CN109225215A - The catalysis material and preparation method thereof of nitrate nitrogen in a kind of efficient selective photo catalytic reduction water - Google Patents
The catalysis material and preparation method thereof of nitrate nitrogen in a kind of efficient selective photo catalytic reduction water Download PDFInfo
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- CN109225215A CN109225215A CN201811311199.4A CN201811311199A CN109225215A CN 109225215 A CN109225215 A CN 109225215A CN 201811311199 A CN201811311199 A CN 201811311199A CN 109225215 A CN109225215 A CN 109225215A
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- 239000000463 material Substances 0.000 title claims abstract description 57
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 title claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 230000001699 photocatalysis Effects 0.000 title description 30
- 238000010531 catalytic reduction reaction Methods 0.000 title description 28
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 94
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 56
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 235000019253 formic acid Nutrition 0.000 claims abstract description 28
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 27
- 230000009467 reduction Effects 0.000 claims abstract description 27
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims abstract description 24
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004202 carbamide Substances 0.000 claims abstract description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004570 mortar (masonry) Substances 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 9
- 239000002105 nanoparticle Substances 0.000 claims description 6
- 238000005660 chlorination reaction Methods 0.000 claims description 3
- 230000001788 irregular Effects 0.000 claims description 3
- 239000002135 nanosheet Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 48
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 24
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 239000003054 catalyst Substances 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 16
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 230000003247 decreasing effect Effects 0.000 abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 26
- 238000006722 reduction reaction Methods 0.000 description 18
- 229910002651 NO3 Inorganic materials 0.000 description 14
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 14
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 10
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 10
- JVMRPSJZNHXORP-UHFFFAOYSA-N ON=O.ON=O.ON=O.N Chemical compound ON=O.ON=O.ON=O.N JVMRPSJZNHXORP-UHFFFAOYSA-N 0.000 description 7
- 239000004408 titanium dioxide Substances 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000013019 agitation Methods 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000004317 sodium nitrate Substances 0.000 description 5
- 235000010344 sodium nitrate Nutrition 0.000 description 5
- -1 hydroxyl radical free radical Chemical class 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Natural products O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- 239000000618 nitrogen fertilizer Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000006902 nitrogenation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 1
- 238000013097 stability assessment Methods 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6522—Chromium
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses the catalysis material preparation methods that nitrate nitrogen in water removal is removed in a kind of reduction of efficient selective, include the following steps: that (1) mixes nine nitric hydrate gadoliniums, chrome green and urea to be placed in alumina crucible, it is uniform that absolute ethyl alcohol and stirring is added；(2) crucible is placed in Muffle furnace and is calcined；(3) solid resulting after calcining is obtained into GdCrO with mortar grinder3Powder；(4) GdCrO made from3Powder is placed in palladium chloride solution, and formic acid is added and carries out ultraviolet light, palladium chloride is reduced to palladium simple substance and is deposited on GdCrO3Surface obtains Pd/GdCrO3, finally it is centrifuged, washed, is dried.Catalysis material prepared by the present invention is compared with traditional catalysis material, prepare high simple yield, reduction catalysts activity height, with faster reaction rate, 98.7% and 100% are respectively reached for nitrate nitrogen removal rate and nitrogen selective, 6 effects are recycled without being decreased obviously, there is good catalytic activity and stability.
Description
Technical field
The invention belongs to environment functional material fields, more particularly to nitre state in a kind of efficient selective photo catalytic reduction water
Catalysis material of nitrogen and preparation method thereof.
