CN113145096A - Preparation method of composite photocatalyst for sewage treatment and product thereof - Google Patents
Preparation method of composite photocatalyst for sewage treatment and product thereof Download PDFInfo
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- CN113145096A CN113145096A CN202110482654.2A CN202110482654A CN113145096A CN 113145096 A CN113145096 A CN 113145096A CN 202110482654 A CN202110482654 A CN 202110482654A CN 113145096 A CN113145096 A CN 113145096A
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- powder
- sludge
- activated carbon
- zncl
- butyl titanate
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- 239000002131 composite material Substances 0.000 title claims abstract description 77
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 43
- 239000010865 sewage Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000010802 sludge Substances 0.000 claims abstract description 118
- 239000000843 powder Substances 0.000 claims abstract description 110
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 108
- 238000002156 mixing Methods 0.000 claims abstract description 46
- 239000000203 mixture Substances 0.000 claims abstract description 45
- 239000012190 activator Substances 0.000 claims abstract description 43
- 238000001035 drying Methods 0.000 claims abstract description 43
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 230000003213 activating effect Effects 0.000 claims abstract description 29
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 27
- 238000005406 washing Methods 0.000 claims abstract description 26
- 238000001816 cooling Methods 0.000 claims abstract description 25
- 230000004913 activation Effects 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000000197 pyrolysis Methods 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 11
- 238000003980 solgel method Methods 0.000 claims abstract description 11
- 239000007791 liquid phase Substances 0.000 claims abstract description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 89
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 74
- 239000000243 solution Substances 0.000 claims description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 36
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- 239000011592 zinc chloride Substances 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 15
- 239000001117 sulphuric acid Substances 0.000 claims description 5
- 235000011149 sulphuric acid Nutrition 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 abstract description 12
- 239000000499 gel Substances 0.000 description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 238000010438 heat treatment Methods 0.000 description 20
- 230000032683 aging Effects 0.000 description 12
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 11
- 239000004021 humic acid Substances 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 238000007789 sealing Methods 0.000 description 11
- 239000011240 wet gel Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000013032 photocatalytic reaction Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 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
- 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
-
- 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
- B01J21/18—Carbon
-
- 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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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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 application discloses a preparation method of a composite photocatalyst for sewage treatment and the composite photocatalyst for sewage treatment, which can be formed by preparing sludge activated carbon from municipal sludge and assembling the sludge activated carbon and titanium dioxide into the composite photocatalyst. The method comprises the following steps: 1) taking sludge from a municipal sewage plant, dehydrating, grinding into powder; 2) thoroughly mixing the powder with an activator, wherein the powder and the activator are mixed by ultrasonic mixing for 0.5 to 3 hours in a ratio of 1 to 9ml of the activator per gram of the powder; 3) carrying out pyrolysis activation on the mixture of the powder and an activating agent, cooling, washing and drying to obtain sludge activated carbon; 4) taking the sludgeFully dispersing the activated carbon in a liquid phase containing butyl titanate, and then obtaining activated carbon-TiO with sludge by a sol-gel method2The gel of the composite material is dried and roasted to prepare the sludge-containing activated carbon-TiO2A composite photocatalyst of the composite material.
Description
Technical Field
The invention relates to a photocatalyst for sewage treatment, in particular to a preparation method of a composite photocatalyst for sewage treatment and the composite photocatalyst for sewage treatment.
Background
The photocatalytic reaction is used as a novel environmental pollution treatment technology, strong oxidant free radicals are generated by absorbing light energy through a catalyst, organic molecules are subjected to oxidative decomposition, degradation, removal and mineralization of the organic substances are effectively realized, and the photocatalytic reaction has good resource friendliness and environmental friendliness and wide application prospect, so that the photocatalytic reaction is widely concerned by researchers. Among them, the semiconductor photocatalysis technology is a hot research point at present because of its advantages of stability, non-toxicity, low price, complete degradation and uneasy secondary pollution. Titanium dioxide has outstanding advantages in oxidation ability, photocatalytic activity, stability, price and the like and is in the core position in photochemical research. However, pure titanium dioxide also has the problems of wide forbidden band width and easy recombination of photo-generated electrons to hole pairs, and the photocatalytic performance of the titanium dioxide is limited, so that the problems need to be adjusted and improved, so that the photocatalytic performance of the titanium dioxide is improved, and the application of the titanium dioxide in the field of recontamination treatment is promoted.
On the other hand, the adsorption method is to separate pollutants by using a porous adsorption material, so that the pollutants are enriched on the adsorption material and are effectively removed from the environment, thereby achieving the purpose of purification. The adsorption method is simple to operate, high in efficiency and not easy to produce secondary pollution, and is one of sewage treatment technologies which are widely applied at present. However, the traditional carbon material has the defects of high cost, difficult recovery, difficult degradation of complex organic matters and the like, and further research is needed to find a more efficient adsorbing material. Sludge, which is a by-product of a municipal sewage plant, contains a large amount of organic substances, and thus has a possibility of being a precursor of activated carbon. If the municipal sludge is made into the sludge activated carbon, the treatment of reduction, harmlessness and reclamation of the municipal sludge can be realized, and the environmental protection concepts of waste utilization and waste preparation by waste are practiced.
Before the application date, no composite photocatalyst which is formed by combining sludge of a municipal sewage plant and a titanium dioxide photocatalyst through preparing sludge activated carbon from municipal sludge and assembling the sludge activated carbon and the titanium dioxide has been found.
Disclosure of Invention
The invention provides a preparation method of a composite photocatalyst for sewage treatment and the composite photocatalyst for sewage treatment, which can be used for preparing sludge activated carbon from municipal sludge and assembling the sludge activated carbon and titanium dioxide into the composite photocatalyst, so that the municipal sludge can be efficiently utilized, and the unexpected effect of removing macromolecular organic matters in sewage can be realized.
