life.
Find a kind of with large specific surface area, and be practical skill with the high-efficient carrier material of titanium dioxide strong bonded
The key of art.Titanium dioxide has that oxidability is strong, reacts at room temperature, organic pollution mineralising is complete, reusable,
The advantages of non-secondary pollution, efficient energy-saving, flexible technique.But there is also the weak point of many, traditional nano-silica
Change titanium suspended phase photochemical catalyst easy in inactivation, easily cohesion, difficult recovery.Titanium dioxide is typically subject to the ultraviolet excitation in the sun, but
The energy of ultraviolet light only accounts for 5% in sunshine, directly excites TiO2Light-catalyzed reaction it is less efficient, so, current light drop
Usually using artificial ultraviolet light as light source, relatively costly, these shortcomings are gradually exposed solution, and nano titanium oxide is loaded
The research of change gets the attention.Research (being criterion with the quantity of document delivered) to titanium dioxide, reached in 2012
Peak, wherein photocatalysis are the emphasis of research.With around raising TiO2Contaminant degradation efficiency, reduce use cost, utilize
Semiconductors coupling, ion doping, load immobilization research etc. are to TiO2It is focus in recent years to be modified.
Activated carbon AC (Activated Carbon) just has as the potential of carrier of photocatalyst.Light-catalyzed reaction process
In, catalyst is smaller to be difficult to reclaim, and this problem is solved so as to need loaded article.Activated carbon, is a kind of high-specific surface area, contains
There are abundant micropore diameter, acidproof corrosion resistant functional material.It is usually used in the industries such as petrochemical industry, electric power, environmental protection, due to its excellent suction
Attached performance, the physicochemical characteristics of stabilization, there is the laudatory title of all-round absorbent.The adsorbing separation such as activated carbon and zeolite, carbon molecular sieve
Material is compared, low cost of manufacture, and specific surface is big, and absorption property is good.Therefore, it is widely used in food, national defence, medical treatment, military affairs
With the field such as daily life.
The content of the resources such as traditional activated carbon preparing raw material, petroleum coke, anthracite, pitch is limited, is non-renewable money
Source, permanent a large amount of uses can destroy the ecological balance.Biomass material, contains abundant, and the regeneration cycle of resource is shorter；Institute
Currently to be appeared to be most promising renewable cleaning resource.The carbon contents such as biomass material, such as stalk, rice husk, shell compared with
Height, has certain feasibility as activated carbon preparing raw material.Therefore, as the widely studied object for preparing activated carbon in recent years.
Its performance is mainly determined by specific surface area, pore structure, aperture and surface functional group etc..With biomass as raw material, lived by being pyrolyzed
Change from preparing active carbon, and load upper TiO2, not only make TiO2Immobilization, separation of solid and liquid easily, is easy to reclaim, and can utilize
The absorption property of activated carbon, by reaction substrate absorption, is enriched with to TiO2Grain surface or near, increase connecing for catalyst and substrate
Probability is touched, the photocatalysis efficiency of composite is improved, increases degradation rate.
The content of the invention
In order to overcome the shortcoming of prior art with it is not enough, primary and foremost purpose of the invention be provide a kind of mesoporous activated carbon/
The preparation method of the photochemical catalyst of the coloured sewage of titanium dioxide degradable.
Another object of the present invention is to provide the mesoporous activated carbon/titanium dioxide prepared by above-mentioned preparation method
Degrade the photochemical catalyst of coloured sewage.
It is still another object of the present invention to provide the photochemical catalyst of the above-mentioned coloured sewage of mesoporous activated carbon/titanium dioxide degradable
Application.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of the photochemical catalyst of the coloured sewage of mesoporous activated carbon/titanium dioxide degradable, comprises the following steps：
(1) pretreatment of activated carbon：
Mesopore activated carbon is taken, is ground, sieving adds deionized water, to carbon dust is flooded；By the mixing of activated carbon and water
Thing carries out microwave treatment, and the sample that will finally process is dried in being put in baking oven, obtains pretreated activated carbon, stand-by.
(2) preparation of sol solutionses：
1. at room temperature by Ti (C4H9O)4In being stirred vigorously down and being slowly dropped to absolute ethyl alcohol and acetic acid, by 15~
The stirring of 20min, obtains the solution A of homogeneous transparent；
2. acetic acid is added to stirring in the solution that deionized water and absolute ethyl alcohol are made into, obtains solution B；
3. pretreated activated carbon is added in A liquid in weighing step (1), and is sufficiently stirred for, and obtains turbid solution
C；
4. with vigorous stirring, by B liquid with being added drop-wise in C, and continue stirring, obtain sol solutionses.
