CN111450861B - Comprising g-C 3 N 4 Composite photocatalyst of B and metal oxide and application thereof in fuel oil denitrification - Google Patents
Comprising g-C 3 N 4 Composite photocatalyst of B and metal oxide and application thereof in fuel oil denitrification Download PDFInfo
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- CN111450861B CN111450861B CN201910059203.0A CN201910059203A CN111450861B CN 111450861 B CN111450861 B CN 111450861B CN 201910059203 A CN201910059203 A CN 201910059203A CN 111450861 B CN111450861 B CN 111450861B
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 87
- 239000002131 composite material Substances 0.000 title claims abstract description 81
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 21
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 21
- 239000000295 fuel oil Substances 0.000 title claims description 12
- 229910003437 indium oxide Inorganic materials 0.000 claims description 27
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical group [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 27
- 239000000047 product Substances 0.000 claims description 27
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 25
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 21
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 21
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052796 boron Inorganic materials 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 9
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 6
- 239000004202 carbamide 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
- -1 sodium tetraphenylborate Chemical group 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 86
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 43
- 230000015556 catabolic process Effects 0.000 abstract description 32
- 238000006731 degradation reaction Methods 0.000 abstract description 32
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 8
- 239000003208 petroleum Substances 0.000 abstract description 8
- 238000004064 recycling Methods 0.000 abstract description 8
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 7
- 239000000446 fuel Substances 0.000 abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000012071 phase Substances 0.000 description 16
- 239000003921 oil Substances 0.000 description 15
- 230000001699 photocatalysis Effects 0.000 description 14
- 238000003756 stirring Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000001354 calcination Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method 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
- 239000002957 persistent organic pollutant Substances 0.000 description 6
- 238000013032 photocatalytic reaction Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite 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
- 238000005516 engineering process Methods 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 230000010355 oscillation Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 3
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical group O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 229910003454 ytterbium oxide Inorganic materials 0.000 description 3
- 229940075624 ytterbium oxide Drugs 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
- 239000000969 carrier Substances 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
- 238000010304 firing 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
- 229920000877 Melamine resin Polymers 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
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 238000004140 cleaning 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
- ZIPLUEXSCPLCEI-UHFFFAOYSA-N cyanamide group Chemical group C(#N)[NH-] ZIPLUEXSCPLCEI-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical group O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 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
- 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
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 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
- 238000006552 photochemical reaction Methods 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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- 231100000331 toxic Toxicity 0.000 description 1
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Images
Classifications
-
- 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
-
- B01J35/39—
-
- 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
Abstract
The invention provides a composition containing g-C 3 N 4 B and metal oxide composite photocatalyst and application thereof in fuel denitrification, and g-C-containing composite photocatalyst is prepared by a hydrothermal-roasting method 3 N 4 The 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 of the composite photocatalyst in degrading nitrogen-containing 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, various nitrogen oxides generated during the combustion of oil products pose serious hazards to the atmospheric environment on 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 CO 2 And H 2 O and the like. So far, the research and development of the photocatalytic oxidation technology in the aspects of gas-liquid phase pollutant degradation, dye-sensitized solar cells, glass surface self-cleaning technology, hydrogen production and oxygen production by photolysis water are rapid, but the research of the photocatalytic oxidation technology in 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: can be prepared by hydrothermal-roasting 3 N 4 B 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-C 3 N 4 The 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-C 3 N 4 B, 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 obtained in examples 1 to 4;
FIG. 2 shows an EDS diagram for 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 addition amount of the composite photocatalyst 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) 3 N 4 ) 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-C 3 N 4 The 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 extensive research and experiments, the inventors surprisingly found that a composite photocatalyst DyVO prepared by compounding metal oxide (indium oxide) and metal vanadate (dysprosium vanadate) with boron-doped graphite-phase carbon nitride 4 /In 2 O 3 /g-C 3 N 4 And 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-C 3 N 4 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.
