CN112439438A - Preparation of bismuth subcarbonate compound material and indoor formaldehyde purification technology - Google Patents
Preparation of bismuth subcarbonate compound material and indoor formaldehyde purification technology Download PDFInfo
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 title claims abstract description 29
- 229940036358 bismuth subcarbonate Drugs 0.000 title claims abstract description 29
- 239000000463 material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- -1 bismuth subcarbonate compound Chemical class 0.000 title claims abstract description 10
- 238000005516 engineering process Methods 0.000 title abstract description 7
- 238000000746 purification Methods 0.000 title abstract description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000003647 oxidation Effects 0.000 claims abstract description 17
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 17
- 230000000694 effects Effects 0.000 claims abstract description 14
- 239000012855 volatile organic compound Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims abstract description 9
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 4
- 230000003197 catalytic effect Effects 0.000 claims abstract description 4
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 4
- 230000007613 environmental effect Effects 0.000 claims abstract description 3
- MGLUJXPJRXTKJM-UHFFFAOYSA-L bismuth subcarbonate Chemical compound O=[Bi]OC(=O)O[Bi]=O MGLUJXPJRXTKJM-UHFFFAOYSA-L 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000010335 hydrothermal treatment Methods 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- GMZOPRQQINFLPQ-UHFFFAOYSA-H dibismuth;tricarbonate Chemical compound [Bi+3].[Bi+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GMZOPRQQINFLPQ-UHFFFAOYSA-H 0.000 claims description 4
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229940036348 bismuth carbonate Drugs 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 230000005587 bubbling Effects 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 238000004817 gas chromatography Methods 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims 4
- 239000001569 carbon dioxide Substances 0.000 claims 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 238000001027 hydrothermal synthesis Methods 0.000 claims 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims 1
- 238000005215 recombination Methods 0.000 claims 1
- 230000006798 recombination Effects 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 238000011282 treatment Methods 0.000 abstract description 5
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
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- GFAJOMHUNNCCJQ-UHFFFAOYSA-N 1,3-dioxetane Chemical compound C1OCO1 GFAJOMHUNNCCJQ-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 206010028813 Nausea Diseases 0.000 description 1
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- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 208000002173 dizziness Diseases 0.000 description 1
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- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
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- 238000001228 spectrum Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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- 239000004408 titanium dioxide Substances 0.000 description 1
- 210000001835 viscera Anatomy 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
- B01J27/236—Hydroxy carbonates
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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Abstract
Preparation of bismuth subcarbonate compound material and indoor formaldehyde purification technology. The invention belongs to the aspect of photocatalytic treatment of indoor toxic organic volatile compounds, bismuth subcarbonate compound materials with different morphologies are synthesized by a simple one-step method, and are used for carrying out catalytic oxidation research on VOCs mainly comprising paraformaldehyde, and the result shows that the bismuth subcarbonate compound material shows excellent catalytic oxidation formaldehyde performance and long-acting stability under the drive of sunlight, and can decompose 300ppm of formaldehyde into CO in an indoor environment2And H2O, removing the residue after 10min of sunlight irradiationThe efficiency reaches 99.099 percent. Meanwhile, the material has good removal effect on benzene and toluene, and is expected to be used for removing indoor VOCs gas. The catalyst synthesized by the method has the advantages of good oxidation effect, environmental friendliness, non-toxic and harmless synthetic raw materials, low price, simple and convenient synthesis method, long-acting stability, and capability of being produced in large scale and being put into the removal of harmful gases such as formaldehyde, benzene, toluene and the like indoors.
Description
Technical Field
The invention relates to a method for synthesizing novel bismuth subcarbonate with different shapes and a compound material thereof and application of the bismuth subcarbonate in purification of indoor formaldehyde and benzene, and relates to the field of indoor gas pollution treatment in engineering and the field of material synthesis and photocatalysis in technology.
Background
The pollution of VOCs in a room is taken as a pollution source which is most frequently contacted by people and mainly comes from paint, coating, building materials, fuel combustion products, electric appliance emission and the like. The components of the compound are mainly aromatic compounds including benzene and toluene and some small molecular aldehydes. Exposure to high concentrations can cause dizziness, nausea, malaise, and even injury to the organs and internal organs or even carcinogenesis.
Activated carbon adsorption is a treatment mode of VOCs with more research and market applications, but at present, research aiming at activated carbon mostly focuses on improving the specific surface area and the surface activity of an adsorbent so as to improve the adsorption capacity of the adsorbent. Taking the currently widely applied diatom ooze adsorption as an example, the diatom ooze can reach an adsorption equilibrium state after adsorbing formaldehyde in the previous period, so that the capacity of continuous adsorption is lost, and therefore the conventional adsorption method is not the primary treatment, and the absorption capacity is limited.
The photocatalysis technology is applied to the field of indoor formaldehyde and benzene treatment as a green technology without secondary pollution, and has the characteristics of no residue, wide applicability and high treatment effect. However, the common photocatalyst such as titanium dioxide does not respond to visible light, and the photocatalyst can oxidize formaldehyde and benzene only by means of ultraviolet irradiation, so that the use cost is increased, and the air purifying capacity of the photocatalyst is limited.
