CN106378124A - Method for treating chromium-containing wastewater by using straw cellulose-cerium oxide composite through photocatalytic reduction - Google Patents
Method for treating chromium-containing wastewater by using straw cellulose-cerium oxide composite through photocatalytic reduction Download PDFInfo
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- CN106378124A CN106378124A CN201610850633.0A CN201610850633A CN106378124A CN 106378124 A CN106378124 A CN 106378124A CN 201610850633 A CN201610850633 A CN 201610850633A CN 106378124 A CN106378124 A CN 106378124A
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- China
- Prior art keywords
- cerium oxide
- stalk cellulose
- oxide compound
- mixed liquor
- hexavalent chromium
- Prior art date
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- Granted
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- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 101
- 239000002351 wastewater Substances 0.000 title claims abstract description 96
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000010902 straw Substances 0.000 title claims abstract description 32
- 239000011651 chromium Substances 0.000 title claims abstract description 31
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 230000009467 reduction Effects 0.000 title claims abstract description 16
- 229910052804 chromium Inorganic materials 0.000 title abstract description 17
- 239000002131 composite material Substances 0.000 title abstract 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000000243 solution Substances 0.000 claims abstract description 67
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000003756 stirring Methods 0.000 claims abstract description 56
- 239000001913 cellulose Substances 0.000 claims abstract description 53
- 229920002678 cellulose Polymers 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052724 xenon Inorganic materials 0.000 claims abstract description 43
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims abstract description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 42
- 239000008367 deionised water Substances 0.000 claims abstract description 41
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 34
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims abstract description 27
- 230000001105 regulatory effect Effects 0.000 claims abstract description 14
- 238000000967 suction filtration Methods 0.000 claims abstract description 14
- NBVHDOZEOGAKLK-UHFFFAOYSA-N [N]=O.CC1C(N(CCC1)C)(C)C Chemical compound [N]=O.CC1C(N(CCC1)C)(C)C NBVHDOZEOGAKLK-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000007146 photocatalysis Methods 0.000 claims description 59
- 238000004140 cleaning Methods 0.000 claims description 52
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 26
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 26
- 239000011521 glass Substances 0.000 claims description 26
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 26
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 26
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 26
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 238000006722 reduction reaction Methods 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 229910001410 inorganic ion Inorganic materials 0.000 claims description 13
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims description 13
- 238000010926 purge Methods 0.000 claims description 13
- 238000007789 sealing Methods 0.000 claims description 13
- 238000002798 spectrophotometry method Methods 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 2
- 150000004677 hydrates Chemical class 0.000 claims description 2
- 238000001035 drying Methods 0.000 abstract 2
- 235000019441 ethanol Nutrition 0.000 abstract 2
- 238000005406 washing Methods 0.000 abstract 2
- 239000005708 Sodium hypochlorite Substances 0.000 abstract 1
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 abstract 1
- 230000001678 irradiating effect Effects 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 69
- 150000001875 compounds Chemical class 0.000 description 26
- 239000000835 fiber Substances 0.000 description 22
- 239000003054 catalyst Substances 0.000 description 14
- 239000012467 final product Substances 0.000 description 11
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- -1 di-iron trioxide molybdenum sulfide compound Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001785 cerium compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
Abstract
The invention relates to a method for treating chromium-containing wastewater by using a straw cellulose-cerium oxide composite through photocatalytic reduction. The method comprises the following steps: dispersing straw pulp in tetramethyl piperidine nitrogen oxide and sodium bromide, dropwise adding an alkaline sodium hypochlorite solution; reacting for several hours while vigorously stirring, and regulating pH of the solution by using sodium hydroxide; carrying out suction filtration, washing and drying to obtain nano straw cellulose; dissolving a proper amount of straw cellulose and a proper amount of cerium nitrate hexahydrate in a mixed solution of deionized water and ethyl alcohol and uniformly stirring, transferring a mixture into a high-pressure reactor for reacting; centrifugally separating the mixture and then washing the mixture with the ethyl alcohol and the deionized water; drying the mixture to obtain a finished straw cellulose-cerium oxide product; adding the finished straw cellulose-cerium oxide product into wastewater containing hexavalent chromium in an initial concentration of 3-10mg/L, uniformly stirring and then irradiating for 30 minutes or longer by using a xenon lamp, and measuring the concentration of the hexavalent chromium in the treated wastewater and calculating the removal rate of the hexavalent chromium. The method for treating the chromium-containing wastewater by using the straw cellulose-cerium oxide composite is high in removal rate of the hexavalent chromium and low in treatment cost, and is environmental-friendly.
Description
Technical field
The present invention relates to a kind of method of stalk cellulose-cerium oxide compound photo catalytic reduction processing waste water containing chrome, belong to
In technical field of sewage.
Background technology
In recent years, the enhancing to environmental protection consciousness with masses, various water process new technologies are arisen at the historic moment.Photocatalysis skill
Art is considered as a kind of to have one of water process new technology of tremendous expansion potentiality.Because it can directly utilize sunshine, ring
The features such as border is friendly, just receives more and more attention.Metallurgical and the booming of mining industry causes to be discharged in environment
Waste water containing heavy metal chromium is increasing, causes grave danger to environment.Chromate waste water is difficult to biological after being discharged into water body
Aquatic animal, plantses and the mankind can be produced potentially hazardous or even carcinogenic by degraded.And photo catalytic reduction Cr VI can be effectively
Reduce the toxicity of chromium.
Cerium oxide is a kind of common rare earth oxide, is also one of popular photochemical catalyst, and its band gap width is 3.2 electronics
Volt.Under normal circumstances, the transition of electronics can only being produced under ultraviolet light, producing a large amount of free radicals thus there is photocatalysis
Reaction.But select mould material if appropriate, cerium oxide is dispersed in template, not only can obtain more preferable photocatalysis
Effect, moreover it is possible to pass through its synergy with mould material, reduces band gap width so that compound has preferably under visible light
Photocatalysis performance.Stalk is common agricultural wastes, has had a lot of documents to confirm that it can use as mould material；And
Stalk can isolate cellulose after suitably out.This can effectively improve the specific surface area of mould material.Therefore, by stalk
Cellulose and cerium oxide are combined can not only be developed the new application of stalk and can also obtain the photochemical catalyst of good photocatalysis performance.
Content of the invention
It is an object of the invention to, overcome problems of the prior art, a kind of processing method of chromate waste water be provided,
The method being specifically related to stalk cellulose-cerium oxide complex catalysts reduction treatment chromate waste water, this compound has excellent
Visible light photocatalysis performance.
