CN111450861A - Comprising g-C3N4Composite photocatalyst of B and metal oxide and application thereof in fuel oil denitrification - Google Patents
Comprising g-C3N4Composite photocatalyst of B and metal oxide and application thereof in fuel oil denitrification Download PDFInfo
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- CN111450861A CN111450861A CN201910059203.0A CN201910059203A CN111450861A CN 111450861 A CN111450861 A CN 111450861A CN 201910059203 A CN201910059203 A CN 201910059203A CN 111450861 A CN111450861 A CN 111450861A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 90
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 22
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 22
- 239000000295 fuel oil Substances 0.000 title claims description 13
- 239000002131 composite material Substances 0.000 claims abstract description 82
- 230000015556 catabolic process Effects 0.000 claims abstract description 31
- 238000006731 degradation reaction Methods 0.000 claims abstract description 31
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 58
- 239000000047 product Substances 0.000 claims description 27
- 229910003437 indium oxide Inorganic materials 0.000 claims description 25
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 22
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 22
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 10
- 229910052796 boron Inorganic materials 0.000 claims description 9
- 239000002957 persistent organic pollutant Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 8
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 229910001868 water Inorganic materials 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- -1 sodium tetraphenylborate Chemical compound 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 5
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 claims description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical group O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 5
- 229910001887 tin oxide Inorganic materials 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- 229910003454 ytterbium oxide Inorganic materials 0.000 claims description 5
- 229940075624 ytterbium oxide Drugs 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 229910052810 boron oxide Inorganic materials 0.000 claims description 2
- ZIPLUEXSCPLCEI-UHFFFAOYSA-N cyanamide group Chemical group C(#N)[NH-] ZIPLUEXSCPLCEI-UHFFFAOYSA-N 0.000 claims description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical group O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 239000008213 purified water Substances 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 82
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 41
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 16
- 239000003208 petroleum Substances 0.000 abstract description 8
- 238000004064 recycling Methods 0.000 abstract description 7
- 239000000446 fuel Substances 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 16
- 239000012071 phase Substances 0.000 description 16
- 239000003921 oil Substances 0.000 description 14
- 230000001699 photocatalysis Effects 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000013032 photocatalytic reaction Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000000593 degrading effect Effects 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000002283 diesel fuel Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 230000009467 reduction Effects 0.000 description 1
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- 231100000331 toxic Toxicity 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
- B01J27/24—Nitrogen 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G32/00—Refining of hydrocarbon oils by electric or magnetic means, by irradiation, or by using microorganisms
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G32/00—Refining of hydrocarbon oils by electric or magnetic means, by irradiation, or by using microorganisms
- C10G32/04—Refining of hydrocarbon oils by electric or magnetic means, by irradiation, or by using microorganisms by particle radiation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/30—Nuclear fission reactors
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Microbiology (AREA)
- General Chemical & Material Sciences (AREA)
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Abstract
The invention provides a composition containing g-C3N4B and metal oxide composite photocatalyst and application thereof in fuel denitrification, and g-C-containing composite photocatalyst is prepared by a hydrothermal-roasting method3N4The composite photocatalyst of B is used for photocatalytic degradation of nitrogen-containing simulated oil (pyridine/petroleum ether), and the degradation rate of pyridine can reach 93.6%. In addition, the composite photocatalyst provided by the invention has good recycling performance, and the degradation rate of pyridine is almost unchanged after the composite photocatalyst is repeatedly used for three times.
Description
Technical Field
The invention relates to a photocatalyst and application thereof, in particular to a preparation method of a composite photocatalyst containing B-doped graphite-phase carbon nitride and application thereof in degrading nitrogenous organic matters in fuel oil.