According to a first aspect of the present invention, there is provided a method for preparing a composite photocatalyst for sewage treatment, the method comprising: 1) taking sludge from a municipal sewage plant, dehydrating, grinding into powder by grinding, and drying for later use; 2) fully mixing the powder with an activating agent, wherein the powder and the activating agent are mixed by ultrasonic wave for 0.5 to 3 hours according to the proportion of adding 1ml to 9ml of the activating agent into each gram of the powder, and the activating agent is ZnCl with the concentration of 2mol/L to 10mol/L2The solution is mixed with 20 to 40 mass percent dilute sulfuric acid solution according to ZnCl2The volume ratio of the solution to the dilute sulphuric acid solution is 1:3 to 9:1, and the relationship between the powder and the activator also includes the use of 0.0005mol to 0.081mol of ZnCl per gram of powder2(ii) a 3) Carrying out pyrolysis activation on the mixture of the powder and an activating agent, cooling, washing and drying to obtain sludge activated carbon; 4) taking the sludge activated carbon, fully dispersing the sludge activated carbon in a liquid phase containing butyl titanate according to the proportion that 14ml to 72 ml of butyl titanate is added into per gram of the sludge activated carbon, and then obtaining the sludge activated carbon-TiO by a sol-gel method2The gel of the composite material is dried and roasted to prepare the sludge-containing activated carbon-TiO2A composite photocatalyst of the composite material.
Optionally, the pyrolysis activation comprises holding the mixture of the powder and the activator at 100 ℃ to 120 ℃ for 24 hours to 60 hours, and then firing at 400 ℃ to 600 ℃ for 0.5 hours to 2 hours.
Optionally, the sol-gel method comprises: slowly dripping butyl titanate into ethanol according to the volume ratio of the butyl titanate to the ethanol of 0.2-0.4, mixing and stirring, dripping hydrochloric acid to adjust the pH value to 2-5.5, and continuously stirring to obtain a mixed solution; then adding the sludge carbon powder into the mixed solution, and continuously stirring; and mixing deionized water and ethanol, stirring, slowly adding the mixture dropwise into the mixed solution, and continuously stirring until the gel is formed.
Preferably, in the step 4), the sludge activated carbon is taken and fully dispersed in a liquid phase containing butyl titanate according to a proportion of adding 15 ml to 30 ml of butyl titanate into each gram of the sludge activated carbon.
Preferably, the relationship between the powder and the activator in step 2) comprises the use of between 0.001 and 0.03mol of ZnCl per gram of powder2(ii) a More preferably, the relationship between the powder and the activator in step 2) comprises the use of between 0.01 and 0.03mol of ZnCl per gram of powder2。
According to a second aspect of the present invention, there is provided a composite photocatalyst for sewage treatment, which is prepared by a method comprising: 1) taking sludge from a municipal sewage plant, dehydrating, grinding into powder by grinding, and drying for later use; 2) fully mixing the powder with an activating agent, wherein the powder and the activating agent are mixed by ultrasonic wave for 0.5 to 3 hours according to the proportion of adding 1ml to 9ml of the activating agent into each gram of the powder, and the activating agent is ZnCl with the concentration of 2mol/L to 10mol/L2The solution is mixed with 20 to 40 mass percent dilute sulfuric acid solution according to ZnCl2The volume ratio of the solution to the dilute sulphuric acid solution is 1:3 to 9:1, and the relationship between the powder and the activator also includes the use of 0.0005mol to 0.081mol of ZnCl per gram of powder2(ii) a 3) Carrying out pyrolysis activation on the mixture of the powder and an activating agent, cooling, washing and drying to obtain sludge activated carbon; 4) taking the sludge activated carbon, fully dispersing the sludge activated carbon in a liquid phase containing butyl titanate according to the proportion of adding 14-72 ml of butyl titanate into each gram of the sludge activated carbon, and then obtaining the sludge by a sol-gel methodActivated carbon-TiO2The gel of the composite material is dried and roasted to prepare the sludge-containing activated carbon-TiO2A composite photocatalyst of the composite material.
Optionally, the pyrolysis activation comprises holding the mixture of the powder and the activator at 100 ℃ to 120 ℃ for 24 hours to 60 hours, and then firing at 400 ℃ to 600 ℃ for 0.5 hours to 2 hours.
Optionally, the sol-gel method comprises: slowly dripping butyl titanate into ethanol according to the volume ratio of the butyl titanate to the ethanol of 0.2-0.4, mixing and stirring, dripping hydrochloric acid to adjust the pH value to 2-5.5, and continuously stirring to obtain a mixed solution; then adding the sludge carbon powder into the mixed solution, and continuously stirring; and mixing deionized water and ethanol, stirring, slowly adding the mixture dropwise into the mixed solution, and continuously stirring until the gel is formed.
Preferably, the sludge activated carbon is fully dispersed in a liquid phase containing butyl titanate according to the proportion of adding 15 ml to 30 ml of butyl titanate into each gram of the sludge activated carbon.
The relation between the powder and the activator in step 2) comprises the use of between 0.001 and 0.03mol of ZnCl per gram of powder2(ii) a More preferably, the relationship between the powder and the activator in step 2) comprises the use of between 0.01 and 0.03mol of ZnCl per gram of powder2。
Experiments show that the removal rate of the composite photocatalyst for sewage treatment on humic acid is obviously superior to that of a pure titanium dioxide photocatalyst under both dark reaction and photocatalysis conditions, and is also close to that of the traditional photocatalyst compounded by activated carbon and titanium dioxide on humic acid.