The technical solution realizing the object of the invention is：A kind of stalk cellulose-cerium oxide compound photo catalytic reduction
The method of processing waste water containing chrome is it is characterised in that comprise the steps：
(1) weigh 10～20 grams of straw pulps, add to containing 0.05～0.2 gram of TEMPO and 0.5～1.5 gram of sodium bromide
The aqueous solution in, obtain the first mixed liquor；
(2) liquor natrii hypochloritis of configuration quality fraction 3～6%, is adjusted with the hydrochloric acid solution of 0.05～0.3 mol/L
Its pH；
(3) liquor natrii hypochloritis obtaining step (2) is slowly added to step (1) gained the first mixed liquor, acutely
Stirring, obtains the second mixed liquor；
(4) pH of the second mixed liquor being obtained with the sodium hydroxide solution regulating step (3) of 0.2～1.0 mol/L, instead
The 3rd mixed liquor should be obtained；
(5) the 3rd mixed liquor suction filtration obtaining step (4) goes after moisture removal, and deionized water cleaning is cleaned, directly repeatedly
PH value to the 3rd mixed liquor is 7.0, the 3rd mixed liquor after cleaning is placed in baking oven to dry at 40～60 DEG C is
Obtain the stalk cellulose of Nano grade；
(6) 5～10mL deionized water and 10～40mL ethanol are mixed and obtain ethanol solution, by six nitric hydrates
The stalk cellulose that cerium, step (4) obtain adds in ethanol solution after mixing, and stirs while adding and makes stalk cellulose equal
Even disperse and make six nitric hydrate ceriums to be completely dissolved, then proceed to add 0.1～0.5g polyvinylpyrrolidone, and stir and make it
Dissolving, obtains the 4th mixed liquor；
(7) the 4th mixed liquor obtaining step (6) is transferred in autoclave, at 160～180 DEG C reaction 15～
24 hours, obtain reacted 5th mixed liquor；
(8) the 5th mixed liquor that step (7) is obtained is centrifuged after moisture removal, is first removed not with ethanol purge
The polyvinylpyrrolidone of reaction, then the deionized water cleaning unreacted inorganic ions of removal, until the pH of the 5th mixed liquor
Value is not less than 6.8, the 5th mixed liquor after cleaning is placed in baking oven to dry at 50～70 DEG C obtains stalk within 10～20 hours
Cellulose-cerium oxide compound finished product；
(9) take 5～10mg stalk cellulose-cerium oxide compound finished product to be added to 40mL and contain in hexavalent chromium wastewater, described
Cr VI initial concentration C containing hexavalent chromium wastewater0For 3～10mg/L, pH value is 4.01～6.93；
(10) being added to containing hexavalent chromium wastewater containing stalk cellulose-cerium oxide compound finished product by step (9) gained
In glass container, sealing；
(11) it is stirred in the camera bellows glass container of step (10) being put into photo catalysis reactor, control temperature to be 25
DEG C, obtain solidliquid mixture；
(12) after terminating through step (11) stirring, open xenon lamp, the solidliquid mixture that step (11) is obtained is under xenon lamp
Irradiate 35～120 minutes, carry out photocatalysis；
(13), after terminating through step (12) photocatalysis, waste water containing dye in the solidliquid mixture of 5mL step (12), mistake are extracted
Filter, obtains clear liquid；
(14) take the clear liquid that 2 milliliters of steps (13) obtain, with determined by ultraviolet spectrophotometry through stalk cellulose-cerium oxide
Hexavalent chromium concentration C after the process of compound photo catalytic reductione；Calculate through stalk cellulose-cerium oxide compound photo catalytic reduction
Hexavalent chromium removal rate=(C/C after processing waste water containing chrome0) * 100%, wherein, C=C0-Ce.
In step (2), pH scope is 9～11.
In step (3), stirring frequency is not less than 200 revs/min.
In step (4), pH scope is 9～11.
In step (6), the quality of described stalk cellulose is 0.05～0.25 gram, the quality of six nitric hydrate ceriums is 20
～50 milligrams.
In step (11), mixing time is 30～60 minutes.
The power of the xenon lamp described in step (12) is 400W.
With respect to prior art, the present invention achieves following beneficial effect：
1. step (2) and step (4) pH must control and could obtain nano level stalk cellulose in suitable scope.
2. add the structure that stalk cellulose is to regulate and control cerium oxide in cerium oxide synthetic system, promote cerium oxide multiple
Compound has bigger specific surface area and more preferable dispersive property, and in catalytic process, stalk cellulose is collaborative with cerium oxide
Effect, can effectively reduce the band gap width of cerium oxide, so that it is guaranteed that gained compound has catalysis activity in visible region.
3. stalk cellulose in stalk cellulose-cerium oxide that the present invention is obtained：The weight of cerium oxide is than about (0.5
～2.5):1, there is chromic performance in excellent photo catalytic reduction water, and cost is relatively low, contain hexavalent chromium wastewater for reduction
There is very high photocatalysis clearance, there is higher potential industrial application value.It is 3～7mg/L and pH for initial concentration
It is worth for 4～6 containing hexavalent chromium wastewater, put in the waste water of 30mL according to 3～10mg di-iron trioxide molybdenum sulfide compound, xenon
After light irradiation 30～90 minutes, clearance is up to more than 70%.
4. it is 5.11 containing hexavalent chromium wastewater for initial concentration for 3mg/L and pH value, according to 6mg stalk cellulose-oxygen
Change cerium compound and put in the waste water of 30mL, xenon lamp irradiates and can substantially be reduced Cr VI for more than 90 minutes.For first
Beginning concentration is 7mg/L and pH value is 5.11 containing hexavalent chromium wastewater, puts into according to 6mg stalk cellulose-cerium oxide compound
In the waste water of 30mL, xenon lamp irradiates and is reduced more than 70% Cr VI for 90 minutes.
It is high that this stalk cellulose-cerium oxide compound processes hexavalent chromium wastewater clearance, and processing cost is low and environmental friendliness.
If can be market-oriented, it will obtain preferable economic benefit.
Brief description
Fig. 1 is the stalk cellulose-cerium oxide compound scanning electron microscope (SEM) photograph of the embodiment of the present invention 1.
Fig. 2 is the stalk cellulose-cerium oxide compound scanning electron microscope (SEM) photograph of the embodiment of the present invention 5.
Fig. 3 is the stalk cellulose-cerium oxide compound scanning electron microscope (SEM) photograph of the embodiment of the present invention 10.
Fig. 4 is the stalk cellulose-chromic design sketch of cerium oxide compound photocatalysis of different quality in the present invention.
Fig. 5 is the stalk cellulose-chromic effect of cerium oxide compound photocatalysis of the present invention with pH value of solution variation diagram.
Specific embodiment
Embodiment 1
A kind of method of stalk cellulose of the present invention-cerium oxide complex catalysts reduction treatment chromate waste water, wraps successively
Include following steps：
(1) weigh 10～20 grams of straw pulps, add to containing 0.05～0.2 gram of TEMPO and 0.5～1.5 gram of sodium bromide
The aqueous solution in；
(2) liquor natrii hypochloritis of configuration quality fraction 3～6%, is adjusted with the hydrochloric acid solution of 0.05～0.3 mol/L
Its pH is in suitable scope；
(3) (2) are slowly added to step (1) gained mixed liquor, are stirred vigorously；
(4) with the sodium hydroxide solution regulating step of 0.2～1.0 mol/L, (3) pH in suitable scope and keeps reacting
A few hours；
(5), after the product suction filtration of step (4) removes moisture removal, deionized water cleaning is cleaned repeatedly, until solution
PH value, close to 7.0, the product after cleaning is placed in baking oven and dries the straw obtaining obtaining final product Nano grade at 40～60 DEG C
Stalk fiber element；
(6) 5～10mL deionized water and 10～40mL ethanol are mixed, weigh the stalk fibre that (5) step obtains
Six plain, appropriate nitric hydrate ceriums, add after mixing in described ethanol solution, stir while adding and make stalk cellulose equal
Even disperse and make six nitric hydrate ceriums to be completely dissolved；Then proceed to add 0.1～0.5g polyvinylpyrrolidone, and stir and make it
Dissolving；
(7) mixture of step (6) is transferred in autoclave, reacts 15～24 hours at 160～180 DEG C；
(8) product of step (7) is centrifuged after moisture removal, is first removed with ethanol purge unreacted
Polyvinylpyrrolidone, then the deionized water cleaning unreacted inorganic ions of removal, until the pH value of solution is not less than 6.8,
Product after cleaning is placed in baking oven and dries that to obtain stalk cellulose-cerium oxide within 10～20 hours multiple at 50～70 DEG C
Compound finished product.