In a preferred embodiment, the metal oxide is indium oxide (In) 2 O 3 )。
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 DyVO 4 /In 2 O 3 /g-C 3 N 4 B, 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 ° respectively 2 O 3 Crystal planes (222), (400), (44) of0) (ii) a DyVO corresponds to 24.9 degrees and 33.5 degrees respectively 4 Crystal planes (200), (112); at 27.3 ℃ corresponds to g-C 3 N 4 Crystal plane (002) of B.
In DyVO 4 /In 2 O 3 /g-C 3 N 4 DyVO can be obviously seen in the B composite semiconductor photocatalyst 4 、In 2 O 3 And g-C 3 N 4 And the three phases B coexist.
The inventors have found that In is formed by direct doping of boron-doped graphite-phase carbon nitride with metallic indium oxide 2 O 3 /g-C 3 N 4 When 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 DyVO 4 /In 2 O 3 /g-C 3 N 4 And 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-C 3 N 4 B；
Preferably, the first and second electrodes are formed of a metal,
in 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 10 g.
The inventor finds that the selection of the dosage ratio of the carbon nitrogen source and the boron source is a relatively critical factor, and when the mass ratio of the carbon nitrogen source to the boron source is 10g.
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 at which the solvent is removed is 60 to 90 deg.C, preferably 70 to 80 deg.C, e.g., 80 deg.C. Stirring is preferred for removing the solvent, to improve 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 inventors have found that the rate of temperature rise during firing is also a factor to be considered, and in the present invention, the rate of temperature rise during firing is 3 to 10 deg.C/min, preferably 4 to 9 deg.C/min, such as 5 deg.C/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-C 3 N 4 B, powder product.
In the invention, the step 2 comprises the following steps:
step 2-1, mixing the raw materials g-C 3 N 4 B 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) 2 O 3 )；
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 metal dysprosium vanadate and boron-doped graphite phase carbon nitride is (0.01-0.25): (0.005-0.15) 1; such as 0.01: 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 one of the important ways to improve the photocatalytic activity of semiconductors during the recombination between the semiconductors.
The inventors also believe that In is formed by indium oxide 2 O 3 DyVO with dysprosium vanadate 4 Boron-doped graphite phase carbon nitride g-C 3 N 4 The 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 too large, and in the present invention, the mass ratio of indium oxide to dysprosium vanadate to boron-doped graphite-phase carbon nitride is more preferably 0.05.
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 10min.
In 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 3h.
The inventors have found that the control of the temperature rise rate during calcination is also critical, and in this step, the temperature rise rate is 3 to 15 ℃/min, preferably 5 to 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 DyVO 4 /In 2 O 3 /g-C 3 N 4 The 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 photocatalytic degradation of nitrogen-containing organic pollutants, such as nitrogen-containing organic pollutants in fuel oil, where a degradation rate may reach 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 invention 4 /In 2 O 3 /g-C 3 N 4 The 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-C 3 N 4 The 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 matters 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) When the composite photocatalyst provided by the invention is used for photocatalytic degradation of nitrogen-containing organic matters in fuel oil, such as pyridine, the composite photocatalyst can be recycled, the use cost is greatly reduced, and the industrial popularization is facilitated.
Examples
3 4 Preparation of g-CNB samples:
mixing and stirring 10g of urea and 10mg of sodium tetraphenylborate in 10mL of deionized water, and ultrasonically oscillating for 10min;
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 grinding 3 N 4 B) Sample, noted D2.
Example 1
Weighing 1g g-C 3 N 4 B and 0.1g dysprosium vanadate DyVO 4 0.01g of indium oxide In 2 O 3 Adding into 10mL methanol, stirring and mixing, and performing ultrasonic treatment for 10min;
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 DyVO 4 /In 2 O 3 /g-C 3 N 4 And B is marked as C1.
Example 2
This example is the same as example 1 except that indium oxide In is added In one step 2 O 3 DyVO vanadate of 0.05g 4 0.08g; finally obtaining the composite photocatalyst DyVO 4 /In 2 O 3 /g-C 3 N 4 B, is marked as C2.
Example 3
This example is the same as example 1 except that indium oxide In is (one) processed 2 O 3 DyVO, 0.1g, dysprosium vanadate 4 0.06g; finally obtaining the composite photocatalyst DyVO 4 /In 2 O 3 /g-C 3 N 4 B, is marked as C3.