Background technique
The fast development of Global Agriculture, a large amount of uses of artificial nitrogenous fertilizer and the discharge of trade effluent, so that nitre state in water
The pollution of nitrogen is got worse.Nitrate nitrogen not only results in water eutrophication in water, can also be converted into nitrite nitrogen, serious prestige
Coerce the health of the mankind.Many governments and tissue all to the control of nitrate in water using the standard that is increasingly stringenter, with this,
The removal of nitrate nitrogen in water body becomes the hot and difficult issue of water treatment field.The method of tradition removal nitrate nitrogen includes ion exchange
Method, hyperfiltration, electrolysis method, biological denitrification method and chemical reduction method etc..But different degrees of inefficient, high cost and complexity
Service condition etc. limit the extensive use of above a variety of methods.Light-catalysed essence is under illumination shooting condition, and light is urged
In catalyst valence band and conduction band redox reaction occurs for " electron-hole pair " and target substance that agent generates respectively.With
The advantages that titanium dioxide is that the photochemical catalyst of representative is good with its stability, at low cost, nonhazardous and secondary pollution is in environmental protection
Field receives extensive attention and develops.However there is also following defects for the photocatalyst treatment technology of titanium dioxide: (1) pure two
Titanium oxide photochemical catalyst reduction removal nitrate nitrogen inefficiency；(2) pure titinium dioxide photochemical catalyst photo catalytic reduction nitre state selectivity
Difference, the by-products such as the higher nitrite nitrogen of concentration easily generated, ammonia nitrogen；(3) titanium dioxide pattern is controlled, its high catalytic activity of exposure is brilliant
The method in face prepares nano-titanium dioxide complex steps, takes a long time, and still remains the more problem of by-product.
The Chinese patent that number of patent application is 2006100461728 discloses a kind of method that photocatalysis removes nitrogen in water,
Metal Supported nano titania catalyst or nitrating titanium dioxide composite catalyst are utilized which disclose a kind of, logical
Under conditions of nitrogen or argon gas removal dissolved oxygen, photochemical catalytic oxidation ammonia nitrogen and photo catalytic reduction oxidation state nitrogen are coupled together, with
Nitrogen is target product, and nitrogen containing component is taken out from water.However the catalysis material of the patent disclosure loaded noble silver it
Nitrogen removal rate is only 38%(ammonia nitrogen afterwards and nitrous nitrogen removal efficiency is respectively 48%, 27%), total nitrogen is gone after adding ferrous ion
Except rate reaches 64%(ammonia nitrogen and nitrite nitrogen is respectively 88%, 43%)；In addition, the introducing of ferrous ion can generate iron cement, it is possible to
The secondary pollution of water body is caused, the load of noble metal also results in the increase of preparation cost.
The Chinese patent that number of patent application is 201610891842 discloses a kind of photo catalytic reduction and removes nitrate nitrogen in water
Method, which disclose a kind of Ag-Ag2O/TiO2Composite photocatalyst body agent, in the case where formic acid does electron donor, into
The reaction of row photo catalytic reduction nitrate nitrogen in water body.However, the catalysis material preparation process that the patent is related to is cumbersome, time-consuming
(at least needing 15 hours or more), low output is difficult large scale preparation and is applied.
The Chinese patent for being 2015102738202 to number of patent application discloses noble metal nano particles selective modification
Titanic oxide material and its preparation method and application, which disclose a kind of dioxies of noble metal nano particles selective modification
Change the preparation method of titanium-based catalysis material and applies the reduction removal in water body nitrate nitrogen.This material is firstly the need of preparation face
The nanometer or micro-scale titanium dioxide crystal of tachyauxesis, reactant need to keep the temperature 48-96 hours under the conditions of 80-240 DEG C, Zhi Houxu
Washing 5-8 times is carried out to product, is ground after 10 hours dry.Hereafter it carries out noble metal decorated, needs to be washed again, do
Dry, grinding and etc..Whole preparation process step is complicated, and time-consuming is long, although catalytic conversion with higher, and it is different
Surely there is very high selectivity, and stability assessment is not carried out to catalyst.
Therefore on the basis of the studies above, traditional titanium dioxide is overcome to need hole and hydroxyl radical free radical on exploitation value band
The hole trapping agents such as formic acid are oxidized to carbon dioxide free radical, largely rely on carbon dioxide radical reduction nitre state
Nitrogen, and be also easy to produce hydroxyl radical free radical and the shortcomings that oxidation leads to low catalytic efficiency, poor selectivity is carried out to intermediate product, prepare one kind
The catalysis material for improving photo catalytic reduction nitrate efficiency will become new research direction.