Background
Nitrogen-containing compounds (organic matters) in oil products (such as gasoline and diesel oil), particularly basic nitrogen-containing compounds, not only affect the stability of the gasoline and the diesel oil, but also affect the continuous deep processing of the gasoline and the diesel oil, such as catalytic reforming, hydrogenation, catalytic cracking and the like; moreover, many nitrogen oxides produced during combustion of oil products pose serious hazards to the atmospheric environment in which humans live. At present, the common methods for removing nitrogen-containing compounds in oil products mainly comprise two types of hydrodenitrogenation and non-hydrodenitrogenation. However, the two treatment methods have the defects of high temperature and high pressure required for reaction, strong dependence on instruments and equipment, poor treatment effect of nitrogen oxides and the like in the actual operation process. These drawbacks limit the widespread use of hydrodenitrogenation and non-hydrodenitrogenation in industrial fields.
Therefore, the search for a simple, economic and environment-friendly oil product denitrification method has important scientific significance for protecting the ecological environment.
The photocatalytic oxidation technology can effectively utilize light energy under mild conditions and generate electrons (e) through light-) And photo-generated holes (h)+) The migration and capture of the oxygen form a series of active oxidation species. These highly active species can completely degrade various toxic and harmful compounds into non-toxic and harmless CO2And H2O and the like. Up to now, the photocatalytic oxidation technology is used for self-cleaning the surfaces of gas-liquid phase pollutants, dye-sensitized solar cells and glassThe research on cleaning technology, hydrogen production and oxygen production by water photolysis and the like is developed rapidly, but the research on the field of oil product denitrification is rarely reported.
Therefore, it is highly desirable to develop a high-efficiency composite photocatalyst for treating environmental pollutants, especially for degrading nitrogen-containing organic pollutants, such as nitrogen-containing organic pollutants in fuel oil.
Disclosure of Invention
In order to solve the above problems, the present inventors have conducted intensive studies and, as a result, have found that: comprising g-C may be prepared by a hydrothermal-roasting process3N4B and a metal oxide, wherein the catalyst can be applied to fuel oil denitrification, and the composite photocatalyst provided by the invention has good recycling performance, thereby completing the invention.
The object of the present invention is to provide the following:
in a first aspect, the present invention provides a composition comprising g-C3N4The composite photocatalyst of B, further comprising a metal oxide, wherein the metal oxide is selected from tin oxide, titanium oxide, ytterbium oxide, indium oxide and yttrium oxide.
Wherein the metal oxide is indium oxide.
The composite photocatalyst is also doped with metal vanadate, and the metal is selected from lanthanum, dysprosium, copper and molybdenum.
In a second aspect, the present invention also provides a process for preparing a composition comprising g-C3N4B, preferably for preparing the composite photocatalyst of the first aspect, the method comprises the following steps:
In a third aspect, the composite photocatalyst of the first aspect or the composite photocatalyst prepared by the method of the second aspect is used for photocatalytic degradation of nitrogen-containing organic pollutants, such as degradation of nitrogen-containing organic matters in fuel oil, and the degradation rate can reach 93.6%.
Drawings
FIG. 1 shows XRD diffraction patterns of products prepared in examples 1-4;
FIG. 2 shows an EDS diagram of the composite catalyst product made in example 2;
FIG. 3 shows a graph of pyridine degradation rate for various examples and comparative products;
FIG. 4 is a graph showing the effect of the amount of the composite photocatalyst provided by the present invention on the degradation rate of pyridine;
FIG. 5 is a graph showing the effect of different concentrations of pyridine on the degradation of pyridine by a composite photocatalyst;
figure 6 shows a graph of the effect of recycling of the composite photocatalyst on pyridine degradation.
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
The present invention is described in detail below.
Currently, the graphite phase carbon nitride (g-C)3N4) The typical organic polymer semiconductor photocatalyst has potential application value in the fields of environmental pollutant purification, clean energy synthesis, solar energy conversion and the like, and related researches are highly concerned by researchers at home and abroad. But due to g-C3N4The relatively narrow photoresponse range and the high recombination rate of photogenerated carriers limit the commercial application of the photogenerated carriers.
