CN111330560B - Preparation method of natural lignin-based photocatalytic material - Google Patents
Preparation method of natural lignin-based photocatalytic material Download PDFInfo
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- 229920005610 lignin Polymers 0.000 title claims abstract description 74
- 239000000463 material Substances 0.000 title claims abstract description 32
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 24
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 22
- 239000002351 wastewater Substances 0.000 claims abstract description 8
- 230000004048 modification Effects 0.000 claims description 16
- 238000012986 modification Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 238000000498 ball milling Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 9
- 235000011089 carbon dioxide Nutrition 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 238000007334 copolymerization reaction Methods 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 5
- 239000012855 volatile organic compound Substances 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 239000011941 photocatalyst Substances 0.000 abstract description 19
- 239000002131 composite material Substances 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 12
- 239000003054 catalyst Substances 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 239000002245 particle Substances 0.000 abstract description 7
- 238000007146 photocatalysis Methods 0.000 abstract description 6
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 3
- 238000009827 uniform distribution Methods 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 19
- 238000001035 drying Methods 0.000 description 12
- 239000004408 titanium dioxide Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 10
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- 238000003756 stirring Methods 0.000 description 7
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 229910021389 graphene Inorganic materials 0.000 description 5
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
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- -1 amine salt Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 235000013824 polyphenols Nutrition 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005576 amination reaction Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007590 electrostatic spraying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 230000006870 function Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229920005615 natural polymer Polymers 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000003265 pulping liquor Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 238000006683 Mannich reaction Methods 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- XQSBLCWFZRTIEO-UHFFFAOYSA-N hexadecan-1-amine;hydrobromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[NH3+] XQSBLCWFZRTIEO-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
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- B01J35/39—
-
- 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
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
-
- 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
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/20—Total organic carbon [TOC]
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of catalyst material preparation, and discloses a preparation method of a natural lignin-based catalytic material. The lignin-based nano metal oxide composite photocatalyst prepared by the method has small particle size of metal oxide, uniform distribution, remarkably improved photocatalytic efficiency, strong catalytic degradation effect on volatile organic matters and high-concentration organic wastewater, and potential application value in the field of photocatalysis, in particular in the field of degradation of volatile organic matters difficult to treat and nitrogen-containing organic pollutants.
Description
Technical Field
The invention belongs to the technical field of catalyst material preparation, and discloses a preparation method of a natural polymer lignin-based catalytic material. Can be applied to the field of photocatalysis, and has potential application value in the field of degradation of volatile organic compounds and nitrogen-containing organic pollutants which are difficult to treat by photocatalysis.
Background
In recent years, with the development of society, serious environmental pollution is caused by organic wastewater discharged in textile and fine chemical production processes, and the problem has been highly valued by global researchers. As a novel and effective green technology, the photocatalysis technology has important application prospect in the fields of environment and energy. The nano titanium dioxide is used as an excellent semiconductor material, has the advantages of stable chemical property, corrosion resistance, acid and alkali resistance, low price and the like, is widely used as a photocatalyst, and can be used for degrading organic pollutants in water. Lignin is one of the most widely occurring sources in nature, being the second most amorphous state of polyphenol polymers with plant kingdom content next to cellulose. It is a renewable, green and environment-friendly natural polymer material. Commercial lignin exists in papermaking black liquor as a byproduct of the papermaking industry and is rarely further processed and utilized, so that resource waste and even environmental problems are caused. Lignin contains rich phenolic hydroxyl groups, so that the lignin has certain reduction performance, and the heterogeneous catalyst taking the lignin as a carrier has attracted attention from researchers,
however, the photocatalytic activity of titanium dioxide is limited by its forbidden bandwidth (the forbidden bandwidth of the rutile phase is 3.0eV, and the forbidden bandwidth of the anatase phase is 3.2 eV), and it can only be excited by ultraviolet light with a wavelength less than 380nm, and the solar light utilization rate is low. On the other hand, when the TiO2 photocatalyst is irradiated with solar light, electrons and holes generated by excitation are easily recombined on the surface and in the body thereof, resulting in low photocatalytic efficiency. The carbon material has good electron transmission capability and a certain sensitization effect on the semiconductor material, and the semiconductor material and the carbon material are compounded together, so that the defects can be overcome to a certain extent. A great deal of researches show that the photocatalytic performance of the carbon material (graphene, carbon fiber, carbon nano tube and the like) and TiO2 are obviously improved by compounding. Document (ACS Applied Materials & Interfaces,2013,5 (3): 1156-1164.) discloses a method for preparing TiO 2/carbon (GR, CNT and C60) nanocomposite materials with different carbon material addition ratios by sol-gel method and hydrothermal method treatment, and researches the photocatalytic performance of the synthesized TiO 2/carbon composite materials by photocatalytic degradation of benzyl alcohol, and by adding GR, CNT and C60, the increase of light absorption intensity in the visible light region can be induced, the visible light response of Ti O2/GR, ti O2/CNT and Ti O2/C60 nanocomposite materials is effectively promoted, and the effective separation of photo-excited electron-hole pairs is promoted, thereby improving the photocatalytic efficiency thereof. Chinese patent CN 107308929a discloses a graphene-nano titanium dioxide composite photocatalyst, which is prepared by synthesizing graphene oxide with graphite powder, adding deionized water to prepare graphene oxide solution, adding hexadecyl ammonium bromide solution and titanium trichloride solution, reacting in a high-pressure reaction kettle, precipitating, and washing to obtain the product. However, the preparation process of the carbon-based material (graphene, carbon nano tube, fullerene and the like) of the carbon-based/Ti O2 composite photocatalyst is complex and expensive, strong acid and strong alkali are needed in the preparation process, and the environmental pollution is serious; the prepared carbon-based material with a certain shape is compounded with TiO2, so that the binding force between the carbon-based material and the TiO2 is weak; meanwhile, carbon-based materials such as graphene and the like are easy to agglomerate, so that the carbon-based materials and titanium dioxide in the prepared composite photocatalyst are unevenly distributed. These problems greatly limit the photocatalytic performance and hinder the commercial application prospect.