(3) preparation of photochemical catalyst：
After the sol solutionses that step (2) is obtained are settled into gel, through spontaneously drying, oven drying, calcining obtains mesoporous work
The photochemical catalyst of the property coloured sewage of charcoal/titanium dioxide degradable.Under nitrogen protection through temperature programming to required temperature.This experiment is forged
The final temperature of burning is preferably 500 DEG C；
Mesopore activated carbon described in step (1) is preferably mesopore activated carbon from activated sludge；
The mesh number of the sieving described in step (1) is preferably 180~220 mesh；
Microwave treatment described in step (1) is to be processed with microwave cleaning device.
The time of the microwave treatment described in step (1) is preferably 25~35min；More preferably 30min.
The specific surface area of the pretreated activated carbon described in step (1) is 404.20~460.10m2/g；Aperture master
Concentrate on 2.5~3.5nm；
Step (2) 1. described in Ti (C4H9O)4, absolute ethyl alcohol and acetic acid volume ratio be preferably (11~13)：(28~
32)：(1.5~2.5)；
Step (2) 2. described in the volume ratio of acetic acid, deionized water and absolute ethyl alcohol be preferably (2.0~3.0)：(1~
3)：(28~32)；
Step (2) 3. described in pretreated activated carbon and step (2) 1. in Ti (C4H9O)4Mass volume ratio
Preferably (3.4~3.6) g：(11~13) mL；
Step (2) 3. described in time of stirring be preferably 25~35min；
Step (2) 4. described in time of stirring be preferably 100~140min；
The time of the natural drying described in step (3) is preferably 36~60h；
The condition of the oven drying described in step (3) is preferably 60~70 DEG C of 36~60h of oven drying.
The temperature of the calcining described in step (3) is preferably 400~600 DEG C.
The specific surface area of activated carbon, pore structure, calcining heat, catalyst amount are crucial comparings in above-mentioned preparation method
, there is large effect for final technique effect, such as the pore structure of charcoal, specific surface area, photocatalyst crystalline structure have
Influence；
A kind of photochemical catalyst of the coloured sewage of mesoporous activated carbon/titanium dioxide degradable, is prepared into by above-mentioned preparation method
Arrive.
The photochemical catalyst of the described coloured sewage of mesoporous activated carbon/titanium dioxide degradable is in coloured sewage degraded field
Using；
The photochemical catalyst of the described coloured sewage of mesoporous activated carbon/titanium dioxide degradable is in coloured sewage degraded field
Using comprising the following steps：
Added into the coloured sewage solution of methylene blue with the catalytic amount of 1g/L~3g/L, degraded.
Needed before experiment to mass concentration for the microwave that the coloured sewage solution of 30mg/L methylene blues carries out about 30min shakes
Swing, add the photochemical catalyst for weighing up 1g/L~3g/L, fix ultraviolet lamp tube；After above-mentioned end-of-job, from opening air pump
During bubbling, degradation time is 120min~180min.
General structure figure such as Fig. 1 of apparatus for photoreaction.By casing, light homemade apparatus for photoreaction ultraviolet lamp tube, air pump
And bubbling flexible pipe composition.Whole reaction mechanism is placed in a lighttight casing, and reaction light source is by middle UV light tube
There is provided, bubbling flexible pipe is connected with air pump, the shape that the fixation with steel wire of bubbling flexible pipe contains liquid device into laminating is positioned over Sheng liquid dress
Inner bottom part is put, and aperture is punctured with across a certain distance in phase, it is ensured that the uniformity of bubbling, improve photochemical catalyst fully and reaction solution
It is sufficiently mixed.
The photochemical catalyst of the described coloured sewage of mesoporous activated carbon/titanium dioxide degradable is in coloured sewage degraded field
Using preferably comprising following steps：
The photochemical catalyst reaction density that 2g/L is added in the coloured sewage solution of methylene blue of 30mg/L is optimal choosing
Select；Basically reached after photocatalysis 150min degradable, degradation rate reaches 98%.Can degradable methylene in a short time
Base is blue, it is also possible to largely reduce catalyst amount；Reach the balance of time and economy.