The solar-driven photocatalysis technology can fundamentally remove indoor formaldehyde, and can utilize renewable clean energy sources such as solar energy and the like to effectively oxidize and decompose waste gas and waste water, thereby improving the environmental problems such as indoor air and the like. Therefore, the method can be used as a sustainable, pollution-free and economic and effective means for removing the pollution of VOCs such as formaldehyde in the room. But the technical bottleneck at present is that a photocatalytic material which has high oxidation capacity, no toxicity, low cost, sunlight drive and long-term effectiveness is difficult to find.
Bismuth subcarbonate Bi2O2CO3(BOC for short) is an environment-friendly photocatalytic material, and has the advantages of no toxicity, low cost, wide band gap (BiO)+And CO3 2-The layers alternate, which is beneficial to the separation of photo-generated charges. Further, since it is highly oxidative and can oxidize a large number of organic molecules by generating OH radicals, it is a potential effective scavenger for VOCs gas pollution sources such as indoor formaldehyde. However, the material is generally wide in band gap, so that it is difficult to directly use sunlight to drive photo-oxidation reaction, which brings great inconvenience and limitation to the application of the material.
The invention provides a novel bismuth subcarbonate-based sunlight-driven indoor formaldehyde degrading material, and formaldehyde is subjected to oxidative decomposition under sunlight irradiation by using the bismuth subcarbonate-based sunlight-driven indoor formaldehyde degrading material. The whole manufacturing process is simple and efficient, and the formaldehyde scavenger is convenient to operate and low in use cost, is effective for a long time and is non-toxic. Therefore, the coating can be compounded with an interior wall coating and applied to the field of indoor air purification.
Disclosure of Invention
The specific technical scheme of the invention is as follows:
preparation of basic bismuth carbonate with different shapes
Preparing flower-shaped basic bismuth carbonate (F-BOC for short): bismuth nitrate, sodium citrate, urea and polyvinylpyrrolidone (PVP) are mixed in sequence and dispersed in the water solution. Then hydrothermally in an autoclave. Grinding to obtain F-BOC;
preparation of spongy bismuth subcarbonate (S-BOC for short): fully mixing bismuth nitrate and sodium citrate powder, dropwise adding ammonia water to adjust the pH value to be alkalescent, and carrying out hydrothermal treatment to obtain S-BOC.
② the combination of basic bismuth carbonates with different shapes (abbreviated as SF-BOC)
And (2) adding the synthesized spongy bismuth subcarbonate with different mass ratios in the synthesis process of the step (1), uniformly stirring, carrying out hydrothermal treatment, washing and drying to obtain SF-BOC.
Drawings
FIG. 1 shows Bi prepared in different morphologies2O2CO3XRD pattern of its composite material, successful synthesis of surface material;
FIG. 2 is a scanning electron micrograph of the prepared sample, a and d are F-BOC, b and e are SF-BOC, and c and F are S-BOC; SEM results show that F-BOC is a flake-assembled flower-shaped ball with a compact structure, S-BOC is a rose-shaped structure formed by sponge sheets, the diameters of the S-BOC and the S-BOC are all about 2 mu m, after compounding, the structure is between the F-BOC and the S-BOC, the flower-shaped ball is of a loose structure, and the ball diameter is enlarged to 2.4 mu m;
FIG. 3 is an in situ DRIFTS spectrum of bismuth subcarbonate; the characteristic peak continuously rises along with the increase of the exposure time in the formaldehyde environment, and when the adsorption time is 150s, the characteristic peak does not obviously change any more, which indicates that the adsorption and desorption equilibrium is reached. In the spectrogram, 977cm-1，1013cm-1，1085cm-1And 1169cm-1At 1563cm, a C = O elongation of formaldehyde dimer was detected-1The peak at (A) is due to asymmetric stretching of-COOH at 1645cm-1Is due to-COO-I.e. it is demonstrated that formic acid and formate intermediate products are formed during the oxidation of formaldehyde. 2358cm-1Due to CO2Characteristic peak of (A), indicating that formaldehyde is oxidized to form CO2. Shows that in the oxidation process of bismuth subcarbonate to formaldehyde, paraformaldehyde firstly forms formaldehyde dimer and formic acid, formate intermediate product, and then is further oxidized into CO2。
FIG. 4 is a graph of SF-BOC oxidation removal performance to 300ppm of formaldehyde under simulated sunlight, a is an oxidation rate graph of different compounding ratios, and b is an oxidation effect graph with a compounding ratio of F-BOC to S-BOC of 10: 1; the compound bismuth subcarbonate has better formaldehyde removal effect than single-shape, wherein the compound ratio of F-BOC to S-BOC is 10:1, the effect is optimal, the removal efficiency reaches 99.099% when the compound bismuth subcarbonate is illuminated for 10min, and as can be seen from a b picture, the main product of formaldehyde oxidation is CO2Only a very small amount of CO is generated, and only less than 20% of formaldehyde is oxidized in the absence of light, which shows that under the synergistic action of illumination and heat, the photo-catalysis plays a main role and is far higher than the thermal catalysis.