The present invention will be further described with reference to the following embodiments. Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
The present invention will now be described more fully hereinafter. Those skilled in the art will be able to implement the inventive arrangements based on these teachings. Before the present invention is explained, it is to be noted that:
in the present specification, the technical solutions and the technical features provided in the respective portions including the following description may be combined with each other without conflict.
Reference throughout this specification to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention.
The terms "comprising," "including," "having," and any variations thereof in this specification and claims and in any related parts thereof, are intended to cover non-exclusive inclusions.
The invention provides a preparation method of a composite photocatalyst for sewage treatment, which comprises the following steps:
1) taking sludge of a municipal sewage plant, dehydrating, grinding into powder by grinding, sieving with a 50-200 mesh sieve, and drying the sieved powder for later use;
2) fully mixing the powder with an activating agent, wherein the powder and the activating agent are mixed by ultrasonic wave for 0.5 to 3 hours according to the proportion of adding 1ml to 9ml of the activating agent into each gram of the powder, and the activating agent is ZnCl with the concentration of 2mol/L to 10mol/L2The solution is mixed with 20 to 40 mass percent dilute sulfuric acid solution according to ZnCl2The volume ratio of the solution to the dilute sulphuric acid solution is 1:3 to 9:1, and the relationship between the powder and the activator also includes the use of 0.0005mol to 0.085mol of ZnCl per gram of powder2；
3) Carrying out pyrolysis activation on the mixture of the powder and an activating agent, cooling, washing and drying to obtain sludge activated carbon;
4) taking the sludge activated carbon, and adding 14-72 ml of titanium into each gram of the sludge activated carbonThe butyl acetate is fully dispersed in a liquid phase containing the butyl titanate in proportion, and then activated carbon-TiO with sludge is obtained by a sol-gel method2The gel of the composite material is dried and roasted to prepare the sludge-containing activated carbon-TiO2A composite photocatalyst of the composite material.
In the above process, ZnCl2The oxidation and dehydration reactions of the powder (sludge) can be realized, and elements such as hydrogen, oxygen and the like in the powder (sludge) can be made to escape in the form of water vapor or other gases, so that a rich pore structure is formed, and the powder (sludge) is converted into the adsorptive material with a loose structure. Sulfuric acid is a strong acid, also has oxidation and dehydration effects, and can dehydrate and carbonize functional groups in powder (sludge) during pyrolysis activation, so that carbon bonds are condensed, and sludge activated carbon with developed pores is generated. ZnCl2Is compounded with sulfuric acid to enhance the oxidation and dehydration performance of the zinc chloride single activator.
Furthermore, ZnCl2The formation of tar can be inhibited, but if the dosage is too low, the inhibiting effect is not enough, and the tar substance obviously blocks the pores of the sludge activated carbon; if the amount is too high, the dehydration condensation reaction of the organic substances in the powder (sludge) proceeds excessively, so that the formed pore structure collapses and ZnCl remains2More particles can also reduce the porosity of the sludge activated carbon. While sulfuric acid can be used as an auxiliary agent to promote dehydration, but the dosage of the sulfuric acid cannot be too high, otherwise, the powder (sludge) is easily carbonized, and more ash is generated. Thus, by experiment, the above method determines that 0.0005mol to 0.085mol of ZnCl is to be used per gram of said powder2On the basis of which the solid-to-liquid ratio of the powder to the activator (i.e. 1ml to 9ml of the activator per gram of the powder), ZnCl, is determined2Respective concentrations of the solution and the dilute sulfuric acid solution and ZnCl2The volume ratio of the solution to the dilute sulfuric acid solution is used for ensuring the adsorption performance of the sludge activated carbon.
In addition, the powder is mixed with the activator by ultrasonic waves for 0.5 to 3 hours, and the ultrasonic waves can destroy biological cells in the powder (sludge), thereby releasing a soluble carbon source.
In the above method, the pyrolysis activation may be performed by a process of maintaining the mixture of the powder and the activator at 100 to 120 ℃ for 24 to 60 hours, and then burning the mixture at 400 to 600 ℃ for 0.5 to 2 hours.
In the above method, the sol-gel method may include: slowly dripping butyl titanate into ethanol according to the volume ratio of the butyl titanate to the ethanol of 0.2-0.4, mixing and stirring, dripping hydrochloric acid to adjust the pH value to 2-5.5, and continuously stirring to obtain a mixed solution; then adding the sludge carbon powder into the mixed solution, and continuously stirring; and mixing deionized water and ethanol, stirring, slowly adding the mixture dropwise into the mixed solution, and continuously stirring until the gel is formed.
In the above method, the gel may be dried by aging the gel in a closed environment for 12 to 48 hours and then drying the gel in an oven. The gel may be calcined at 400 to 600 ℃ for 1 to 3 hours under a nitrogen atmosphere.
Examples
Example 1
The sludge taken from a sludge plant is crushed and ground into powder, and the powder is sieved by a 100-mesh sieve and dried for later use. 2mol/L of ZnCl2And mixing the solution with concentrated sulfuric acid with the mass fraction of 20% according to the volume ratio of 1:3 to obtain the composite activator. The powder and the obtained composite activator are mixed according to the mass ratio: mixing at a volume of 1g to 1ml, stirring, performing ultrasonic treatment for 1h, maintaining the temperature in an oven at 100 ℃ for 24h, activating, burning at 500 ℃ for 1h in a tube furnace, cooling, repeatedly washing with hot water to neutrality, and drying. Calculated 0.0005mol of ZnCl is used per gram of said powder2。
Slowly dripping 3mL of butyl titanate into 14mL of ethanol, mixing and stirring at the rotating speed of 400rpm for 0.25h, dripping hydrochloric acid to adjust the pH value of the solution to be about 4, and continuously stirring for 0.2 h; 0.1g of sludge activated carbon is added into the solution, and the stirring is continued for 0.2 h. 3mL of deionized water and 3mL of ethanol were mixed with stirring, slowly added dropwise to the above solution, and stirring was continued until a gel was formed and then stopped. Mixing the wet gelAnd (3) sealing and aging for 12h, and drying in a 100-DEG C oven for 12h to obtain xerogel. Placing the xerogel in a tubular furnace, heating to 400 ℃ at a heating rate of 1 ℃/min under the condition of continuously introducing nitrogen, keeping for 3h, and then cooling to room temperature to obtain the sludge-containing activated carbon-TiO2And taking out the composite photocatalyst of the composite material, washing with water and drying for later use.
