CN113522264B - Sludge ash modified titanium oxide-biochar composite photocatalyst and preparation method and application thereof - Google Patents
Sludge ash modified titanium oxide-biochar composite photocatalyst and preparation method and application thereof Download PDFInfo
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- CN113522264B CN113522264B CN202110911748.7A CN202110911748A CN113522264B CN 113522264 B CN113522264 B CN 113522264B CN 202110911748 A CN202110911748 A CN 202110911748A CN 113522264 B CN113522264 B CN 113522264B
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- 239000010802 sludge Substances 0.000 title claims abstract description 89
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 47
- 150000003608 titanium Chemical class 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002028 Biomass Substances 0.000 claims abstract description 20
- 238000001354 calcination Methods 0.000 claims description 19
- 238000000227 grinding Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 230000001105 regulatory effect Effects 0.000 claims description 9
- 239000010902 straw Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000002023 wood Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 150000002506 iron compounds Chemical class 0.000 claims description 3
- -1 phosphorus compound Chemical class 0.000 claims description 2
- 239000002910 solid waste Substances 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract description 2
- 239000002956 ash Substances 0.000 description 48
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 34
- 229910021529 ammonia Inorganic materials 0.000 description 15
- 230000001699 photocatalysis Effects 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003344 environmental pollutant Substances 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 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
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8634—Ammonia
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of photocatalysts, in particular to a sludge ash modified titanium oxide-biochar composite photocatalyst, a preparation method and application thereof, wherein the composite photocatalyst comprises titanium oxide, sludge ash and porous biochar, wherein the porous biochar is used as a carrier, and the titanium oxide and the sludge ash are loaded on the porous biochar; the composite photocatalyst comprises 20-30 wt% of titanium oxide, 10-15 wt% of sludge ash and the balance of porous biochar based on the total amount of the composite photocatalyst; the main gain components of the sludge ash modified titanium oxide-biochar composite photocatalyst provided by the invention are both from incineration ash of byproduct sludge of a sewage treatment plant and lignocellulose biomass, belong to the recycling utilization of solid wastes, effectively reduce the production cost of the composite photocatalyst, and have wide market application prospects.
Description
Technical Field
The invention relates to the fields of photocatalyst technology and solid waste resource utilization, in particular to a sludge ash modified titanium oxide-biochar composite photocatalyst and a preparation method and application thereof.
Background
Along with the continuous development of social economy, environmental protection consciousness of the whole society is continuously improved, and how to solve various environmental pollution brought by the economic development becomes a difficult problem to be solved urgently. The photocatalysis technology is an environmental pollution treatment technology which utilizes a photocatalysis material to perform oxidation-reduction reaction with pollutants under the ultraviolet/visible light illumination condition to degrade the pollutants into carbon dioxide, water and some simple micromolecular substances. The photocatalysis technology has the advantages of low cost, strong adaptability, and no toxicity and pollution of the product. The photocatalytic material is the core of the photocatalytic technology, and the nano titanium dioxide is a photocatalytic material widely applied in commercialization and has the advantages of good chemical stability, no toxicity, no harm, recycling and low cost. However, titanium dioxide has some defects in catalyzing and degrading sludge drying odor, such as the titanium dioxide only can play a catalytic role under the condition of ultraviolet irradiation, and the titanium dioxide has low pollutant adsorption capacity and low degradation efficiency. Therefore, how to improve the efficiency of photocatalytic degradation of the sludge drying odor by the titanium dioxide is particularly critical to the degradation efficiency of ammonia which is a main component of the sludge drying odor.
At present, in the prior art, titanium dioxide is mainly loaded on a plurality of porous carriers, such as active carbon, molecular sieve and the like, and the photocatalysis efficiency of the titanium dioxide is improved by improving the adsorption efficiency of pollutants. However, porous carriers such as activated carbon tend to be expensive, resulting in increased costs. Although some patent technologies use solid waste as a carrier, such as fly ash and biochar, the patent technologies still only use the porosity of the carrier to improve the pollutant adsorption capacity, and the improvement of the photocatalytic performance of the titanium oxide base is not obvious.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a sludge ash modified titanium oxide-biochar composite photocatalyst which has the advantages of low cost, high pollutant adsorption efficiency, and high degradation efficiency of ammonia gas which is a main component of sludge drying odor.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
the sludge ash modified titanium oxide-biochar composite photocatalyst comprises titanium oxide, sludge ash and porous biochar, wherein the porous biochar is used as a carrier, and the titanium oxide and the sludge ash are loaded on the porous biochar;
the composite photocatalyst comprises 20-30 wt% of titanium oxide, 10-15 wt% of sludge ash and the balance of porous biochar based on the total amount of the composite photocatalyst.