Example 4
This example is the same as example 1 except that indium oxide In is added In one step 2 O 3 DyVO, 0.2g, dysprosium vanadate 4 0.04g; finally obtaining the composite photocatalyst DyVO 4 /In 2 O 3 /g-C 3 N 4 B, is marked as C4.
Comparative example
Comparative example 1
Mixing and stirring 10g of urea in 10mL of deionized water, and carrying out ultrasonic oscillation for 10min;
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 grinding 3 N 4 ) Sample, noted D1.
Comparative example 2
5% in prepared according to example 2 of CN107790163A 2 O 3 /g-C 3 N 4 B, is marked as D3.
Comparative example 3
The preparation process according to example 2 in CN107790163A is distinguished in that 0.005g of dysprosium vanadate DyVO is also added during the addition of indium oxide 4 Preparing to obtain DyVO 4 /In 2 O 3 /g-C 3 N 4 And B is marked as D4.
Comparative example 4
Weighing 1g g-C 3 N 4 B and 0.08g dysprosium vanadate DyVO 4 0.05g of indium oxide In 2 O 3 Adding into 10mL methanol, stirring and mixing, and performing ultrasonic treatment for 10min;
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 DyVO 4 /In 2 O 3 /g-C 3 N 4 B, is 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 used 3 N 4 B) The sample was prepared according to CN107790163A, and the final product DyVO was obtained 4 /In 2 O 3 /g-C 3 N 4 B, is 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 were measured, along with a blank of indium oxide (denoted as D7), a blank of dysprosium vanadate (denoted as D8), and g-C 3 N 4 The XRD spectrum of B (marked as D2) shows that the result is shown in figure 1.
As can be seen from FIG. 1, in the composite photocatalyst DyVO 4 /In 2 O 3 /g-C 3 N 4 In B, three phases are commonAnd (4) storing. With DyVO 4 And In 2 O 3 Increased content of DyVO 4 Crystal plane of (200) and In 2 O 3 Respectively, the intensity of the (222) crystal plane of (a) is enhanced.
Experimental example 2 EDS Spectroscopy analysis of samples
DyVO prepared in example 2 4 /In 2 O 3 /g-C 3 N 4 EDS (electron-directed spectroscopy) analysis is carried out on the B (C2) composite photocatalyst product, and the result is shown in figure 2.
As can be seen from FIG. 2, dyVO 4 /In 2 O 3 /g-C 3 N 4 Dy, V, O, in, C, N and B elements exist In the B (C2) composite photocatalyst product, which shows that DyVO 4 /In 2 O 3 /g-C 3 N 4 DyVO in B (C2) composite photocatalyst 4 、In 2 O 3 And g-C 3 N 4 The three phases B coexist.
Experimental example 3 photocatalytic activity analysis of sample I
Test examples 1 to 4, comparative example 1 (g-C) 3 N 4 ) Comparative examples 2 to 5, indium oxide blank (D7), dysprosium vanadate blank (D8), g-C 3 N 4 And B (D2) degradation rate of pyridine in nitrogen-containing simulated oil (pyridine/petroleum ether).
The nitrogenous simulated oil is prepared from pyridine with certain mass and petroleum ether with the boiling range of 90-120 ℃ into the nitrogenous simulated oil with the mass fractions of 4 microgramme/g, 8 microgramme/g and 12 microgramme/g;
a certain amount of photocatalyst and 50mL of simulated oil are placed on a Shanghai-Lunang BL-GHX-V multi-test tube while stirring a photochemical reaction instrument, the mixture is magnetically stirred for 1h to achieve adsorption-desorption balance, and then a 500W xenon lamp is used as a visible light source for illumination. Taking supernatant according to a certain time, and measuring and analyzing the basic nitrogen content of the nitrogen-containing simulated oil by using a basic nitrogen measuring method (SH/T0162-92) in petroleum products. The results are shown in FIG. 3.