Example 2
The sludge taken from a sludge plant is crushed and ground into powder, and the powder is sieved by a 100-mesh sieve and dried for later use. Adding 5mol/L ZnCl2And mixing the solution with concentrated sulfuric acid with the mass fraction of 30% according to the volume ratio of 3:1 to obtain the composite activator. The powder and the obtained composite activator are mixed according to the mass ratio: mixing the materials in a volume of 1g to 4ml, stirring uniformly, performing ultrasonic treatment for 1h, keeping the temperature of the mixture in a 100 ℃ oven for 24h, putting the mixture into a tubular furnace after activation, burning the mixture for 1h at 500 ℃, cooling, repeatedly washing the mixture with hot water to be neutral, and drying the mixture for later use. Calculated, about 0.0015mol of ZnCl is used per gram of said powder2。
Slowly dripping 3mL of butyl titanate into 14mL of ethanol, mixing and stirring at the rotating speed of 400rpm for 0.25h, dripping hydrochloric acid to adjust the pH value of the solution to be about 4, and continuously stirring for 0.2 h; 0.1g of sludge activated carbon is added into the solution, and the stirring is continued for 0.2 h. 3mL of deionized water and 3mL of ethanol were mixed with stirring, slowly added dropwise to the above solution, and stirring was continued until a gel was formed and then stopped. And (3) sealing and aging the wet gel for 12h, and drying in a 100-DEG oven for 12h to obtain dry gel. Placing the xerogel in a tubular furnace, heating to 400 ℃ at a heating rate of 1 ℃/min under the condition of continuously introducing nitrogen, keeping for 3h, and then cooling to room temperature to obtain the sludge-containing activated carbon-TiO2And taking out the composite photocatalyst of the composite material, washing with water and drying for later use.
Example 3
The sludge taken from a sludge plant is crushed and ground into powder, and the powder is sieved by a 100-mesh sieve and dried for later use. Adding 10mol/L ZnCl2And mixing the solution with concentrated sulfuric acid with the mass fraction of 40% according to the volume ratio of 9:1 to obtain the composite activator. The powder and the obtained composite activator are mixed according to the mass ratio: volume ratio of 1g to 8mlMixing, stirring, ultrasonic treating for 1 hr, maintaining in 100 deg.C oven for 24 hr, activating, burning at 500 deg.C for 1 hr, cooling, washing with hot water to neutrality, and drying. It was calculated that about 0.072mol of ZnCl was used per gram of said powder2。
Slowly dripping 3mL of butyl titanate into 14mL of ethanol, mixing and stirring at the rotating speed of 400rpm for 0.25h, dripping hydrochloric acid to adjust the pH value of the solution to be about 4, and continuously stirring for 0.2 h; 0.1g of sludge activated carbon is added into the solution, and the stirring is continued for 0.2 h. 3mL of deionized water and 3mL of ethanol were mixed with stirring, slowly added dropwise to the above solution, and stirring was continued until a gel was formed and then stopped. And (3) sealing and aging the wet gel for 12h, and drying in a 100-DEG oven for 12h to obtain dry gel. Placing the xerogel in a tubular furnace, heating to 400 ℃ at a heating rate of 1 ℃/min under the condition of continuously introducing nitrogen, keeping for 3h, and then cooling to room temperature to obtain the sludge-containing activated carbon-TiO2And taking out the composite photocatalyst of the composite material, washing with water and drying for later use.
Example 4
The sludge taken from a sludge plant is crushed and ground into powder, and the powder is sieved by a 100-mesh sieve and dried for later use. 3mol/L of ZnCl2And mixing the solution with concentrated sulfuric acid with the mass fraction of 25% according to the volume ratio of 1:3 to obtain the composite activator. The powder and the obtained composite activator are mixed according to the mass ratio: mixing the raw materials in a volume of 1g to 1ml, stirring uniformly, performing ultrasonic treatment for 1h, keeping the temperature of the mixture in a 100 ℃ oven for 24h, putting the mixture into a tubular furnace after activation, burning the mixture for 1h at 500 ℃, cooling, repeatedly washing the mixture with hot water to be neutral, and drying the mixture for later use. Calculated, about 0.00075mol of ZnCl is used per gram of said powder2。
Slowly dripping 3mL of butyl titanate into 14mL of ethanol, mixing and stirring at the rotating speed of 400rpm for 0.25h, dripping hydrochloric acid to adjust the pH value of the solution to be about 4, and continuously stirring for 0.2 h; 0.1g of sludge activated carbon is added into the solution, and the stirring is continued for 0.2 h. 3mL of deionized water and 3mL of ethanol were mixed with stirring, slowly added dropwise to the above solution, and stirring was continued until a gel was formed and then stopped. And (3) sealing and aging the wet gel for 12h, and drying in a 100-DEG oven for 12h to obtain dry gel. Will be provided withThe dried gel is placed in a tubular furnace, is heated to 400 ℃ at the heating rate of 1 ℃/min under the condition of continuously introducing nitrogen, is kept for 3 hours, and is cooled to room temperature to obtain the sludge-containing activated carbon-TiO2And taking out the composite photocatalyst of the composite material, washing with water and drying for later use.
