CN115487862A - Low-titanium blast furnace slag zeolite/cuprous oxide composite photocatalyst and preparation method and application thereof - Google Patents
Low-titanium blast furnace slag zeolite/cuprous oxide composite photocatalyst and preparation method and application thereof Download PDFInfo
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- CN115487862A CN115487862A CN202211189279.3A CN202211189279A CN115487862A CN 115487862 A CN115487862 A CN 115487862A CN 202211189279 A CN202211189279 A CN 202211189279A CN 115487862 A CN115487862 A CN 115487862A
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- 239000010936 titanium Substances 0.000 title claims abstract description 114
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 114
- 239000002893 slag Substances 0.000 title claims abstract description 110
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 70
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000010457 zeolite Substances 0.000 title claims abstract description 70
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 38
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229940112669 cuprous oxide Drugs 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 57
- 239000000243 solution Substances 0.000 claims description 36
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 17
- 239000008103 glucose Substances 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000011449 brick Substances 0.000 claims description 8
- 230000036571 hydration Effects 0.000 claims description 8
- 238000006703 hydration reaction Methods 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 230000015556 catabolic process Effects 0.000 claims description 7
- 238000006731 degradation reaction Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 6
- 229940012189 methyl orange Drugs 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 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 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 230000004927 fusion Effects 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000002386 leaching Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 12
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 6
- 230000004298 light response Effects 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 description 10
- 239000010842 industrial wastewater Substances 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052729 chemical element Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- -1 papermaking Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The invention relates to a low-titanium blast furnace slag zeolite/cuprous oxide composite photocatalyst as well as a preparation method and application thereof, belonging to the technical field of photocatalyst preparation. The invention discloses a low-titanium blast furnace slag zeolite/cuprous oxide composite photocatalyst, which is mainly characterized in that nano cuprous oxide is loaded on a carrier of low-titanium blast furnace slag zeolite, has better photocatalytic performance and is mixed with pure cuprous oxide (Cu) 2 O) phase ratio, the low titanium blast furnace slag zeolite/cuprous oxide (Cu) of the invention 2 O) the visible light response capability and the photocatalytic degradation capability of the composite photocatalyst are obviously enhanced, the high-value utilization of the low-titanium blast furnace slag is realized, and a new way for utilizing the low-titanium blast furnace slag is developed.
Description
Technical Field
The invention belongs to the technical field of photocatalyst preparation, and relates to a low-titanium blast furnace slag zeolite/cuprous oxide composite photocatalyst as well as a preparation method and application thereof.
Background
The industrial wastewater discharge in China mainly comes from industries such as petrifaction, coal, papermaking, textile, pharmacy, metallurgy, food and the like, and has the characteristics of complex types, great harm, lasting effect, great treatment difficulty and the like. In particular, industrial wastewater contains a large amount of artificially synthesized organic pollutants, is difficult to convert and degrade into harmless substances in the nature, not only can act on human bodies through food chain enrichment and harm health, but also can pollute soil and underground water and is extremely difficult to restore. Therefore, toxic refractory organic pollutants in industrial wastewater are important links which are not negligible in water environment treatment.
The photocatalysis technology is a green advanced oxidation technology for deeply treating toxic and nondegradable organic pollutants in industrial wastewater, wherein TiO is compared with the traditional water treatment material 2 The photocatalytic material has the advantages of mild reaction conditions, thorough pollutant degradation and no secondary pollution, and has wide application prospects in the field of organic pollutant treatment. However, the development of the photocatalytic material with low price and excellent performance is an important direction for the development of the technology because the photocatalytic material has high production cost and seriously limits the development of the photocatalytic material in industrial application.
The titanium-containing blast furnace slag is used as main solid waste generated by smelting vanadium-titanium magnetite in a blast furnace, and is currently utilized in the forms of building materials, fertilizers, titanium dioxide and enriched titanium extraction. In the prior art, titanium-containing blast furnace slag with medium and high titanium content is mostly used as a raw material, so that a large amount of low-titanium blast furnace slag is stockpiled, land is occupied, and a series of secondary pollution is caused to the environment. While the main component SiO of the low-titanium blast furnace slag 2 、TiO 2 And Al 2 O 3 The total content reaches 50 percent, and is a good choice for synthesizing the photocatalytic material. Furthermore, cu 2 O has the characteristics of high photoresponse activity and good stability in the field of photocatalysis, but the nano Cu 2 O is difficult to recycle in the wastewater treatment process, and the fixation of O on zeolite can effectively solve the problem of nano Cu 2 The recycling of O. Therefore, the zeolite is synthesized by taking the low-titanium blast furnace slag as a raw material, so that the resource utilization of valuable elements such as Si, al and Ti can be realized, the cost of the composite photocatalytic material for wastewater treatment can be reduced, and the cost of the composite photocatalytic material for wastewater treatment can be reducedEffectively improves the added value of the low-titanium blast furnace slag product, and solves the problems of the treatment of the low-titanium blast furnace slag and the recycling of the nano Cu 2O.
