CN106378124B - A kind of method of stalk cellulose-cerium oxide compound photo catalytic reduction processing waste water containing chrome - Google Patents
A kind of method of stalk cellulose-cerium oxide compound photo catalytic reduction processing waste water containing chrome Download PDFInfo
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- CN106378124B CN106378124B CN201610850633.0A CN201610850633A CN106378124B CN 106378124 B CN106378124 B CN 106378124B CN 201610850633 A CN201610850633 A CN 201610850633A CN 106378124 B CN106378124 B CN 106378124B
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- cerium oxide
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- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 99
- 239000002351 wastewater Substances 0.000 title claims abstract description 93
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 65
- VYZAMTAEIAYCRO-UHFFFAOYSA-N chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000010531 catalytic reduction reaction Methods 0.000 title claims abstract description 15
- 238000004140 cleaning Methods 0.000 claims abstract description 79
- 239000000243 solution Substances 0.000 claims abstract description 67
- 239000001913 cellulose Substances 0.000 claims abstract description 63
- 229920002678 cellulose Polymers 0.000 claims abstract description 63
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims abstract description 62
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 235000019441 ethanol Nutrition 0.000 claims abstract description 43
- 229910052724 xenon Inorganic materials 0.000 claims abstract description 43
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon(0) 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 40
- 239000000203 mixture Substances 0.000 claims abstract description 29
- JHJLBTNAGRQEKS-UHFFFAOYSA-M Sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims abstract description 27
- 239000010902 straw Substances 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000000967 suction filtration Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- NBVHDOZEOGAKLK-UHFFFAOYSA-N [N]=O.CC1C(N(CCC1)C)(C)C Chemical class [N]=O.CC1C(N(CCC1)C)(C)C NBVHDOZEOGAKLK-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000007146 photocatalysis Methods 0.000 claims description 59
- 238000003756 stirring Methods 0.000 claims description 45
- 239000011651 chromium Substances 0.000 claims description 33
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl 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
- 239000007788 liquid Substances 0.000 claims description 15
- 229910052684 Cerium Inorganic materials 0.000 claims description 13
- 238000007792 addition Methods 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 13
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000004090 dissolution Methods 0.000 claims description 13
- 150000004677 hydrates Chemical class 0.000 claims description 13
- 229910001410 inorganic ion Inorganic materials 0.000 claims description 13
- 238000006722 reduction reaction Methods 0.000 claims description 13
- 230000001105 regulatory Effects 0.000 claims description 13
- 238000002798 spectrophotometry method Methods 0.000 claims description 13
- 238000007789 sealing Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- 150000001875 compounds Chemical group 0.000 claims description 6
- 239000003643 water by type Substances 0.000 claims 1
- 229940075581 sodium bromide Drugs 0.000 abstract description 13
- SUKJFIGYRHOWBL-UHFFFAOYSA-N Sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 abstract 1
- 239000005708 Sodium hypochlorite Substances 0.000 abstract 1
- 238000005259 measurement Methods 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 description 44
- 239000000047 product Substances 0.000 description 25
- 239000000835 fiber Substances 0.000 description 22
- 229910052804 chromium Inorganic materials 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 14
- OFJATJUUUCAKMK-UHFFFAOYSA-N Cerium(IV) oxide Chemical compound [O-2]=[Ce+4]=[O-2] OFJATJUUUCAKMK-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000284 extract Substances 0.000 description 3
- 230000003197 catalytic Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000001965 increased Effects 0.000 description 2
- 239000002154 agricultural waste Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000000711 cancerogenic Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000024881 catalytic activity Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001785 cerium compounds Chemical class 0.000 description 1
- 230000004059 degradation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002708 enhancing Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000003199 nucleic acid amplification method 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
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000001131 transforming Effects 0.000 description 1
Abstract
The present invention relates to a kind of stalk cellulose-cerium oxide compound photo catalytic reduction processing waste water containing chrome methods.Include the following steps: that straw pulp is dispersed in tetramethyl piperidine nitrogen oxides and sodium bromide, sodium hypochlorite solution alkaline is added dropwise；Lower reaction a few hours are vigorously stirred, the pH of previous solu is adjusted with sodium hydroxide；Suction filtration cleans nanometer stalk cellulose obtained by drying；It is dissolved in the mixed solution of deionized water and ethyl alcohol and stirs evenly containing appropriate stalk cellulose, six nitric hydrate ceriums, mixture, which is transferred in autoclave, to react；It is cleaned after centrifuge separation with ethyl alcohol and deionized water；Drying obtains stalk cellulose-cerium oxide finished product；Being added into initial concentration is 3 ~ 10 mg/L containing in hexavalent chromium wastewater, is irradiated 30 minutes or more with xenon lamp after mixing evenly, and measurement treated hexavalent chromium concentration simultaneously calculates removal rate.The stalk cellulose-cerium oxide compound processing hexavalent chromium wastewater removal rate is high, and processing cost is low and environmental-friendly.
Description
Technical field
The present invention relates to a kind of stalk cellulose-cerium oxide compound photo catalytic reduction processing waste water containing chrome methods, belong to
In technical field of sewage.
