CN111408361A - Formaldehyde degradation material based on waste lead-zinc ore tailings and preparation method thereof - Google Patents
Formaldehyde degradation material based on waste lead-zinc ore tailings and preparation method thereof Download PDFInfo
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- CN111408361A CN111408361A CN202010239432.3A CN202010239432A CN111408361A CN 111408361 A CN111408361 A CN 111408361A CN 202010239432 A CN202010239432 A CN 202010239432A CN 111408361 A CN111408361 A CN 111408361A
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 173
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000000463 material Substances 0.000 title claims abstract description 50
- 230000015556 catabolic process Effects 0.000 title claims abstract description 37
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 37
- 239000002699 waste material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 230000000593 degrading effect Effects 0.000 claims abstract description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 28
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 13
- 239000004570 mortar (masonry) Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 abstract description 12
- 239000002131 composite material Substances 0.000 abstract description 7
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 238000013329 compounding Methods 0.000 abstract description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LLQPHQFNMLZJMP-UHFFFAOYSA-N Fentrazamide Chemical compound N1=NN(C=2C(=CC=CC=2)Cl)C(=O)N1C(=O)N(CC)C1CCCCC1 LLQPHQFNMLZJMP-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 238000004867 photoacoustic spectroscopy Methods 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 231100001239 persistent pollutant Toxicity 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 231100000378 teratogenic Toxicity 0.000 description 1
- 230000003390 teratogenic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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Classifications
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/80—Type of catalytic reaction
- B01D2255/802—Photocatalytic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/45—Gas separation or purification devices adapted for specific applications
- B01D2259/4508—Gas separation or purification devices adapted for specific applications for cleaning air in buildings
Abstract
A formaldehyde degradation material based on waste lead-zinc ore tailings and a preparation method thereof are disclosed, wherein TiO is used for degrading formaldehyde2And uniformly mixing the waste lead-zinc mine tailings and grinding the mixture uniformly to prepare the formaldehyde degradation material based on the waste lead-zinc mine tailings. TiO22The mass ratio of the lead-zinc tailings to the lead-zinc tailings is 2.5:1-20: 1. The invention relates to a method for compounding P25TiO by using waste tailings2A novel composite photocatalytic material system is prepared, and the performance of degrading formaldehyde under the action of visible light is realized. The method is simple to operate, realizes effective utilization of waste, changes waste into valuable, and has a wide application prospect.
Description
Technical Field
The invention relates to a formaldehyde degradation material based on waste lead-zinc ore tailings and a preparation method thereof.
Background
Formaldehyde has been recognized by the world health organization as a carcinogenic and teratogenic substance and is one of the major gaseous pollutants of modern indoor air. Some interior decoration materials, furniture, carpets and the like can continuously release formaldehyde gas to affect the indoor environment and human health for a long time. The photocatalysis technology can completely degrade formaldehyde into nontoxic CO by illumination2But is of great interest. TiO22Because of the advantages of low price, stability and the like, the TiO-based photocatalyst is widely applied to photocatalytic reaction as a catalyst, but pure TiO2The forbidden band is wide, and the photocatalyst only responds to ultraviolet light, and electrons and holes are easy to recombine, so that the photocatalytic activity and the catalytic efficiency are reduced. The ultraviolet light accounts for only about 5% of the solar spectrum, while the visible light accounts for more than 45% of the solar spectrum, thus improving TiO2The light absorption range of (2) is the key to the development of efficient visible light photocatalytic materials. The visible light absorption and photo-generated charge separation of TiO2 has been improved in the literature by doping, semiconductor recombination, metal recombination, and the like, for example in TiO2Depositing noble metal on the surface, and enriching TiO through electrons on the metal surface2The electron density on the surface is reduced, thereby inhibiting the recombination of carriers and improving TiO2Photocatalytic activity of (1). However, at present, TiO2Most of the composite materials are expensive, and further application of the composite materials is limited.
In China, lead-zinc polymetallic mineral reserves are rich in resources, but tailings of the lead-zinc polymetallic mineral reserves belong to a class of persistent pollutants, so that the lead-zinc polymetallic mineral reserves occupy land and cause resource loss. At present, the utilization rate of tailings in China is only about 8%. Therefore, the utilization of the lead-zinc tailings is a significant research.