Therefore, low titanium blast furnace slag zeolite and cuprous oxide (Cu) are required 2 O) to prepare the photocatalyst which is efficient and stable, meets the requirements of energy conservation and emission reduction and is suitable for circular economy.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a low-titanium blast furnace slag zeolite/cuprous oxide composite photocatalyst; the second purpose of the invention is to provide a preparation method of the low-titanium blast furnace slag zeolite/cuprous oxide composite photocatalyst; the invention also aims to provide application of the low-titanium blast furnace slag zeolite/cuprous oxide composite photocatalyst in catalyzing methyl orange degradation.
In order to achieve the purpose, the invention provides the following technical scheme:
1. the composite photocatalyst comprises a low-titanium blast furnace slag zeolite carrier and nano cuprous oxide loaded on the carrier.
Preferably, the low-titanium blast furnace slag zeolite carrier is prepared according to the following method:
(1) Adding the low-titanium blast furnace slag as a raw material into hydrochloric acid (HCl), stirring for 1-4 times, washing with water, drying, crushing and screening to obtain acid-leaching titanium slag with the particle size of 200 meshes;
(2) Mixing the acid-leached titanium slag with sodium hydroxide (NaOH), roasting at 500-700 ℃ for 2-4 h, fully cooling, crushing and screening to obtain alkali-fused titanium slag with the particle size of 200 meshes;
(3) The alkali fusion titanium slag, deionized water and sodium metaaluminate (NaAlO) 2 ) Mixing and stirring for 1-3 h, and carrying out hydrothermal reaction for 8h at the temperature of 80-100 ℃ to obtain the low-titanium blast furnace slag zeolite.
More preferably, in the step (1), the concentration of the hydrochloric acid is 2 to 5mol/L;
the mass volume ratio of the low-titanium blast furnace slag to the hydrochloric acid is 0.0625-0.125.
Further preferably, in the step (2), the mass ratio of the acid-leached titanium slag to the sodium hydroxide is 1.5.
Further preferably, in the step (3), the alkali-molten titanium slag is deionized water and sodium metaaluminate (NaAlO) 2 ) The mass-to-volume ratio of (A) is 5-7.
2. The preparation method of the composite photocatalyst comprises the following steps:
(1) Adding low-titanium blast furnace slag zeolite into soluble Cu-containing material 2+ Adding polyvinylpyrrolidone (PVP) into the salt solution after ultrasonic oscillation to mix uniformly, continuously dropwise adding a NaOH solution, and stirring for 30min to obtain a mixed solution;
(2) Placing the mixed solution in the step (1) in a constant-temperature water bath, heating at the constant temperature of 60 ℃ for 10-30 min, and then slowly dropwise adding glucose (C) 6 H 12 O 6 ) Stirring the solution for 30-60 min to obtain a brick red precipitate hydration mixture;
(3) Repeatedly cleaning the brick red precipitate hydration mixture in the step (2) by using deionized water and absolute ethyl alcohol, and drying at 40-60 ℃ for 12-24 h to obtain the low-titanium blast furnace slag zeolite/cuprous oxide (Cu) 2 O) the composite photocatalyst.
Preferably, in the step (1), the soluble Cu is contained 2+ Cu in solution of salt 2+ The concentration of (A) is 0.0025-0.01 mol/L;
the low-titanium blast furnace slag zeolite and the soluble Cu-containing zeolite 2+ Cu in solution of salt 2+ The mass ratio of (A) to (B) is 1.
Preferably, in the step (1), the concentration of the NaOH solution is 0.1-2 mol/L; the mass ratio of the low-titanium blast furnace slag zeolite to NaOH in the NaOH solution is (1) from 0.168 to 3.357,g;
the mass ratio of the low-titanium blast furnace slag zeolite to polyvinylpyrrolidone (PVP) is 1.699-1.398.