According to the following steps photocatalysis chromate waste water is carried out using the stalk cellulose-cerium oxide compound of the present invention：(1) take
6mg stalk cellulose-cerium oxide compound finished product is added to 30mL and contains in hexavalent chromium wastewater, the described sexavalence containing hexavalent chromium wastewater
Chromium initial concentration C0For 3mg/L, pH value is 4.02；(2) by step (1) stalk cellulose-cerium oxide the compound of gained containing six
Valency chrome waste water is added in glass container, sealing；(3) glass container of step (2) is put in the camera bellows of photo catalysis reactor,
Stirring 30 minutes, controls temperature to be 25 DEG C；(4), after stirring terminates, open xenon lamp, by step solidliquid mixture (3) under xenon lamp
Irradiate 30～90 minutes, xenon lamp power is 400W；(5) after photocatalysis terminates, extract 5mL step (4) containing hexavalent chromium wastewater, mistake
Filter；(6) take 2mL clear liquid, the hexavalent chromium concentration Ce after being processed with determined by ultraviolet spectrophotometry is 0.0mg/L；(7) calculate light to urge
Clearance after change=1- (Ce/C0) * 100%=100%.
Embodiment 2
A kind of method of stalk cellulose of the present invention-cerium oxide complex catalysts reduction treatment chromate waste water, wraps successively
Include following steps：
(1) weigh 10～20 grams of straw pulps, add to containing 0.05～0.2 gram of TEMPO and 0.5～1.5 gram of sodium bromide
The aqueous solution in；
(2) liquor natrii hypochloritis of configuration quality fraction 3～6%, is adjusted with the hydrochloric acid solution of 0.05～0.3 mol/L
Its pH is in suitable scope；
(3) (2) are slowly added to step (1) gained mixed liquor, are stirred vigorously；
(4) with the sodium hydroxide solution regulating step of 0.2～1.0 mol/L, (3) pH in suitable scope and keeps reacting
A few hours；
(5), after the product suction filtration of step (4) removes moisture removal, deionized water cleaning is cleaned repeatedly, until solution
PH value, close to 7.0, the product after cleaning is placed in baking oven and dries the straw obtaining obtaining final product Nano grade at 40～60 DEG C
Stalk fiber element；
(6) 5～10mL deionized water and 10～40mL ethanol are mixed, weigh the stalk fibre that (5) step obtains
Six plain, appropriate nitric hydrate ceriums, add after mixing in described ethanol solution, stir while adding and make stalk cellulose equal
Even disperse and make six nitric hydrate ceriums to be completely dissolved；Then proceed to add 0.1～0.5g polyvinylpyrrolidone, and stir and make it
Dissolving；
(7) mixture of step (6) is transferred in autoclave, reacts 15～24 hours at 160～180 DEG C；
(8) product of step (7) is centrifuged after moisture removal, is first removed with ethanol purge unreacted
Polyvinylpyrrolidone, then the deionized water cleaning unreacted inorganic ions of removal, until the pH value of solution is not less than 6.8,
Product after cleaning is placed in baking oven and dries that to obtain stalk cellulose-cerium oxide within 10～20 hours multiple at 50～70 DEG C
Compound finished product.
According to the following steps photocatalysis chromate waste water is carried out using the stalk cellulose-cerium oxide compound of the present invention：(1) take
6mg stalk cellulose-cerium oxide compound finished product is added to 30mL and contains in hexavalent chromium wastewater, the described sexavalence containing hexavalent chromium wastewater
Chromium initial concentration C0For 3mg/L, pH value is 5.11；(2) by step (1) stalk cellulose-cerium oxide the compound of gained containing six
Valency chrome waste water is added in glass container, sealing；(3) by step, glass container (2) is put in the camera bellows of photo catalysis reactor,
Stirring 30 minutes, controls temperature to be 25 DEG C；(4), after stirring terminates, open xenon lamp, by the solidliquid mixture of step (3) in xenon lamp
Lower irradiation 30～90 minutes, xenon lamp power is 400W；(5) after photocatalysis terminates, extract 5mL step (4) containing hexavalent chromium wastewater,
Filter；(6) take 2mL clear liquid, the hexavalent chromium concentration Ce after being processed with determined by ultraviolet spectrophotometry is 0.0mg/L；(7) calculate light
Clearance after catalysis=1- (Ce/C0) * 100%=100%.
Embodiment 3
A kind of method of stalk cellulose of the present invention-cerium oxide complex catalysts reduction treatment chromate waste water, wraps successively
Include following steps：
(1) weigh 10～20 grams of straw pulps, add to containing 0.05～0.2 gram of TEMPO and 0.5～1.5 gram of sodium bromide
The aqueous solution in；
(2) liquor natrii hypochloritis of configuration quality fraction 3～6%, is adjusted with the hydrochloric acid solution of 0.05～0.3 mol/L
Its pH is in suitable scope；
(3) (2) are slowly added to step (1) gained mixed liquor, are stirred vigorously；
(4) with the sodium hydroxide solution regulating step of 0.2～1.0 mol/L, (3) pH in suitable scope and keeps reacting
A few hours；
(5), after the product suction filtration of step (4) removes moisture removal, deionized water cleaning is cleaned repeatedly, until solution
PH value, close to 7.0, the product after cleaning is placed in baking oven and dries the straw obtaining obtaining final product Nano grade at 40～60 DEG C
Stalk fiber element；
(6) 5～10mL deionized water and 10～40mL ethanol are mixed, weigh the stalk fibre that (5) step obtains
Six plain, appropriate nitric hydrate ceriums, add after mixing in described ethanol solution, stir while adding and make stalk cellulose equal
Even disperse and make six nitric hydrate ceriums to be completely dissolved；Then proceed to add 0.1～0.5g polyvinylpyrrolidone, and stir and make it
Dissolving；
(7) mixture of step (6) is transferred in autoclave, reacts 15～24 hours at 160～180 DEG C；
(8) product of step (7) is centrifuged after moisture removal, is first removed with ethanol purge unreacted
Polyvinylpyrrolidone, then the deionized water cleaning unreacted inorganic ions of removal, until the pH value of solution is not less than 6.8,
Product after cleaning is placed in baking oven and dries that to obtain stalk cellulose-cerium oxide within 10～20 hours multiple at 50～70 DEG C
Compound finished product.