Disclosure of Invention
The invention aims to provide a formaldehyde degradation material based on waste lead-zinc ore tailings and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
formaldehyde degradation material based on waste lead-zinc ore tailings, comprising TiO2With lead-zinc tailings, and TiO2The mass ratio of the lead-zinc tailings to the lead-zinc tailings is 2.5:1-20: 1.
A method for preparing formaldehyde degradation material based on waste lead-zinc ore tailings comprises the step of mixing TiO with water2And uniformly mixing the waste lead-zinc mine tailings and grinding the mixture uniformly to prepare the formaldehyde degradation material based on the waste lead-zinc mine tailings.
Hair brushIn a further development, the TiO compound is2The mass ratio of the lead-zinc tailings to the lead-zinc tailings is 2.5:1-20: 1.
In a further development of the invention, the TiO is2The mass ratio of the lead-zinc tailings to the lead-zinc tailings is 5: 1. 10: 1. 15: 1 or 20: 1.
the invention further improves that the grinding is specifically as follows: ground in a mortar for at least 30 minutes.
In a further development of the invention, the TiO is2Model number P25.
Compared with the prior art, the invention has the following beneficial effects: the invention uses lead-zinc mine tailings and TiO2Compounding of TiO to absorb only UV light2Has obvious absorption in visible light region, and the material composition is favorable to the effective separation of photon-generated electrons and holes and the reduction of overpotential of reduction reaction, so as to raise the activity of catalyst greatly and make TiO possess high activity2The formaldehyde can be degraded by the excitation reaction under the normal white light source. The enrichment method by physical grinding is simple and convenient to operate. The invention successfully utilizes the lead-zinc tailings and TiO2And the tailings are changed into valuable things, so that secondary development of the tailings is realized. The degradable material prepared by the method is easy to obtain, excellent in stability and long in service life. The method is simple to operate, realizes effective utilization of waste, changes waste into valuable, and has a wide application prospect.
Drawings
FIG. 1 is a graph of formaldehyde degradation.
FIG. 2 shows CO in the degradation of formaldehyde2Yield plot of (2).
Fig. 3 is an X-ray diffraction (XRD) pattern.
FIG. 4 is a UV-VIS spectrum.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings.
The invention provides a formaldehyde degradation material based on waste lead-zinc ore tailings, which comprises TiO2With lead-zinc tailings, and TiO2The mass ratio of the lead-zinc tailings to the lead-zinc tailings is 2.5:1-20: 1.
The preparation method of the formaldehyde degradation material comprises the following steps: mixing TiO with the model number of P252And uniformly mixing the formaldehyde degradation material with the lead-zinc mine tailings, and then grinding the mixture in a mortar for at least 30 minutes to prepare the formaldehyde degradation material based on the waste lead-zinc mine tailings.
TiO2The mass ratio of the lead-zinc tailings to the lead-zinc tailings is 2.5:1-20:1, preferably TiO2The mass ratio of the lead-zinc tailings to the lead-zinc tailings is 5: 1. 10: 1. 15: 1 or 20: 1.
the formaldehyde degradation material can degrade formaldehyde in air under visible light, and when the formaldehyde degradation material is tested in the invention, a light source used for photocatalysis is 100W white light L ED.
1) Taking a reagent formaldehyde solution, and taking materials of lead-zinc ore tailings and TiO2An instrument innova photoacoustic spectrometry gas detector;
wherein, TiO2Is P25 model
2) Adding P25TiO2And mixed grinding with the lead-zinc ore tailings, wherein the amount of the tailings is fixed to be 2g, and the grinding is carried out according to the weight ratio of the lead-zinc ore tailings: p25TiO2Is 5:1,10: 1,15: 1,20: 1 ratio, P25TiO20.4g, 0.2g, 0.134g, 0.1 g. Grinding for at least 30 min.