Preferably, in step (3), glucose (C) 6 H 12 O 6 ) The concentration of the solution is 0.05-2 mol/L; the low-titanium blast furnace slag zeolite and glucose (C) in the step (1) 6 H 12 O 6 ) The mass ratio of glucose in the solution is 1.
3. The composite photocatalyst is applied to catalyzing methyl orange degradation.
The invention has the beneficial effects that:
1. the invention discloses a low-titanium blast furnace slag zeolite/cuprous oxide composite photocatalyst, which is mainly characterized in that nano cuprous oxide is loaded on a carrier of low-titanium blast furnace slag zeolite, has better photocatalytic performance and is mixed with pure cuprous oxide (Cu) 2 O) phase ratio, the low titanium blast furnace slag zeolite/cuprous oxide (Cu) of the invention 2 O) the visible light response capability and the photocatalytic degradation capability of the composite photocatalyst are obviously enhanced, the high-value utilization of the low-titanium blast furnace slag is realized, and a new way for utilizing the low-titanium blast furnace slag is developed.
2. The invention also discloses a preparation method of the low-titanium blast furnace slag zeolite/cuprous oxide composite photocatalyst, and the preparation method is simple and convenient in preparation process, high in controllability, easy to popularize and remarkable in economic benefit. The invention mainly takes low-titanium blast furnace slag zeolite which is prepared by modifying low-titanium blast furnace slag obtained by smelting vanadium titano-magnetite as a raw material as a carrier and cuprous oxide (Cu) 2 O) load is mounted, and the device has the advantages of stable performance and low cost; meanwhile, the method realizes the full utilization of valuable chemical elements in the low-titanium blast furnace slag, reduces the negative influence on the environment, and has good social benefit.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention may be realized and attained by the means of the instrumentalities and combinations particularly pointed out hereinafter.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
The compositions (mass percentages) of the raw material low-titanium blast furnace slag used in the following examples are shown in table 1 below.
Table 1 composition of the raw low titanium blast furnace slag used in the examples:
example 1
A low-titanium blast furnace slag zeolite/cuprous oxide composite photocatalyst is prepared by the following steps:
(1) Preparing low-titanium blast furnace slag zeolite: adding the low-titanium blast furnace slag into an HCl solution with the concentration of 5mol/L (wherein the mass volume ratio of the low-titanium blast furnace slag to the HCl solution is 1; then mixing the titanium slag with NaOH according to the mass ratio of 1.5; then it is mixed with deionized water, naAlO in a mass to volume ratio of 6 2 Mixing, stirring for 3h, and carrying out hydrothermal reaction for 8h at 100 ℃ to obtain the low-titanium blast furnace slag zeolite.
(2) Adding 0.01mol/L CuSO into the obtained low-titanium blast furnace slag zeolite 4 In solution (wherein low titanium blast furnace slag zeolite and CuSO 4 Cu in (1) 2+ The mass ratio of the low-titanium blast furnace slag zeolite to the NaOH solution is 2.
(3) Then placing the obtained mixed solution in a constant temperature water bath kettle at 60 ℃ for heat preservation for 10min, and then slowly dropwise adding 0.18mol/L glucose (C) 6 H 12 O 6 ) Solution (low titanium blast furnace slag zeolite and glucose (C) 6 H 12 O 6 ) The mass ratio of glucose in the solution is 1)The hydrated mixture precipitated brick red.
(4) Repeatedly cleaning the brick red precipitate hydration mixture with deionized water and absolute ethyl alcohol, and drying at 60 ℃ for 12h to obtain the low-titanium blast furnace slag zeolite/cuprous oxide (Cu) 2 O) the composite photocatalyst.
50mg of the low titanium blast furnace slag zeolite/cuprous oxide (Cu) prepared as described above 2 O) adding the composite photocatalyst into 10mg/L methyl orange solution, and performing a visible light photocatalytic degradation methyl orange performance test, wherein the degradation rate can reach 65.06% when the test time is 120 min.
Example 2
A low-titanium blast furnace slag zeolite/cuprous oxide composite photocatalyst is prepared by the following steps:
(1) Preparing low-titanium blast furnace slag zeolite: adding the low-titanium blast furnace slag into an HCl solution with the concentration of 2mol/L (wherein the mass volume ratio of the low-titanium blast furnace slag to the HCl solution is 1; then mixing the titanium slag with NaOH according to the mass ratio of 1.5; it was then mixed with deionized water, naAlO in a mass to volume ratio of 7 2 Mixing, stirring for 1h, and carrying out hydrothermal reaction for 8h at 100 ℃ to obtain the low-titanium blast furnace slag zeolite.
