CN113522264A - 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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- CN113522264A CN113522264A CN202110911748.7A CN202110911748A CN113522264A CN 113522264 A CN113522264 A CN 113522264A CN 202110911748 A CN202110911748 A CN 202110911748A CN 113522264 A CN113522264 A CN 113522264A
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- titanium oxide
- sludge ash
- composite photocatalyst
- sludge
- biochar
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- 239000010802 sludge Substances 0.000 title claims abstract description 87
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 51
- 150000003608 titanium Chemical class 0.000 title claims abstract description 22
- 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 39
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002028 Biomass Substances 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000010902 straw Substances 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 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
- 150000002506 iron compounds Chemical class 0.000 claims description 3
- 150000003018 phosphorus compounds Chemical class 0.000 claims description 3
- 239000002910 solid waste Substances 0.000 abstract description 5
- 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
- 239000002029 lignocellulosic biomass Substances 0.000 abstract 1
- 239000002956 ash Substances 0.000 description 46
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 31
- 230000001699 photocatalysis Effects 0.000 description 13
- 229910021529 ammonia Inorganic materials 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000006731 degradation reaction Methods 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
- 239000007789 gas Substances 0.000 description 5
- 239000004408 titanium dioxide Substances 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
- 238000011056 performance test Methods 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 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
- 239000000969 carrier Substances 0.000 description 3
- 230000003197 catalytic effect Effects 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
- 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
- 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
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 230000002829 reductive effect Effects 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
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 239000003054 catalyst Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000001514 detection method Methods 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
- 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
- 230000001678 irradiating effect Effects 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
- 239000002808 molecular sieve Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- UIZQFHQWIGAPHX-UHFFFAOYSA-N oxygen(2-) titanium(4+) dihydrate Chemical compound O.O.[O-2].[O-2].[Ti+4] UIZQFHQWIGAPHX-UHFFFAOYSA-N 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
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 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
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000009566 rice Nutrition 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
- QPILZZVXGUNELN-UHFFFAOYSA-N sodium;4-amino-5-hydroxynaphthalene-2,7-disulfonic acid Chemical compound [Na+].OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 QPILZZVXGUNELN-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method 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
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- 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
本发明涉及光催化剂技术领域，特别涉及一种污泥灰修饰氧化钛‑生物炭复合光催化剂及其制备方法、应用，所述的复合光催化剂包括氧化钛、污泥灰和多孔生物炭，其中，所述多孔生物炭为载体，所述氧化钛和污泥灰负载在所述多孔生物炭上；以所述复合光催化剂的总量计，所述复合光催化剂包含20重量％‑30重量％的氧化钛，10重量％‑15重量％的污泥灰，其余为多孔生物炭；本发明提供的污泥灰修饰氧化钛‑生物炭复合光催化剂，其主要增益成分均来自污水处理厂副产物污泥的焚烧灰和木质纤维素生物质，属于固体废弃物资源化利用，有效的降低了复合光催化剂的生产成本，具有广阔的市场应用前景。The invention relates to the technical field of photocatalysts, in particular to a sludge ash-modified titanium oxide-biochar composite photocatalyst and a preparation method and application thereof. The composite photocatalyst includes titanium oxide, sludge ash and porous biochar, wherein , the porous biochar is a carrier, and the titanium oxide and sludge ash are supported on the porous biochar; based on the total amount of the composite photocatalyst, the composite photocatalyst comprises 20%-30% by weight titanium oxide, 10%-15% by weight of sludge ash, and the rest are porous biochar; the sludge ash modified titanium oxide-biochar composite photocatalyst provided by the present invention, the main gain components of which are all from by-products of sewage treatment plants The sludge incineration ash and lignocellulosic biomass belong to the resource utilization of solid waste, which effectively reduces the production cost of composite photocatalysts and has broad 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
With the continuous development of social economy, the environmental awareness of the whole society is continuously improved, and the problem of solving various environmental pollutions caused by the economic development becomes a problem to be solved urgently. The photocatalysis technology is an environmental pollution treatment technology which utilizes a photocatalysis material to carry out oxidation-reduction reaction with pollutants under the condition of ultraviolet/visible light illumination so as to degrade the pollutants into carbon dioxide, water and some simple small molecular substances. The photocatalysis technology has the advantages of low cost, strong adaptability, and nontoxic and pollution-free products. 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, harmlessness, recyclability and low cost. However, titanium dioxide has some defects in catalytic degradation of sludge drying odor, such as the problem that titanium dioxide only can play a catalytic role under the condition of ultraviolet illumination, and has low degradation efficiency due to weak pollutant adsorption capacity. Therefore, how to improve the efficiency of degrading sludge drying odor by titanium dioxide photocatalysis, especially the degradation efficiency of ammonia gas which is the main component of sludge drying odor, is very important.