Fig. 5 is a formaldehyde oxidation cycle chart of bismuth subcarbonate, and after twenty cycles, the catalytic effect of bismuth subcarbonate on formaldehyde is not reduced at all, which indicates that the prepared bismuth subcarbonate not only has good oxidation effect, but also has good stability, which may be attributed to the interaction of two morphologies.
FIG. 6 is a VOC oxidation effect chart, wherein SF-BOC has good effects on formaldehyde, toluene and benzene, the oxidation rates are 99.20%, 91.89% and 80.71% respectively, and the VOC oxidation effect chart is more stable to formaldehyde.
The present invention will be further described with reference to the following examples.
Example 1:
weighing 0.03g of SF-BOC, adding 3mL of absolute ethyl alcohol, performing ultrasonic treatment for 1min to uniformly disperse the catalyst in the ethanol, uniformly spin-coating the dispersed catalyst on a watch glass with the diameter of 6cm, drying at 60 ℃, placing the coated sheet in a reactor with the volume of 2 liters after drying, and arranging an air circulation device with a light source of a 300W xenon lamp. Formaldehyde and benzene in the reactor are brought into the reaction device by an air bubbling method, the concentration is controlled by adjusting air flow, and the change of substances in the reaction gas is detected by using a gas infrared detector and a gas chromatography. The reaction conditions are changed, activity measurement is carried out, and the results are respectively shown in figures 3-6, and 99.099% of paraformaldehyde can be degraded in a gas phase reactor under the irradiation of simulated sunlight for 10 min.
Claims (8)
1. The preparation method of the bismuth subcarbonate and the compound material thereof with different shapes comprises the following steps:
step 1, preparation of flower-shaped basic bismuth carbonate (F-BOC for short)
Sequentially mixing bismuth nitrate, sodium citrate, urea and polyvinylpyrrolidone (PVP) uniformly and dispersing in an aqueous solution; then hydrothermal treatment is carried out in a high-pressure kettle; cooling, filtering, washing, drying and grinding to obtain F-BOC;
step 2, preparation of spongy bismuth subcarbonate (S-BOC for short)
Fully mixing bismuth nitrate and sodium citrate powder, dropwise adding ammonia water to adjust the pH value to be alkalescent, carrying out hydrothermal treatment, washing and drying to obtain S-BOC;
step 3, preparation of mixed morphology bismuth subcarbonate compound material (SF-BOC for short)
And (2) adding the synthesized spongy bismuth subcarbonate with different mass ratios in the synthesis process of the step (1), uniformly stirring, carrying out hydrothermal treatment, washing and drying to obtain SF-BOC.
2. The use method of the bismuth subcarbonate and the compound material thereof with different shapes for purifying indoor formaldehyde and VOC comprises the following steps:
step 1: weighing 0.03g of SF-BOC, adding 3mL of absolute ethyl alcohol, performing ultrasonic treatment for 1min to uniformly disperse the catalyst in the ethanol, uniformly spin-coating the dispersed catalyst on a watch glass with the diameter of 6cm, drying at 60 ℃, placing the coated sheet in a reactor with the volume of 2 liters after drying, and arranging an air circulation device with a light source of a 300W xenon lamp; formaldehyde, benzene and toluene in the reactor are brought into a reaction device by an air bubbling method, the concentration is controlled by adjusting air flow, and the change of substances in reaction gas is detected by using a gas infrared detector and a gas chromatography; the reaction conditions are changed, activity measurement is carried out, and the results are respectively shown in figures 3-6, and 99.099% of paraformaldehyde can be degraded in a gas phase reactor under the irradiation of simulated sunlight for 10 min.
3. The preparation method of bismuth subcarbonate and its built-up material with different morphologies as claimed in claim 1, wherein in steps 1, 2, and 3, hydrothermal condition is constant temperature at 180 ℃ for 12 h.
4. The preparation method of bismuth subcarbonate and the compound material thereof with different morphologies according to claim 1, wherein the heteromorphic interface recombination of the bismuth subcarbonate with different morphologies is realized by a one-step hydrothermal method.
5. The reaction conditions for purifying indoor formaldehyde and VOCs as claimed in claim 2, wherein the reaction conditions completely simulate indoor environment.
6. The reaction conditions of claim 2, wherein formaldehyde, benzene and toluene can be oxidized into carbon dioxide and water by using simulated sunlight, and the selectivity of the product carbon dioxide is extremely high (more than 99%).
7. The reaction for purifying formaldehyde and VOCs in a room as claimed in claim 2, which is used for catalytic oxidation of VOCs mainly comprising formaldehyde under sunlight, wherein the removal efficiency of the bismuth subcarbonate compound material with a mixed morphology to 300ppm formaldehyde can reach 99.099% within 10 minutes.
8. The mixed-morphology bismuth subcarbonate compound material according to claim 2 treats indoor VOCs (including formaldehyde, benzene, toluene and other volatile gases), and is characterized by having good effects on formaldehyde, toluene and benzene, and the oxidation rates of the materials are 99.20%, 91.89% and 80.71% respectively under simulated indoor environmental conditions.
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