The inventor tries to dope the modified graphite phase carbon nitride so as to obtain a composite photocatalyst with better performance;
after a great deal of research and experiments, the inventors surprisingly found that a composite photocatalyst DyVO is prepared by compounding metal oxide (indium oxide) and metal vanadate (dysprosium vanadate) with boron-doped graphite-phase carbon nitride4/In2O3/g-C3N4And B, the catalyst has excellent performance in the aspect of photocatalytic degradation of nitrogen-containing simulated oil (pyridine/petroleum ether).
According to a first aspect of the present invention there is provided a composition comprising g-C3N4The composite photocatalyst of B, further comprising a metal oxide, wherein the metal oxide is selected from tin oxide, titanium oxide, ytterbium oxide, indium oxide and yttrium oxide.
In a preferred embodiment, the metal oxide is indium oxide (In)2O3)。
In a preferred embodiment, the composite photocatalyst is further doped with a metal vanadate, wherein the metal is selected from lanthanum, dysprosium, copper and molybdenum, and is preferably dysprosium.
In the invention, the composite photocatalyst is DyVO4/In2O3/g-C3N4B, diffraction peaks exist in XRD patterns of 24.9 degrees, 27.3 degrees, 30.4 degrees, 33.5 degrees, 35.4 degrees and 50.9 degrees; in at 30.4 °, 35.4 °, 50.9 ° respectively2O3Crystal planes (222), (400), (440); DyVO corresponds to 24.9 degrees and 33.5 degrees respectively4Crystal planes (200), (112); at 27.3 ℃ corresponds to g-C3N4Crystal plane (002) of B.
In DyVO4/In2O3/g-C3N4DyVO can be obviously seen in the B composite semiconductor photocatalyst4、In2O3And g-C3N4The three phases B coexist.
The inventors have found that In formed by directly doping boron-doped graphite-phase carbon nitride with metallic indium oxide2O3/g-C3N4When B is used for degrading nitrogen-containing organic matters in fuel (fuel denitrification), the performance of B is not as good as that of B used for degrading azo organic dyes (such as methyl orange).
The inventors did not give up and continued to make extensive attempts and studies of other composite photocatalysts. Finally, the inventors surprisingly found that when a very small amount of dysprosium vanadate is doped into the boron-doped graphite-phase carbon nitride together with a small amount of indium oxide, the obtained composite photocatalyst DyVO4/In2O3/g-C3N4And B shows excellent performance in the aspect of fuel oil denitrification.
According to a second aspect of the present invention, there is provided a method for preparing the composite photocatalyst, comprising the steps of:
Wherein the content of the first and second substances,
the step 1 comprises the following steps:
step 1-1, uniformly mixing a carbon nitrogen source and a boron source in a solvent;
step 1-2, removing the solvent;
step 1-3, roasting, grinding to obtain a product g-C3N4B；
Preferably, the first and second electrodes are formed of a metal,
in the step 1-1, the carbon-nitrogen source is selected from cyanamide, dicyandiamide, melamine and urea; the boron source is selected from boron oxide, boric acid, sodium tetraphenylborate and potassium tetraphenylborate;
in a preferred embodiment, the carbon nitrogen source is urea; the boron source is sodium tetraphenylborate.
In a further preferred embodiment, the mass ratio of the carbon nitrogen source to the boron source is 10g (5-15) mg, such as 10g:10 mg.
The inventor finds that the selection of the dosage ratio of the carbon nitrogen source and the boron source is a more critical factor, and when the mass ratio of the carbon nitrogen source to the boron source is 10g:10mg, the performance of the obtained final product is the best.
The solvent is water, and is more preferably deionized water, distilled water or purified water; more preferably deionized water.
In a preferred embodiment, in step 1-1, ultrasonic oscillation is adopted for dispersion for 10min during mixing, so that the raw materials are better dispersed, the mixing is more uniform, and the prepared product is more uniform and has better performance.
