CN113262803A - Method for preparing photocatalyst by taking lignin as raw material and photocatalyst - Google Patents
Method for preparing photocatalyst by taking lignin as raw material and photocatalyst Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 38
- 229920005610 lignin Polymers 0.000 title claims abstract description 24
- 239000002994 raw material Substances 0.000 title claims abstract description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 50
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000011593 sulfur Substances 0.000 claims abstract description 49
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 49
- 238000001035 drying Methods 0.000 claims abstract description 28
- 238000005406 washing Methods 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 24
- 238000001354 calcination Methods 0.000 claims abstract description 20
- 229920001732 Lignosulfonate Polymers 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 230000007935 neutral effect Effects 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 17
- 229920005552 sodium lignosulfonate Polymers 0.000 claims description 14
- 238000003837 high-temperature calcination Methods 0.000 claims description 10
- 239000007832 Na2SO4 Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 229910000343 potassium bisulfate Inorganic materials 0.000 claims description 2
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 12
- 239000011148 porous material Substances 0.000 abstract description 10
- 238000002360 preparation method Methods 0.000 abstract description 7
- 239000003575 carbonaceous material Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract 2
- 231100001239 persistent pollutant Toxicity 0.000 abstract 1
- 238000001782 photodegradation Methods 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 24
- 230000001699 photocatalysis Effects 0.000 description 20
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 description 20
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 description 20
- 239000003054 catalyst Substances 0.000 description 12
- 239000004098 Tetracycline Substances 0.000 description 11
- 229960002180 tetracycline Drugs 0.000 description 11
- 229930101283 tetracycline Natural products 0.000 description 11
- 235000019364 tetracycline Nutrition 0.000 description 11
- 150000003522 tetracyclines Chemical class 0.000 description 11
- 238000002791 soaking Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000006731 degradation reaction Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000002835 absorbance Methods 0.000 description 7
- 230000003213 activating effect Effects 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 7
- 239000002253 acid Substances 0.000 description 5
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 5
- 239000011363 dried mixture Substances 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000001994 activation Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 239000011651 chromium Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000000287 crude extract Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002699 waste material Substances 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- B01J35/23—
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- B01J35/39—
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- B01J35/615—
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- B01J35/617—
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- B01J35/618—
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- B01J35/633—
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- B01J35/635—
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- B01J35/638—
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- 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
- C02F2101/34—Organic compounds containing oxygen
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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
- C02F2101/38—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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a method for preparing a photocatalyst by taking lignin as a raw material, which comprises the steps of uniformly mixing lignosulfonate with sulfur-containing Na salt or sulfur-containing K salt, calcining at high temperature, washing to be neutral after reaction, and drying to obtain a sulfur-doped carbon nano photocatalyst. The method realizes high-value utilization of lignosulfonate, and has the advantages of simple preparation method, low price of the obtained carbon material, developed pore structure, high photodegradation activity on persistent pollutants in water and good adsorption effect.
Description
Technical Field
The invention belongs to the technical field of comprehensive utilization of resources, and particularly relates to a method for preparing a photocatalyst by taking lignin as a raw material and the photocatalyst.
Background
The black liquor is waste water produced in paper industry, contains a large amount of lignosulfonate, other suspended solids, organic pollutants, inorganic matters and the like, and can cause serious pollution if directly discharged into water. Therefore, the method has important significance for separating and extracting various substances in the black liquor and realizing high-value utilization of the substances. The lignosulfonate can be widely applied to the aspects of concrete water reducing agents, oil well exploitation aids, adsorbing materials and the like through methods of modification, processing, conversion and the like.
The photocatalyst uses sunlight as an energy source, has a clean reaction process, is environment-friendly, and is particularly suitable for pollutant degradation such as tetracycline degradation and Cr degradation6+Has great advantages in the reactions such as photocatalytic reduction and the like. At present, the photocatalyst is mainly made of inorganic substances (such as TiO)2ZnO, CdS), low quantum efficiency, narrow range of absorbed sunlight, etc. And some two-dimensional carbon materials, e.g. graphene, g-C3N4And the like, the preparation process is relatively complex, the cost of the precursor raw material is high, and the preparation process has the defects of large environmental pollution and the like. Compared with the precursors, the photocatalyst prepared by using cheap and renewable biomass as a raw material has greater potential.