Summary of the invention
The purpose of the present invention is the photochemical catalysts for current titanium dioxide there is reduction removal nitrate nitrogen low efficiency, selection
Property difference and uncontrollable problem, provide in a kind of efficient selective photo catalytic reduction water the catalysis material of nitrate nitrogen and
Preparation method.
The present invention is achieved by the following technical solutions:
The catalysis material preparation method of nitrate nitrogen in water removal is gone in a kind of efficient selective reduction, is included the following steps:
(1) nine nitric hydrate gadoliniums, chrome green and urea are mixed and is placed in alumina crucible, absolute ethyl alcohol and stirring is added
Uniformly；
(2) crucible is placed in Muffle furnace and is calcined；
(3) solid resulting after calcining is obtained into GdCrO with mortar grinder3Powder；
(4) by GdCrO made from step (3)3Powder is placed in palladium chloride solution, and formic acid is added and carries out ultraviolet light, chlorine
Change palladium to be reduced to palladium simple substance and be deposited on GdCrO3Surface is finally centrifuged, is washed, is dried, and catalysis material Pd/ is made
GdCrO3。
The catalysis material preparation method of nitrate nitrogen in water removal is gone in a kind of efficient selective reduction of the present invention, into
The technical solution that one step solves is that the molar ratio of nine nitric hydrate gadoliniums, chrome green and urea is 1 in the step (1):
(0.5-1):4。
The catalysis material preparation method of nitrate nitrogen in water removal is gone in a kind of efficient selective reduction of the present invention, into
The technical solution that one step solves is that the volume ratio of dehydrated alcohol and mixed reactant is 1:2 in the step (1).
The catalysis material preparation method of nitrate nitrogen in water removal is gone in a kind of efficient selective reduction of the present invention, into
One step solve technical solution be, in the step (2) heating temperature of Muffle furnace be 800 DEG C, heating rate be 5-8 DEG C/
Min, reaction time 4h.
The catalysis material preparation method of nitrate nitrogen in water removal is gone in a kind of efficient selective reduction of the present invention, into
The technical solution that one step solves is that the molar ratio of formic acid and palladium chloride is (2-4) in the step (4): 1.
The catalysis material preparation method of nitrate nitrogen in water removal is gone in a kind of efficient selective reduction of the present invention, into
The technical solution that one step solves is palladium and GdCrO in the step (4)3Mass ratio be (0.5-2): 100；The ultraviolet light
Irradiation time is 100-120min.
Efficient selective catalysis material and its application as made from above-mentioned preparation method, also in protection model of the invention
In enclosing, the catalysis material is Pd nano particle and GdCrO3Complex, GdCrO3With irregular nano-sheet shape
Looks, Pd are attached to the GdCrO with the nano particle of simple substance form3Surface on, the average diameter of Pd is in catalysis material
The catalysis material needs of 5.7nm, above-mentioned preparation use in liquid environment, can restore nitrate nitrogen in water removal.
The present invention is that raw material is short by high temperature with chrome green, gadolinium nitrate, urea, dehydrated alcohol, palladium chloride, formic acid etc.
Time calcining can be made, and since prepared catalyst has relatively negative conduction band value (- 2.02V vs NHE), conduction band electron is also
Former very competent, nitrate nitrogen improves the efficiency of photo catalytic reduction nitrate mainly on conduction band by electron reduction, while Pd
Load not only further improves GdCrO3Photocatalysis efficiency, and be conducive to conversion of the nitrite nitrogen to nitrogen, it is significant to improve
The selectivity of photo catalytic reduction nitrate.
Novel GdCrO prepared by the present invention3Catalysis material has following excellent compared with traditional TiO 2-based catalyst
Gesture:
1. the catalysis material reduction catalysts activity of preparation is high, there is faster reaction rate.
2. the removal rate of nitrate nitrogen and the selectivity for generating nitrogen are high, the by-products production quantity such as nitrite nitrogen and ammonia nitrogen is low.