3) Adding P25TiO2And putting the lead-zinc ore tailings and the composite materials in the four proportions into an innova photoacoustic spectrometry gas detector respectively to measure the formaldehyde adsorption quantity. The detection time interval is one minute, and the measurement objects comprise formaldehyde, carbon dioxide, carbon monoxide, pressure and moisture.
The test stage is divided into two stages of light adding and light not adding, and the shading treatment is firstly carried out. When the reaction reaches the carbon dioxide stability (formaldehyde can be adsorbed and desorbed), injecting formaldehyde to keep the light shading and the light adding initial formaldehyde concentration the same, wherein the light shading and the light adding initial formaldehyde concentration are both 30ppm, adding a white light source for illumination, and ending the measurement after the carbon dioxide concentration reaches the stability.
The following are specific examples.
Example 1
The method for developing the formaldehyde degradation material with high added value based on the waste lead-zinc ore tailings comprises the following steps:
the raw material components and the dosage are as follows:
lead-zinc tailings, P25TiO2(ii) a Wherein, the tailings: p25TiO2The mass ratio is 5: 1.
mixing the lead-zinc tailings and P25TiO2The raw materials are put into a mortar to be ground for 30 minutes to prepare the formaldehyde degradation material.
Example 2
The method for developing the formaldehyde degradation material with high added value based on the waste lead-zinc ore tailings comprises the following steps:
the raw material components and the dosage are as follows:
lead-zinc tailings, P25TiO2(ii) a Wherein, the tailings: p25TiO2The mass ratio is 10: 1.
mixing the lead-zinc tailings and P25TiO2The raw materials are put into a mortar to be ground for 30 minutes to prepare the formaldehyde degradation material.
Example 3
The method for developing the formaldehyde degradation material with high added value based on the waste lead-zinc ore tailings comprises the following steps:
the raw material components and the dosage are as follows:
lead-zinc tailings, P25TiO2(ii) a Wherein, the tailings: p25TiO2The mass ratio is 15: 1.
mixing the lead-zinc tailings and P25TiO2The raw materials are put into a mortar to be ground for 30 minutes to prepare the formaldehyde degradation material.
Example 4
The method for developing the formaldehyde degradation material with high added value based on the waste lead-zinc ore tailings comprises the following steps:
the raw material components and the dosage are as follows:
lead-zinc tailings, P25TiO2(ii) a Wherein, the tailings: p25TiO2The mass ratio is 20: 1.
mixing the lead-zinc tailings and P25TiO2The raw materials are put into a mortar to be ground for 30 minutes to prepare the formaldehyde degradation material.
The performance of the formaldehyde degradation material prepared by the method is characterized as follows:
1) amount of carbon dioxide and formaldehyde varies
FIG. 1 is a lead-zinc tailing, P25 TiO2And the relationship between the concentration of the formaldehyde degraded by the photocatalysis of the materials mixed in different proportions and the reaction time, as can be seen from figure 1, the degradation curve in the figure shows that the formaldehyde degradation curve is obtained from lead-zinc tailings and P25TiO2There is little reduction in formaldehyde concentration, which is mainly caused by the adsorption of formaldehyde by the material. The performance of the catalyst for degrading formaldehyde after being compounded is obviously improved, but the performance of each catalyst is also greatly different, wherein when lead-zinc ore tailings and P25TiO are used2When the mass ratio is 5:1, the degradation performance of the formaldehyde is optimal.
FIG. 2 is a graph of the amount of carbon dioxide produced by the degradation of formaldehyde by all components versus time, as can be seen from FIG. 2, in the lead-zinc tailings and P25TiO2In the presence of CO in the reaction system2The yield of (A) does not change significantly with time, which is the same as the above-mentioned lead-zinc tailings and P25TiO2The adsorption effect on formaldehyde is consistent. As shown in FIG. 4, the post-catalyst combination produces CO2The performance is obviously improved, which shows that formaldehyde is actually degraded on the surface of the composite material under illumination to generate CO2。
In addition, formaldehyde degradation of different materials in the absence of light produces CO2The performance of the material is tested, and all the materials can not react with formaldehyde to generate CO under the condition of no light addition2。
2) X-ray diffraction (XRD) pattern
Figure 3 is an X-ray diffraction (XRD) pattern of all materials. FIG. 1 shows P25TiO2Is a mixed structure of anatase and rutile, which is consistent with the literature report. The lead-zinc mine tailings are relatively complex in components, and an XRD (X-ray diffraction) pattern contains various substances. Prepared lead-zinc ore tailings and P25TiO2The XRD patterns of the mixed materials with different proportions have diffraction peaks of the two materials, which shows that the composite material really contains the two materials, and the two materials are mixed with P25TiO in the composite material2The ratio increases, with increasing peak intensity, in comparison with the addition of TiO2Consistent with the increase in. As can be seen from the figure, Pd/Zn-TiO2The diffraction peak positions of the catalyst are consistent, and tailings and TiO can be found2And correspondingly.