According to the following steps photocatalysis chromate waste water is carried out using the stalk cellulose-cerium oxide compound of the present invention：(1) take
6mg stalk cellulose-cerium oxide compound finished product is added to 30mL and contains in hexavalent chromium wastewater, the described sexavalence containing hexavalent chromium wastewater
Chromium initial concentration C0For 3mg/L, pH value is 5.97；(2) containing the stalk cellulose of step (1) gained-cerium oxide compound
Hexavalent chromium wastewater is added in glass container, sealing；(3) glass container of step (2) is put into the camera bellows of photo catalysis reactor
In, stir 30 minutes, control temperature to be 25 DEG C；(4), after stirring terminates, open xenon lamp, by the solidliquid mixture of step (3) in xenon
Irradiate 30～90 minutes under lamp, xenon lamp power is 400W；(5), after photocatalysis terminates, extract giving up containing Cr VI of 5mL step (4)
Water, filters；(6) take 2mL clear liquid, the hexavalent chromium concentration Ce after being processed with determined by ultraviolet spectrophotometry is 0.054mg/L；(7)
Calculate the clearance=1- (Ce/C after photocatalysis0) * 100%=98.2%.
Embodiment 4
A kind of method of stalk cellulose of the present invention-cerium oxide complex catalysts reduction treatment chromate waste water, wraps successively
Include following steps：
(1) weigh 10～20 grams of straw pulps, add to containing 0.05～0.2 gram of TEMPO and 0.5～1.5 gram of sodium bromide
The aqueous solution in；
(2) liquor natrii hypochloritis of configuration quality fraction 3～6%, is adjusted with the hydrochloric acid solution of 0.05～0.3 mol/L
Its pH is in suitable scope；
(3) (2) are slowly added to step (1) gained mixed liquor, are stirred vigorously；
(4) with the sodium hydroxide solution regulating step of 0.2～1.0 mol/L, (3) pH in suitable scope and keeps reacting
A few hours；
(5), after the product suction filtration of step (4) removes moisture removal, deionized water cleaning is cleaned repeatedly, until solution
PH value, close to 7.0, the product after cleaning is placed in baking oven and dries the straw obtaining obtaining final product Nano grade at 40～60 DEG C
Stalk fiber element；
(6) 5～10mL deionized water and 10～40mL ethanol are mixed, weigh the stalk fibre that (5) step obtains
Six plain, appropriate nitric hydrate ceriums, add after mixing in described ethanol solution, stir while adding and make stalk cellulose equal
Even disperse and make six nitric hydrate ceriums to be completely dissolved；Then proceed to add 0.1～0.5g polyvinylpyrrolidone, and stir and make it
Dissolving；
(7) mixture of step (6) is transferred in autoclave, reacts 15～24 hours at 160～180 DEG C；
(8) product of step (7) is centrifuged after moisture removal, is first removed with ethanol purge unreacted
Polyvinylpyrrolidone, then the deionized water cleaning unreacted inorganic ions of removal, until the pH value of solution is not less than 6.8,
Product after cleaning is placed in baking oven and dries that to obtain stalk cellulose-cerium oxide within 10～20 hours multiple at 50～70 DEG C
Compound finished product.
According to the following steps photocatalysis chromate waste water is carried out using the stalk cellulose-cerium oxide compound of the present invention：(1) take
6mg stalk cellulose-cerium oxide compound finished product is added to 30mL and contains in hexavalent chromium wastewater, the described sexavalence containing hexavalent chromium wastewater
Chromium initial concentration C0For 3mg/L, pH value is 6.93；(2) containing the stalk cellulose of step (1) gained-cerium oxide compound
Hexavalent chromium wastewater is added in glass container, sealing；(3) glass container of step (2) is put into the camera bellows of photo catalysis reactor
In, stir 30 minutes, control temperature to be 25 DEG C；(4), after stirring terminates, open xenon lamp, by the solidliquid mixture of step (3) in xenon
Irradiate 30～90 minutes under lamp, xenon lamp power is 400W；(5), after photocatalysis terminates, extract giving up containing Cr VI of 5mL step (4)
Water, filters；(6) take 2mL clear liquid, the hexavalent chromium concentration Ce after being processed with determined by ultraviolet spectrophotometry is 0.237mg/L；(7)
Calculate the clearance=1- (Ce/C after photocatalysis0) * 100%=92.1%.
Embodiment 5
A kind of method of stalk cellulose of the present invention-cerium oxide complex catalysts reduction treatment chromate waste water, wraps successively
Include following steps：
(1) weigh 10～20 grams of straw pulps, add to containing 0.05～0.2 gram of TEMPO and 0.5～1.5 gram of sodium bromide
The aqueous solution in；
(2) liquor natrii hypochloritis of configuration quality fraction 3～6%, is adjusted with the hydrochloric acid solution of 0.05～0.3 mol/L
Its pH is in suitable scope；
(3) (2) are slowly added to step (1) gained mixed liquor, are stirred vigorously；
(4) with the sodium hydroxide solution regulating step of 0.2～1.0 mol/L, (3) pH in suitable scope and keeps reacting
A few hours；
(5), after the product suction filtration of step (4) removes moisture removal, deionized water cleaning is cleaned repeatedly, until solution
PH value, close to 7.0, the product after cleaning is placed in baking oven and dries the straw obtaining obtaining final product Nano grade at 40～60 DEG C
Stalk fiber element；
(6) 5～10mL deionized water and 10～40mL ethanol are mixed, weigh the stalk fibre that (5) step obtains
Six plain, appropriate nitric hydrate ceriums, add after mixing in described ethanol solution, stir while adding and make stalk cellulose equal
Even disperse and make six nitric hydrate ceriums to be completely dissolved；Then proceed to add 0.1～0.5g polyvinylpyrrolidone, and stir and make it
Dissolving；
(7) mixture of step (6) is transferred in autoclave, reacts 15～24 hours at 160～180 DEG C；
(8) product of step (7) is centrifuged after moisture removal, is first removed with ethanol purge unreacted
Polyvinylpyrrolidone, then the deionized water cleaning unreacted inorganic ions of removal, until the pH value of solution is not less than 6.8,
Product after cleaning is placed in baking oven and dries that to obtain stalk cellulose-cerium oxide within 10～20 hours multiple at 50～70 DEG C
Compound finished product.
According to the following steps photocatalysis chromate waste water is carried out using the stalk cellulose-cerium oxide compound of the present invention：(1) take
3mg stalk cellulose-cerium oxide compound finished product is added to 30mL and contains in hexavalent chromium wastewater, the described sexavalence containing hexavalent chromium wastewater
Chromium initial concentration C0For 3mg/L, pH value is 5.11；(2) containing the stalk cellulose of step (1) gained-cerium oxide compound
Hexavalent chromium wastewater is added in glass container, sealing；(3) glass container of step (2) is put into the camera bellows of photo catalysis reactor
In, stir 30 minutes, control temperature to be 25 DEG C；(4), after stirring terminates, open xenon lamp, by the solidliquid mixture of step (3) in xenon
Irradiate 30～90 minutes under lamp, xenon lamp power is 400W；(5), after photocatalysis terminates, extract giving up containing Cr VI of 5mL step (4)
Water, filters；(6) take 2mL clear liquid, the hexavalent chromium concentration Ce after being processed with determined by ultraviolet spectrophotometry is 0.876mg/L；(7) count
Calculate the clearance=1- (Ce/C after photocatalysis0) * 100%=70.8%.