3. preparation process is simple, time-consuming short, yield is high.
Detailed description of the invention
In Fig. 1, (a) is GdCrO of the present invention3SEM figure；It (b) is de GdCrO of the present invention3TEM figure；
It (c) is Pd/GdCrO of the present invention3TEM figure；It (d) is Pd nano particle diameter distribution map of the present invention；(e)
For Pd/ GdCrO of the present invention3HRTEM figure；It (f) is Pd/ GdCrO of the present invention3EDS figure.
Fig. 2 is the GdCrO after load Pd of the present invention3The 3d orbital electron energy spectrum diagram of electronic energy spectrum and Pd.
Fig. 3 is photocatalytic reaction device schematic diagram of the present invention.
Fig. 4 is GdCrO in comparative example 13The effect picture of photo catalytic reduction nitrate nitrogen in water body.
Fig. 5 is 0.5%wt Pd/GdCrO in embodiment 23The effect picture of photo catalytic reduction nitrate nitrogen in water body.
Fig. 6 is 1%wt Pd/GdCrO in embodiment 33The effect picture of photo catalytic reduction nitrate nitrogen in water body.
Fig. 7 is 2%wt Pd/GdCrO in embodiment 43The effect picture of photo catalytic reduction nitrate nitrogen in water body.
Fig. 8 is 1%wt Pd/GdCrO in embodiment 53The effect picture that photo catalytic reduction nitrate nitrogen in water body is recycled.
Fig. 9 is the XPS figure of reaction front and back material in embodiment 5.
Figure 10 is the XRD diagram of reaction front and back material in embodiment 5.
Serial number in figure, 1- reaction vessel, 2- thermometer, 3- probe tube, 4- high-pressure sodium lamp, 5- magnetic stirring apparatus.
Specific embodiment
Summary of the invention of the invention is further described with reference to the accompanying drawings and examples.
Embodiment 1
Material preparation process:
The catalysis material preparation method of nitrate nitrogen in water removal is gone in a kind of efficient selective reduction, is included the following steps:
(1) nine nitric hydrate gadoliniums, chrome green and urea are mixed according to the ratio of the ratio between the amount of substance 1:0.5:4 and is placed
In alumina crucible, 10mL dehydrated alcohol is added and did not had reagent to stir evenly；
(2) crucible is placed in Muffle furnace, rises to 800 DEG C with the heating rate of 5 DEG C/min, then calcining 4 is small at 800 DEG C
When；
(3) obtained solid prepares GdCrO with mortar grinder after calcining3Powder；
(4) GdCrO for preparing 2g step (3)3Powder is added in palladium chloride solution, and formic acid is added and passes through as electron donor
Palladium chloride is reduced to palladium simple substance and is deposited on GdCrO by ultraviolet lighting3Surface obtains Pd/GdCrO3, finally by centrifugation, washing,
Drying obtains Pd/GdCrO3Catalysis material；Wherein, palladium and GdCrO in palladium chloride3Mass ratio 0.5:100, formic acid and chlorination
The molar ratio of palladium is 2:1, light application time 120min.
The characterization that SEM, TEM and EDS are carried out to the product of above-mentioned each step preparation, as shown in Figure 1, in the material of preparation
Include the elements such as Gd, Cr, O, Pd, GdCrO3With irregular nano-sheet pattern, Pd is attached with the nano particle of simple substance form
In the GdCrO3Surface on and Pd average diameter be 5.7nm.