Example 5
The sludge taken from a sludge plant is crushed and ground into powder, and the powder is sieved by a 100-mesh sieve and dried for later use. 2mol/L of ZnCl2And mixing the solution with concentrated sulfuric acid with the mass fraction of 25% according to the volume ratio of 1:1 to obtain the composite activator. The powder and the obtained composite activator are mixed according to the mass ratio: mixing the raw materials in a volume of 1g to 1ml, stirring uniformly, performing ultrasonic treatment for 1h, keeping the temperature of the mixture in a 100 ℃ oven for 24h, putting the mixture into a tubular furnace after activation, burning the mixture for 1h at 500 ℃, cooling, repeatedly washing the mixture with hot water to be neutral, and drying the mixture for later use. Calculated, about 0.001mol of ZnCl is used per gram of said powder2。
Slowly dripping 3mL of butyl titanate into 14mL of ethanol, mixing and stirring at the rotating speed of 400rpm for 0.25h, dripping hydrochloric acid to adjust the pH value of the solution to be about 4, and continuously stirring for 0.2 h; 0.1g of sludge activated carbon is added into the solution, and the stirring is continued for 0.2 h. 3mL of deionized water and 3mL of ethanol were mixed with stirring, slowly added dropwise to the above solution, and stirring was continued until a gel was formed and then stopped. And (3) sealing and aging the wet gel for 12h, and drying in a 100-DEG oven for 12h to obtain dry gel. Placing the xerogel in a tubular furnace, heating to 400 ℃ at a heating rate of 1 ℃/min under the condition of continuously introducing nitrogen, keeping for 3h, and then cooling to room temperature to obtain the sludge-containing activated carbon-TiO2And taking out the composite photocatalyst of the composite material, washing with water and drying for later use.
Example 6
The sludge taken from a sludge plant is crushed and ground into powder, and the powder is sieved by a 100-mesh sieve and dried for later use. 4mol/L of ZnCl2And mixing the solution with concentrated sulfuric acid with the mass fraction of 30% according to the volume ratio of 4:1 to obtain the composite activator. The powder and the obtained composite activator are mixed according to the mass ratio: mixing at a volume of 1g to 8ml, stirring, ultrasonic treating for 1 hr, maintaining in 100 deg.C oven for 24 hr, and activatingThen putting the mixture into a tube furnace to be burned for 1h at 500 ℃, repeatedly washing the mixture with hot water to be neutral after cooling, and drying the mixture for later use. Calculated, about 0.0256mol of ZnCl is used per gram of said powder2。
Slowly dripping 3mL of butyl titanate into 14mL of ethanol, mixing and stirring at the rotating speed of 400rpm for 0.25h, dripping hydrochloric acid to adjust the pH value of the solution to be about 4, and continuously stirring for 0.2 h; 0.1g of sludge activated carbon is added into the solution, and the stirring is continued for 0.2 h. 3mL of deionized water and 3mL of ethanol were mixed with stirring, slowly added dropwise to the above solution, and stirring was continued until a gel was formed and then stopped. And (3) sealing and aging the wet gel for 12h, and drying in a 100-DEG oven for 12h to obtain dry gel. Placing the xerogel in a tubular furnace, heating to 400 ℃ at a heating rate of 1 ℃/min under the condition of continuously introducing nitrogen, keeping for 3h, and then cooling to room temperature to obtain the sludge-containing activated carbon-TiO2And taking out the composite photocatalyst of the composite material, washing with water and drying for later use.
Example 7
The sludge taken from a sludge plant is crushed and ground into powder, and the powder is sieved by a 100-mesh sieve and dried for later use. Adding 10mol/L ZnCl2The solution and concentrated sulfuric acid with the mass fraction of 40% are mixed according to the weight ratio of 9:1 to obtain the composite activator. The powder and the obtained composite activator are mixed according to the mass ratio: mixing the materials in a volume of 1g to 9ml, stirring uniformly, carrying out ultrasonic treatment for 1h, keeping the temperature of the mixture in a 100 ℃ oven for 24h, putting the mixture into a tubular furnace after activation, burning the mixture for 1h at 500 ℃, cooling, repeatedly washing the mixture with hot water to be neutral, and drying the mixture for later use. Calculated, about 0.081mol ZnCl is used per gram of said powder2。
Slowly dripping 3mL of butyl titanate into 14mL of ethanol, mixing and stirring at the rotating speed of 400rpm for 0.25h, dripping hydrochloric acid to adjust the pH value of the solution to be about 4, and continuously stirring for 0.2 h; 0.1g of sludge activated carbon is added into the solution, and the stirring is continued for 0.2 h. 3mL of deionized water and 3mL of ethanol were mixed with stirring, slowly added dropwise to the above solution, and stirring was continued until a gel was formed and then stopped. And (3) sealing and aging the wet gel for 12h, and drying in a 100-DEG oven for 12h to obtain dry gel. The xerogel is placed in a tubular furnace and is continuously aerated with nitrogen at 1 DEG CHeating to 400 ℃ at a heating rate of/min, keeping for 3h, and then cooling to room temperature to obtain activated carbon-TiO containing sludge2And taking out the composite photocatalyst of the composite material, washing with water and drying for later use.