Embodiment 6
A kind of method of stalk cellulose of the present invention-cerium oxide complex catalysts reduction treatment chromate waste water, wraps successively
Include following steps：
(1) weigh 10～20 grams of straw pulps, add to containing 0.05～0.2 gram of TEMPO and 0.5～1.5 gram of sodium bromide
The aqueous solution in；
(2) liquor natrii hypochloritis of configuration quality fraction 3～6%, is adjusted with the hydrochloric acid solution of 0.05～0.3 mol/L
Its pH is in suitable scope；
(3) (2) are slowly added to step (1) gained mixed liquor, are stirred vigorously；
(4) with the sodium hydroxide solution regulating step of 0.2～1.0 mol/L, (3) pH in suitable scope and keeps reacting
A few hours；
(5), after the product suction filtration of step (4) removes moisture removal, deionized water cleaning is cleaned repeatedly, until solution
PH value, close to 7.0, the product after cleaning is placed in baking oven and dries the straw obtaining obtaining final product Nano grade at 40～60 DEG C
Stalk fiber element；
(6) 5～10mL deionized water and 10～40mL ethanol are mixed, weigh the stalk fibre that (5) step obtains
Six plain, appropriate nitric hydrate ceriums, add after mixing in described ethanol solution, stir while adding and make stalk cellulose equal
Even disperse and make six nitric hydrate ceriums to be completely dissolved；Then proceed to add 0.1～0.5g polyvinylpyrrolidone, and stir and make it
Dissolving；
(7) mixture of step (6) is transferred in autoclave, reacts 15～24 hours at 160～180 DEG C；
(8) product of step (7) is centrifuged after moisture removal, is first removed with ethanol purge unreacted
Polyvinylpyrrolidone, then the deionized water cleaning unreacted inorganic ions of removal, until the pH value of solution is not less than 6.8,
Product after cleaning is placed in baking oven and dries that to obtain stalk cellulose-cerium oxide within 10～20 hours multiple at 50～70 DEG C
Compound finished product.
According to the following steps photocatalysis chromate waste water is carried out using the stalk cellulose-cerium oxide compound of the present invention：(1) take
5mg stalk cellulose-cerium oxide compound finished product is added to 30mL and contains in hexavalent chromium wastewater, the described sexavalence containing hexavalent chromium wastewater
Chromium initial concentration C0For 3mg/L, pH value is 5.11；(2) containing the stalk cellulose of step (1) gained-cerium oxide compound
Hexavalent chromium wastewater is added in glass container, sealing；(3) glass container of step (2) is put into the camera bellows of photo catalysis reactor
In, stir 30 minutes, control temperature to be 25 DEG C；(4), after stirring terminates, open xenon lamp, by the solidliquid mixture of step (3) in xenon
Irradiate 30～90 minutes under lamp, xenon lamp power is 400W；(5), after photocatalysis terminates, extract giving up containing Cr VI of 5mL step (4)
Water, filters；(6) take 2mL clear liquid, the hexavalent chromium concentration Ce after being processed with determined by ultraviolet spectrophotometry is 0.222mg/L；(7)
Calculate the clearance=1- (Ce/C after photocatalysis0) * 100%=92.6%.
Embodiment 7
A kind of method of stalk cellulose of the present invention-cerium oxide complex catalysts reduction treatment chromate waste water, wraps successively
Include following steps：
(1) weigh 10～20 grams of straw pulps, add to containing 0.05～0.2 gram of TEMPO and 0.5～1.5 gram of sodium bromide
The aqueous solution in；
(2) liquor natrii hypochloritis of configuration quality fraction 3～6%, is adjusted with the hydrochloric acid solution of 0.05～0.3 mol/L
Its pH is in suitable scope；
(3) (2) are slowly added to step (1) gained mixed liquor, are stirred vigorously；
(4) and keep reacting in suitable scope with sodium hydroxide solution regulating step (3) pH of 0.2～1.0 mol/L
A few hours；
(5), after the product suction filtration of step (4) removes moisture removal, deionized water cleaning is cleaned repeatedly, until solution
PH value, close to 7.0, the product after cleaning is placed in baking oven and dries the straw obtaining obtaining final product Nano grade at 40～60 DEG C
Stalk fiber element；
(6) 5～10mL deionized water and 10～40mL ethanol are mixed, weigh the stalk fibre that (5) step obtains
Six plain, appropriate nitric hydrate ceriums, add after mixing in described ethanol solution, stir while adding and make stalk cellulose equal
Even disperse and make six nitric hydrate ceriums to be completely dissolved；Then proceed to add 0.1～0.5g polyvinylpyrrolidone, and stir and make it
Dissolving；
(7) mixture of step (6) is transferred in autoclave, reacts 15～24 hours at 160～180 DEG C；
(8) product of step (7) is centrifuged after moisture removal, is first removed with ethanol purge unreacted
Polyvinylpyrrolidone, then the deionized water cleaning unreacted inorganic ions of removal, until the pH value of solution is not less than 6.8,
Product after cleaning is placed in baking oven and dries that to obtain stalk cellulose-cerium oxide within 10～20 hours multiple at 50～70 DEG C
Compound finished product.
According to the following steps photocatalysis chromate waste water is carried out using the stalk cellulose-cerium oxide compound of the present invention：(1) take
8mg stalk cellulose-cerium oxide compound finished product is added to 30mL and contains in hexavalent chromium wastewater, the described sexavalence containing hexavalent chromium wastewater
Chromium initial concentration C0For 3mg/L, pH value is 5.11；(2) containing the stalk cellulose of step (1) gained-cerium oxide compound
Hexavalent chromium wastewater is added in glass container, sealing；(3) glass container of step (2) is put into the camera bellows of photo catalysis reactor
In, stir 30 minutes, control temperature to be 25 DEG C；(4), after stirring terminates, open xenon lamp, by the solidliquid mixture of step (3) in xenon
Irradiate 30～90 minutes under lamp, xenon lamp power is 400W；(5), after photocatalysis terminates, extract giving up containing Cr VI of 5mL step (4)
Water, filters；(6) take 2mL clear liquid, the hexavalent chromium concentration Ce after being processed with determined by ultraviolet spectrophotometry is 0.0mg/L；(7) count
Calculate the clearance=1- (Ce/C after photocatalysis0) * 100%=100%.
Embodiment 8
A kind of method of stalk cellulose of the present invention-cerium oxide complex catalysts reduction treatment chromate waste water, wraps successively
Include following steps：
(1) weigh 10～20 grams of straw pulps, add to containing 0.05～0.2 gram of TEMPO and 0.5～1.5 gram of sodium bromide
The aqueous solution in；
(2) liquor natrii hypochloritis of configuration quality fraction 3～6%, is adjusted with the hydrochloric acid solution of 0.05～0.3 mol/L
Its pH is in suitable scope；
(3) (2) are slowly added to step (1) gained mixed liquor, are stirred vigorously；
(4) and keep reacting in suitable scope with sodium hydroxide solution regulating step (3) pH of 0.2～1.0 mol/L
A few hours；
(5), after the product suction filtration of step (4) removes moisture removal, deionized water cleaning is cleaned repeatedly, until solution
PH value, close to 7.0, the product after cleaning is placed in baking oven and dries the straw obtaining obtaining final product Nano grade at 40～60 DEG C
Stalk fiber element；
(6) 5～10mL deionized water and 10～40mL ethanol are mixed, weigh the stalk fibre that (5) step obtains
Six plain, appropriate nitric hydrate ceriums, add after mixing in described ethanol solution, stir while adding and make stalk cellulose equal
Even disperse and make six nitric hydrate ceriums to be completely dissolved；Then proceed to add 0.1～0.5g polyvinylpyrrolidone, and stir and make it
Dissolving；
(7) by step, mixture (6) is transferred in autoclave, reacts 15～24 hours at 160～180 DEG C；
(8) to step, product (7) is centrifuged after moisture removal, is first removed unreacted with ethanol purge
Polyvinylpyrrolidone, then the deionized water cleaning unreacted inorganic ions of removal, until the pH value of solution is not less than 6.8,
Product after cleaning is placed in baking oven and dries that to obtain stalk cellulose-cerium oxide within 10～20 hours multiple at 50～70 DEG C
Compound finished product.