At present, in the existing patent technology, titanium dioxide is mainly loaded on some porous carriers, such as activated carbon, molecular sieves and the like, and the photocatalytic efficiency of the titanium dioxide is improved by improving the adsorption efficiency of pollutants. However, porous supports such as activated carbon tend to be expensive, resulting in increased costs. Although there are some patent technologies that use solid waste as carriers, such as fly ash and biochar, these patent technologies still only use the porosity of the carriers to improve the pollutant adsorption capacity, and do not significantly improve the photocatalytic performance of titania-based catalysts.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a sludge ash modified titanium oxide-biochar composite photocatalyst which has the advantages of low cost, high pollutant adsorption efficiency and high degradation efficiency particularly on ammonia gas which is a main component of sludge drying odor.
In order to achieve the purpose, the invention adopts the following technical scheme:
the composite photocatalyst comprises titanium oxide, sludge ash and porous biochar, wherein the porous biochar is 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 porous biochar based on the total weight 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 the biomass powder, and sieving 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, adjusting the pH value to 1-2, stirring and mixing for 30min, adjusting 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 sieved by a 20-30-mesh sieve.
In a further technical scheme, in the step (1), the biomass is selected from one or more of straw, straw and wood chip.
In a further technical scheme, in the step (1), the municipal sludge is calcined for 5 hours at 800 ℃ in the air atmosphere, is taken out after being cooled to room temperature, and is ground to obtain sludge ash;
the mass fraction of phosphorus compounds and iron compounds 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 200 mL.
In a further technical scheme, in the step (3), the calcining treatment conditions at least satisfy 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 derived from incineration ash of byproduct sludge of a sewage treatment plant and lignocellulose biomass, the solid waste resource utilization is realized, the production cost of the composite photocatalyst is effectively reduced, and the composite photocatalyst has wide market application prospect;
2. the sludge ash modified titanium oxide-biochar composite photocatalyst provided by the invention can effectively utilize visible light, and the application range of the titanium oxide-based photocatalytic material is expanded;
3. the sludge ash modified titanium oxide-biochar composite photocatalyst provided by the invention has stronger acidity, and is beneficial to the degradation of ammonia gas which is the main component of biological 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 and low price and easiness in obtaining of all raw materials.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
In order to make the technical means, the creation features, the achievement purposes and the effects of the invention easy to understand, the invention is further clarified with the specific embodiments.
The invention provides a sludge ash modified titanium oxide-biological carbon composite photocatalyst, which comprises titanium oxide, sludge ash and porous biological carbon, wherein the porous biological carbon is a carrier, and the titanium oxide and the sludge ash are loaded on the porous biological carbon;
the composite photocatalyst comprises 20-30 wt% of titanium oxide, 10-15 wt% of sludge ash and the balance porous biochar based on the total weight of the composite photocatalyst.
According to the technical scheme provided by the invention, the titanium oxide-biochar composite photocatalytic material is modified and modified by sludge ash, Lewis acids such as aluminum, iron and phosphorus and Bronsted acid elements in the sludge ash are fully utilized to improve the adsorption capacity of the main component ammonia in sludge drying odor and the iron phosphate component after the sludge ash acid modification has visible light catalytic capacity, and the titanium oxide is subjected to in-situ treatment by reductive gases such as hydrogen generated in the biomass pyrolysis carbonization process, so that the defect of titanium oxide oxygen vacancy is improved, and the visible light utilization degree is improved; that is, the scheme provided by the invention makes full use of 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 the visible light utilization degree of the composite photocatalyst, and improves the degradation efficiency of the main component ammonia gas of the biological drying malodorous gas.