Background technique
In recent years, the enhancing with masses to environmental protection consciousness, various water process new technologies are come into being.Photocatalysis skill
Art is considered as a kind of one of water process new technology with tremendous expansion potentiality.Since it can directly utilize sunlight, ring
The features such as border is friendly just receives more and more attention.Metallurgy and the booming of mining industry cause to be discharged into environment
Waste water containing heavy metal chromium is increasing, causes grave danger to environment.Chromate waste water be discharged into after water body be difficult to it is biological
Degradation can generate aquatic animal, plants and the mankind potentially hazardous or even carcinogenic.And photo catalytic reduction Cr VI can be effectively
Reduce the toxicity of chromium.
Cerium oxide is one of a kind of common rare earth oxide, and popular photochemical catalyst, and band gap width is 3.2 electronics
Volt.Under normal conditions, the transition that electronics can only be generated under ultraviolet light generates a large amount of free radicals to which photocatalysis occur
Reaction.But mould material is selected if appropriate, cerium oxide is dispersed in template, better photocatalysis can be not only obtained
Effect, moreover it is possible to by the synergistic effect of itself and mould material, band gap width is reduced, so that compound has preferably under visible light
Photocatalysis performance.Stalk is common agricultural wastes, has had many documents to confirm that it can be used as mould material；And
Stalk can isolate cellulose after suitably coming out.This can effectively improve the specific surface area of mould material.Therefore, by stalk
Cellulose and the compound new application that can not only develop stalk of cerium oxide can also obtain the photochemical catalyst of good photocatalysis performance.
Summary of the invention
It is an object of the present invention to overcome problems of the prior art, a kind of processing method of chromate waste water is provided,
More particularly to stalk cellulose-cerium oxide complex catalysts reduction treatment chromate waste water method, this compound has excellent
Visible light photocatalysis performance.
Realizing the technical solution of 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, which comprises the steps of:
(1) 10~20 grams of straw pulps are weighed, are added to TEMPO and 0.5~1.5 gram of sodium bromide containing 0.05~0.2 gram
Aqueous solution in, obtain the first mixed liquor；
(2) liquor natrii hypochloritis of configuration quality score 3~6% is adjusted with the hydrochloric acid solution of 0.05~0.3 mol/L
Its pH, pH range are 9~11；
(3) liquor natrii hypochloritis that step (2) obtains is slowly added into the first mixed liquor obtained by step (1), acutely
Stirring, obtains the second mixed liquor；
(4) pH, pH of the second mixed liquor obtained with the sodium hydroxide solution regulating step (3) of 0.2~1.0 mol/L
Range is 9~11, and reaction obtains third mixed liquor；
(5) it after the third mixed liquor suction filtration that step (4) obtains being removed moisture removal, is cleaned with deionized water and is cleaned repeatedly, directly
PH value to third mixed liquor is 7.0, and the third mixed liquor after cleaning is placed in baking oven and is dried i.e. at 40~60 DEG C
Obtain the stalk cellulose of Nano grade；
(6) 5~10mL deionized water and 10~40mL ethyl alcohol are uniformly mixed and obtain ethanol solution, by six nitric hydrates
The stalk cellulose that cerium, step (5) obtain is added in ethanol solution after mixing, and stirring while adding keeps stalk cellulose equal
It is even to disperse and be completely dissolved six nitric hydrate ceriums, addition 0.1~0.5g polyvinylpyrrolidone is then proceeded to, and stirring makes it
Dissolution, obtains the 4th mixed liquor；
(7) the 4th mixed liquor that step (6) obtains is transferred in autoclave, at 160~180 DEG C react 15~
24 hours, the 5th mixed liquor after being reacted；
(8) after moisture removal is centrifuged in the 5th mixed liquor obtained to step (7), removal first is cleaned not with ethyl alcohol
The polyvinylpyrrolidone of reaction, then the unreacted inorganic ions of removal is cleaned with deionized water, 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 10~20 hours at 50~70 DEG C obtains stalk
Cellulose-cerium oxide compound finished product；
(9) it takes 5~10mg stalk cellulose-cerium oxide compound finished product to be added to 30mL to contain in hexavalent chromium wastewater, it is described
Cr VI initial concentration C containing hexavalent chromium wastewater0For 3~7mg/L, pH value is 4.01~6.93；
(10) it is added to containing hexavalent chromium wastewater containing stalk cellulose-cerium oxide compound finished product by step (9) is resulting
In glass container, sealing；
(11) glass container of step (10) is put into the camera bellows of photo catalysis reactor and is stirred, controlled at 25
DEG C, obtain solidliquid mixture；
(12) after through step (11) stirring, xenon lamp is opened, the solidliquid mixture that step (11) is obtained is under xenon lamp
Irradiation 35~120 minutes carries out photocatalysis；
(13) after through step (12) photocatalysis, waste water containing dye in the solidliquid mixture of 5mL step (12), mistake are extracted
Filter, obtains clear liquid；
(14) clear liquid for taking 2 milliliters of steps (13) to obtain, with determined by ultraviolet spectrophotometry through stalk cellulose-cerium oxide
Compound photo catalytic reduction treated hexavalent chromium concentration Ce；It calculates 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 (3), stirring frequency is not less than 200 revs/min.
In step (6), the quality of the 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 xenon lamp described in step (12) is 400W.
Compared with the existing technology, the present invention achieve it is following the utility model has the advantages that
1. step (2) and step (4) pH must be controlled could obtain nanoscale stalk cellulose in suitable range.