(2) Adding 0.005mol/L CuSO into the obtained low-titanium blast furnace slag zeolite 4 In solution (wherein low titanium blast furnace slag zeolite and CuSO 4 Cu in (1) 2+ The mass ratio of (1).
(3) Then placing the obtained mixed solution in a constant temperature water bath kettle at 60 ℃ for heat preservation for 10min, and then slowly dropwise adding 0.05mol/L glucose (C) 6 H 12 O 6 ) Solution (low titanium blast furnace slag zeolite and glucose (C) 6 H 12 O 6 ) The mass ratio of glucose in the solution was 1.378) and stirred for 50min to obtain a brick-red precipitate hydration mixture.
(4) Repeatedly washing the brick red precipitate hydration mixture with deionized water and anhydrous ethanol, and drying at 40 deg.C for 24 hr to obtain low-titanium blast furnace slag zeolite/cuprous oxide (Cu) 2 O) the composite photocatalyst.
50mg of the low titanium blast furnace slag zeolite/cuprous oxide (Cu) prepared in example 2 above was added 2 O) adding the composite photocatalyst into 10mg/L methyl orange solution, and performing a visible light photocatalytic degradation methyl orange performance test, wherein the degradation rate can reach 62.78% when the test time is 120 min.
Example 3
The preparation method of the low-titanium blast furnace slag zeolite/cuprous oxide composite photocatalyst comprises the following steps:
(1) Preparing low-titanium blast furnace slag zeolite: adding the low-titanium blast furnace slag into an HCl solution with the concentration of 2.5mol/L (wherein the mass volume ratio of the low-titanium blast furnace slag to the HCl solution is 1; then mixing the titanium slag with NaOH according to the mass ratio of 1.5 to 2, roasting for 4 hours at 500 ℃, fully cooling, crushing and sieving to obtain 200-mesh alkali fusion titanium slag; then, the mixture was mixed with deionized water, naAlO in a mass-to-volume ratio of 5 2 Mixing, stirring for 2h, and carrying out hydrothermal reaction for 24h at 80 ℃ to obtain the low-titanium blast furnace slag zeolite.
(2) Adding 0.0025mol/L CuSO into the obtained low-titanium blast furnace slag zeolite 4 In solution (wherein low titanium blast furnace slag zeolite and CuSO 4 The mass ratio of the low titanium blast furnace slag zeolite to the NaOH solution is 1.
(3) Then placing the obtained mixed solution in a constant temperature water bath kettle at 60 ℃ for heat preservation for 30min, and then slowly dropwise adding 2.0mol/L glucose (C) 6 H 12 O 6 ) Solution (low titanium blast furnace slag zeolite and glucose (C) 6 H 12 O 6 ) The mass ratio of glucose in the solution was 1.
(4) Repeatedly washing the brick red precipitate hydration mixture with deionized water and anhydrous ethanol, and drying at 60 deg.C for 12 hr to obtain low-titanium blast furnace slag zeolite/cuprous oxide (Cu) 2 O) the composite photocatalyst.
50mg of the above-prepared low titanium blast furnace slag zeolite/cuprous oxide (Cu) 2 O) adding the composite photocatalyst into 10mg/L methyl orange solution, and performing a visible light photocatalytic degradation methyl orange performance test, wherein the degradation rate can reach 59.62% when the test time is 120 min.
In conclusion, the invention discloses a low-titanium blast furnace slag zeolite/cuprous oxide composite photocatalyst, which is mainly characterized in that nano cuprous oxide is loaded on a carrier of low-titanium blast furnace slag zeolite, has better photocatalytic performance and is combined with pure cuprous oxide (Cu) 2 O) phase ratio, the low titanium blast furnace slag zeolite/cuprous oxide (Cu) of the invention 2 O) the visible light response capability and the photocatalytic degradation capability of the composite photocatalyst are obviously enhanced, the high-value utilization of the low-titanium blast furnace slag is realized, and a new way for utilizing the low-titanium blast furnace slag is developed. The invention also discloses a preparation method of the low-titanium blast furnace slag zeolite/cuprous oxide composite photocatalyst, and the preparation method is simple and convenient in preparation process, high in controllability, easy to popularize and remarkable in economic benefit. The invention mainly takes low-titanium blast furnace slag zeolite which is prepared by modifying low-titanium blast furnace slag obtained by smelting vanadium titano-magnetite as a raw material as a carrier and cuprous oxide (Cu) 2 O) load is mounted, so that the device has the advantages of stable performance and low cost; meanwhile, the method realizes the full utilization of valuable chemical elements in the low-titanium blast furnace slag, reduces the negative influence on the environment, and has good social benefit.