According to the following steps photocatalysis chromate waste water is carried out using the stalk cellulose-cerium oxide compound of the present invention：(1) take
10mg stalk cellulose-cerium oxide compound finished product be added to 30mL contain hexavalent chromium wastewater in, described containing hexavalent chromium wastewater six
Valency chromium initial concentration C0For 3mg/L, pH value is 5.11；(2) by the stalk cellulose of step (1) gained-cerium oxide compound
It is added in glass container containing hexavalent chromium wastewater, sealing；(3) glass container of step (2) is put into the dark of photo catalysis reactor
In case, stir 30 minutes, control temperature to be 25 DEG C；(4), after stirring terminates, open xenon lamp, the solidliquid mixture of step (3) is existed
Irradiate 30～90 minutes under xenon lamp, xenon lamp power is 400W；(5) after photocatalysis terminates, extract 5mL step (4) containing Cr VI
Waste water, filters；(6) take 2mL clear liquid, the hexavalent chromium concentration Ce after being processed with determined by ultraviolet spectrophotometry is 0.0mg/L；(7)
Calculate the clearance=1- (Ce/C after photocatalysis0) * 100%=100%.
Embodiment 9
A kind of method of stalk cellulose of the present invention-cerium oxide complex catalysts reduction treatment chromate waste water, wraps successively
Include following steps：
(1) weigh 10～20 grams of straw pulps, add to containing 0.05～0.2 gram of TEMPO and 0.5～1.5 gram of sodium bromide
The aqueous solution in；
(2) liquor natrii hypochloritis of configuration quality fraction 3～6%, is adjusted with the hydrochloric acid solution of 0.05～0.3 mol/L
Its pH is in suitable scope；
(3) (2) are slowly added to step (1) gained mixed liquor, are stirred vigorously；
(4) with the sodium hydroxide solution regulating step of 0.2～1.0 mol/L, (3) pH in suitable scope and keeps reacting
A few hours；
(5), after the product suction filtration of step (4) removes moisture removal, deionized water cleaning is cleaned repeatedly, until solution
PH value, close to 7.0, the product after cleaning is placed in baking oven and dries the straw obtaining obtaining final product Nano grade at 40～60 DEG C
Stalk fiber element；
(6) 5～10mL deionized water and 10～40mL ethanol are mixed, weigh the stalk fibre that (5) step obtains
Six plain, appropriate nitric hydrate ceriums, add after mixing in described ethanol solution, stir while adding and make stalk cellulose equal
Even disperse and make six nitric hydrate ceriums to be completely dissolved；Then proceed to add 0.1～0.5g polyvinylpyrrolidone, and stir and make it
Dissolving；
(7) mixture of step (6) is transferred in autoclave, reacts 15～24 hours at 160～180 DEG C；
(8) product of step (7) is centrifuged after moisture removal, is first removed with ethanol purge unreacted
Polyvinylpyrrolidone, then the deionized water cleaning unreacted inorganic ions of removal, until the pH value of solution is not less than 6.8,
Product after cleaning is placed in baking oven and dries that to obtain stalk cellulose-cerium oxide within 10～20 hours multiple at 50～70 DEG C
Compound finished product.
According to the following steps photocatalysis chromate waste water is carried out using the stalk cellulose-cerium oxide compound of the present invention：(1) take
6mg stalk cellulose-cerium oxide compound finished product is added to 30mL and contains in hexavalent chromium wastewater, the described sexavalence containing hexavalent chromium wastewater
Chromium initial concentration C0For 5mg/L, pH value is 5.11；(2) containing the stalk cellulose of step (1) gained-cerium oxide compound
Hexavalent chromium wastewater is added in glass container, sealing；(3) glass container of step (2) is put into the camera bellows of photo catalysis reactor
In, stir 30 minutes, control temperature to be 25 DEG C；(4), after stirring terminates, open xenon lamp, by the solidliquid mixture of step (3) in xenon
Irradiate 30～90 minutes under lamp, xenon lamp power is 400W；(5), after photocatalysis terminates, extract giving up containing Cr VI of 5mL step (4)
Water, filters；(6) take 2mL clear liquid, the hexavalent chromium concentration Ce after being processed with determined by ultraviolet spectrophotometry is 0.585mg/L；(7)
Calculate the clearance=1- (Ce/C after photocatalysis0) * 100%=88.3%.
Embodiment 10
A kind of method of stalk cellulose of the present invention-cerium oxide complex catalysts reduction treatment chromate waste water, wraps successively
Include following steps：
(1) weigh 10～20 grams of straw pulps, add to containing 0.05～0.2 gram of TEMPO and 0.5～1.5 gram of sodium bromide
The aqueous solution in；
(2) liquor natrii hypochloritis of configuration quality fraction 3～6%, is adjusted with the hydrochloric acid solution of 0.05～0.3 mol/L
Its pH is in suitable scope；
(3) (2) are slowly added to step (1) gained mixed liquor, are stirred vigorously；
(4) with the sodium hydroxide solution regulating step of 0.2～1.0 mol/L, (3) pH in suitable scope and keeps reacting
A few hours；
(5), after the product suction filtration of step (4) removes moisture removal, deionized water cleaning is cleaned repeatedly, until solution
PH value, close to 7.0, the product after cleaning is placed in baking oven and dries the straw obtaining obtaining final product Nano grade at 40～60 DEG C
Stalk fiber element；
(6) 5～10mL deionized water and 10～40mL ethanol are mixed, weigh the stalk fibre that (5) step obtains
Six plain, appropriate nitric hydrate ceriums, add after mixing in described ethanol solution, stir while adding and make stalk cellulose equal
Even disperse and make six nitric hydrate ceriums to be completely dissolved；Then proceed to add 0.1～0.5g polyvinylpyrrolidone, and stir and make it
Dissolving；
(7) mixture of step (6) is transferred in autoclave, reacts 15～24 hours at 160～180 DEG C；
(8) to step, product (7) is centrifuged after moisture removal, is first removed unreacted with ethanol purge
Polyvinylpyrrolidone, then the deionized water cleaning unreacted inorganic ions of removal, until the pH value of solution is not less than 6.8,
Product after cleaning is placed in baking oven and dries that to obtain stalk cellulose-cerium oxide within 10～20 hours multiple at 50～70 DEG C
Compound finished product.