In recent years, research and development institutions at home and abroad carry out a great deal of work on sulfur-doped carbon materials. The sulfur-doped activated carbon has a developed pore structure and unique surface properties, and shows great potential in the fields of fuel cells, supercapacitors, heterogeneous catalysis, chemical sensors and the like. However, the preparation of the sulfur-containing photocatalyst by using the lignosulfonate as a raw material has not been reported.
The patent (201610700903.X) discloses a method for preparing activated carbon from crude extract of papermaking black liquor-lignosulfonateA method. Firstly, adding a crude extract of papermaking black liquor, namely lignosulfonate, into a hydrochloric acid solution to obtain a section of acid extract; adding a phosphoric acid solution into the first-stage acid leaching matter for ultrasonic leaching to obtain a second-stage acid leaching matter; introducing 0.1m3And h, discharging air by using nitrogen, and performing microwave heating and activation on the obtained two-stage acid leaching matters to obtain the activated carbon. The activated carbon obtained in this way has no photocatalytic effect.
The patent (201910503951.3, a sulfur-rich activated carbon and its preparation method) discloses a sulfur-rich activated carbon and its preparation method, the sulfur-rich activated carbon comprises sulfur and activated carbon, wherein sulfur is uniformly loaded on the activated carbon in the form of elemental sulfur. The preparation method of the sulfur-rich activated carbon comprises the steps of activating petroleum coke, contacting with acid gas for reaction after activation, and finally washing and drying to obtain the sulfur-rich activated carbon. The activated carbon obtained by the method only contains sulfur simple substance, and the material has no photocatalysis.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made keeping in mind the above and/or other problems occurring in the prior art.
The invention aims to provide a method for preparing a photocatalyst by taking lignin as a raw material and the photocatalyst, wherein lignosulfonate is activated at high temperature and introduced with sulfur species to prepare a sulfur-doped carbon nano photocatalyst, so that high-value utilization of waste is realized.
In order to solve the technical problems, the invention provides the following technical scheme: a method for preparing a photocatalyst by taking lignin as a raw material comprises the steps of uniformly mixing lignosulfonate with sulfur-containing Na salt or sulfur-containing K salt, calcining at a high temperature, washing to be neutral after reaction, and drying to obtain the sulfur-doped carbon nano photocatalyst.
As a method of the invention from ligninA preferred embodiment of the method for preparing a photocatalyst for a starting material, wherein: the sulfur-containing Na salt comprises Na2S、Na2SO3、Na2S2O3、NaHSO3、NaHSO4、Na2SO4One or more of;
the sulfur-containing K salt comprises K2S、K2SO3、K2S2O3、KHSO3、KHSO4、K2SO4One or more of (a).
As a preferable embodiment of the method for preparing the photocatalyst from lignin according to the present invention, wherein: and (3) calcining at high temperature, namely calcining at 300-1000 ℃.
As a preferable embodiment of the method for preparing the photocatalyst from lignin according to the present invention, wherein: the high-temperature calcination is carried out at the temperature of 500 ℃.
As a preferable embodiment of the method for preparing the photocatalyst from lignin according to the present invention, wherein: and (3) high-temperature calcination, wherein the heating rate is 3-10 ℃/min, and the calcination time is 1-2 hours.
As a preferable embodiment of the method for preparing the photocatalyst from lignin according to the present invention, wherein: the sodium lignosulfonate is uniformly mixed with sulfur-containing Na salt or sulfur-containing K salt, the sulfur-containing Na salt or the sulfur-containing K salt is stirred in water until the sulfur-containing Na salt or the sulfur-containing K salt is completely dissolved, sodium lignosulfonate is added, and the mixture is soaked for 18-36 hours.
As a preferable embodiment of the method for preparing the photocatalyst from lignin according to the present invention, wherein: before the high-temperature calcination, the solution after the impregnation is subjected to oil bath at 80 ℃ to evaporate water, and the solution is dried in an oven.