2. it is the structure in order to regulate and control cerium oxide that stalk cellulose is added in cerium oxide synthetic system, promote cerium oxide multiple
Closing object has bigger specific surface area and better dispersion performance, and in catalytic process, stalk cellulose is cooperateed with cerium oxide
Effect, can be effectively reduced the band gap width of cerium oxide, so that it is guaranteed that gained compound has catalytic activity in visible region.
3. stalk cellulose in stalk cellulose-cerium oxide produced by the present invention: the weight ratio of cerium oxide is about (0.5
~2.5): 1, the performance with Cr VI in excellent photo catalytic reduction water, and cost is relatively low, contains hexavalent chromium wastewater for restoring
With very high photocatalysis removal rate, potential industrial application value with higher.It is 3~7mg/L and pH for initial concentration
Value, containing hexavalent chromium wastewater, is put into the waste water of 30mL for 4~6 according to 3~10mg stalk cellulose-cerium oxide compound,
After xenon lamp irradiates 30~90 minutes, removal rate is up to 70% or more.
4. being 3mg/L for initial concentration and pH value is 5.11 containing hexavalent chromium wastewater, according to 6mg stalk cellulose-oxygen
Change cerium compound to put into the waste water of 30mL, Cr VI can be reduced substantially within xenon lamp irradiation 90 minutes or more.For first
Beginning concentration is 7mg/L and pH value is 5.11 containing hexavalent chromium wastewater, is put into according to 6mg stalk cellulose-cerium oxide compound
In the waste water of 30mL, xenon lamp irradiates 90 minutes to be reduced more than 70% Cr VI.
The stalk cellulose-cerium oxide compound processing hexavalent chromium wastewater removal rate is high, and processing cost is low and environmental-friendly.
If can be market-oriented, it will obtain preferable economic benefit.
Detailed description of the invention
Fig. 1 is stalk cellulose-cerium oxide compound scanning electron microscope (SEM) photograph of the embodiment of the present invention 1.
Fig. 2 is stalk cellulose-cerium oxide compound scanning electron microscope (SEM) photograph of the embodiment of the present invention 5.
Fig. 3 is stalk cellulose-cerium oxide compound scanning electron microscope (SEM) photograph of the embodiment of the present invention 10.
Fig. 4 is stalk cellulose-cerium oxide compound photocatalysis Cr VI effect picture of different quality in the present invention.
Fig. 5 is stalk cellulose of the invention-cerium oxide compound photocatalysis Cr VI effect with pH value of solution variation diagram.
Specific embodiment
Embodiment 1
A kind of stalk cellulose of the invention-cerium oxide complex catalysts reduction treatment chromate waste water method, is successively wrapped
Include following steps:
(1) 10~20 grams of straw pulps are weighed, are added to TEMPO and 0.5~1.5 gram of sodium bromide containing 0.05~0.2 gram
Aqueous solution in；
(2) liquor natrii hypochloritis of configuration quality score 3~6% is adjusted with the hydrochloric acid solution of 0.05~0.3 mol/L
Its pH is in suitable range；
(3) (2) are slowly added into step (1) gained mixed liquor, are vigorously stirred；
(4) with the sodium hydroxide solution regulating step of 0.2~1.0 mol/L, (3) pH in suitable range and keeps reacting
A few hours；
(5) it after the reaction product suction filtration of step (4) removes moisture removal, is cleaned with deionized water and is cleaned repeatedly, until solution
Reaction product after cleaning is placed in baking oven the drying at 40~60 DEG C and obtains the straw up to Nano grade by pH value close to 7.0
Stalk fiber element；
(6) 5~10mL deionized water and 10~40mL ethyl alcohol are uniformly mixed, weigh (5) stalk fibre that step obtains
Plain, suitable six nitric hydrates cerium, is added in the ethanol solution, stirring while adding keeps stalk cellulose equal after mixing
It is even to disperse and be completely dissolved six nitric hydrate ceriums；Addition 0.1~0.5g polyvinylpyrrolidone is then proceeded to, and stirring makes it
Dissolution；
(7) mixture of step (6) is transferred in autoclave, is reacted 15~24 hours at 160~180 DEG C；
(8) after moisture removal being centrifuged to the reaction product of step (7), it is unreacted that removal first is cleaned with ethyl alcohol
Polyvinylpyrrolidone, then the unreacted inorganic ions of removal is cleaned with deionized water, until the pH value of solution is not less than 6.8,
Reaction product after cleaning is placed in baking oven and dries that obtain stalk cellulose-cerium oxide within 10~20 hours multiple at 50~70 DEG C
Close object finished product.
Photocatalysis chromate waste water is carried out using stalk cellulose of the invention-cerium oxide compound according to the following steps: (1) being taken
6mg stalk cellulose-cerium oxide compound finished product is added to 30mL and contains in hexavalent chromium wastewater, the sexavalence containing hexavalent chromium wastewater
Chromium initial concentration C0For 3mg/L, pH value 4.02；(2) by step, (1) resulting stalk cellulose-cerium oxide compound contains six
Valence chromium waste water is added in glass container, sealing；(3) glass container of step (2) is put into the camera bellows of photo catalysis reactor,
Stirring 30 minutes, controlled at 25 DEG C；(4) after stirring, xenon lamp is opened, by the solidliquid mixture of step (3) under xenon lamp
Irradiation 30~90 minutes, xenon lamp power are 400W；(5) after photocatalysis, that extracts 5mL step (4) contains hexavalent chromium wastewater, mistake
Filter；(6) 2mL clear liquid is taken, treated that hexavalent chromium concentration Ce is 0.0mg/L with determined by ultraviolet spectrophotometry；(7) light is calculated to urge
Removal rate=1- (Ce/C after change0) * 100%=100%.