When photochemical catalyst addition is 1g/L, degradation rate reaches 53% after photocatalysis 3h；It is in photochemical catalyst addition
Degradation efficiency during 2g/L is essentially 2 times of 1g/L, therefore is added in the coloured sewage solution of methylene blue of actual 30mg/L
The catalytic amount of 2g/L is optimal selection.The more activated carbons of middle hole number, carried titanium dioxide effect is better.
Mechanism of the invention is：The present invention passes through the Different treatments such as pretreatment, using sol gel process, program control
Temperature carries out calcination treatment, prepares low cost, the TiO with highlight catalytic active2Catalyst.
The present invention has the following advantages and effect relative to prior art：
(1) mesopore pore structure is conducive to improving suction-operated and the degradation efficiency of photocatalytic process；500 DEG C are calcined sample
Mesopore activated carbon catalyst for titanium dioxide loaded is 1g/L in loaded photocatalyst consumption, and degradation rate reaches after photocatalysis 3h
53%.The more activated carbons of middle hole number, carried titanium dioxide effect is better；
(2) rising of calcining heat, makes titanium dioxide anatase crystal type more complete, and crystallite dimension also increases rapidly；At this
In experiment, 500 DEG C is optimal calcining heat.
(3) the catalyst reaction concentration that 2g/L is added in the methylene blue solution of 30mg/L is optimal selection；
Basically reach degradable after photocatalysis 150min, degradation rate reaches 98%.
(4) it is the method for load carried titanium dioxide with biomass carbon, solves the recovery of titanium dioxide optical catalyst,
Strengthen the photocatalysis efficiency of catalyst.Postgraduate's substance A C/TiO2Preparation method contribute to photochemical catalyst to optimize so that light
Catalyst can more fit practical application.It is applied in real life in production, life and environmental protection by achievement in research
Go, improve economy to greatest extent and advocate the construction of environment friendly society.Specific surface, calcining temperature that the present invention is studied
Degree and influence of the catalyst amount to photocatalysis performance, can provide the experience of preciousness for production and living and follow-up research.
Brief description of the drawings
Fig. 1 is the general structure figure of apparatus for photoreaction；Wherein, 1：Ultraviolet lamp tube, 2：Holding frame for luminous tube, 3：Liquid beaker is contained,
4：Wireway, 5：Air pump, 6：Light tight casing, 7：Electric wire/socket.
Fig. 2 is Different treatments absorbent charcoal material (absorption) pore size distribution curve in embodiment 1.
Fig. 3 is Different treatments absorbent charcoal material (desorption) pore size distribution curve in embodiment 1.
Fig. 4 be in embodiment 2 different calcining heats to bamboo charcoal/TiO2The influence of the crystal phase structure of photochemical catalyst.
Fig. 5 be in embodiment 2 different calcining heats to bamboo charcoal/TiO2Light-catalysed influence.
Fig. 6 is different catalyst reaction concentration in embodiment 3 to light-catalysed influence.
Specific embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited
In this.
Embodiment 1
(1) by the charing of raw material, activation：Raw material is mainly oil tea shell, with the charing/activation integral of this lab design
Muffle furnace carries out carbonizing/activation experiment, is passed through nitrogen and water vapour in activation process, the flow of steam be respectively 0.3mL/min,
0.5mL/min, can obtain the activated carbon of different specific surfaces and aperture structure.
(2) activated carbon obtained in the 0.3mL/min steam flows of step (1) is carried out with the business bamboo activated carbon of purchase
Different pretreatments.A classes：20.0g activated carbon from activated sludge is taken in beaker, 1mol/L NaOH solutions are added, 30min, mistake is soaked
Filter, and with deionized water rinsing 3 times.Will rinse, filtering after activated carbon add about 8% HNO3(20mL is added by 140mL water
65%~68%HNO3It is formulated), boil 1h.Suction filtration, and be washed with deionized water to neutrality, it is put into oven for drying stand-by.B
Class：Activated carbon from activated sludge is taken in mortar, the screen cloth of 200 mesh is clayed into power and cross.Appropriate 200 mesh activated carbon is taken in beaker,
Deionized water is added, to carbon dust is flooded.The beaker that will be equipped with activated carbon and water is put into microwave cleaning device that to carry out 30min clear
Wash.The sample that will finally process be put in baking oven dry it is stand-by.
(3) the pretreated activity obtained without the activated carbon, step (2) that pre-process for preparing step (1)
Charcoal carries out specific surface area analysis and pore analysis, the results are shown in Table 1 and Fig. 2.