The invention also provides a preparation method of the sludge ash modified titanium oxide-biochar composite photocatalyst, which comprises the following steps:
(1) Grinding and sieving biomass for later use;
calcining municipal sludge, and grinding to obtain sludge ash for later use;
(2) Uniformly mixing biomass, sludge ash and titanium oxide, grinding, adding a dilute hydrochloric acid solution, regulating the pH value to 1-2, stirring and mixing for 30min, regulating the pH value to be neutral, and filtering to obtain a mixed solid;
(3) And (3) placing the mixed solid obtained in the step (2) into a vacuum furnace for calcination treatment, wherein the obtained solid product is the sludge ash modified titanium oxide-biochar composite photocatalyst.
In a further technical scheme, in the step (1), the biomass is ground and then is screened by a 20-30-mesh sieve.
In a further technical scheme, in the step (1), the biomass is selected from one or more than one composition of straw, rice straw and wood dust.
In a further technical scheme, in the step (1), the municipal sludge is calcined for 5 hours in an air atmosphere at 800 ℃, taken out after being cooled to room temperature, and ground to obtain sludge ash;
the mass fraction of the phosphorus compound and the iron compound in the sludge ash is more than or equal to 20 percent.
In a further technical scheme, in the step (2), the weight ratio of the biomass to the sludge ash to the titanium oxide is 1: (0.15-0.2): (0.2-0.3);
the concentration of the dilute hydrochloric acid solution is 1mol/L, and the addition amount of the dilute hydrochloric acid solution is 200mL.
In a further technical scheme, in the step (3), the conditions of the calcination treatment at least meet the following conditions: the calcination temperature is 400-600 ℃ and the calcination time is 0.5-1.5 hours.
Compared with the prior art, the invention has the following technical effects:
1. the main gain components of the sludge ash modified titanium oxide-biochar composite photocatalyst provided by the invention are both from incineration ash of byproduct sludge of a sewage treatment plant and lignocellulose biomass, belong to the recycling utilization of solid wastes, effectively reduce the production cost of the composite photocatalyst, and have wide market application prospects;
2. the sludge ash modified titanium oxide-biochar composite photocatalyst provided by the invention can effectively utilize visible light, and expands the application range of titanium oxide-based photocatalytic materials;
3. the sludge ash modified titanium oxide-biochar composite photocatalyst provided by the invention has stronger acidity, and is beneficial to degradation of ammonia gas which is a main component of biologically drying malodorous gas;
4. the preparation method of the sludge ash modified titanium oxide-biochar composite photocatalyst provided by the invention has the advantages of simplicity in operation, low cost and easiness in obtaining all raw materials.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The invention is further described in the following with reference to specific embodiments in order to make the technical means, the creation characteristics, the achievement of the purpose and the effect of the invention easy to understand.
The invention provides a sludge ash modified titanium oxide-biochar composite photocatalyst, which comprises titanium oxide, sludge ash and porous biochar, wherein the porous biochar is used as a carrier, and the titanium oxide and the sludge ash are loaded on the porous biochar;
the composite photocatalyst comprises 20-30 wt% of titanium oxide, 10-15 wt% of sludge ash and the balance of porous biochar based on the total amount of the composite photocatalyst.
In the technical scheme provided by the invention, the technical concept is that the sludge ash is utilized to modify the titanium oxide-biochar composite photocatalytic material, lewis acid and Bronsted acid elements such as aluminum, iron, phosphorus and the like are fully utilized in the sludge ash so as to improve the adsorption capacity of ammonia gas which is a main component in the sludge drying odor and the visible light catalytic capacity of an iron phosphate component after the sludge ash is modified, and the titanium oxide is treated in situ by reducing gases such as hydrogen and the like generated in the biomass pyrolysis carbonization process, so that the oxygen vacancy defect of the titanium oxide is improved, and the visible light availability is improved; that is, the scheme provided by the invention fully utilizes elements such as iron, aluminum, phosphorus and the like in the incineration ash and the reducing atmosphere generated by biomass pyrolysis to enhance the overall acidity and visible light availability of the composite photocatalyst, and improves the degradation efficiency of ammonia gas which is a main component of the biologically dried malodorous gas.
The obtained composite photocatalytic material has high overall acidity, high visible light utilization, excellent ammonia adsorption performance on the main component of sludge drying odor, high efficiency of photocatalytic degradation of sludge drying odor, simple method operation and capability of realizing solid waste resource utilization.
The invention also provides a preparation method of the sludge ash modified titanium oxide-biochar composite photocatalyst, which comprises the following steps:
(1) Grinding and sieving biomass for later use;
calcining municipal sludge, and grinding to obtain sludge ash for later use;
(2) Uniformly mixing biomass, sludge ash and titanium oxide, grinding, adding a dilute hydrochloric acid solution, regulating the pH value to 1-2, stirring and mixing for 30min, regulating the pH value to be neutral, and filtering to obtain a mixed solid;
(3) And (3) placing the mixed solid obtained in the step (2) into a vacuum furnace for calcination treatment, wherein the obtained solid product is the sludge ash modified titanium oxide-biochar composite photocatalyst.