Lignin is a high molecular polymer with a three-dimensional space network structure, has high carbon content and multiple active functional groups, and is an excellent precursor for preparing carbon materials, wherein the reserve of lignin in nature is inferior to that of cellulose. Industrial lignin is mainly derived from byproducts of pulp and paper industry: the lignin sulfonate in the red pulping liquor by the sulfurous acid method and the alkali lignin in the black pulping liquor by the alkali method are mostly treated and discharged as waste liquid. The effective utilization of the industrial lignin can save resources and is beneficial to reducing environmental burden. The lignin is used as a template for preparing titanium dioxide, for example, in the literature (forest engineering, 2015 (3): 54-56.) the alkali lignin is used as a raw material, and the lignin amine salt obtained by the Mannich reaction is added into hydrochloric acid solution of butyl titanate, subjected to hydrothermal reaction at 80-130 ℃ for 72 hours, and sintered at 500 ℃ for 10 hours to obtain titanium dioxide nano particles. Chinese patent CN106824151A discloses a lignin-based mesoporous titanium dioxide photocatalytic material, a preparation method and application, wherein titanium tetrachloride is added into an alkali lignin solution, the pH is regulated to 1-5, heating is carried out for a period of time at 60-100 ℃, ammonia water is added, centrifugal separation is carried out, ball milling is carried out, calcination is carried out at 400-600 ℃ for 5h, and the lignin is removed, thus obtaining the titanium dioxide. Although titanium dioxide with better performance can be obtained by the method for preparing titanium dioxide by taking lignin as a template, the preparation process is complex, hydrothermal, ball milling and other processes are required, and long-time calcination is generally required for removing the template, so that the cost is increased, and the lignin is not fully utilized
In the existing preparation of the lignin carbon/titanium dioxide composite photocatalyst, as titanium alkoxide of a titanium dioxide precursor is extremely easy to hydrolyze and cannot be well dispersed in lignin solution, the precursor can only be slowly added into lignin aqueous solution, so that the obtained titanium dioxide particles are larger, no strong acting force exists between titanium dioxide and lignin, and the coating amount of lignin is smaller. These factors have greatly limited the development of lignin carbon-based nano metal oxide photocatalysts prepared from lignin as a carbon source.
Disclosure of Invention
In order to solve the problem of the preparation of the photocatalyst by taking the limited lignin as a raw material, the preparation method of the natural lignin-based photocatalytic material is provided, the lignin is modified firstly, then the small-particle-size catalyst is prepared, the distribution is uniform, and the photocatalytic efficiency is high.
The invention adopts the technical proposal for solving the problems that: a method for preparing natural lignin-based photocatalytic material comprises the following steps,
s1, modification: firstly, modifying natural lignin separated from plants;
s2, mixing: adding dry ice and nano metal oxide into the modified natural lignin, and ball milling the mixture in a ball mill to prepare a lignin-nano metal oxide mixture;
s3, drying: heating the mixture at 100-900 deg.c for 1-24 hr to obtain nanometer catalytic material.
Further, the S1 modification: lignin modification includes, but is not limited to, amine-based cationization, sulfomethylation, multiple monomer graft copolymerization, and the like.
Further, the step S2 is mixed: the amount of the added dry ice is 0.01-10 times of the mass dosage of the lignin, and the amount of the added metal oxide is 0.01-1 time of the mass dosage of the lignin.