The preparation of the absorbent charcoal carrier of table 1 and preprocess method
Find out from Fig. 2 and Fig. 3, the specific surface of sample 1-500,2-500,3-500 and 4-500 all contains mesopore, and aperture is main
Concentrate on 3nm.The single-point mesopore Capacity Ratio of 2-500 and 3-500 is larger, and in the case of same holes total capacity, they are had
Middle hole number it is fewer than 1-500 and 4-500.
From table 2 it can also be seen that the specific surface area that 4-500 has is maximum, the specific surface area that 2-500 has is minimum
's；And 1-500 is compared with 3-500, in terms of single-point pore volume and aperture is all smaller, therefore in same holes total pore volume situation
Under, with more middle hole numbers.
The pore structure parameter of the Different treatments absorbent charcoal material of table 2
| Sample | SBET/m2/g | Vtot/cm3/g | WBET/nm |
| 1st batch：1-500 | 289.40 | 0.183 | 2.52 |
| 2nd batch：2-500 | 241.88 | 0.207 | 3.42 |
| 3rd batch：3-500 | 404.20 | 0.260 | 2.57 |
| 4th batch：4-500 | 460.10 | 0.264 | 2.30 |
Embodiment 2
(1) bamboo charcoal after will be pretreated, carries out sol-gel process carried titanium dioxide, and respectively at tube furnace 400
DEG C, 500 DEG C, calcined by temperature programming at 600 DEG C.From XRD spectrum (Fig. 4) it can also be seen that with the rising of calcining heat,
Anatase crystal type gradually tends to improving and sharp, while crystallite dimension also increases rapidly.
(2) catalyst after calcining is carried out the photocatalysis experiment under the same terms, different calcining heats is probed into catalysis
The influence of agent photocatalytic effect.By experiment, can set up and change over time, degraded of the different calcining heats to methylene blue solution
The image of situation (being represented with solution concentration content), such as Fig. 5.
Be can be seen that by Fig. 5,500 DEG C of catalytic performances having of calcining heat are optimal.By experiment, obtaining Fig. 5 can be with
It is obvious to obtain to draw a conclusion：At least there are 2 influences of factor, i.e. crystal formation integrality and crystal grain chi to catalyst in calcining heat
It is very little.For this experiment, the excellent situation of catalyst of the different calcining heats for being drawn is arranged as：4-500>4-600>4-400.
Embodiment 3
(1) methylene blue is configured to the solution of 30mg/L, other experiment conditions are constant；
(2) bamboo charcoal/TiO of different dosages is investigated2(under 500 DEG C of calcination conditions) photochemical catalyst is in different periods to degradation rate
Influence situation.Photochemical catalyst is referred to：DEG C calcining bamboo charcoal/TiO of sample 4-500, i.e., 5002。
Found out by Fig. 6, under identical reaction solution concentration, catalysts are higher in the concentration of solution, adsorption efficiency and
The disposal efficiency is higher.Meanwhile, the degradation efficiency when catalyst charge is 2g/L is essentially 2 times of 1g/L.But now
Continue to increase catalyst reaction concentration, then light degradation effect is not increased with multiple but increase becomes very slow.Therefore in reality
The catalytic amount that 2g/L is added in the methylene blue solution of border 30mg/L is optimal selection, can be degradable in a short time
Methylene blue, it is also possible to largely reduce catalyst amount；Reach the balance of time and economy.
Above-described embodiment is the present invention preferably implementation method, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from Spirit Essence of the invention and the change, modification, replacement made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the photochemical catalyst of the coloured sewage of mesoporous activated carbon/titanium dioxide degradable, it is characterised in that include
Following steps：
(1) pretreatment of activated carbon：
Mesopore activated carbon is taken, is ground, sieving adds deionized water, to carbon dust is flooded；The mixture of activated carbon and water is entered
Row microwave treatment, the sample that will finally process is dried in being put in baking oven, obtains pretreated activated carbon, stand-by；
(2) preparation of sol solutionses：
1. at room temperature by Ti (C4H9O)4In being stirred vigorously down and being slowly dropped to absolute ethyl alcohol and acetic acid, by 15~20min's
Stirring, obtains the solution A of homogeneous transparent；
2. acetic acid is added to stirring in the solution that deionized water and absolute ethyl alcohol are made into, obtains solution B；
3. pretreated activated carbon is added in A liquid in weighing step (1), and is sufficiently stirred for, and obtains turbid solution C；
4. with vigorous stirring, by B liquid with being added drop-wise in C, and continue stirring, obtain sol solutionses；
(3) preparation of photochemical catalyst：
After the sol solutionses that step (2) is obtained are settled into gel, through spontaneously drying, oven drying, calcining obtains mesoporous activated
The photochemical catalyst of the coloured sewage of charcoal/titanium dioxide degradable.