As a preferable embodiment of the method for preparing the photocatalyst from lignin according to the present invention, wherein: the mass ratio of the raw material to the sulfur-containing Na salt or the sulfur-containing K salt is 0.05-20: 1.
as a preferable embodiment of the method for preparing the photocatalyst from lignin according to the present invention, wherein: the mass ratio of the raw material to the sulfur-containing Na salt or the sulfur-containing K salt is 1: 1.
another object of the present invention is to provide a photocatalyst prepared by any one of the above methods for preparing a photocatalyst from lignin, wherein the obtained photocatalyst has a developed pore structure, contains abundant surface functional groups, and has excellent adsorption and photocatalytic properties.
Compared with the prior art, the invention has the following beneficial effects:
(1) compared with the traditional photocatalyst, the method takes the lignosulfonate from the black liquor as the raw material, the prepared photocatalyst is low in price and high in photocatalytic efficiency, and the high-value utilization of the lignosulfonate is realized.
(2) By using the sulfur-containing activating agent, sulfur species with photocatalytic activity can be introduced, and the function of activating the pore structure of the carbon material can be achieved, so that the obtained photocatalyst has the advantages of large specific surface area, high photocatalytic efficiency and the like.
(3) The sulfonic acid group in the lignosulfonate raw material can generate sulfur species with photocatalytic activity in the pyrolysis or activation process, the process is simple, and the obtained photocatalyst is low in price and suitable for industrial application.
(4) The sulfur-doped carbon nano photocatalyst obtained by using the sulfur-containing activating agent has a developed pore structure, contains rich surface functional groups and has excellent adsorption and photocatalytic properties.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
FIG. 1 is an infrared spectrum of a catalyst prepared in examples 1 to 6 of the present invention;
FIG. 2 shows N in catalysts prepared in examples 1 to 6 of the present invention2Adsorption-desorption curves;
FIG. 3 shows the reaction results of the catalysts prepared in examples 1 to 4 of the present invention for photocatalytic degradation of tetracycline in wastewater;
FIG. 4 shows the results of the reaction of the catalysts prepared in examples 5 and 6 of the present invention to degrade tetracycline in wastewater by photocatalysis;
FIG. 5 shows the result of the reaction of the catalyst prepared in example 7 of the present invention for photocatalytic degradation of chromium ions in wastewater.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof are described in detail below with reference to examples of the specification.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
(1) 5 g of sodium lignosulfonate is calcined at 500 ℃ for 2 hours at 5 ℃/min to obtain the unactivated sulfur-doped carbon nano photocatalyst which is marked as S-C.
Example 2
(1) 32 g of sodium sulfide nonahydrate is taken and put in 400 ml of water, stirred until the sodium sulfide nonahydrate is completely dissolved, 10 g of sodium lignosulphonate is added, dipped for 24 hours, dried by distillation in oil bath at 80 ℃, and dried in an oven;
(2) calcining at 500 ℃ for 2 hours at 5 ℃/min, washing with 0.1mol/L hydrochloric acid, then washing to neutrality with water, and drying at 100 ℃ overnight to obtain the sulfur-doped carbon nano photocatalyst which is marked as S-AC (1: 1).
Example 3
(1) 62 g of sodium sulfide nonahydrate is taken and put in 400 ml of water, stirred until the sodium sulfide nonahydrate is completely dissolved, 10 g of sodium lignosulphonate is added, dipped for 24 hours, dried by distillation in oil bath at 80 ℃, and dried in an oven;
(2) calcining at 500 ℃ for 2 hours at 5 ℃/min, washing with 0.1mol/L hydrochloric acid, then washing to neutrality with water, and drying at 100 ℃ overnight to obtain the sulfur-doped carbon nano photocatalyst which is marked as S-AC (1: 2).
Example 4
(1) Taking 15.5 g of sodium sulfide nonahydrate in 400 ml of water, stirring until the sodium sulfide nonahydrate is completely dissolved, adding 10 g and 5 g of sodium lignosulphonate, soaking for 24 hours, drying the sodium sulfide nonahydrate in an oil bath at 80 ℃ to dryness, and drying the sodium sulfide nonahydrate in an oven;
(2) calcining at 500 deg.C for 2 hr at 5 deg.C/min, washing with 0.1mol/L hydrochloric acid, washing to neutrality, and drying at 100 deg.C overnight to obtain sulfur-doped carbon nano photocatalyst labeled as S-AC (1: 0.5).