In step 1-2, the temperature for removing the solvent is 60-90 ℃, preferably 70-80 ℃, such as 80 ℃. Stirring is preferred for solvent removal, improving efficiency.
In the step 1-3, the roasting temperature is 450-600 ℃.
In a preferred embodiment, the calcination temperature is 550 ℃ and the calcination time is 2 hours.
The inventor finds that the temperature rise rate during roasting is also a factor to be considered, and in the invention, the roasting temperature rise rate is 3-10 ℃/min, preferably 4-9 ℃/min, such as 5 ℃/min.
In the present invention, after completion of calcination, the temperature is lowered to room temperature, and the solid is ground to obtain uniform g-C3N4B, powder product.
In the invention, the step 2 comprises the following steps:
step 2-1, mixing the raw materials g-C3N4B and metal oxide are dispersed in the dispersant;
step 2-1, removing the dispersing agent;
and 2-3, roasting to obtain the final product composite photocatalyst.
Preferably, the first and second electrodes are formed of a metal,
in step 2-1, the raw material further comprises metal vanadate, wherein the metal is selected from lanthanum, dysprosium, copper and molybdenum; the metal oxide is selected from tin oxide, titanium oxide, ytterbium oxide, indium oxide and yttrium oxide;
in a preferred embodiment, the metal vanadate is dysprosium vanadate (DyVO)4) (ii) a The metal oxide is indium oxide (In)2O3)；
In one embodiment, the mass ratio of the metal oxide to the dysprosium vanadate metal and the boron-doped graphite-phase carbon nitride is (0.001-0.5): (0.001-0.1) 1;
further, the mass ratio of the metal oxide (indium oxide) to the dysprosium vanadate metal and the boron-doped graphite-phase carbon nitride is (0.01-0.25): (0.005-0.15) 1; e.g., 0.01:0.005:1, 0.05:0.08:1,0.1:0.005:1,0.2:0.005:1, 0.01:0.01:1,0.01:0.1:1,0.05:0.01:1,0.1:0.01:1,0.1:0.06:1, 0.2:0.01:1,0.2:0.04:1.
The present inventors have found that indium oxide has many excellent characteristics, is an n-type semiconductor material, and has been widely used in many fields. Indium oxide can be used as a photocatalyst independently, and can be compounded with other semiconductors to have high photocatalytic efficiency, so that the indium oxide has various special properties.
The present inventors considered that one of the important ways to improve the photocatalytic activity of semiconductors when they are combined with each other.
The inventors also believe that In is formed by indium oxide2O3DyVO with dysprosium vanadate4Boron-doped graphite phase carbon nitride g-C3N4The B recombination is probably because the difference of energy band positions can inhibit the rapid recombination of electrons and holes and regulate and control the response to light, thereby improving the photocatalytic efficiency of the composite photocatalyst. However, the inventors found that the doping amount of dysprosium vanadate and indium oxide is not so large, and in the present invention, it is more preferable that the mass ratio of indium oxide to dysprosium vanadate to boron-doped graphite-phase carbon nitride is 0.05:0.08: 1.
In step 2-1, the dispersant used is an alcohol, preferably methanol, ethanol, isopropanol, more preferably methanol.
In a preferred embodiment, in the step 2-1, the raw materials are dispersed by using ultrasonic oscillation, so that the raw materials are mixed and dispersed in the dispersing agent more uniformly, and the final product is more uniform and has better performance. Ultrasonic oscillation is preferred for 10 min.
In the step 2-2, the temperature for removing the dispersing agent is 50-80 ℃, such as 60 ℃; in a preferred embodiment, the dispersant is removed by stirring.
In the step 2-3, the roasting temperature is 400-550 ℃, such as 450 ℃; the roasting time is 2-5 h, such as 3 h.
The inventor finds that the control of the temperature rise rate during roasting is also critical, and in the step, the temperature rise rate is 3-15 ℃/min, preferably 5-13 ℃/min, such as 8 ℃/min.