Embodiment 2
A kind of stalk cellulose of the invention-cerium oxide complex catalysts reduction treatment chromate waste water method, is successively wrapped
Include following steps:
(1) 10~20 grams of straw pulps are weighed, are added to TEMPO and 0.5~1.5 gram of sodium bromide containing 0.05~0.2 gram
Aqueous solution in；
(2) liquor natrii hypochloritis of configuration quality score 3~6% is adjusted with the hydrochloric acid solution of 0.05~0.3 mol/L
Its pH is in suitable range；
(3) (2) are slowly added into mixed liquor obtained by step (1), are vigorously stirred；
(4) with the sodium hydroxide solution regulating step of 0.2~1.0 mol/L, (3) pH in suitable range and keeps reacting
A few hours；
(5) it after the reaction product suction filtration of step (4) removes moisture removal, is cleaned with deionized water and is cleaned repeatedly, until solution
Reaction product after cleaning is placed in baking oven the drying at 40~60 DEG C and obtains the straw up to Nano grade by pH value close to 7.0
Stalk fiber element；
(6) 5~10mL deionized water and 10~40mL ethyl alcohol are uniformly mixed, weigh (5) stalk fibre that step obtains
Plain, suitable six nitric hydrates cerium, is added in the ethanol solution, stirring while adding keeps stalk cellulose equal after mixing
It is even to disperse and be completely dissolved six nitric hydrate ceriums；Addition 0.1~0.5g polyvinylpyrrolidone is then proceeded to, and stirring makes it
Dissolution；
(7) mixture of step (6) is transferred in autoclave, is reacted 15~24 hours at 160~180 DEG C；
(8) after moisture removal being centrifuged to the reaction product of step (7), it is unreacted that removal first is cleaned with ethyl alcohol
Polyvinylpyrrolidone, then the unreacted inorganic ions of removal is cleaned with deionized water, until the pH value of solution is not less than 6.8,
Reaction product after cleaning is placed in baking oven and dries that obtain stalk cellulose-cerium oxide within 10~20 hours multiple at 50~70 DEG C
Close object finished product.
Photocatalysis chromate waste water is carried out using stalk cellulose of the invention-cerium oxide compound according to the following steps: (1) being taken
6mg stalk cellulose-cerium oxide compound finished product is added to 30mL and contains in hexavalent chromium wastewater, the sexavalence containing hexavalent chromium wastewater
Chromium initial concentration C0For 3mg/L, pH value 5.11；(2) by step, (1) resulting stalk cellulose-cerium oxide compound contains six
Valence chromium waste water is added in glass container, sealing；(3) glass container of step (2) is put into the camera bellows of photo catalysis reactor,
Stirring 30 minutes, controlled at 25 DEG C；(4) after stirring, xenon lamp is opened, by the solidliquid mixture of step (3) in xenon lamp
Lower irradiation 30~90 minutes, xenon lamp power are 400W；(5) after photocatalysis, that extracts 5mL step (4) contains hexavalent chromium wastewater,
Filtering；(6) 2mL clear liquid is taken, treated that hexavalent chromium concentration Ce is 0.0mg/L with determined by ultraviolet spectrophotometry；(7) light is calculated
Removal rate=1- (Ce/C after catalysis0) * 100%=100%.
Embodiment 3
A kind of stalk cellulose of the invention-cerium oxide complex catalysts reduction treatment chromate waste water method, is successively wrapped
Include following steps:
(1) 10~20 grams of straw pulps are weighed, are added to TEMPO and 0.5~1.5 gram of sodium bromide containing 0.05~0.2 gram
Aqueous solution in；
(2) liquor natrii hypochloritis of configuration quality score 3~6% is adjusted with the hydrochloric acid solution of 0.05~0.3 mol/L
Its pH is in suitable range；
(3) (2) are slowly added into mixed liquor obtained by step (1), are vigorously stirred；
(4) with the sodium hydroxide solution regulating step of 0.2~1.0 mol/L, (3) pH in suitable range and keeps reacting
A few hours；
(5) it after the reaction product suction filtration of step (4) removes moisture removal, is cleaned with deionized water and is cleaned repeatedly, until solution
Reaction product after cleaning is placed in baking oven the drying at 40~60 DEG C and obtains the straw up to Nano grade by pH value close to 7.0
Stalk fiber element；
(6) 5~10mL deionized water and 10~40mL ethyl alcohol are uniformly mixed, weigh (5) stalk fibre that step obtains
Plain, suitable six nitric hydrates cerium, is added in the ethanol solution, stirring while adding keeps stalk cellulose equal after mixing
It is even to disperse and be completely dissolved six nitric hydrate ceriums；Addition 0.1~0.5g polyvinylpyrrolidone is then proceeded to, and stirring makes it
Dissolution；
(7) mixture of step (6) is transferred in autoclave, is reacted 15~24 hours at 160~180 DEG C；
(8) after moisture removal being centrifuged to the reaction product of step (7), it is unreacted that removal first is cleaned with ethyl alcohol
Polyvinylpyrrolidone, then the unreacted inorganic ions of removal is cleaned with deionized water, until the pH value of solution is not less than 6.8,
Reaction product after cleaning is placed in baking oven and dries that obtain stalk cellulose-cerium oxide within 10~20 hours multiple at 50~70 DEG C
Close object finished product.