The obtained composite photocatalytic material has high overall acidity, high visible light utilization degree, 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 the biomass powder, and sieving 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, adjusting the pH value to 1-2, stirring and mixing for 30min, adjusting 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 sieved by a 20-30-mesh sieve.
In the present invention, in the step (1), the biomass is preferably one or a combination of more than one selected from straw, rice straw and wood chip.
In the invention, the municipal sludge is calcined to remove organic matters in the municipal sludge, so that sludge ash is obtained, and active components in the municipal sludge are ensured to have a stable state when in use. As a specific implementation mode of municipal sludge calcination, in the step (1), the municipal sludge is calcined for 5 hours at 800 ℃ in the air atmosphere, 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 by mass percent: 28.6 percent of silicon oxide, 20 percent of ferric oxide, 9.7 percent of aluminum oxide, 16.3 percent of calcium oxide, 22.5 percent of phosphorus pentoxide and 3 percent of magnesium oxide, and the balance of trace compounds such as sodium, potassium, sulfur and the like.
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 the main active component and the auxiliary active component in the composite photocatalytic material can exist and be regulated in a proper proportion after sludge ash and titanium oxide from different sources 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 200 mL.
According to the method provided by the invention, in the step (3), the calcining treatment conditions at least satisfy the following conditions: the calcination temperature is 400-600 ℃, and the calcination time is 0.5-1.5 hours.
The invention also provides an 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 illustrated 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 straws, and sieving the ground straws with a 20-mesh sieve for later use;
calcining municipal sludge in an air atmosphere at 800 ℃ for 5 hours, taking out after cooling to room temperature, and grinding to obtain sludge ash; through detection, the sludge ash comprises the following components in percentage by mass: 28.6 percent of silicon oxide, 20 percent of ferric oxide, 9.7 percent of aluminum oxide, 16.3 percent of calcium oxide, 22.5 percent of phosphorus pentoxide and 3 percent of magnesium oxide, and the balance of trace compounds such as sodium, potassium, sulfur and the like;
(2) uniformly mixing 10g of straw powder, 2g of sludge ash and 3g of titanium oxide (DeguoSa P25), grinding, adding 200mL of 1M dilute hydrochloric acid solution, adjusting the pH value to 1, stirring and mixing for 30min, adjusting 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.
And (3) performance testing: the obtained composite photocatalyst is flatly laid in a photocatalytic reaction bin, and ammonia gas standard gas is introduced to serve as sludge drying odor model gas to enable the initial ammonia gas concentration in the reaction bin to be 300 ppm; and respectively irradiating the reaction bin by using a visible light source and an ultraviolet light source, and detecting every 10 min. The result shows that the ammonia removal rate reaches 91.50% after 1h under the ultraviolet irradiation; the ammonia removal rate can reach 64.10% after 3h under the irradiation of visible light.
Example 2
This example is substantially the same as the preparation method of the composite photocatalyst in example 1, except that the biomass is replaced by wood chips; and (5) keeping the other conditions unchanged, and preparing the composite photocatalyst.
The performance test is carried out according to the method in the embodiment 1, and the result shows that the ammonia removal rate reaches 90.80% after 1 hour under the ultraviolet irradiation; the ammonia removal rate can reach 65.20% after 3h under the irradiation of visible light.
Comparative example 1
The preparation method of the composite photocatalyst in the comparative example is basically the same as that of the composite photocatalyst in the example 1, except that in the step (2), 10g of straw powder, 0g of sludge ash and 3g of titanium oxide (de gu sai P25) are uniformly mixed and ground; and (5) keeping the other conditions unchanged, and preparing the composite photocatalyst.
The performance test is carried out according to the method in the embodiment 1, and the result shows that the ammonia removal rate reaches 77.10% after 1h under the ultraviolet irradiation; the ammonia removal rate can reach 37.20% after 3 hours under the irradiation of visible light.
Comparative example 2
The preparation method of the composite photocatalyst in the comparative example is basically the same as that of the composite photocatalyst in the example 1, except that in the step (2), 10g of straw powder, 2g of sludge ash and 0g of titanium oxide (de gu sai P25) are uniformly mixed and ground; and (5) keeping the other conditions unchanged, and preparing the composite photocatalyst.