The inventor also finds that the calcination temperature is more preferably 450 ℃, the calcination time is more preferably 3 hours, and under the condition, the obtained composite photocatalyst DyVO4/In2O3/g-C3N4The B performance is better.
The inventor believes that this is probably because under such conditions, the obtained composite photocatalyst has more uniform surface appearance and higher photocatalytic activity, and the formed surface structure is more favorable for photocatalytic degradation of nitrogen-containing simulated oil (pyridine/petroleum ether).
According to a third aspect of the present invention, there is provided a use of the composite photocatalyst according to the first aspect or the composite photocatalyst prepared by the method according to the second aspect, in the photocatalytic degradation of nitrogen-containing organic pollutants, such as in the degradation of nitrogen-containing organic pollutants in fuel oil, where the degradation rate is up to 93.6%.
Furthermore, the degradation rate of the composite photocatalyst on pyridine can reach 93.6%.
In the invention, the composite photocatalyst has a degradation rate of 93.6% to pyridine in nitrogen-containing simulated oil (pyridine/petroleum ether) in a photocatalytic reaction for 5 hours.
In addition, the composite photocatalyst DyVO provided by the invention4/In2O3/g-C3N4The B has good recycling performance, and the degradation rate of the pyridine is almost unchanged after the B is repeatedly used for three times.
According to the invention there is provided a composition comprising g-C3N4The composite photocatalyst of the B and the metal oxide and the application thereof in the denitrification of fuel oil have the following beneficial effects:
(1) the composite photocatalyst provided by the invention is environment-friendly and has high photocatalytic activity;
(2) the preparation method of the composite photocatalyst provided by the invention is simple, and the used equipment is few in types;
(3) the composite photocatalyst provided by the invention can be used for photocatalytic degradation of nitrogen-containing organic pollutants, such as degradation of nitrogen-containing organic pollutants in fuel oil, the degradation rate of pyridine in nitrogen-containing simulated oil (pyridine/petroleum ether) can reach 93.6%, and the degradation rate of pyridine is almost unchanged after repeated use;
(4) the composite photocatalyst provided by the invention can be recycled when used for photocatalytic degradation of nitrogen-containing organic matters in fuel oil, such as pyridine, so that the use cost is greatly reduced, and the industrial popularization is facilitated.
Examples
3 4Preparation of g-CNB samples:
mixing and stirring 10g of urea and 10mg of sodium tetraphenylborate in 10m L deionized water, and ultrasonically oscillating for 10 min;
stirring, and evaporating in 80 deg.C water bath;
then the system is put into a muffle furnace after being dried by distillation, the heating rate is 5 ℃/min, the temperature is raised to 550 ℃, the system is roasted for 2h at 550 ℃, and the boron-doped graphite phase carbon nitride (g-C) is obtained after room temperature grinding3N4B) Sample, noted D2.
Example 1
Weighing 1g g-C3N4B and 0.1g dysprosium vanadate DyVO40.01g of indium oxide In2O3Adding into 10m L methanol, stirring, mixing, and performing ultrasonic treatment for 10 min;
then stirring in a water bath at 60 ℃ to remove the methanol;
placing in a muffle furnace, heating to 450 deg.C at a heating rate of 8 deg.C/min, calcining at 450 deg.C for 3h, and grinding at room temperature to obtain the product, composite photocatalyst DyVO4/In2O3/g-C3N4B, is marked as C1.
Example 2
This example is the same as example 1 except that indium oxide In is (one) processed2O3DyVO, 0.05g, dysprosium vanadate40.08 g; finally obtaining the composite photocatalyst DyVO4/In2O3/g-C3N4B, is marked as C2.
Example 3
This example is the same as example 1 except that indium oxide In is (one) processed2O3DyVO, 0.1g, dysprosium vanadate40.06 g; finally obtaining the composite photocatalyst DyVO4/In2O3/g-C3N4B, is marked as C3.