According to the following steps photocatalysis chromate waste water is carried out using the stalk cellulose-cerium oxide compound of the present invention：(1) take
6mg stalk cellulose-cerium oxide compound finished product is added to 30mL and contains in hexavalent chromium wastewater, the described sexavalence containing hexavalent chromium wastewater
Chromium initial concentration C0For 7mg/L, pH value is 5.11；(2) containing the stalk cellulose of step (1) gained-cerium oxide compound
Hexavalent chromium wastewater is added in glass container, sealing；(3) glass container of step (2) is put into the camera bellows of photo catalysis reactor
In, stir 30 minutes, control temperature to be 25 DEG C；(4), after stirring terminates, open xenon lamp, by the solidliquid mixture of step (3) in xenon
Irradiate 30～90 minutes under lamp, xenon lamp power is 400W；(5), after photocatalysis terminates, extract giving up containing Cr VI of 5mL step (4)
Water, filters；(6) take 2mL clear liquid, the hexavalent chromium concentration Ce after being processed with determined by ultraviolet spectrophotometry is 1.792mg/L；(7)
Calculate the clearance=1- (Ce/C after photocatalysis0) * 100%=74.4%.
Embodiment 11
A kind of method of stalk cellulose of the present invention-cerium oxide complex catalysts reduction treatment chromate waste water, wraps successively
Include following steps：
(1) weigh 10～20 grams of straw pulps, add to containing 0.05～0.2 gram of TEMPO and 0.5～1.5 gram of sodium bromide
The aqueous solution in；
(2) liquor natrii hypochloritis of configuration quality fraction 3～6%, is adjusted with the hydrochloric acid solution of 0.05～0.3 mol/L
Its pH is in suitable scope；
(3) (2) are slowly added to step (1) gained mixed liquor, are stirred vigorously；
(4) with the sodium hydroxide solution regulating step of 0.2～1.0 mol/L, (3) pH in suitable scope and keeps reacting
A few hours；
(5), after the product suction filtration of step (4) removes moisture removal, deionized water cleaning is cleaned repeatedly, until solution
PH value, close to 7.0, the product after cleaning is placed in baking oven and dries the straw obtaining obtaining final product Nano grade at 40～60 DEG C
Stalk fiber element；
(6) 5～10mL deionized water and 10～40mL ethanol are mixed, weigh the stalk fibre that (5) step obtains
Six plain, appropriate nitric hydrate ceriums, add after mixing in described ethanol solution, stir while adding and make stalk cellulose equal
Even disperse and make six nitric hydrate ceriums to be completely dissolved；Then proceed to add 0.1～0.5g polyvinylpyrrolidone, and stir and make it
Dissolving；
(7) mixture of step (6) is transferred in autoclave, reacts 15～24 hours at 160～180 DEG C；
(8) product of step (7) is centrifuged after moisture removal, is first removed with ethanol purge unreacted
Polyvinylpyrrolidone, then the deionized water cleaning unreacted inorganic ions of removal, until the pH value of solution is not less than 6.8,
Product after cleaning is placed in baking oven and dries that to obtain stalk cellulose-cerium oxide within 10～20 hours multiple at 50～70 DEG C
Compound finished product.
According to the following steps photocatalysis chromate waste water is carried out using the stalk cellulose-cerium oxide compound of the present invention：(1) take
6mg stalk cellulose-cerium oxide compound finished product is added to 30mL and contains in hexavalent chromium wastewater, the described sexavalence containing hexavalent chromium wastewater
Chromium initial concentration C0For 10mg/L, pH value is 5.11；(2) containing the stalk cellulose of step (1) gained-cerium oxide compound
Hexavalent chromium wastewater is added in glass container, sealing；(3) glass container of step (2) is put into the camera bellows of photo catalysis reactor
In, stir 30 minutes, control temperature to be 25 DEG C；(4), after stirring terminates, open xenon lamp, by the solidliquid mixture of step (3) in xenon
Irradiate 30～90 minutes under lamp, xenon lamp power is 400W；(5), after photocatalysis terminates, extract giving up containing Cr VI of 5mL step (4)
Water, filters；(6) take 2mL clear liquid, the hexavalent chromium concentration Ce after being processed with determined by ultraviolet spectrophotometry is 7.130mg/L；(7)
Calculate the clearance=1- (Ce/C after photocatalysis0) * 100%=28.7%.
Data summarization such as following table to embodiment 1～embodiment 11, and drawn according to the data of embodiment 2,5,6,7,8
Become Fig. 4, according to the data drafting pattern 5 of embodiment 1～4.
Can be seen that for 3mg/L and pH value is 4.02～6.93 containing Cr VI for initial concentration from summary sheet and Fig. 5
Waste water, puts in the waste water of 30mL according to 6mg stalk cellulose-cerium oxide compound, and Hg lamp irradiation removes for more than 90 minutes
Rate is all more than 90%.
Can be seen that under same pH from summary sheet and Fig. 4, stalk cellulose-cerium oxide is combined within the specific limits
The increase of thing throwing amount, clearance gradually steps up；Can be seen that from summary sheet and Fig. 5 and throw in stalk cellulose-cerium oxide compound
In the case of amount identical, when pH value is located between 4.02～5.11, clearance highest.
In literary composition, unreceipted percentage concentration is concentration expressed in percentage by weight.Photo catalysis reactor can be using Shanghai than bright experiment instrument
The sh-yz-B type photo catalysis reactor of device Co., Ltd.
The foregoing is only the preferable possible embodiments of the present invention, the non-patent protection model therefore limiting to the present invention
Enclose.In addition to the implementation, the present invention can also have other embodiment, for example can be by ratios such as the quality of each composition and volumes
Example amplifies several times.All employing equivalents or the technical scheme of equivalent transformation formation, all fall within the protection model of application claims
In enclosing.The present invention can pass through without the technical characteristic of description or be realized using prior art, will not be described here.