Embodiment 2
The catalysis material preparation method of nitrate nitrogen in water removal is gone in a kind of efficient selective reduction, is included the following steps:
(1) nine nitric hydrate gadoliniums, chrome green and urea are mixed according to the ratio of the ratio between the amount of substance 1:1:4 and is placed in
In alumina crucible, 10mL dehydrated alcohol is added and did not had reagent to stir evenly；
(2) crucible is placed in Muffle furnace, rises to 800 DEG C with the heating rate of 6 DEG C/min, then calcining 4 is small at 800 DEG C
When；
(3) obtained solid prepares GdCrO with mortar grinder after calcining3Powder；
(4) GdCrO for preparing 2g step (3)3Powder is added in palladium chloride solution, and formic acid is added and passes through as electron donor
Palladium chloride is reduced to palladium simple substance and is deposited on GdCrO by ultraviolet lighting3Surface obtains Pd/GdCrO3, finally by centrifugation, washing,
Drying obtains Pd/GdCrO3Catalysis material；Wherein, palladium and GdCrO in palladium chloride3Mass ratio 0.5:100, formic acid and chlorination
The molar ratio of palladium is 2:1, light application time 120min；
(5) sodium nitrate solution that nitrate concentration is 50mg/L (0.8mmol) is placed in Photoreactor, 0.5wt% step is added
Suddenly the Pd/GdCrO3 catalyst of (4) preparation, dosage 0.5g/L are secretly adsorbed under the conditions of magnetic agitation rotating speed 350rpm
30min, is then added 1 mL formic acid solution, and the formic acid solution concentration is 1mol/L；It opens cooling and water bath device and keeps anti-
Answering temperature is 25 DEG C, and the ultraviolet source for opening 350W high-pressure sodium lamp carries out the reaction of photo catalytic reduction nitrate nitrogen, time 100
min。
Denitrification effect as shown in Figure 5, reacts by 100 minutes photo catalytic reductions, has loaded the GdCrO of 0.5wt% Pd3It is right
Nitrate removal rate reaches 92.8%, and the ammonia nitrogen generated in reaction process maintains always reduced levels less than 1%, and nitrite nitrogen contains
It is only 5.1% that amount, which is also significantly suppressed content, since nitrite nitrogen is selectively converted to ammonia nitrogen under the catalytic action of Pd,
Nitrogen selective is increased substantially to 94.1%.Absolutely prove that the load of 0.5wt% Pd had both improved photo catalytic reduction nitrate
Efficiency, and improve nitrogen selective.
Embodiment 3
(1) nine nitric hydrate gadoliniums, chrome green and urea are mixed according to the ratio of the ratio between the amount of substance 1:1:4 and is placed in
In alumina crucible, 10mL dehydrated alcohol is added and did not had reagent to stir evenly；
(2) crucible is placed in Muffle furnace, rises to 800 DEG C with the heating rate of 6 DEG C/min, then calcining 4 is small at 800 DEG C
When；
(3) obtained solid prepares GdCrO with mortar grinder after calcining3Powder；
(4) GdCrO for preparing 2g step (3)3Powder is added in palladium chloride solution, and formic acid is added and passes through as electron donor
Palladium chloride is reduced to palladium simple substance and is deposited on GdCrO by ultraviolet lighting3Surface obtains Pd/GdCrO3, finally by centrifugation, washing,
Drying obtains Pd/GdCrO3Catalysis material；Wherein, palladium and GdCrO in palladium chloride3Mass ratio 1:100, formic acid and palladium chloride
Molar ratio be 3:1, light application time 120min；
(5) sodium nitrate solution that nitrate concentration is 50mg/L (0.8mmol) is placed in Photoreactor, 1wt% step is added
(4) Pd/GdCrO prepared3Catalyst, dosage 0.5g/L are secretly adsorbed under the conditions of magnetic agitation rotating speed 350rpm
30min, is then added 1mL formic acid solution, and the formic acid solution concentration is 1mol/L；It opens cooling and water bath device and keeps reaction
Temperature is 25 DEG C, and the ultraviolet source for opening 350W high-pressure sodium lamp carries out the reaction of photo catalytic reduction nitrate nitrogen, and the time is 100 min.
Denitrification effect as shown in Figure 6, reacts by 100 minutes photo catalytic reductions, has loaded the GdCrO of 1wt% Pd3To nitre
Hydrochlorate removal rate reaches 98.7%, and the ammonia nitrogen generated in reaction process continues close to 0, nitrous nitrogen content also by 20 minutes when
Peak drop to 0, nitrogen selective reaches 100%.The load for illustrating 1wt% Pd is optimum load amount.