Example 8
The sludge taken from a sludge plant is crushed and ground into powder, and the powder is sieved by a 100-mesh sieve and dried for later use. Adding 5mol/L ZnCl2And mixing the solution with concentrated sulfuric acid with the mass fraction of 30% according to the volume ratio of 3:1 to obtain the composite activator. The powder and the obtained composite activator are mixed according to the mass ratio: mixing the materials in a volume of 1g to 4ml, stirring uniformly, performing ultrasonic treatment for 1h, keeping the temperature of the mixture in a 100 ℃ oven for 24h, putting the mixture into a tubular furnace after activation, burning the mixture for 1h at 500 ℃, cooling, repeatedly washing the mixture with hot water to be neutral, and drying the mixture for later use. Calculated, about 0.015mol of ZnCl is used per gram of said powder2。
Slowly dripping 6mL of butyl titanate into 22mL of ethanol, mixing and stirring at the rotating speed of 400rpm for 1h, dripping hydrochloric acid to adjust the pH value of the solution to be about 4, and continuously stirring for 0.2 h; 0.4g of sludge activated carbon is added into the solution, and the stirring is continued for 0.2 h. 5mL of deionized water and 6mL of ethanol were mixed with stirring, slowly added dropwise to the above solution, and stirring was continued until a gel was formed and then stopped. And (3) sealing and aging the wet gel for 12h, and drying in a 100-DEG oven for 12h to obtain dry gel. Placing the xerogel in a tubular furnace, heating to 400 ℃ at the heating rate of 1 ℃/min under the condition of continuously introducing nitrogen, keeping for 3h, and then cooling to room temperature to obtain the sludge-containing activated carbon-TiO2And taking out the composite photocatalyst of the composite material, washing with water and drying for later use.
Example 9
The sludge taken from a sludge plant is crushed and ground into powder, and the powder is sieved by a 100-mesh sieve and dried for later use. Adding 5mol/L ZnCl2And mixing the solution with concentrated sulfuric acid with the mass fraction of 30% according to the volume ratio of 3:1 to obtain the composite activator. The powder and the obtained composite activator are mixed according to the mass ratio: mixing at a volume of 1g:4ml, stirring, ultrasonic treating for 1 hr, maintaining in 100 deg.C oven for 24 hr, activating, burning at 500 deg.C for 1 hr, cooling, and repeatedly washing with hot water until the temperature is reachedAnd (5) neutralizing and drying for later use. Calculated, about 0.015mol of ZnCl is used per gram of said powder2。
Slowly dripping 6mL of butyl titanate into 22mL of ethanol, mixing and stirring at the rotating speed of 400rpm for 1h, dripping hydrochloric acid to adjust the pH value of the solution to be about 4, and continuously stirring for 0.2 h; 0.15g of sludge activated carbon is added into the solution, and the stirring is continued for 0.2 h. 5mL of deionized water and 6mL of ethanol were mixed with stirring, slowly added dropwise to the above solution, and stirring was continued until a gel was formed and then stopped. And (3) sealing and aging the wet gel for 12h, and drying in a 100-DEG oven for 12h to obtain dry gel. Placing the xerogel in a tubular furnace, heating to 400 ℃ at the heating rate of 1 ℃/min under the condition of continuously introducing nitrogen, keeping for 3h, and then cooling to room temperature to obtain the sludge-containing activated carbon-TiO2And taking out the composite photocatalyst of the composite material, washing with water and drying for later use.
Comparative example
Comparative example 1
The titanium dioxide photocatalyst was prepared using a sol-gel method. Slowly dripping 3mL of butyl titanate into 14mL of ethanol, mixing and stirring at the rotating speed of 400rpm for 0.25h, dripping hydrochloric acid to adjust the pH value of the solution to be about 4, and continuously stirring for 0.2 h; 3mL of deionized water and 3mL of ethanol were mixed with stirring, slowly added dropwise to the above solution, and stirring was continued until a gel was formed and then stopped. And (3) sealing and aging the wet gel for 12h, and drying in a 100-DEG oven for 12h to obtain dry gel. Placing the xerogel in a tubular furnace, heating to 400 ℃ at the heating rate of 1 ℃/min under the condition of continuously introducing nitrogen, keeping for 3h, and then cooling to room temperature to obtain TiO2And taking out the photocatalyst, washing with water and drying for later use.
Comparative example 2
74 μm (200 mesh) of powdered activated carbon was taken and analytically pure. Then, slowly dripping 3mL of butyl titanate into 14mL of ethanol, mixing and stirring at the rotating speed of 400rpm for 0.25h, dripping hydrochloric acid to adjust the pH value of the solution to be about 4, and continuously stirring for 0.2 h; 0.1g of powdered activated carbon was added to the solution and stirring was continued for 0.2 h. Mixing 3mL of deionized water with 3mL of ethanol under stirring, slowly adding dropwise into the above solution, and stirring until gel is formedAnd (4) stirring. And (3) sealing and aging the wet gel for 12h, and drying in a 100-DEG oven for 12h to obtain dry gel. Placing the xerogel in a tubular furnace, heating to 400 ℃ at a heating rate of 1 ℃/min under the condition of continuously introducing nitrogen, keeping for 3h, and then cooling to room temperature to obtain the sludge-containing activated carbon-TiO2And taking out the composite photocatalyst of the composite material, washing with water and drying for later use.
Effect of the experiment
I. Experimental methods
The samples obtained in examples 1-9 and comparative examples 1-2 were used as sewage treatment agents for comparison of the removal effect of actual wastewater pollutants.
Taking 11 parts of humic acid solution with each concentration of 10mg/L as a treatment object, respectively adding 1g/L of samples obtained in examples 1-9 and comparative examples 1-2 at room temperature, respectively carrying out oscillation reaction under the conditions of light shielding and simulated sunlight, taking supernate after 2 hours of reaction, filtering, determining the concentration of humic acid, and calculating the removal rate of humic acid according to the concentration of humic acid in the supernate and the initial concentration (namely 10 mg/L).