Finally, the above embodiments are only intended to illustrate the technical solutions of the present invention and not to limit the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all of them should be covered by the claims of the present invention.
Claims (10)
1. The low-titanium blast furnace slag zeolite/cuprous oxide composite photocatalyst is characterized by comprising a low-titanium blast furnace slag zeolite carrier and nano cuprous oxide loaded on the carrier.
2. The composite photocatalyst of claim 1, wherein the low-titanium blast furnace slag zeolite support is prepared by the following method:
(1) Adding the low-titanium blast furnace slag as a raw material into hydrochloric acid (HCl), stirring for 1-4 h, washing with water, drying, crushing and screening to obtain acid-leaching titanium slag with the particle size of 200 meshes;
(2) Mixing the acid-leaching titanium slag with sodium hydroxide (NaOH), roasting for 2-4 h at 500-700 ℃, fully cooling, crushing and screening to obtain alkali fusion titanium slag with the particle size of 200 meshes;
(3) The alkali fusion titanium slag, deionized water and sodium metaaluminate (NaAlO) 2 ) Mixing and stirring for 1-3 h, and carrying out hydrothermal reaction for 8-24 h at the temperature of 80-100 ℃ to obtain the low-titanium blast furnace slag zeolite.
3. The composite photocatalyst as claimed in claim 2, wherein in step (1), the concentration of the hydrochloric acid is 2-5 mol/L;
the mass volume ratio of the low-titanium blast furnace slag to the hydrochloric acid is 0.0625-0.125.
4. The composite photocatalyst as claimed in claim 2, wherein in step (2), the mass ratio of the acid-leached titanium slag to the sodium hydroxide is 1.5.
5. The composite photocatalyst as claimed in claim 2, wherein in step (3), the alkali-fused titanium slag, deionized water and sodium metaaluminate (NaAlO) 2 ) The mass volume ratio of (1) is 5-7.
6. A process for the preparation of a composite photocatalyst as claimed in any one of claims 1 to 5, which process comprises the steps of:
(1) Adding low-titanium blast furnace slag zeolite into soluble Cu-containing material 2+ Adding polyvinylpyrrolidone (PVP) into the salt solution after ultrasonic oscillation to mix uniformly, continuously dripping NaOH solution, and stirring for 30min to obtain a mixed solution;
(2) Placing the mixed solution in the step (1) in a constant-temperature water bath, heating at the constant temperature of 60 ℃ for 10-30 min, and then slowly dropwise adding glucose (C) 6 H 12 O 6 ) Stirring the solution for 30-60 min to obtain a brick red precipitate hydration mixture;
(3) Repeatedly cleaning the brick red precipitate hydration mixture in the step (2) by using deionized water and absolute ethyl alcohol, and drying at 40-60 ℃ for 12-24 h to obtain the low-titanium blast furnace slag zeolite/cuprous oxide (Cu) 2 O) the composite photocatalyst.
7. The method according to claim 6, wherein in the step (1), the soluble Cu is contained 2+ Cu in solution of salt 2+ The concentration of (A) is 0.0025-0.01 mol/L;
the low-titanium blast furnace slag zeolite and the soluble Cu-containing zeolite 2+ Cu in solution of salt 2+ The mass ratio of (1) to (0.2238) to (0.895).
8. The method according to claim 6, wherein in the step (1), the concentration of the NaOH solution is 0.1 to 2mol/L; the mass ratio of the low-titanium blast furnace slag zeolite to NaOH in the NaOH solution is 1.168-3.357,mol;
the mass ratio of the low-titanium blast furnace slag zeolite to polyvinylpyrrolidone (PVP) is 1.699-1.398.
9. The method according to claim 6, wherein in the step (3), glucose (C) 6 H 12 O 6 ) The concentration of the solution is 0.05-2 mol/L; the low titanium content in the step (1) is highSlag zeolite and glucose (C) 6 H 12 O 6 ) The mass ratio of glucose in the solution is 1.
10. The use of the composite photocatalyst of any one of claims 1 to 5 in catalyzing the degradation of methyl orange.
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