Embodiment 4
(1) nine nitric hydrate gadoliniums, chrome green and urea are mixed according to the ratio of the ratio between the amount of substance 1:1:4 and is placed in
In alumina crucible, 10mL dehydrated alcohol is added and did not had reagent to stir evenly；
(2) crucible is placed in Muffle furnace, rises to 800 DEG C with the heating rate of 6 DEG C/min, then calcining 4 is small at 800 DEG C
When；
(3) obtained solid prepares GdCrO with mortar grinder after calcining3Powder；
(4) GdCrO for preparing 2g step (3)3Powder is added in palladium chloride solution, and formic acid is added and passes through as electron donor
Palladium chloride is reduced to palladium simple substance and is deposited on GdCrO by ultraviolet lighting3Surface obtains Pd/GdCrO3, finally by centrifugation, washing,
Drying obtains Pd/GdCrO3Catalysis material；Wherein, palladium and GdCrO in palladium chloride3Mass ratio 2:100, formic acid and palladium chloride
Molar ratio be 4:1, light application time 120min；
(5) sodium nitrate solution that nitrate concentration is 50mg/L (0.8mmol) is placed in Photoreactor, 2wt% step is added
(4) Pd/GdCrO prepared3Catalyst, dosage 0.5g/L are secretly adsorbed under the conditions of magnetic agitation rotating speed 350rpm
30min, is then added 1 mL formic acid solution, and the formic acid solution concentration is 1mol/L；It opens cooling and water bath device and keeps anti-
Answering temperature is 25 DEG C, and the ultraviolet source for opening 350W high-pressure sodium lamp carries out the reaction of photo catalytic reduction nitrate nitrogen, time 100
min。
Denitrification effect as shown in Figure 7, reacts by 100 minutes photo catalytic reductions, has loaded the GdCrO of 2wt% Pd3To nitre
Hydrochlorate removal rate reaches 93.1%, and the ammonia nitrogen generated in reaction process maintains always reduced levels and is finally reduced to 0, Asia
Maximum concentration when nitrate nitrogen content was by 20 minutes drops to 4.4%, and nitrogen selective is increased substantially to 95.1%.Illustrate 2wt%
The load of Pd equally improves the efficiency and nitrogen selective of photo catalytic reduction nitrate, but is not optimum load amount, Pd's
Load capacity is excessively likely to become the complex centre of catalysis material electron hole instead, declines photocatalysis efficiency.
Embodiment 5
(1) nine nitric hydrate gadoliniums, chrome green and urea are mixed according to the ratio of the ratio between the amount of substance 1:1:4 and is placed in
In alumina crucible, 10mL dehydrated alcohol is added and did not had reagent to stir evenly；
(2) crucible is placed in Muffle furnace, rises to 800 DEG C with the heating rate of 5 DEG C/min, then calcining 4 is small at 800 DEG C
When；
(3) obtained solid prepares GdCrO with mortar grinder after calcining3Powder；
(4) GdCrO for preparing 2 g steps (3)3Powder is added in palladium chloride solution, and formic acid is added and passes through as electron donor
Palladium chloride is reduced to palladium simple substance and is deposited on GdCrO by ultraviolet lighting3Surface obtains Pd/GdCrO3, finally by centrifugation, washing,
Drying obtains Pd/GdCrO3Catalysis material；Wherein, palladium and GdCrO in palladium chloride3Mass ratio 1:100, formic acid and palladium chloride
Molar ratio be 3:1, light application time 100min；
(5) sodium nitrate solution that nitrate concentration is 50mg/L (0.8mmol) is placed in Photoreactor, 12wt% step is added
(4) Pd/GdCrO prepared3Catalyst, dosage 0.5g/L are secretly adsorbed under the conditions of magnetic agitation rotating speed 350rpm
30min, is then added 1mL formic acid solution, and the formic acid solution concentration is 1mol/L；It opens cooling and water bath device and keeps reaction
Temperature is 25 DEG C, and the ultraviolet source for opening 350W high-pressure sodium lamp carries out the reaction of photo catalytic reduction nitrate nitrogen, and the time is 100 min.