Further, the step S2 is mixed: nano metal oxides include, but are not limited to, semiconductor catalytic materials such as ZnO, seO and Cu 2 O, etc.; magnetic catalytic material, fe 2 O 3 ，Fe 3 O 4 NiO, coO, etc.
Further, the step S3 is to dry: the lignin-based nano metal oxide composite is heated to 400-800 ℃ in an inert atmosphere and calcined for 1-4 hours to obtain the lignin carbon-based nano metal oxide composite photocatalyst, and the catalytic material can be directly applied to photocatalytic degradation of VOCs or high-concentration organic wastewater.
According to the method, natural lignin polymer separated from plants is modified, amination modification, grafting modification and the like are carried out according to the properties of adsorbed substances according to the application requirements of products, dry ice and nano metal oxide are mixed, and the mixture is placed in a ball mill for ball milling to prepare a lignin-metal oxide mixture, wherein the aim is to remove branches on lignin, convert phenolic hydroxyl into carboxyl and embed the metal oxide into lignin gaps. The mixture is then formed into a particulate catalytic material. The preparation method comprises, but is not limited to, binder addition extrusion molding, electrostatic spraying granulation, or pyrolysis carbonization and activation of the obtained lignin-metal oxide mixture to prepare the porous adsorption-catalysis composite material.
The lignin-based nano metal oxide composite photocatalyst prepared by the method has small particle size of metal oxide, uniform distribution, remarkably improved photocatalytic efficiency, strong catalytic degradation effect on volatile organic matters and high-concentration organic wastewater, and potential application value in the field of photocatalysis, in particular in the field of degradation of volatile organic matters difficult to treat and nitrogen-containing organic pollutants.
Detailed Description
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto. The materials referred to in the following examples are all available from commercial sources.
Example 1
A preparation method of a natural lignin-based photocatalytic material comprises the following specific steps:
s1, modification: taking 100g of lignin, adding 200g of water and 120mL of 1.5% (mass concentration) NaOH aqueous solution, stirring for 20 minutes, adding 10g of formaldehyde, continuously stirring for 20 minutes, then adding 20ml of ethylenediamine while stirring, heating in a water bath at 100 ℃, and refluxing and stirring for 3 hours to obtain an aminated modified lignin sample;
s2, mixing: drying the sample obtained in S1 in an oven at 105 ℃ for 24 hours, taking out, adding 10g of nano TiO2 (particle size 10 nm) and 10g of dry ice, putting into a ball milling tank, and simultaneously putting 300g of Al with diameter of 3mm 2 O 3 Grinding balls, placing the grinding balls in a planetary ball mill, setting the rotating speed to be 500RPM, and ball milling for 3 hours to obtain a lignin-based nano titanium dioxide mixture;
s3, drying: and (3) placing the nano titanium dioxide mixture obtained in the step (S2) in an atmosphere furnace, reacting for 3 hours at 700 ℃ in N2 atmosphere, continuously introducing a small amount of water vapor, fully reacting for 1 hour at 900 ℃, and stopping heating until the temperature in the furnace is reduced to room temperature, thus obtaining the lignin carbon-based nano metal oxide composite photocatalyst.
Example 2
The preparation method of the natural lignin-based photocatalytic material comprises the steps of preparing natural high-molecular lignin, aminating and modifying the natural high-molecular lignin, adding nano TiO2 and dry ice according to a mass ratio, placing the nano TiO2 and the dry ice into a planetary ball mill for ball milling, and preparing the obtained powder into the nano composite matrix catalytic material by adopting an electrostatic spraying method.
The method comprises the following specific steps:
s1, modification: lignin is aminated and modified as in example 1;
s2, mixing: drying the sample obtained in S1 in an oven at 105 ℃ for 24 hours, taking out, adding 10g of nano TiO2 (particle size 10 nm) and 10g of dry ice, putting into a ball milling tank, and simultaneously putting 300g of Al with diameter of 3mm 2 O 3 Grinding balls, setting a rotating speed of 500RPM for a planetary ball mill, and ball milling for 3 hours to obtain a lignin-based nano titanium dioxide mixture;
s3, drying: and (3) placing the nano titanium dioxide mixture obtained in the step (S2) in an atmosphere furnace, reacting for 3 hours at 700 ℃ in N2 atmosphere, continuously introducing a small amount of water vapor, fully reacting for 1 hour at 900 ℃, stopping heating, knowing that the temperature in the furnace is reduced to room temperature, and removing a sample to obtain the lignin carbon-based nano metal oxide composite photocatalyst.