Example 5
(1) Taking 31 g of sodium sulfide nonahydrate in 400 ml of water, stirring until the sodium sulfide nonahydrate is completely dissolved, adding 10 g of sodium lignosulfonate and 5 g of sodium lignosulfonate, soaking for 24 hours, drying the sodium sulfide nonahydrate in an oil bath at 80 ℃ to dryness, and drying the sodium sulfide nonahydrate in an oven;
(2) calcining at 700 deg.C for 2 hr at 5 deg.C/min, washing with 0.1mol/L hydrochloric acid, washing to neutrality, and drying at 100 deg.C overnight to obtain sulfur-doped carbon nano photocatalyst labeled as S-AC (1:1,700 deg.C).
Example 6
(1) Taking 31 g of sodium sulfide nonahydrate in 400 ml of water, stirring until the sodium sulfide nonahydrate is completely dissolved, adding 10 g of sodium lignosulfonate and 5 g of sodium lignosulfonate, soaking for 24 hours, drying the sodium sulfide nonahydrate in an oil bath at 80 ℃ to dryness, and drying the sodium sulfide nonahydrate in an oven;
(2) calcining at 900 deg.C for 2 hr at 5 deg.C/min, washing with 0.1mol/L hydrochloric acid, washing to neutrality, and drying at 100 deg.C overnight to obtain sulfur-doped carbon nano photocatalyst labeled as S-AC (1:1,900 deg.C).
Performance testing
The infrared spectrum test of the sulfur-doped carbon nano photocatalyst prepared in the examples 1 to 6 was performed, and the test result is shown in fig. 1, and it can be seen from fig. 1 that the lignosulfonate becomes a sulfur-doped carbon material after being carbonized.
The sulfur-doped carbon nano photocatalyst prepared in the examples 1 to 6 was subjected to a pore structure parameter test, and the N content of the sample was measured by a physical adsorption apparatus2The adsorption-desorption curves and the test results are shown in table 1 and fig. 2.
TABLE 1
As can be seen from the test results, the sulfur-doped carbon nanophotocatalysts prepared in examples 2, 3 and 4 have a relatively developed pore structure by using a sulfur-containing activator, whereas the specific surface areas of S-AC (1:1,700 ℃) and S-AC (1:1,900 ℃) prepared under high-temperature calcination conditions are relatively large, the specific surface areas of S-AC (1:1,700 ℃) and S-AC (1:1,900 ℃) prepared under high-temperature calcination conditions are relatively developed pore structures, and the specific surface areas of S-AC (1:2,500 ℃) prepared in example 3 are relatively small.
The sulfur-doped carbon nano photocatalyst prepared in the embodiment 1-6 is subjected to a photocatalytic activity test, and the test method comprises the following steps: and (3) adding 50mg of sulfur-doped carbon nano photocatalyst into 20mg/L tetracycline solution, placing the tetracycline solution in the dark for adsorption for half an hour, illuminating for 3 hours under visible light, and measuring the absorbance at 357 nm. In the test process, it is found that, because the specific surface areas of S-AC (1:1,700 ℃) and S-AC (1:1,900 ℃) prepared under the high-temperature calcination condition are large, tetracycline can be completely degraded within 30min by using 50mg of catalysts S-AC (1:1,700 ℃) and S-AC (1:1,900 ℃), and the catalyst mass is reduced to 5mg in order to judge whether the two have the photocatalytic activity. Thus, the results of the adsorption performance test of examples 1 to 4 are shown in fig. 3, and the results of the adsorption performance test of examples 5 and 6 are shown in fig. 4.
As can be seen from FIG. 3, S-AC (1:0.5,500 ℃) prepared in example 4 has no photocatalytic activity basically, and the sulfur-doped carbon nano-photocatalyst prepared in examples 1-3 has excellent photocatalytic performance.
As can be seen from FIG. 4, S-AC (1:1,700 ℃ C.) and S-AC (1:1,900 ℃ C.) prepared under high temperature calcination conditions have substantially no photocatalytic activity.