Photo catalytic reduction nitrate nitrogen in water body be recycled effect picture as shown in figure 8, by 6 this recycling after, it is right
98.7% and 100% are respectively reached in nitrate nitrogen removal rate and nitrogen selective, 6 effects are recycled without being decreased obviously.
XPS, XRD characterization such as Fig. 9 and 10 of reaction front and back material, as seen from the figure, the crystal structure of reaction front and back material is simultaneously
Nothing is substantially change, and Pd exists with elemental stage, illustrates that material has preferable stability.
Comparative example 1
The catalysis material preparation method of nitrate nitrogen in water removal is gone in a kind of efficient selective reduction, is included the following steps:
(1) nine nitric hydrate gadoliniums, chrome green and urea are mixed according to the ratio of the ratio between the amount of substance 1:0.5:4 and is placed
In alumina crucible, 10mL dehydrated alcohol is added and did not had reagent to stir evenly；
(2) crucible is placed in Muffle furnace, rises to 800 DEG C with the heating rate of 5 DEG C/min, then calcining 4 is small at 800 DEG C
When；
(3) obtained solid prepares GdCrO with mortar grinder after calcining3Powder；
(4) sodium nitrate solution that nitrate concentration is 50mg/L (0.8mmol) is placed in Photoreactor, the above-mentioned step of 2g is added
Suddenly the GdCrO of (3) preparation3Powder, dosage 0.5g/L secretly adsorb 30min under the conditions of magnetic agitation rotating speed 350rpm, with
1mL formic acid solution is added afterwards, the formic acid solution concentration is 1mol/L；Opening cooling and water bath device and keeping reaction temperature is 25
DEG C, the ultraviolet source for opening 350W high-pressure sodium lamp carries out the reaction of photo catalytic reduction nitrate nitrogen, and the time is 120 min.
Denitrification effect as shown in Figure 4, reacted, nitrate removal rate reaches 9%, although instead by 100 minutes photo catalytic reductions
The ammonia nitrogen that should be generated in the process maintains 2.8%, but nitrous nitrogen content reaches 11.8%, and nitrogen selective is only 81.4%.
In conclusion the catalysis material of nitrate nitrogen and tradition in water removal are gone in the reduction of efficient selective prepared by the present invention
Catalysis material compare, prepare that simple yield is high, reduction catalysts activity is high, has faster reaction rate, for nitrate nitrogen
Removal rate and nitrogen selective respectively reach 98.7% and 100%, and 6 effects are recycled without being decreased obviously, have good
Catalytic activity and stability.
What has been described above is only a preferred embodiment of the present invention, it is noted that for those of ordinary skill in the art
For, without departing from the concept of the premise of the invention, various modifications and improvements can be made, these belong to the present invention
Protection scope.
Claims (9)
1. the catalysis material preparation method that nitrate nitrogen in water removal is removed in a kind of efficient selective reduction, which is characterized in that including such as
Lower step:
(1) nine nitric hydrate gadoliniums, chrome green and urea are mixed and is placed in alumina crucible, absolute ethyl alcohol and stirring is added
Uniformly；
(2) crucible is placed in Muffle furnace and is calcined；
(3) solid resulting after calcining is obtained into GdCrO with mortar grinder3Powder；
(4) by GdCrO made from step (3)3Powder is placed in palladium chloride solution, and formic acid is added and carries out ultraviolet light, chlorination
Palladium is reduced to palladium simple substance and is deposited on GdCrO3Surface is finally centrifuged, is washed, is dried, and catalysis material Pd/ is made
GdCrO3。
2. the catalysis material preparation method of nitrate nitrogen in water removal is gone in efficient selective reduction according to claim 1,
It is characterized in that, the molar ratio of nine nitric hydrate gadoliniums, chrome green and urea is 1:(0.5-1 in the step (1)): 4.