Photocatalysis chromate waste water is carried out using stalk cellulose of the invention-cerium oxide compound according to the following steps: (1) being taken
6mg stalk cellulose-cerium oxide compound finished product is added to 30mL and contains in hexavalent chromium wastewater, the sexavalence containing hexavalent chromium wastewater
Chromium initial concentration C0For 3mg/L, pH value 5.97；(2) the resulting stalk cellulose of step (1)-cerium oxide compound is contained
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, it stirs 30 minutes, controlled at 25 DEG C；(4) after stirring, xenon lamp is opened, by the solidliquid mixture of step (3) in xenon
It is irradiated 30~90 minutes under lamp, xenon lamp power is 400W；(5) after photocatalysis, the useless containing Cr VI of 5mL step (4) is extracted
Water, filtering；(6) 2mL clear liquid is taken, treated that hexavalent chromium concentration Ce is 0.054mg/L with determined by ultraviolet spectrophotometry；(7)
Removal rate=1- (Ce/C after calculating photocatalysis0) * 100%=98.2%.
Embodiment 4
A kind of stalk cellulose of the invention-cerium oxide complex catalysts reduction treatment chromate waste water method, is successively wrapped
Include following steps:
(1) 10~20 grams of straw pulps are weighed, are added to TEMPO and 0.5~1.5 gram of sodium bromide containing 0.05~0.2 gram
Aqueous solution in；
(2) liquor natrii hypochloritis of configuration quality score 3~6% is adjusted with the hydrochloric acid solution of 0.05~0.3 mol/L
Its pH is in suitable range；
(3) (2) are slowly added into step (1) gained mixed liquor, are vigorously stirred；
(4) with the sodium hydroxide solution regulating step of 0.2~1.0 mol/L, (3) pH in suitable range and keeps reacting
A few hours；
(5) it after the reaction product suction filtration of step (4) removes moisture removal, is cleaned with deionized water and is cleaned repeatedly, until solution
Reaction product after cleaning is placed in baking oven the drying at 40~60 DEG C and obtains the straw up to Nano grade by pH value close to 7.0
Stalk fiber element；
(6) 5~10mL deionized water and 10~40mL ethyl alcohol are uniformly mixed, weigh (5) stalk fibre that step obtains
Plain, suitable six nitric hydrates cerium, is added in the ethanol solution, stirring while adding keeps stalk cellulose equal after mixing
It is even to disperse and be completely dissolved six nitric hydrate ceriums；Addition 0.1~0.5g polyvinylpyrrolidone is then proceeded to, and stirring makes it
Dissolution；
(7) mixture of step (6) is transferred in autoclave, is reacted 15~24 hours at 160~180 DEG C；
(8) after moisture removal being centrifuged to the reaction product of step (7), it is unreacted that removal first is cleaned with ethyl alcohol
Polyvinylpyrrolidone, then the unreacted inorganic ions of removal is cleaned with deionized water, until the pH value of solution is not less than 6.8,
Reaction product after cleaning is placed in baking oven and dries that obtain stalk cellulose-cerium oxide within 10~20 hours multiple at 50~70 DEG C
Close object finished product.
Photocatalysis chromate waste water is carried out using stalk cellulose of the invention-cerium oxide compound according to the following steps: (1) being taken
6mg stalk cellulose-cerium oxide compound finished product is added to 30mL and contains in hexavalent chromium wastewater, the sexavalence containing hexavalent chromium wastewater
Chromium initial concentration C0For 3mg/L, pH value 6.93；(2) the resulting stalk cellulose of step (1)-cerium oxide compound is contained
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, it stirs 30 minutes, controlled at 25 DEG C；(4) after stirring, xenon lamp is opened, by the solidliquid mixture of step (3) in xenon
It is irradiated 30~90 minutes under lamp, xenon lamp power is 400W；(5) after photocatalysis, the useless containing Cr VI of 5mL step (4) is extracted
Water, filtering；(6) 2mL clear liquid is taken, treated that hexavalent chromium concentration Ce is 0.237mg/L with determined by ultraviolet spectrophotometry；(7)
Removal rate=1- (Ce/C after calculating photocatalysis0) * 100%=92.1%.