2. the preparation method of the photochemical catalyst of the coloured sewage of mesoporous activated carbon/titanium dioxide degradable according to claim 1,
It is characterized in that：
The mesh number of the sieving described in step (1) is 180~220 mesh；
The time of the microwave treatment described in step (1) is 25~35min；
The specific surface area of the pretreated activated carbon described in step (1) is 404.20~460.10m2/g；Mainly concentrate in aperture
In 2.5~3.5nm.
3. the preparation method of the photochemical catalyst of the coloured sewage of mesoporous activated carbon/titanium dioxide degradable according to claim 1,
It is characterized in that：
Step (2) 1. described in Ti (C4H9O)4, absolute ethyl alcohol and acetic acid volume ratio be (11~13)：(28~32)：(1.5
~2.5)；
Step (2) 2. described in acetic acid, deionized water and absolute ethyl alcohol volume ratio be (2.0~3.0)：(1~3)：(28~
32)。
4. the preparation method of the photochemical catalyst of the coloured sewage of mesoporous activated carbon/titanium dioxide degradable according to claim 1,
It is characterized in that：
Step (2) 3. described in pretreated activated carbon and step (2) 1. in Ti (C4H9O)4Mass volume ratio be
(3.4~3.6) g：(11~13) mL.
5. the preparation method of the photochemical catalyst of the coloured sewage of mesoporous activated carbon/titanium dioxide degradable according to claim 1,
It is characterized in that：
Step (2) 3. described in stirring time be 25~35min；
Step (2) 4. described in stirring time be 100~140min.
6. the preparation method of the photochemical catalyst of the coloured sewage of mesoporous activated carbon/titanium dioxide degradable according to claim 1,
It is characterized in that：
The time of the natural drying described in step (3) is 36~60h；
The condition of the oven drying described in step (3) is 60~70 DEG C of 36~60h of oven drying.
7. the preparation method of the photochemical catalyst of the coloured sewage of mesoporous activated carbon/titanium dioxide degradable according to claim 1,
It is characterized in that：
The temperature of the calcining described in step (3) is 400~600 DEG C.
8. a kind of photochemical catalyst of the coloured sewage of mesoporous activated carbon/titanium dioxide degradable, it is characterised in that：By claim 1
Preparation method described in~7 any one is prepared.
9. the photochemical catalyst of the coloured sewage of mesoporous activated carbon/titanium dioxide degradable described in claim 8 is degraded in coloured sewage
Application in field.
10. application according to claim 9, it is characterised in that comprise the following steps：
Added into the coloured sewage solution of methylene blue with the catalytic amount of 1g/L~3g/L, degraded.
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| CN107570141A (en) * | 2017-10-16 | 2018-01-12 | 河海大学 | A kind of activated carbon supported bismuth tungstate photocatalyst and preparation method and application |
| CN110776110A (en) * | 2019-10-18 | 2020-02-11 | 黑龙江大学 | Method for treating phenolic wastewater by integrated photocatalysis-microorganism-adsorption process |
| CN110817870A (en) * | 2018-08-14 | 2020-02-21 | 北京中科奥水环保工程技术有限公司 | Activated carbon production process based on visible light catalytic regeneration |
| CN112354533A (en) * | 2020-11-02 | 2021-02-12 | 中国石油大学(华东) | Preparation method of biomimetic synthesis active carbon-titanium dioxide composite material |
| CN113680317A (en) * | 2021-08-26 | 2021-11-23 | 中国矿业大学 | Titanium dioxide/coal-based hierarchical pore film foam carbon composite material and preparation method thereof |
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| CN107570141A (en) * | 2017-10-16 | 2018-01-12 | 河海大学 | A kind of activated carbon supported bismuth tungstate photocatalyst and preparation method and application |
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| CN114749198A (en) * | 2021-12-27 | 2022-07-15 | 西北民族大学 | Nano C-TiO2NBSMethod for preparing photocatalyst |
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