As can be seen from FIG. 3, the composite photocatalyst DyVO of the present invention 4 /In 2 O 3 /g-C 3 N 4 The photocatalytic activity of B is obviously higher than that of pure DyVO 4 、In 2 O 3 、g-C 3 N 4 And B, the activity of the catalyst. Wherein, dyVO 4 ：In 2 O 3 ：g-C 3 N 4 The B is 0.08 4 /In 2 O 3 /g-C 3 N 4 B 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 examples 4 /In 2 O 3 /g-C 3 N 4 Activity 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,
the curve a represents that the adding amount of the composite photocatalyst product is 1.00g/L (namely 1.00g of the composite photocatalyst is added into 1L of nitrogen-containing simulation oil);
the curve b represents that the adding amount of the composite photocatalyst product is 1.25g/L;
curve c represents the dosage of the composite photocatalyst product is 1.50g/L;
the curve d represents that the adding amount of the composite photocatalyst product is 1.75g/L;
as can be seen from fig. 4, when the amount of catalyst added was small, the degradation rate of pyridine gradually increased with the increase in the amount of catalyst. The adding amount of the composite photocatalyst is 1.50g/L, and the degradation rate of pyridine reaches 93.6% when the photocatalytic reaction is carried out for 5 hours. The amount of the catalyst is continuously increased, and the degradation rate of the pyridine is gradually reduced.
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 DyVO 4 /In 2 O 3 /g-C 3 N 4 The 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 μ 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 the initial concentration of pyridine is not too high.
This may be attributed primarily to three reasons: firstly, with the gradual increase of the initial concentration of pyridine, the number of pyridine molecules capable of being adsorbed on the surface of the catalyst is increased, 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 cause intermediate products generated in the photocatalytic reaction not to be effectively decomposed in time but to be adsorbed on the surface of the catalyst, which undoubtedly hinders the reaction efficiency of the photocatalytic 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 of 1 photocatalyst application;
curve b represents the degradation curve for 2 photocatalyst uses;
curve c represents the degradation curve of 3 photocatalyst uses.
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 invention 4 /In 2 O 3 /g-C 3 N 4 The product of 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 denitrification. When the initial concentration of pyridine is 4 mug/g, the dosage of the composite photocatalyst (product in example 2) is 1.5g/L, and the illumination is carried out for 5 hours by a 500W xenon lamp, the degradation rate of the pyridine reaches 93.6%. Moreover, 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.
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 embodiments and implementations of the invention without departing from the spirit and scope of the invention, and are within the scope of the invention. The scope of the invention is defined by the appended claims.
Claims (2)
1. Containing g-C 3 N 4 The application of the composite photocatalyst of B in the denitrification of fuel oil is characterized in that,
the composite photocatalyst also comprises a metal oxide, wherein the metal oxide is indium oxide;
the composite photocatalyst is also doped with metal vanadate, wherein the metal vanadate is DyVO 4 ；
The mass ratio of the indium oxide to the metal dysprosium vanadate and boron-doped graphite-phase carbon nitride is (0.001-0.5): (0.001-0.1) 1;
the above-mentionedComprising g-C 3 N 4 The preparation method of the composite photocatalyst comprises the following steps:
step 1, preparation of g-C 3 N 4 B；
The step 1 comprises the following steps:
step 1-1, uniformly mixing a carbon nitrogen source and a boron source in a solvent, wherein the carbon nitrogen source is urea, the boron source is sodium tetraphenylborate, the solvent is deionized water, and the mass ratio of the carbon nitrogen source to the boron source is 10000 (5-15);
step 1-2, removing the solvent;
step 1-3, roasting at the roasting temperature of 450-600 ℃, and grinding to obtain a product g-C 3 N 4 B；
Step 2, preparing a catalyst containing g-C 3 N 4 B, a composite photocatalyst;
the step 2 comprises the following steps:
step 2-1, raw materials g-C 3 N 4 B and metal oxide are dispersed in the dispersant;
step 2-2, removing the dispersing agent;
step 2-3, roasting at the roasting temperature of 400-550 ℃ for 2-5 hours to obtain a final product composite photocatalyst;
in the step 2-1, the raw material further comprises metal vanadate, wherein the metal is dysprosium; the metal oxide is indium oxide.
2. The use according to claim 1, wherein in step 2-3, the roasting temperature is 450 ℃; the roasting time is 3h.
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