Example 7
(1) Taking 31 g of sodium sulfide nonahydrate in 400 ml of water, stirring until the sodium sulfide nonahydrate is completely dissolved, adding 10 g of sodium lignosulfonate and 5 g of sodium lignosulfonate, soaking for 24 hours, drying the sodium sulfide nonahydrate in an oil bath at 80 ℃ to dryness, and drying the sodium sulfide nonahydrate in an oven;
(2) calcining at 500 ℃ for 2 hours at 5 ℃/min, washing with 0.1mol/L hydrochloric acid, then washing to neutrality, and drying to obtain the sulfur-doped carbon nano photocatalyst marked as S-AC (1: 1).
(3) Taking Cr with the concentration of 10mg/l6+Adding 50mg of sulfur-doped carbon nano photocatalyst, placing the photocatalyst in the dark for adsorption for 2 hours, then illuminating for 3 hours under visible light, and measuring the absorbance at 352 nm. As shown in FIG. 5, it can be seen from FIG. 5 that the removal rate of Cr ions reached 80 or more after 3 hours of the reaction.
Example 8
(1) Taking 10 g of Na2S2O3Stirring the mixture in 400 ml of water until the mixture is completely dissolved, adding 10 g of sodium lignin sulfonate, soaking the mixture for 24 hours, evaporating the water in an oil bath at the temperature of 80 ℃ to dryness, and drying the dried mixture in an oven;
(2) calcining at 500 deg.C for 2 hr at 5 deg.C/min, washing with 0.1mol/L hydrochloric acid, washing to neutrality, and drying to obtain sulfur-doped carbon nano photocatalyst labeled as S-AC (1:1) -Na2S2O3。
(3) Taking 20mg/L tetracycline solution, adding 50mg catalyst, adsorbing in dark for half an hour, illuminating for 3 hours under visible light, measuring its absorbance at 357nm, and its degradation rate reaches 100%.
Example 9
(1) Taking 10 g of Na2S2O3Stirring the mixture in 400 ml of water until the mixture is completely dissolved, adding 10 g of sodium lignin sulfonate, soaking the mixture for 24 hours, evaporating the water in an oil bath at the temperature of 80 ℃ to dryness, and drying the dried mixture in an oven;
(2) calcining at 500 deg.C for 2 hr at 5 deg.C/min, washing with 0.1mol/L hydrochloric acid, washing to neutrality, and drying to obtain sulfur-doped carbon nano photocatalyst labeled as S-AC (1:1) -Na2S2O3。
(3) Taking 20mg/L tetracycline solution, adding 50mg catalyst, adsorbing in dark for half an hour, illuminating for 3 hours under visible light, measuring its absorbance at 357nm, and its degradation rate reaches 100%.
Example 10
(1) 20 g of Na are taken2SO4Stirring the mixture in 400 ml of water until the mixture is completely dissolved, adding 10 g of sodium lignin sulfonate, soaking the mixture for 24 hours, evaporating the water in an oil bath at the temperature of 80 ℃ to dryness, and drying the dried mixture in an oven;
(2) calcining at 500 deg.C for 2 hr at 5 deg.C/min, washing with 0.1mol/L hydrochloric acid, washing to neutrality, and drying to obtain sulfur-doped carbon nano photocatalyst labeled as S-AC (1:2) -Na2SO4。
(3) Taking 20mg/L tetracycline solution, adding 50mg catalyst, placing in dark for half an hour for adsorption, illuminating for 3 hours under visible light, measuring its absorbance at 357nm, and its degradation rate is greater than 99%.
Example 11
(1) Taking 10 g of K2SO3Stirring the mixture in 400 ml of water until the mixture is completely dissolved, adding 10 g of sodium lignin sulfonate, soaking the mixture for 24 hours, evaporating the water in an oil bath at the temperature of 80 ℃ to dryness, and drying the dried mixture in an oven;
(2) calcining at 500 deg.C for 2 hr at 5 deg.C/min, washing with 0.1mol/L hydrochloric acid, washing to neutrality, and drying to obtain sulfur-doped carbon nano photocatalyst labeled as S-AC (1:2) -K2SO3。
(3) Taking 20mg/L tetracycline solution, adding 50mg catalyst, placing in dark for half an hour for adsorption, illuminating for 3 hours under visible light, measuring its absorbance at 357nm, and its degradation rate is greater than 99%.