For convenient comparison, the removal rate of humic acid measured under the dark condition was graded: the grade A + was defined when the removal rate was 35% (containing) to 40% (containing), the grade A was defined when the removal rate was 30% (containing) to 35% (containing), the grade B was defined when the removal rate was 25% (containing) to 30% (containing) (27.5% or more of the grade B + and 27.5% or less of the grade B-were defined), the grade C was defined when the removal rate was 20% (containing) to 25% (containing), and the grade D was defined when the removal rate was 15% (containing) to 20% (containing).
For convenient comparison, the removal rate of humic acid measured under the condition of simulated sunlight is graded: the grade A + was defined when the removal rate was 40% (containing) to 45% (containing), the grade A was defined when the removal rate was 35% (containing) to 40% (containing), the grade B was defined when the removal rate was 30% (containing) to 35% (containing) (32.5% or more of the grade B + and 32.5% or less of the grade B-were defined), the grade C was defined when the removal rate was 25% (containing) to 30% (containing), and the grade D was defined when the removal rate was 20% (containing) to 25% (containing).
Comparison of Experimental results
The experimental results are shown in table 1.
TABLE 1
As shown in Table 1, the removal rate of humic acid was significantly improved in examples 1 to 9 as compared with comparative example 1. Example 8 has a humic acid removal rate equivalent to that of comparative example 2, but example 8 is superior to comparative example 2 in that the raw material of example 8 is sludge from a sludge plant. The other examples have the advantages that the removal rate of humic acid reaches at least B grade, and the raw materials of the examples are sludge of a sludge plant, so the cost is high.
The contents of the present invention have been explained above. Those skilled in the art will be able to implement the invention based on these teachings. All other embodiments, which can be derived by a person skilled in the art from the description above without inventive step, shall fall within the scope of protection of the present invention.
Claims (10)
1. A preparation method of a composite photocatalyst for sewage treatment is characterized by comprising the following steps: 1) taking sludge of a municipal sewage plant, dehydrating, grinding into powder by grinding, sieving with a 50-200 mesh sieve, and drying the sieved powder for later use; 2) fully mixing the powder with an activating agent, wherein the powder and the activating agent are mixed by ultrasonic wave for 0.5 to 3 hours according to the proportion of adding 1ml to 9ml of the activating agent into each gram of the powder, and the activating agent is ZnCl with the concentration of 2mol/L to 10mol/L2The solution is mixed with 20 to 40 mass percent dilute sulfuric acid solution according to ZnCl2The volume ratio of the solution to the dilute sulphuric acid solution is 1:3 to 9:1, and the relationship between the powder and the activator also includes the use of 0.0005mol to 0.081mol of ZnCl per gram of powder2(ii) a 3) Carrying out pyrolysis activation on the mixture of the powder and an activating agent, cooling, washing and drying to obtain sludge activated carbon; 4) taking the sludge activated carbon, and fully dispersing the sludge activated carbon in butyl titanate-containing according to the proportion of adding 14ml to 72 ml of butyl titanate into per gram of the sludge activated carbonThen obtaining the sludge activated carbon-TiO by a sol-gel method2The gel of the composite material is dried and roasted to prepare the sludge-containing activated carbon-TiO2A composite photocatalyst of the composite material.
2. The method of claim 1, wherein: the pyrolysis activation comprises keeping the mixture of the powder and the activator at 100-120 ℃ for 24-60 hours, and then burning at 400-600 ℃ for 0.5-2 hours.
3. The method of claim 1, wherein the sol-gel process comprises: slowly dripping butyl titanate into ethanol according to the volume ratio of the butyl titanate to the ethanol of 0.2-0.4, mixing and stirring, dripping hydrochloric acid to adjust the pH value to 2-5.5, and continuously stirring to obtain a mixed solution; then adding the sludge carbon powder into the mixed solution, and continuously stirring; and mixing deionized water and ethanol, stirring, slowly adding the mixture dropwise into the mixed solution, and continuously stirring until the gel is formed.
4. The method of claim 1, 2 or 3, wherein: in the step 4), the sludge activated carbon is fully dispersed in a liquid phase containing butyl titanate according to the proportion that 15 ml to 30 ml of butyl titanate is added into each gram of the sludge activated carbon.
5. The method of claim 1, 2 or 3, wherein: the relation between the powder and the activator in step 2) comprises the use of between 0.001 and 0.03mol of ZnCl per gram of powder2(ii) a More preferably, the relationship between the powder and the activator in step 2) comprises the use of between 0.01 and 0.03mol of ZnCl per gram of powder2。
6. The composite photocatalyst for sewage treatment is characterized by being prepared by the following methodThe method comprises the following steps: 1) taking sludge from a municipal sewage plant, dehydrating, grinding into powder by grinding, and drying for later use; 2) fully mixing the powder with an activating agent, wherein the powder and the activating agent are mixed by ultrasonic wave for 0.5 to 3 hours according to the proportion of adding 1ml to 9ml of the activating agent into each gram of the powder, and the activating agent is ZnCl with the concentration of 2mol/L to 10mol/L2The solution is mixed with 20 to 40 mass percent dilute sulfuric acid solution according to ZnCl2The volume ratio of the solution to the dilute sulphuric acid solution is 1:3 to 9:1, and the relationship between the powder and the activator also includes the use of 0.0005mol to 0.081mol of ZnCl per gram of powder2(ii) a 3) Carrying out pyrolysis activation on the mixture of the powder and an activating agent, cooling, washing and drying to obtain sludge activated carbon; 4) taking the sludge activated carbon, fully dispersing the sludge activated carbon in a liquid phase containing butyl titanate according to the proportion that 14ml to 72 ml of butyl titanate is added into per gram of the sludge activated carbon, and then obtaining the sludge activated carbon-TiO by a sol-gel method2The gel of the composite material is dried and roasted to prepare the sludge-containing activated carbon-TiO2A composite photocatalyst of the composite material.