Example 3
S1, modification: 100g of lignin is taken, 1500g of deionized water is added, the mixture is added into a flask with stirring rod and reflux condensation, the temperature is raised to 40 ℃, dilute hydrochloric acid is slowly added to adjust the pH to 2, then 50g of 30% hydrogen peroxide aqueous solution is added, stirring and heating are carried out at 50 ℃ for 2 hours, then the temperature is raised to 80 ℃, 40g of sodium bisulphite and 30g of 30% formaldehyde aqueous solution are added, the constant temperature reaction is carried out for 12 hours, and then the mixture is cooled to room temperature, thus obtaining a crude product. The anionic resin was then soaked overnight with 2M aqueous sodium hydroxide solution and the cationic resin was soaked overnight with 2M aqueous hydrochloric acid solution. Sequentially flowing the obtained crude product through anion exchange resin and cation exchange resin, then washing the anion resin and the cation resin by using distilled water until the pH value of the cleaning solution is nearly neutral to obtain an extracting solution, and performing rotary evaporation on the extracting solution and then vacuum drying to obtain sulfomethylation modified lignin;
s2, mixing: as in example 1;
s3, drying: as in example 1.
Example 4
S1, modification: taking 100g of lignin, adding 200g of water, simultaneously adding 20g of phenol and 50g of 30-concentration formaldehyde aqueous solution, adding into a flask with stirring rod and reflux condensation, heating to 100 ℃, reacting for 12 hours, stopping the reaction, cooling, removing water in the reaction liquid by using a rotary evaporator, drying in a constant-temperature drying box at 100 ℃ for 12 hours, and drying to obtain lignin molecular monomer grafting copolymerization products;
s2, mixing: as in example 1;
s3, drying: as in example 1.
Example 5
S1, modification: sulfomethylation modification of lignin as in example 3;
s2, mixing: same as in example 2;
s3, drying: same as in example 2;
example 6
S1, modification: grafting copolymerization modification of lignin multielement monomer in the same way as in example 4;
s2, mixing: same as in example 2;
s3, drying: as in example 2.
The following demonstrates the function of the invention by UV photocatalytic degradation experiments on high concentration organic wastewater.
Comparative example 1: no photocatalyst is added;
example 1: the catalyst is an amination modified nano composite particle photocatalysis material;
example 2: the catalyst is an aminated modified nano composite photocatalytic material;
example 3: the catalyst is lignin sulfomethylation modified nano composite base photocatalytic material;
example 4: the catalyst is a lignin multielement monomer grafting copolymerization nanocomposite base photocatalytic material;
example 5: the catalyst is lignin sulfomethylation modified carbon-based nano metal oxide composite photocatalyst;
example 6: the catalyst is a lignin multielement monomer grafting copolymerization modified carbon-based nano metal oxide composite photocatalyst;
the TOC (total organic carbon) value of the high-concentration organic wastewater adopted in the experiment is 20000mg/L, and the catalyst dosage is 10g/1000g of wastewater
| Detecting items | TOC after 5min | TOC after 10min | TOC after 15min | TOC after 20min |
| Comparative example 1 | 19200 | 19100 | 18600 | 18500 |
| Example 1 | 14200 | 8900 | 5900 | 2800 |
| Example 2 | 14010 | 12140 | 8750 | 6800 |
| Example 3 | 10250 | 9800 | 7850 | 4850 |
| Example 4 | 8750 | 6500 | 3800 | 2950 |
| Example 5 | 6900 | 5500 | 2800 | 1800 |
| Example 6 | 5800 | 4500 | 2900 | 2200 |
The function of the invention is verified by experiments on UV photocatalytic degradation of VOCs as follows.
Comparative example 2: no photocatalyst is added;
example 1: the photocatalyst is a particle catalytic material;
example 2: a nano metal oxide composite photocatalyst;
the waste gas VOCs non-methane total hydrocarbon adopted in the experiment is 1000mg/L, and the space velocity of the catalyst is 300-1000h -1 。
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made therein without departing from the spirit and scope of the invention, which is defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (1)
1. The application of the natural lignin-based photocatalytic material in photocatalytic degradation of VOCs or high-concentration organic wastewater is characterized in that the specific preparation process of the natural lignin-based photocatalytic material is that,
s1, modification: firstly, modifying natural lignin separated from plants, wherein lignin modification comprises amino cationization, sulfomethylation or multi-monomer grafting copolymerization;
s2, mixing: adding dry ice and nano metal oxide into the modified natural lignin, wherein the amount of the added dry ice is 0.01-10 times of the mass dosage of the lignin, the amount of the added nano metal oxide is 0.01-1 time of the mass dosage of the lignin, and the nano metal oxide is nano TiO 2 Ball milling in ball mill to obtain lignin-nanometer metal oxide mixture;
s3, heating: heating the mixture to 400-800 ℃ in an inert atmosphere, calcining for 1-4 hours, continuously introducing a small amount of steam, fully reacting for 1 hour at 900 ℃, and stopping heating until the temperature in the furnace is reduced to room temperature, thus preparing the natural lignin-based photocatalytic material.
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