Example 4
This example is the same as example 1 except that indium oxide In is (one) processed2O3DyVO, 0.2g, dysprosium vanadate4Is 004 g; finally obtaining the composite photocatalyst DyVO4/In2O3/g-C3N4B, is marked as C4.
Comparative example
Comparative example 1
Mixing and stirring 10g of urea in 10m L deionized water, and ultrasonically oscillating for 10 min;
stirring, and evaporating in 80 deg.C water bath;
then the system is put into a muffle furnace after being dried by distillation, the heating rate is 8 ℃/min, the temperature is raised to 550 ℃, the system is roasted for 2h at 550 ℃, and the graphite phase carbon nitride (g-C) is obtained after room temperature grinding3N4) Sample, noted D1.
Comparative example 2
Preparation according to example 2 of CN107790163A to give 5% In2O3/g-C3N4B, marked as D3.
Comparative example 3
The preparation process according to example 2 in CN107790163A is distinguished in that, during the addition of indium oxide, 0.005g of dysprosium vanadate DyVO is also added4Preparing to obtain DyVO4/In2O3/g-C3N4B, marked as D4.
Comparative example 4
Weighing 1g g-C3N4B and 0.08g dysprosium vanadate DyVO40.05g of indium oxide In2O3Adding into 10m L methanol, stirring, mixing, and performing ultrasonic treatment for 10 min;
then stirring in a water bath at 60 ℃ to remove the methanol;
placing in a muffle furnace, heating to 550 ℃ at a heating rate of 8 ℃/min, roasting at 550 ℃ for 3h, and grinding at room temperature to obtain the product composite photocatalyst DyVO4/In2O3/g-C3N4B, marked as D5.
Comparative example 5
The same procedure as in example 2 was followed, except that boron-doped graphite-phase carbon nitride (g-C) was used3N4B) The sample was prepared according to CN107790163A, and the final product DyVO was obtained4/In2O3/g-C3N4B, marked as D6.
Examples of the experiments
XRD analysis of sample of Experimental example 1
The composite photocatalyst products obtained in examples 1 to 4, and a blank indium oxide (recorded as D7), a blank dysprosium vanadate (recorded as D8), and g-C were measured3N4The XRD spectrum of B (marked as D2) shows the result in figure 1.
As can be seen from FIG. 1, in the composite photocatalyst DyVO4/In2O3/g-C3N4In B, three phases coexist. With DyVO4And In2O3Increased content of DyVO4Crystal plane (200) of (1) and In2O3Respectively, the intensity of the (222) crystal plane of (A) is enhanced.
Experimental example 2 EDS Spectroscopy analysis of samples
DyVO prepared in example 24/In2O3/g-C3N4The product of the B (C2) composite photocatalyst is subjected to EDS (EDS Spectroscopy) and the result is shown in figure 2.
As can be seen from FIG. 2, DyVO4/In2O3/g-C3N4Dy, V, O, In, C, N and B elements exist In the B (C2) composite photocatalyst product, which indicates DyVO4/In2O3/g-C3N4DyVO in B (C2) composite photocatalyst4、In2O3And g-C3N4The three phases B coexist.
Experimental example 3 photocatalytic activity analysis of sample I
Test examples 1 to 4, comparative example 1 (g-C)3N4) Comparative examples 2 to 5, indium oxide blank (D7), dysprosium vanadate blank (D8), g-C3N4And B (D2) degradation rate of pyridine in nitrogen-containing simulated oil (pyridine/petroleum ether).
The nitrogen-containing simulated oil is prepared from pyridine with a certain mass and petroleum ether with a boiling range of 90-120 ℃ and has mass fractions of 4 mug/g, 8 mug/g and 12 mug/g;
a certain amount of photocatalyst and 50m L simulated oil are placed in a Shanghai Bilang B L-GHX-V multi-test tube, and are stirred on a photochemical reactor at the same time, the mixture is magnetically stirred for 1h to achieve adsorption-desorption balance, then a 500W xenon lamp is used as a visible light source for illumination, supernatant is taken according to a certain time, and the basic nitrogen content of the nitrogen-containing simulated oil is measured and analyzed by adopting a basic nitrogen measurement method (SH/T0162-92) in petroleum products, and the result is shown in figure 3.