Example 12
(1) 10 g of KHSO is taken3Stirring the mixture in 400 ml of water until the mixture is completely dissolved, adding 10 g of sodium lignin sulfonate, soaking the mixture for 24 hours, evaporating the water in an oil bath at the temperature of 80 ℃ to dryness, and drying the dried mixture in an oven;
(2) calcining at 500 deg.C for 2 hr at 5 deg.C/min, washing with 0.1mol/L hydrochloric acid, washing to neutrality, and drying to obtain sulfur-doped carbon nano photocatalyst labeled as S-AC (1:2) -KHSO3。
(3) Taking 20mg/L tetracycline solution, adding 50mg catalyst, placing in dark for half an hour for adsorption, illuminating for 3 hours under visible light, measuring its absorbance at 357nm, and its degradation rate is greater than 99%.
Compared with the traditional photocatalyst, the method takes the lignosulfonate from the black liquor as the raw material, the prepared photocatalyst is low in price and high in photocatalytic efficiency, and the high-value utilization of the lignosulfonate is realized.
By using the sulfur-containing activating agent, the invention can not only introduce sulfur species with photocatalytic activity, but also play a role in activating the pore structure of the carbon material, and the obtained photocatalyst has the advantages of large specific surface area, high photocatalytic efficiency and the like.
The sulfonic acid group in the lignosulfonate raw material can generate sulfur species with photocatalytic activity in the pyrolysis or activation process, the process is simple, and the obtained photocatalyst is low in price and suitable for industrial application.
The nano carbon photocatalyst obtained by using the sulfur-containing activating agent has a developed pore structure, contains rich surface functional groups and has excellent adsorption and photocatalytic properties.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should 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 of the present invention, which should be covered by the claims of the present invention.
Claims (10)
1. A method for preparing a photocatalyst by taking lignin as a raw material is characterized by comprising the following steps: the method comprises the following steps of uniformly mixing lignosulfonate serving as a raw material with a sulfur-containing Na salt or a sulfur-containing K salt, calcining at a high temperature, washing to be neutral after reaction, and drying to obtain the sulfur-doped carbon nano photocatalyst.
2. The method for preparing photocatalyst from lignin as claimed in claim 1, wherein: the sulfur-containing Na salt comprises Na2S、Na2SO3、Na2S2O3、NaHSO3、NaHSO4、Na2SO4One or more of;
the sulfur-containing K salt comprises K2S、K2SO3、K2S2O3、KHSO3、KHSO4、K2SO4One or more of (a).
3. The method for preparing photocatalyst from lignin as claimed in claim 1 or 2, wherein: and (3) calcining at high temperature, namely calcining at 300-1000 ℃.
4. The method for preparing photocatalyst from lignin as claimed in claim 3, wherein: the high-temperature calcination is carried out at the temperature of 500 ℃.
5. The method for preparing photocatalyst from lignin as claimed in any one of claims 1, 2 and 4, wherein: and (3) high-temperature calcination, wherein the heating rate is 3-10 ℃/min, and the calcination time is 1-2 hours.
6. The method for preparing photocatalyst from lignin as claimed in any one of claims 1, 2 and 4, wherein: the sodium lignosulfonate is uniformly mixed with sulfur-containing Na salt or sulfur-containing K salt, the sulfur-containing Na salt or the sulfur-containing K salt is stirred in water until the sulfur-containing Na salt or the sulfur-containing K salt is completely dissolved, sodium lignosulfonate is added, and the mixture is soaked for 18-36 hours.
7. The method for preparing photocatalyst from lignin as claimed in claim 6, wherein: before the high-temperature calcination, the solution after the impregnation is subjected to oil bath at 80 ℃ to evaporate water, and the solution is dried in an oven.
8. The method for preparing photocatalyst from lignin as claimed in any one of claims 1, 2, 4 and 7, wherein: the mass ratio of the raw material to the sulfur-containing Na salt or the sulfur-containing K salt is 0.05-20: 1.
9. the method for preparing photocatalyst from lignin as claimed in claim 8, wherein: the mass ratio of the raw material to the sulfur-containing Na salt or the sulfur-containing K salt is 1: 1.
10. the photocatalyst prepared by the method for preparing the photocatalyst by using the lignin as the raw material according to any one of claims 1 to 9.
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