Further, according to the method provided by the invention, in the step (1), the biomass is ground and then is screened by a 20-30-mesh screen.
In the present invention, preferably, in the step (1), the biomass is selected from one or more of straw, rice straw, and wood chips.
In the invention, the purpose of calcining municipal sludge is to remove organic matters in the municipal sludge to obtain sludge ash, and meanwhile, the active components in the municipal sludge are ensured to have a relatively stable state in use. In the step (1), the municipal sludge is calcined in an air atmosphere at 800 ℃ for 5 hours, and is taken out after being cooled to room temperature and ground to obtain sludge ash; the mass fractions of phosphorus compounds and iron compounds in the sludge ash are respectively more than or equal to 20 percent. Specifically, in a specific embodiment of the present invention, the sludge ash comprises the following components in percentage by mass: 28.6% of silicon oxide, 20% of ferric oxide, 9.7% of aluminum oxide, 16.3% of calcium oxide, 22.5% of phosphorus pentoxide, 3% of magnesium oxide and the balance of sodium, potassium, sulfur and other trace compounds.
According to the method provided by the invention, in order to ensure that odor with different concentrations generated in different time periods of sludge drying can be effectively adsorbed and degraded, and ensure that main active components and auxiliary active components in the composite photocatalytic material can exist and be regulated and controlled in a proper proportion after sludge ash with different sources and titanium oxide are added; the weight ratio of the biomass to the sludge ash to the titanium oxide is 1: (0.15-0.2): (0.2-0.3); the concentration of the dilute hydrochloric acid solution is 1mol/L, and the addition amount of the dilute hydrochloric acid solution is 200mL.
According to the method provided by the invention, in the step (3), the condition of the calcination treatment at least meets the following conditions: the calcination temperature is 400-600 ℃ and the calcination time is 0.5-1.5 hours.
The invention also provides application of the sludge ash modified titanium oxide-biochar composite photocatalyst in sludge drying odor treatment.
The sludge ash modified titanium oxide-biochar composite photocatalyst provided by the invention is further described by specific examples.
Example 1
The embodiment provides a preparation method of a sludge ash modified titanium oxide-biochar composite photocatalyst, which comprises the following steps:
(1) Grinding the straw, and sieving with a 20-mesh sieve for standby;
calcining municipal sludge in an air atmosphere at 800 ℃ for 5 hours, taking out the municipal sludge after cooling to room temperature, and grinding to obtain sludge ash; the detected sludge ash comprises the following components in percentage by mass: 28.6% of silicon oxide, 20% of ferric oxide, 9.7% of aluminum oxide, 16.3% of calcium oxide, 22.5% of phosphorus pentoxide, 3% of magnesium oxide and the balance of sodium, potassium, sulfur and other trace compounds;
(2) Uniformly mixing 10g of straw powder, 2g of sludge ash and 3g of titanium oxide (Degusai P25), grinding, adding 200mL of 1M dilute hydrochloric acid solution, regulating the pH value to 1, stirring and mixing for 30min, regulating the pH value to be neutral, and filtering to obtain a mixed solid;
(3) And (3) placing the mixed solid obtained in the step (2) in a vacuum furnace, calcining at 550 ℃ for 1 hour, and cooling to normal temperature to obtain a solid product, namely the sludge ash modified titanium oxide-biochar composite photocatalyst.
Performance test: spreading the obtained composite photocatalyst in a photocatalytic reaction bin, and introducing ammonia standard gas as sludge drying odor model gas to enable the initial ammonia concentration in the reaction bin to be 300ppm; and respectively using a visible light source and an ultraviolet light source to irradiate the reaction bin, and detecting every 10 min. The result shows that the ammonia removal rate reaches 91.50% after 1h under the irradiation of ultraviolet light; the ammonia removal rate can reach 64.10% after 3 hours under the irradiation of visible light.
Example 2
The preparation method of the composite photocatalyst in this example is basically the same as that in example 1, except that biomass is replaced with wood chips; the rest conditions are unchanged, and the composite photocatalyst is prepared.
Performance tests were carried out according to the method in example 1, and the results show that the ammonia removal rate reaches 90.80% after 1 hour under ultraviolet irradiation; the ammonia removal rate can reach 65.20% after 3 hours under the irradiation of visible light.
Comparative example 1
The comparative example was substantially the same as the preparation method of the composite photocatalyst in example 1, except that 10g of straw powder, 0g of sludge ash and 3g of titanium oxide (de-solid plug P25) were uniformly mixed and ground in step (2); the rest conditions are unchanged, and the composite photocatalyst is prepared.