3. the catalysis material preparation method of nitrate nitrogen in water removal is gone in efficient selective reduction according to claim 1,
It is characterized in that, the volume ratio of dehydrated alcohol and mixed reactant is 1:2 in the step (1).
4. the catalysis material preparation method of nitrate nitrogen in water removal is gone in efficient selective reduction according to claim 1,
It is characterized in that, the heating temperature of Muffle furnace is 800 DEG C in the step (2), and heating rate is 5-8 DEG C/min, and the reaction time is
4h。
5. the catalysis material preparation method of nitrate nitrogen in water removal is gone in efficient selective reduction according to claim 1,
It is characterized in that, the molar ratio of formic acid and palladium chloride is (2-4) in the step (4): 1.
6. the catalysis material preparation method of nitrate nitrogen in water removal is gone in efficient selective reduction according to claim 1,
It is characterized in that, palladium and GdCrO in the step (4)3Mass ratio be (0.5-2): 100；The ultraviolet light time is
100-120min。
7. the catalysis material that nitrate nitrogen in water removal is removed in a kind of efficient selective reduction, which is characterized in that appointed by claim 1-6
Method described in one is made；The catalysis material is Pd nano particle and GdCrO3Complex, GdCrO3With irregular
Nano-sheet pattern, Pd is attached to the GdCrO with the nano particle of simple substance form3Surface on.
8. the catalysis material of nitrate nitrogen in water removal, feature are gone in a kind of efficient selective reduction according to claim 7
It is, the average diameter of Pd is 5.7nm in the catalysis material.
9. catalysis material as claimed in claim 7 is used to restore the application for removing nitrate nitrogen in water removal.
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| PCT/CN2018/120813 WO2020093517A1 (en) | 2018-11-06 | 2018-12-13 | Photocatalytic material for efficient and selective reduction and removal of nitrate nitrogen in water, and preparation method thereof |
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|---|---|---|---|---|
| CN110316895A (en) * | 2019-08-06 | 2019-10-11 | 东北师范大学 | A kind of processing method of the industrial wastewater containing high concentration nitrate |
| CN113198515A (en) * | 2021-05-19 | 2021-08-03 | 上海城投原水有限公司 | Ternary photocatalyst and preparation method and application thereof |
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| CN117511432A (en) * | 2024-01-05 | 2024-02-06 | 山东旭贝新材料有限公司 | Ultraviolet-transparent fluorine-containing polymer film and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105148972A (en) * | 2015-09-10 | 2015-12-16 | 上海大学 | Preparation method and application of novel catalyst for reducing nitrate nitrogen in water under visible light condition |
| CN106315755A (en) * | 2016-10-13 | 2017-01-11 | 天津工业大学 | Method for removing nitrate nitrogen from water by photocatalytic reduction |
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2018
- 2018-11-06 CN CN201811311199.4A patent/CN109225215A/en not_active Withdrawn
- 2018-12-13 WO PCT/CN2018/120813 patent/WO2020093517A1/en active Application Filing
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105148972A (en) * | 2015-09-10 | 2015-12-16 | 上海大学 | Preparation method and application of novel catalyst for reducing nitrate nitrogen in water under visible light condition |
| CN106315755A (en) * | 2016-10-13 | 2017-01-11 | 天津工业大学 | Method for removing nitrate nitrogen from water by photocatalytic reduction |
Non-Patent Citations (1)
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| ZHIANG HOU 等: "Novel Pd/GdCrO3 composite for photo-catalytic reduction of nitrate to N2 with high selectivity and activity", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110316895A (en) * | 2019-08-06 | 2019-10-11 | 东北师范大学 | A kind of processing method of the industrial wastewater containing high concentration nitrate |
| CN113198515A (en) * | 2021-05-19 | 2021-08-03 | 上海城投原水有限公司 | Ternary photocatalyst and preparation method and application thereof |
| CN113198515B (en) * | 2021-05-19 | 2023-07-28 | 上海城投原水有限公司 | Ternary photocatalyst and preparation method and application thereof |
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