Embodiment 5
A kind of stalk cellulose of the invention-cerium oxide complex catalysts reduction treatment chromate waste water method, is successively wrapped
Include following steps:
(1) 10~20 grams of straw pulps are weighed, are added to TEMPO and 0.5~1.5 gram of sodium bromide containing 0.05~0.2 gram
Aqueous solution in；
(2) liquor natrii hypochloritis of configuration quality score 3~6% is adjusted with the hydrochloric acid solution of 0.05~0.3 mol/L
Its pH is in suitable range；
(3) (2) are slowly added into mixed liquor obtained by step (1), are vigorously stirred；
(4) with the sodium hydroxide solution regulating step of 0.2~1.0 mol/L, (3) pH in suitable range and keeps reacting
A few hours；
(5) it after the reaction product suction filtration of step (4) removes moisture removal, is cleaned with deionized water and is cleaned repeatedly, until solution
Reaction product after cleaning is placed in baking oven the drying at 40~60 DEG C and obtains the straw up to Nano grade by pH value close to 7.0
Stalk fiber element；
(6) 5~10mL deionized water and 10~40mL ethyl alcohol are uniformly mixed, weigh (5) stalk fibre that step obtains
Plain, suitable six nitric hydrates cerium, is added in the ethanol solution, stirring while adding keeps stalk cellulose equal after mixing
It is even to disperse and be completely dissolved six nitric hydrate ceriums；Addition 0.1~0.5g polyvinylpyrrolidone is then proceeded to, and stirring makes it
Dissolution；
(7) mixture of step (6) is transferred in autoclave, is reacted 15~24 hours at 160~180 DEG C；
(8) after moisture removal being centrifuged to the reaction product of step (7), it is unreacted that removal first is cleaned with ethyl alcohol
Polyvinylpyrrolidone, then the unreacted inorganic ions of removal is cleaned with deionized water, until the pH value of solution is not less than 6.8,
Reaction product after cleaning is placed in baking oven and dries that obtain stalk cellulose-cerium oxide within 10~20 hours multiple at 50~70 DEG C
Close object finished product.
Photocatalysis chromate waste water is carried out using stalk cellulose of the invention-cerium oxide compound according to the following steps: (1) being taken
3mg stalk cellulose-cerium oxide compound finished product is added to 30mL and contains in hexavalent chromium wastewater, the sexavalence containing hexavalent chromium wastewater
Chromium initial concentration C0For 3mg/L, pH value 5.11；(2) the resulting stalk cellulose of step (1)-cerium oxide compound is contained
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, it stirs 30 minutes, controlled at 25 DEG C；(4) after stirring, xenon lamp is opened, by the solidliquid mixture of step (3) in xenon
It is irradiated 30~90 minutes under lamp, xenon lamp power is 400W；(5) after photocatalysis, the useless containing Cr VI of 5mL step (4) is extracted
Water, filtering；(6) 2mL clear liquid is taken, treated that hexavalent chromium concentration Ce is 0.876mg/L with determined by ultraviolet spectrophotometry；(7) count
Removal rate=1- (Ce/C after calculating photocatalysis0) * 100%=70.8%.
Embodiment 6
A kind of stalk cellulose of the invention-cerium oxide complex catalysts reduction treatment chromate waste water method, is successively wrapped
Include following steps:
(1) 10~20 grams of straw pulps are weighed, are added to TEMPO and 0.5~1.5 gram of sodium bromide containing 0.05~0.2 gram
Aqueous solution in；
(2) liquor natrii hypochloritis of configuration quality score 3~6% is adjusted with the hydrochloric acid solution of 0.05~0.3 mol/L
Its pH is in suitable range；
(3) (2) are slowly added into mixed liquor obtained by step (1), are vigorously stirred；
(4) with the sodium hydroxide solution regulating step of 0.2~1.0 mol/L, (3) pH in suitable range and keeps reacting
A few hours；
(5) it after the reaction product suction filtration of step (4) removes moisture removal, is cleaned with deionized water and is cleaned repeatedly, until solution
Reaction product after cleaning is placed in baking oven the drying at 40~60 DEG C and obtains the straw up to Nano grade by pH value close to 7.0
Stalk fiber element；
(6) 5~10mL deionized water and 10~40mL ethyl alcohol are uniformly mixed, weigh (5) stalk fibre that step obtains
Plain, suitable six nitric hydrates cerium, is added in the ethanol solution, stirring while adding keeps stalk cellulose equal after mixing
It is even to disperse and be completely dissolved six nitric hydrate ceriums；Addition 0.1~0.5g polyvinylpyrrolidone is then proceeded to, and stirring makes it
Dissolution；
(7) mixture of step (6) is transferred in autoclave, is reacted 15~24 hours at 160~180 DEG C；
(8) after moisture removal being centrifuged to the reaction product of step (7), it is unreacted that removal first is cleaned with ethyl alcohol
Polyvinylpyrrolidone, then the unreacted inorganic ions of removal is cleaned with deionized water, until the pH value of solution is not less than 6.8,
Reaction product after cleaning is placed in baking oven and dries that obtain stalk cellulose-cerium oxide within 10~20 hours multiple at 50~70 DEG C
Close object finished product.
Photocatalysis chromate waste water is carried out using stalk cellulose of the invention-cerium oxide compound according to the following steps: (1) being taken
5mg stalk cellulose-cerium oxide compound finished product is added to 30mL and contains in hexavalent chromium wastewater, the sexavalence containing hexavalent chromium wastewater
Chromium initial concentration C0For 3mg/L, pH value 5.11；(2) the resulting stalk cellulose of step (1)-cerium oxide compound is contained
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, it stirs 30 minutes, controlled at 25 DEG C；(4) after stirring, xenon lamp is opened, by the solidliquid mixture of step (3) in xenon
It is irradiated 30~90 minutes under lamp, xenon lamp power is 400W；(5) after photocatalysis, the useless containing Cr VI of 5mL step (4) is extracted
Water, filtering；(6) 2mL clear liquid is taken, treated that hexavalent chromium concentration Ce is 0.222mg/L with determined by ultraviolet spectrophotometry；(7)
Removal rate=1- (Ce/C after calculating photocatalysis0) * 100%=92.6%.