As can be seen from FIG. 3, the composite photocatalyst DyVO of the present invention4/In2O3/g-C3N4The photocatalytic activity of B is obviously higher than that of pure DyVO4、In2O3、g-C3N4B the activity of the catalyst. Wherein, DyVO4：In2O3：g-C3N4The composite photocatalyst DyVO when B is 0.08:0.05:14/In2O3/g-C3N4B is the most active. After 5 hours of visible light illumination, the degradation rate of the composite photocatalyst on pyridine can reach 93.6 percent, and the photocatalytic activity of the composite photocatalyst is higher than that of DyVO of all the composite photocatalysts of comparative examples4/In2O3/g-C3N4Activity of B.
Experimental example 4 photocatalytic activity analysis of sample II
The effect of the amount of the composite photocatalyst (product of example 2) added on the degradation rate of pyridine was tested, and the result is shown in FIG. 4.
Wherein, in figure 4,
curve a represents the amount of the composite photocatalyst product added at 1.00 g/L (i.e. 1.00g of composite photocatalyst is added to 1L nitrogen-containing simulated oil);
curve b represents the dosage of the composite photocatalyst product of 1.25 g/L;
curve c represents the dosage of the composite photocatalyst product of 1.50 g/L;
curve d represents the dosage of the composite photocatalyst product of 1.75 g/L;
as can be seen from FIG. 4, when the amount of the catalyst added is small, the degradation rate of pyridine gradually increases with the increase of the amount of the catalyst, the amount of the composite photocatalyst added is 1.50 g/L, and the photocatalytic reaction lasts for 5 hours, the degradation rate of pyridine reaches 93.6%.
The present inventors believe that this may be because, when the photocatalytic reaction is just started, increasing the amount of the added catalyst significantly increases the effective surface area of the catalyst participating in the reaction, generates more active sites for the photocatalytic reaction, and thus increases the reaction efficiency between the catalyst and the contaminants. However, when the amount of the catalyst added is continuously increased, the degree of coverage of catalyst particles with each other is gradually increased, so that the turbidity of the pyridine solution is increased, which undoubtedly hinders the projection and absorption of light, thereby resulting in a decrease in the degradation rate of pyridine.
Experimental example 5 photocatalytic activity analysis of sample III
Determination of different initial concentrations of pyridine for the composite photocatalyst DyVO4/In2O3/g-C3N4The effect of B (product of example 2) on pyridine degradation is shown in FIG. 5.
Wherein, in FIG. 5, curve a represents the pyridine concentration of 4. mu.g/g (i.e., the mass ratio of pyridine to petroleum ether);
curve b represents a pyridine concentration of 8. mu.g/g;
curve c represents the pyridine concentration at 12. mu.g/g.
As can be seen from FIG. 5, the degradation rate of the product of example 2, which is a composite photocatalyst, on pyridine is decreased as the initial concentration of pyridine is increased from 4. mu.g/g to 12. mu.g/g. That is to say that the initial concentration of pyridine is not too high.
This may be attributed primarily to three reasons: firstly, with the increasing initial concentration of pyridine, the number of pyridine molecules capable of being adsorbed on the surface of the catalyst is more and more, which leads to the generation of OH and h on the surface of the catalyst+The corresponding reduction of the active species; secondly, the higher the concentration of the pyridine solution, the stronger the absorption capacity of the pyridine solution to light, so that the effective illumination intensity for generating a photon-generated carrier by the catalyst is obviously weakened; third, too high a pyridine concentration may result in the intermediate products generated in the photocatalytic reaction not being efficiently decomposed in time but being adsorbed on the surface of the catalyst, which undoubtedly hinders lightThe reaction efficiency of the catalytic reaction.