The performance test is carried out according to the method in the embodiment 1, and the result shows that the ammonia removal rate reaches 51.60 percent after 1 hour under the ultraviolet irradiation; the ammonia removal rate can reach 26.90 percent after 3 hours under the irradiation of visible light.
Comparative example 3
The preparation method of the composite photocatalyst in the comparative example is basically the same as that of the composite photocatalyst in the example 1, except that the adopted sludge ash comprises 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 and 4% of magnesium oxide, and the balance of trace compounds such as sodium, potassium, sulfur and the like; and (5) keeping the other conditions unchanged, and preparing the composite photocatalyst.
The performance test is carried out according to the method in the embodiment 1, and the result shows that the ammonia removal rate reaches 78.70% after 1 hour under the ultraviolet irradiation; the ammonia removal rate can reach 48.60% after 3h under the irradiation of visible light.
The technical scheme provided by the invention has the advantages that the titanium oxide is modified and modified by the sludge ash, so that the oxygen vacancy defect of the titanium oxide is improved, the visible light utilization degree is improved, and the excellent ammonia gas removal effect can be realized under the irradiation of the visible light.
The foregoing shows and describes the general principles, essential features, and inventive features of this invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (8)
1. The composite photocatalyst of titanium oxide and biological carbon modified by sludge ash is characterized by comprising titanium oxide, sludge ash and porous biological carbon, wherein the porous biological carbon is a carrier, and the titanium oxide and the sludge ash are loaded on the porous biological carbon;
the composite photocatalyst comprises 20-30 wt% of titanium oxide, 10-15 wt% of sludge ash and the balance porous biochar based on the total weight of the composite photocatalyst.
2. The preparation method of the sludge ash modified titanium oxide-biochar composite photocatalyst is characterized by comprising the following steps of:
(1) grinding the biomass powder, and sieving 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, adjusting the pH value to 1-2, stirring and mixing for 30min, adjusting 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.
3. The method according to claim 2, wherein in the step (1), the biomass powder is ground and then is processed by a 20-30-mesh sieve.
4. The method of claim 2, wherein in step (1), the biomass is selected from one or more of straw, and wood chips.
5. The method according to claim 2, wherein in the step (1), the municipal sludge is calcined at 800 ℃ in the air atmosphere for 5 hours, taken out after being cooled to room temperature, and ground to obtain sludge ash;
the mass fraction of phosphorus compounds and iron compounds in the sludge ash is more than or equal to 20 percent.
6. The method according to claim 2, wherein in the step (2), the weight ratio of the biomass, the sludge ash and 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 200 mL.
7. The method according to claim 2, wherein in the step (3), the calcination treatment is performed under conditions at least satisfying: the calcination temperature is 400-600 ℃, and the calcination time is 0.5-1.5 hours.
8. The application of the sludge ash modified titanium oxide-biochar composite photocatalyst in sludge drying odor treatment according to claim 1.
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| CN115679369A (en) * | 2022-11-16 | 2023-02-03 | 合肥水泥研究设计院有限公司 | Sludge ash modified tin oxide composite electrocatalyst and preparation method and application thereof |
| WO2023016311A1 (en) * | 2021-08-10 | 2023-02-16 | 合肥水泥研究设计院有限公司 | Sludge-ash-modified titanium oxide-biochar composite photocatalyst, preparation method therefor and application thereof |
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| CN116889871B (en) * | 2023-07-14 | 2024-03-01 | 广东韩研活性炭科技股份有限公司 | Titanium-loaded catalyst activated carbon with lasting strong pollution cleaning and preparation method thereof |
| CN117414829B (en) * | 2023-10-19 | 2024-09-03 | 四川大学 | Preparation method and application of municipal sewage sludge carbon-based catalyst |
| CN119186546B (en) * | 2024-10-11 | 2025-04-29 | 广东韩研活性炭科技股份有限公司 | Nano-scale activated carbon for purifying VOCs and preparation method thereof |
| CN119236939B (en) * | 2024-12-05 | 2025-03-21 | 临沂大学 | A treatment agent for efficiently removing heavy metals from industrial sewage and a preparation method thereof |
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