Embodiment 7
A kind of stalk cellulose of the invention-cerium oxide complex catalysts reduction treatment chromate waste water method, is successively wrapped
Include following steps:
(1) 10~20 grams of straw pulps are weighed, are added to TEMPO and 0.5~1.5 gram of sodium bromide containing 0.05~0.2 gram
Aqueous solution in；
(2) liquor natrii hypochloritis of configuration quality score 3~6% is adjusted with the hydrochloric acid solution of 0.05~0.3 mol/L
Its pH is in suitable range；
(3) (2) are slowly added into mixed liquor obtained by step (1), are vigorously stirred；
(4) it in suitable range and keeps reacting with sodium hydroxide solution regulating step (3) pH of 0.2~1.0 mol/L
A few hours；
(5) it after the reaction product suction filtration of step (4) removes moisture removal, is cleaned with deionized water and is cleaned repeatedly, until solution
Reaction product after cleaning is placed in baking oven the drying at 40~60 DEG C and obtains the straw up to Nano grade by pH value close to 7.0
Stalk fiber element；
(6) 5~10mL deionized water and 10~40mL ethyl alcohol are uniformly mixed, weigh (5) stalk fibre that step obtains
Plain, suitable six nitric hydrates cerium, is added in the ethanol solution, stirring while adding keeps stalk cellulose equal after mixing
It is even to disperse and be completely dissolved six nitric hydrate ceriums；Addition 0.1~0.5g polyvinylpyrrolidone is then proceeded to, and stirring makes it
Dissolution；
(7) mixture of step (6) is transferred in autoclave, is reacted 15~24 hours at 160~180 DEG C；
(8) after moisture removal being centrifuged to the reaction product of step (7), it is unreacted that removal first is cleaned with ethyl alcohol
Polyvinylpyrrolidone, then the unreacted inorganic ions of removal is cleaned with deionized water, until the pH value of solution is not less than 6.8,
Reaction product after cleaning is placed in baking oven and dries that obtain stalk cellulose-cerium oxide within 10~20 hours multiple at 50~70 DEG C
Close object finished product.
Photocatalysis chromate waste water is carried out using stalk cellulose of the invention-cerium oxide compound according to the following steps: (1) being taken
8mg stalk cellulose-cerium oxide compound finished product is added to 30mL and contains in hexavalent chromium wastewater, the sexavalence containing hexavalent chromium wastewater
Chromium initial concentration C0For 3mg/L, pH value 5.11；(2) the resulting stalk cellulose of step (1)-cerium oxide compound is contained
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, it stirs 30 minutes, controlled at 25 DEG C；(4) after stirring, xenon lamp is opened, by the solidliquid mixture of step (3) in xenon
It is irradiated 30~90 minutes under lamp, xenon lamp power is 400W；(5) after photocatalysis, the useless containing Cr VI of 5mL step (4) is extracted
Water, filtering；(6) 2mL clear liquid is taken, treated that hexavalent chromium concentration Ce is 0.0mg/L with determined by ultraviolet spectrophotometry；(7) it counts
Removal rate=1- (Ce/C after calculating photocatalysis0) * 100%=100%.
Embodiment 8
A kind of stalk cellulose of the invention-cerium oxide complex catalysts reduction treatment chromate waste water method, is successively wrapped
Include following steps:
(1) 10~20 grams of straw pulps are weighed, are added to TEMPO and 0.5~1.5 gram of sodium bromide containing 0.05~0.2 gram
Aqueous solution in；
(2) liquor natrii hypochloritis of configuration quality score 3~6% is adjusted with the hydrochloric acid solution of 0.05~0.3 mol/L
Its pH is in suitable range；
(3) (2) are slowly added into mixed liquor obtained by step (1), are vigorously stirred；
(4) it in suitable range and keeps reacting with sodium hydroxide solution regulating step (3) pH of 0.2~1.0 mol/L
A few hours；
(5) it after the reaction product suction filtration of step (4) removes moisture removal, is cleaned with deionized water and is cleaned repeatedly, until solution
Reaction product after cleaning is placed in baking oven the drying at 40~60 DEG C and obtains the straw up to Nano grade by pH value close to 7.0
Stalk fiber element；
(6) 5~10mL deionized water and 10~40mL ethyl alcohol are uniformly mixed, weigh (5) stalk fibre that step obtains
Plain, suitable six nitric hydrates cerium, is added in the ethanol solution, stirring while adding keeps stalk cellulose equal after mixing
It is even to disperse and be completely dissolved six nitric hydrate ceriums；Addition 0.1~0.5g polyvinylpyrrolidone is then proceeded to, and stirring makes it
Dissolution；
(7) mixture of step (6) is transferred in autoclave, is reacted 15~24 hours at 160~180 DEG C；
(8) after moisture removal being centrifuged to the reaction product of step (7), it is unreacted that removal first is cleaned with ethyl alcohol
Polyvinylpyrrolidone, then the unreacted inorganic ions of removal is cleaned with deionized water, until the pH value of solution is not less than 6.8,
Reaction product after cleaning is placed in baking oven and dries that obtain stalk cellulose-cerium oxide within 10~20 hours multiple at 50~70 DEG C
Close object finished product.