Experimental example 6 photocatalytic activity analysis of sample IV
The recycling efficiency (i.e. the effect of the number of recycling times on the degradation rate of pyridine) of the composite photocatalyst (product of example 2) was determined, and the results are shown in FIG. 6.
Wherein, in figure 6,
curve a represents the degradation curve for 1 photocatalyst use;
curve b represents the degradation curve for 2 photocatalyst uses;
curve c represents the degradation curve of 3 photocatalyst applications.
As can be seen from fig. 6, when the catalyst is repeatedly recycled three times, the degradation rate is slightly decreased but the decrease is not large.
This shows that the composite photocatalyst DyVO prepared by the invention4/In2O3/g-C3N4The product of the embodiment 2 has better recycling performance and has extremely important value for future practical application.
In conclusion, the composite photocatalyst provided by the invention can be applied to fuel oil denitrification, when the initial concentration of pyridine is 4 mug/g, the dosage of the composite photocatalyst (product in example 2) is 1.5 g/L, and the composite photocatalyst is illuminated by a 500W xenon lamp for 5 hours, the degradation rate of pyridine reaches 93.6%.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. Containing g-C3N4B composite photocatalyst, its special featureCharacterized in that the composite photocatalyst also comprises metal oxide, and the metal oxide is selected from tin oxide, titanium oxide, ytterbium oxide, indium oxide and yttrium oxide.
2. The composite photocatalyst of claim 1, wherein the metal oxide is indium oxide.
3. The composite photocatalyst of claim 2, wherein the composite photocatalyst is further doped with a metal vanadate, the metal being selected from lanthanum, dysprosium, copper, molybdenum.
4. The composite photocatalyst of claim 3, wherein the metal vanadate is DyVO4。
5. A process for preparing a composition containing g-C3N4B, preferably for the preparation of a composite photocatalyst as claimed in any one of claims 1 to 4, characterised in that it comprises the following steps:
step 1, preparation of g-C3N4B；
Step 2, preparing a catalyst containing g-C3N4And B, a composite photocatalyst.
6. The method of claim 5, wherein step 1 comprises the steps of:
step 1-1, uniformly mixing a carbon nitrogen source and a boron source in a solvent;
step 1-2, removing the solvent;
step 1-3, roasting, grinding to obtain a product g-C3N4B；
Preferably, the first and second electrodes are formed of a metal,
in the step 1-1, the carbon-nitrogen source is selected from cyanamide, dicyandiamide, melamine and urea; the boron source is selected from boron oxide, boric acid, sodium tetraphenylborate and potassium tetraphenylborate;
the solvent is water, and is more preferably deionized water, distilled water or purified water;
in the step 1-3, the roasting temperature is 450-600 ℃.
7. The method of claim 5, wherein step 2 comprises the steps of:
step 2-1, mixing the raw materials g-C3N4B and metal oxide are dispersed in the dispersant;
step 2-2, removing the dispersing agent;
and 2-3, roasting to obtain the final product composite photocatalyst.
8. The method according to claim 7, wherein in step 2-1, the feedstock further comprises a metal vanadate, the metal being selected from lanthanum, dysprosium, copper, molybdenum; the metal oxide is selected from tin oxide, titanium oxide, ytterbium oxide, indium oxide and yttrium oxide.
9. The method according to claim 7 or 8, wherein in step 2-3, the roasting temperature is 400-550 ℃, such as 450 ℃; the roasting time is 2-5 h, such as 3 h.
10. Use of the composite photocatalyst according to any one of claims 1 to 4 or the composite photocatalyst prepared by the method according to any one of claims 5 to 9, for photocatalytic degradation of nitrogen-containing organic pollutants, such as nitrogen-containing organic pollutants in fuel oil, with a degradation rate of 93.6%.
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