7. The composite photocatalyst of claim 6, wherein: the pyrolysis activation comprises keeping the mixture of the powder and the activator at 100-120 ℃ for 24-60 hours, and then burning at 400-600 ℃ for 0.5-2 hours.
8. The composite photocatalyst of claim 6, wherein the sol-gel process comprises: slowly dripping butyl titanate into ethanol according to the volume ratio of the butyl titanate to the ethanol of 0.2-0.4, mixing and stirring, dripping hydrochloric acid to adjust the pH value to 2-5.5, and continuously stirring to obtain a mixed solution; then adding the sludge carbon powder into the mixed solution, and continuously stirring; and mixing deionized water and ethanol, stirring, slowly adding the mixture dropwise into the mixed solution, and continuously stirring until the gel is formed.
9. The composite photocatalyst of claim 6, 7 or 8, wherein: and (3) fully dispersing the sludge activated carbon into a liquid phase containing butyl titanate according to the proportion that 15 ml to 30 ml of butyl titanate is added into each gram of the sludge activated carbon.
10. The composite photocatalyst of claim 6, 7 or 8, wherein: the relation between the powder and the activator in step 2) comprises the use of between 0.001 and 0.03mol of ZnCl per gram of powder2(ii) a More preferably, the relationship between the powder and the activator in step 2) comprises the use of between 0.01 and 0.03mol of ZnCl per gram of powder2。
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|---|---|---|---|---|
| CN113828392A (en) * | 2021-09-22 | 2021-12-24 | 江苏京源环保股份有限公司 | Integrated production device of composite magnetic medium for water treatment and use method thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000237770A (en) * | 1999-02-17 | 2000-09-05 | Ebara Corp | Purifying method for water by powdery activated carbon and photocatalyst |
| JP2008055372A (en) * | 2006-09-01 | 2008-03-13 | Japan Science & Technology Agency | Water cleaning agent and its manufacturing method |
| WO2008076082A1 (en) * | 2006-12-20 | 2008-06-26 | Nanyang Technological University | Microspheric tio2 photocatalyst |
| CN101574652A (en) * | 2009-06-12 | 2009-11-11 | 长沙理工大学 | Loaded photo-catalyst and preparation method and use thereof |
| CN102021676A (en) * | 2010-11-11 | 2011-04-20 | 东华大学 | Preparation method of titanium dioxide/active carbon composite nanofibrous membrane |
| CN105032388A (en) * | 2015-07-21 | 2015-11-11 | 河北科技大学 | Sludge activated carbon-loaded TiO2 complex photocatalyst and application thereof |
| CN105195093A (en) * | 2015-10-21 | 2015-12-30 | 四川大学 | Modified walnut shell active carbon adsorbent and preparation method thereof |
| CN105817201A (en) * | 2016-05-20 | 2016-08-03 | 张能力 | Method for preparing acetic acid activation sludge-based adsorbent |
| CN106140087A (en) * | 2016-07-22 | 2016-11-23 | 四川大学 | A kind of sludge activity carbon adsorbent for sewage dephosphorization and preparation method thereof |
| CN106345411A (en) * | 2016-09-30 | 2017-01-25 | 东莞市联洲知识产权运营管理有限公司 | Rare metal-based sludge activated carbon and application thereof in removal of sulfur, ammonia and phosphorus |
-
2021
- 2021-04-30 CN CN202110482654.2A patent/CN113145096A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000237770A (en) * | 1999-02-17 | 2000-09-05 | Ebara Corp | Purifying method for water by powdery activated carbon and photocatalyst |
| JP2008055372A (en) * | 2006-09-01 | 2008-03-13 | Japan Science & Technology Agency | Water cleaning agent and its manufacturing method |
| WO2008076082A1 (en) * | 2006-12-20 | 2008-06-26 | Nanyang Technological University | Microspheric tio2 photocatalyst |
| CN101574652A (en) * | 2009-06-12 | 2009-11-11 | 长沙理工大学 | Loaded photo-catalyst and preparation method and use thereof |
| CN102021676A (en) * | 2010-11-11 | 2011-04-20 | 东华大学 | Preparation method of titanium dioxide/active carbon composite nanofibrous membrane |
| CN105032388A (en) * | 2015-07-21 | 2015-11-11 | 河北科技大学 | Sludge activated carbon-loaded TiO2 complex photocatalyst and application thereof |
| CN105195093A (en) * | 2015-10-21 | 2015-12-30 | 四川大学 | Modified walnut shell active carbon adsorbent and preparation method thereof |
| CN105817201A (en) * | 2016-05-20 | 2016-08-03 | 张能力 | Method for preparing acetic acid activation sludge-based adsorbent |
| CN106140087A (en) * | 2016-07-22 | 2016-11-23 | 四川大学 | A kind of sludge activity carbon adsorbent for sewage dephosphorization and preparation method thereof |
| CN106345411A (en) * | 2016-09-30 | 2017-01-25 | 东莞市联洲知识产权运营管理有限公司 | Rare metal-based sludge activated carbon and application thereof in removal of sulfur, ammonia and phosphorus |
Non-Patent Citations (3)
| Title |
|---|
| SHON HK ET AL.: "titania produced from Ti-salt flocculated sludge: photocatalytic activity under solar light", 《JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY》 * |
| 李梦红: "氯化锌硫酸复配制备污泥活性炭及其表征", 《非金属矿》 * |
| 柳欢欢: "活性炭负载TiO2光催化剂的制备及光催化性能的研究", 《安全与环境学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113828392A (en) * | 2021-09-22 | 2021-12-24 | 江苏京源环保股份有限公司 | Integrated production device of composite magnetic medium for water treatment and use method thereof |
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