3) Ultraviolet-visible absorption spectrum diagram
FIG. 4 is a UV-VIS absorption spectrum of all materials. As can be seen from the figure, P25TiO2Light absorption is mainly concentrated in the ultraviolet region, which is consistent with literature reports. Lead-zinc mine tailings and P25TiO2The material after compounding generates a weak absorption peak in a visible light region, which is mainly caused by compounding of the lead-zinc ore tailings, and the addition of the lead-zinc ore tailings is really favorable for the absorption of visible light catalysis of the material.
The invention successfully utilizes the physical method to lead the zinc tailings of the lead ore and the TiO2The method is successfully compounded, the wavelength of the absorbed light is increased, the tailings are changed into valuable, and the mixed substances can absorb and degrade formaldehyde under a white light source.
The invention is based on TiO2The lead-zinc tailings containing a plurality of metal compounds are simply ground to obtain the lead-zinc tailings-TiO2The mixture is found to have the performance of efficiently degrading formaldehyde, and valuable components in the tailings are utilized, so that the resource utilization of the lead-zinc ore tailings is realized.
Claims (6)
1. A formaldehyde degradation material based on waste lead-zinc ore tailings is characterized by comprising TiO2With lead-zinc tailings, and TiO2The mass ratio of the lead-zinc tailings to the lead-zinc tailings is 2.5:1-20: 1.
2. A preparation method of formaldehyde degradation material based on waste lead-zinc ore tailings is characterized in that TiO is added2And uniformly mixing the waste lead-zinc mine tailings and grinding the mixture uniformly to prepare the formaldehyde degradation material based on the waste lead-zinc mine tailings.
3. The preparation method of the formaldehyde degradation material based on the waste lead-zinc ore tailings as claimed in claim 1, wherein the TiO is2The mass ratio of the lead-zinc tailings to the lead-zinc tailings is 2.5:1-20: 1.
4. Preparation of formaldehyde degrading material based on waste lead-zinc ore tailings according to claim 1Method characterized in that TiO2The mass ratio of the lead-zinc tailings to the lead-zinc tailings is 5: 1. 10: 1. 15: 1 or 20: 1.
5. the preparation method of the formaldehyde degradation material based on the waste lead-zinc ore tailings as claimed in claim 1, wherein the grinding specifically comprises: ground in a mortar for at least 30 minutes.
6. The preparation method of the formaldehyde degradation material based on the waste lead-zinc ore tailings as claimed in claim 1, wherein the TiO is2Model number P25.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113649031A (en) * | 2021-08-19 | 2021-11-16 | 唐山学院 | TiO22/NaNiF6Composite photocatalyst and preparation method thereof |
| CN113663686A (en) * | 2021-07-30 | 2021-11-19 | 昆明理工大学 | Method for preparing photocatalytic material by utilizing lead-zinc tailings and application |
| CN115414943A (en) * | 2022-09-29 | 2022-12-02 | 山西农业大学 | Photocatalytic material prepared from iron tailings and method and application thereof |
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Cited By (4)
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| CN115414943A (en) * | 2022-09-29 | 2022-12-02 | 山西农业大学 | Photocatalytic material prepared from iron tailings and method and application thereof |
| CN115414943B (en) * | 2022-09-29 | 2023-09-08 | 山西农业大学 | Photocatalytic material prepared from iron tailings, and method and application thereof |
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Application publication date: 20200714 |