Performance tests were carried out according to the method in example 1, and the results showed that the ammonia removal rate reached 77.10% after 1 hour under ultraviolet irradiation; the ammonia removal rate can reach 37.20% after 3 hours under the irradiation of visible light.
Comparative example 2
The comparative example was substantially the same as the preparation method of the composite photocatalyst in example 1, except that 10g of straw powder, 2g of sludge ash and 0g of titanium oxide (de-solid plug P25) were uniformly mixed and ground in step (2); the rest conditions are unchanged, and the composite photocatalyst is prepared.
Performance tests were carried out according to the method in example 1, and the results showed that the ammonia removal rate reached 51.60% after 1 hour under ultraviolet irradiation; the ammonia removal rate can reach 26.90% after 3 hours under the irradiation of visible light.
Comparative example 3
The comparative example is basically the same as the preparation method of the composite photocatalyst in example 1, except that the sludge ash is used with the following components in percentage by mass: 31.5% of silicon oxide, 10.7% of ferric oxide, 8.7% of aluminum oxide, 41% of calcium oxide, 4% of phosphorus pentoxide, 4% of magnesium oxide and the balance of sodium, potassium, sulfur and other trace compounds; the rest conditions are unchanged, and the composite photocatalyst is prepared.
Performance tests were carried out according to the method in example 1, and the results showed that the ammonia removal rate reached 78.70% after 1 hour under ultraviolet irradiation; the ammonia removal rate can reach 48.60% after 3 hours under the irradiation of visible light.
According to the technical scheme provided by the invention, the sludge ash is used for modifying the titanium oxide, so that the oxygen vacancy defect of the titanium oxide is improved, the visible light availability is improved, and the excellent ammonia removal effect can be realized under the irradiation of visible light.
The foregoing has outlined and described the basic principles, main features and features of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made therein without departing from the spirit and scope of the invention, which is defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (5)
1. The sludge ash modified titanium oxide-biochar composite photocatalyst is characterized by comprising titanium oxide, sludge ash and porous biochar, wherein the porous biochar is used as a carrier, and the titanium oxide and the sludge ash are loaded on the porous biochar;
the composite photocatalyst comprises 20-30 wt% of titanium oxide, 10-15 wt% of sludge ash and the balance of porous biochar based on the total amount of the composite photocatalyst;
the preparation method of the sludge ash modified titanium oxide-biochar composite photocatalyst comprises the following steps:
(1) Grinding and sieving biomass for later use;
calcining municipal sludge, and grinding to obtain sludge ash for later use;
(2) Uniformly mixing biomass, sludge ash and titanium oxide, grinding, adding a dilute hydrochloric acid solution, regulating the pH value to 1-2, stirring and mixing for 30min, regulating the pH value to be neutral, and filtering to obtain a mixed solid;
(3) Calcining the mixed solid obtained in the step (2) in a vacuum furnace to obtain a solid product, namely the sludge ash modified titanium oxide-biochar composite photocatalyst;
in the step (1), calcining the municipal sludge in an air atmosphere at 800 ℃ for 5 hours, taking out the municipal sludge after cooling to room temperature, and grinding to obtain sludge ash;
the mass fraction of the phosphorus compound and the iron compound in the sludge ash is more than or equal to 20 percent;
in the step (2), the weight ratio of the biomass to the sludge ash to the titanium oxide is 1: (0.15-0.2): (0.2-0.3);
the concentration of the dilute hydrochloric acid solution is 1mol/L, and the addition amount of the dilute hydrochloric acid solution is 200mL.
2. The method of claim 1, wherein in step (1), the biomass is ground and then screened through a 20-30 mesh screen.
3. The method of claim 1, wherein in step (1), the biomass is selected from one or a combination of two or more of straw, wood chips.
4. The method of claim 1, wherein in step (3), the conditions of the calcination treatment at least satisfy: the calcination temperature is 400-600 ℃ and the calcination time is 0.5-1.5 hours.
5. The use of the sludge ash modified titanium oxide-biochar composite photocatalyst according to claim 1 in sludge drying odor treatment.
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| PCT/CN2022/109972 WO2023016311A1 (en) | 2021-08-10 | 2022-08-03 | Sludge-ash-modified titanium oxide-biochar composite photocatalyst, preparation method therefor and application thereof |
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| CN113522264B (en) * | 2021-08-10 | 2023-10-10 | 合肥水泥研究设计院有限公司 | Sludge ash modified titanium oxide-biochar composite photocatalyst and preparation method and application thereof |
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| JP2002003869A (en) * | 2000-06-23 | 2002-01-09 | Kawasaki Heavy Ind Ltd | Waste and its storage container |
| CN1480254A (en) * | 2003-06-13 | 2004-03-10 | 彭云龙 | Photocatalyst composite new type carbon absorption material as well as preparing method and usage |
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