Claims (7)
1. a kind of method of stalk cellulose-cerium oxide compound photo catalytic reduction processing waste water containing chrome is it is characterised in that include
Following steps：
（1）Weigh 10 ~ 20 grams of straw pulps, add to containing 0.05 ~ 0.2 gram tetramethyl piperidine nitrogen oxides TEMPO and 0.5 ~
In the aqueous solution of 1.5 grams of sodium bromides, obtain the first mixed liquor；
（2）The liquor natrii hypochloritis of configuration quality fraction 3 ~ 6%, adjusts its pH with the hydrochloric acid solution of 0.05 ~ 0.3 mol/L；
（3）By step（2）The liquor natrii hypochloritis obtaining is slowly added to step（1）In gained first mixed liquor, it is stirred vigorously,
Obtain the second mixed liquor；
（4）Sodium hydroxide solution regulating step with 0.2 ~ 1.0 mol/L（3）The pH of the second mixed liquor obtaining, reaction obtains
3rd mixed liquor；
（5）By step（4）After the 3rd mixed liquor suction filtration obtaining removes moisture removal, deionized water cleaning is cleaned repeatedly, until the
The pH value of three mixed liquors is 7.0, the 3rd mixed liquor after cleaning is placed in baking oven to dry at 40 ~ 60 DEG C obtains Nano grade
Stalk cellulose；
（6）5 ~ 10 ml deionized water and 10 ~ 40 milliliters of ethanol are mixed and obtain ethanol solution, by six nitric hydrates
Cerium, step（4）The stalk cellulose obtaining adds in ethanol solution after mixing, and stirs while adding and makes stalk cellulose equal
Even disperse and make six nitric hydrate ceriums to be completely dissolved, then proceed to add 0.1 ~ 0.5 gram of polyvinylpyrrolidone, and stir and make it
Dissolving, obtains the 4th mixed liquor；
（7）By step（6）The 4th mixed liquor obtaining is transferred in autoclave, and at 160 ~ 180 DEG C, reaction 15 ~ 24 is little
When, obtain reacted 5th mixed liquor；
（8）To step（7）After the 5th mixed liquor obtaining is centrifuged moisture removal, first remove unreacted with ethanol purge
Polyvinylpyrrolidone, then deionized water cleaning remove unreacted inorganic ions, until the 5th mixed liquor pH value not
Less than 6.8, the 5th mixed liquor after cleaning is placed in baking oven dry at 50 ~ 70 DEG C obtain within 10 ~ 20 hours stalk cellulose-
Cerium oxide compound finished product；
（9）Take 5 ~ 10 milligrams of stalk celluloses-cerium oxide compound finished product to be added to 40 milliliters to contain in hexavalent chromium wastewater, described contain
The Cr VI initial concentration C of hexavalent chromium wastewater0For 3 ~ 10 mg/litre, pH value is 4.01 ~ 6.93；
（10）By step（9）Gained be added to glass containing stalk cellulose-cerium oxide compound finished product containing hexavalent chromium wastewater
In container, sealing；
（11）By step（10）Glass container put in the camera bellows of photo catalysis reactor and be stirred, control temperature to be 25 DEG C,
Obtain solidliquid mixture；
（12）Through step（11）After stirring terminates, open xenon lamp, by step（11）The solidliquid mixture obtaining irradiates under xenon lamp
35 ~ 120 minutes, carry out photocatalysis；
（13）Through step（12）After photocatalysis terminates, extract 5 milliliters of treated steps（12）Solidliquid mixture, filter, obtain
To clear liquid；
（14）Take 2 milliliters of steps（13）The clear liquid obtaining, is combined through stalk cellulose-cerium oxide with determined by ultraviolet spectrophotometry
Object light is catalyzed the hexavalent chromium concentration C after reduction treatmente；Calculate and process through stalk cellulose-cerium oxide compound photo catalytic reduction
Hexavalent chromium removal rate after chromate waste water=（C/ C0）* 100%, C=C0-Ce.
2. a kind of stalk cellulose according to claim 1-cerium oxide compound photo catalytic reduction processing waste water containing chrome
Method is it is characterised in that step（2）In, pH scope is 9 ~ 11.
3. a kind of stalk cellulose according to claim 1-cerium oxide compound photo catalytic reduction processing waste water containing chrome
Method is it is characterised in that step（3）In, stirring frequency is not less than 200 revs/min.
4. a kind of stalk cellulose according to claim 1-cerium oxide compound photo catalytic reduction processing waste water containing chrome
Method is it is characterised in that step（4）In, pH scope is 9 ~ 11.
5. a kind of stalk cellulose according to claim 1-cerium oxide compound photo catalytic reduction processing waste water containing chrome
Method is it is characterised in that step（6）In, the quality of described stalk cellulose is 0.05 ~ 0.25 gram, six nitric hydrate ceriums
Quality is 20 ~ 50 milligrams.
6. a kind of stalk cellulose according to claim 1-cerium oxide compound photo catalytic reduction processing waste water containing chrome
Method is it is characterised in that step（11）In, mixing time is 30 ~ 60 minutes.
7. a kind of stalk cellulose according to claim 1-cerium oxide compound photo catalytic reduction processing waste water containing chrome
Method is it is characterised in that step（12）The power of described xenon lamp is 400W.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112076731A (en) * | 2020-08-31 | 2020-12-15 | 镇江市高等专科学校 | Loaded with nano CeO2Preparation method of particle composite biomass membrane and application of particle composite biomass membrane in tellurium extraction |
| CN113125521A (en) * | 2021-04-26 | 2021-07-16 | 中国石油大学(华东) | MoS2/CeO2Composite gas-sensitive material and preparation method and application thereof |
| CN115353639A (en) * | 2022-07-12 | 2022-11-18 | 昆明理工大学 | Method for preparing potassium humate by using corn straws and application |
| CN116237022A (en) * | 2023-02-23 | 2023-06-09 | 南京信息工程大学 | Preparation method and application of fixed nano-hydrated cerium oxide |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101485988A (en) * | 2009-02-18 | 2009-07-22 | 南京工业大学 | Catalyst for catalysis treatment of biomass with microwave and ultraviolet light as well as preparation method and application thereof |
| CN101780952A (en) * | 2010-03-26 | 2010-07-21 | 上海交通大学 | Method for preparing loading functional oxide porous carbon |
| US20100221160A1 (en) * | 2009-02-27 | 2010-09-02 | Kaveh Adib | Ceria-Zirconia-Zeolite Catalyst Body |
| CN103272597A (en) * | 2013-05-31 | 2013-09-04 | 陕西师范大学 | Preparation method and application of metallic oxide/cotton fiber composite material |
| CN105758913A (en) * | 2016-05-16 | 2016-07-13 | 扬州大学 | Preparation method of straw cellulose-molybdenum disulfide complex modified electrode and application of straw cellulose-molybdenum disulfide complex modified electrode in detecting nitrite in water body |
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101485988A (en) * | 2009-02-18 | 2009-07-22 | 南京工业大学 | Catalyst for catalysis treatment of biomass with microwave and ultraviolet light as well as preparation method and application thereof |
| US20100221160A1 (en) * | 2009-02-27 | 2010-09-02 | Kaveh Adib | Ceria-Zirconia-Zeolite Catalyst Body |
| CN101780952A (en) * | 2010-03-26 | 2010-07-21 | 上海交通大学 | Method for preparing loading functional oxide porous carbon |
| CN103272597A (en) * | 2013-05-31 | 2013-09-04 | 陕西师范大学 | Preparation method and application of metallic oxide/cotton fiber composite material |
| CN105758913A (en) * | 2016-05-16 | 2016-07-13 | 扬州大学 | Preparation method of straw cellulose-molybdenum disulfide complex modified electrode and application of straw cellulose-molybdenum disulfide complex modified electrode in detecting nitrite in water body |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112076731A (en) * | 2020-08-31 | 2020-12-15 | 镇江市高等专科学校 | Loaded with nano CeO2Preparation method of particle composite biomass membrane and application of particle composite biomass membrane in tellurium extraction |
| CN113125521A (en) * | 2021-04-26 | 2021-07-16 | 中国石油大学(华东) | MoS2/CeO2Composite gas-sensitive material and preparation method and application thereof |
| CN115353639A (en) * | 2022-07-12 | 2022-11-18 | 昆明理工大学 | Method for preparing potassium humate by using corn straws and application |
| CN115353639B (en) * | 2022-07-12 | 2023-08-08 | 昆明理工大学 | Method for preparing potassium humate by using corn straw and application |
| CN116237022A (en) * | 2023-02-23 | 2023-06-09 | 南京信息工程大学 | Preparation method and application of fixed nano-hydrated cerium oxide |
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