Photocatalysis chromate waste water is carried out using stalk cellulose of the invention-cerium oxide compound according to the following steps: (1) being taken
10mg stalk cellulose-cerium oxide compound finished product is added to 30mL and contains in hexavalent chromium wastewater, six containing hexavalent chromium wastewater
Valence chromium initial concentration C0For 3mg/L, pH value 5.11；(2) by the resulting stalk cellulose of step (1)-cerium oxide compound
It is added in glass container, seals containing hexavalent chromium wastewater；(3) glass container of step (2) is put into the dark of photo catalysis reactor
In case, stir 30 minutes, controlled at 25 DEG C；(4) after stirring, xenon lamp is opened, the solidliquid mixture of step (3) is existed
It is irradiated 30~90 minutes under xenon lamp, xenon lamp power is 400W；(5) after photocatalysis, that extracts 5mL step (4) contains Cr VI
Waste water, filtering；(6) 2mL clear liquid is taken, treated that hexavalent chromium concentration Ce is 0.0mg/L with determined by ultraviolet spectrophotometry；(7)
Removal rate=1- (Ce/C after calculating photocatalysis0) * 100%=100%.
Embodiment 9
A kind of stalk cellulose of the invention-cerium oxide complex catalysts reduction treatment chromate waste water method, is successively wrapped
Include following steps:
(1) 10~20 grams of straw pulps are weighed, are added to TEMPO and 0.5~1.5 gram of sodium bromide containing 0.05~0.2 gram
Aqueous solution in；
(2) liquor natrii hypochloritis of configuration quality score 3~6% is adjusted with the hydrochloric acid solution of 0.05~0.3 mol/L
Its pH is in suitable range；
(3) (2) are slowly added into mixed liquor obtained by step (1), are vigorously stirred；
(4) with the sodium hydroxide solution regulating step of 0.2~1.0 mol/L, (3) pH in suitable range and keeps reacting
A few hours；
(5) it after the reaction product suction filtration of step (4) removes moisture removal, is cleaned with deionized water and is cleaned repeatedly, until solution
Reaction product after cleaning is placed in baking oven the drying at 40~60 DEG C and obtains the straw up to Nano grade by pH value close to 7.0
Stalk fiber element；
(6) 5~10mL deionized water and 10~40mL ethyl alcohol are uniformly mixed, weigh (5) stalk fibre that step obtains
Plain, suitable six nitric hydrates cerium, is added in the ethanol solution, stirring while adding keeps stalk cellulose equal after mixing
It is even to disperse and be completely dissolved six nitric hydrate ceriums；Addition 0.1~0.5g polyvinylpyrrolidone is then proceeded to, and stirring makes it
Dissolution；
(7) mixture of step (6) is transferred in autoclave, is reacted 15~24 hours at 160~180 DEG C；
(8) after moisture removal being centrifuged to the reaction product of step (7), it is unreacted that removal first is cleaned with ethyl alcohol
Polyvinylpyrrolidone, then the unreacted inorganic ions of removal is cleaned with deionized water, until the pH value of solution is not less than 6.8,
Reaction product after cleaning is placed in baking oven and dries that obtain stalk cellulose-cerium oxide within 10~20 hours multiple at 50~70 DEG C
Close object finished product.
Photocatalysis chromate waste water is carried out using stalk cellulose of the invention-cerium oxide compound according to the following steps: (1) being taken
6mg stalk cellulose-cerium oxide compound finished product is added to 30mL and contains in hexavalent chromium wastewater, the sexavalence containing hexavalent chromium wastewater
Chromium initial concentration C0For 5mg/L, pH value 5.11；(2) the resulting stalk cellulose of step (1)-cerium oxide compound is contained
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, it stirs 30 minutes, controlled at 25 DEG C；(4) after stirring, xenon lamp is opened, by the solidliquid mixture of step (3) in xenon
It is irradiated 30~90 minutes under lamp, xenon lamp power is 400W；(5) after photocatalysis, the useless containing Cr VI of 5mL step (4) is extracted
Water, filtering；(6) 2mL clear liquid is taken, treated that hexavalent chromium concentration Ce is 0.585mg/L with determined by ultraviolet spectrophotometry；(7)
Removal rate=1- (Ce/C after calculating photocatalysis0) * 100%=88.3%.
Embodiment 10
A kind of stalk cellulose of the invention-cerium oxide complex catalysts reduction treatment chromate waste water method, is successively wrapped
Include following steps:
(1) 10~20 grams of straw pulps are weighed, are added to TEMPO and 0.5~1.5 gram of sodium bromide containing 0.05~0.2 gram
Aqueous solution in；
(2) liquor natrii hypochloritis of configuration quality score 3~6% is adjusted with the hydrochloric acid solution of 0.05~0.3 mol/L
Its pH is in suitable range；
(3) (2) are slowly added into mixed liquor obtained by step (1), are vigorously stirred；
(4) with the sodium hydroxide solution regulating step of 0.2~1.0 mol/L, (3) pH in suitable range and keeps reacting
A few hours；
(5) it after the reaction product suction filtration of step (4) removes moisture removal, is cleaned with deionized water and is cleaned repeatedly, until solution
Reaction product after cleaning is placed in baking oven the drying at 40~60 DEG C and obtains the straw up to Nano grade by pH value close to 7.0
Stalk fiber element；
(6) 5~10mL deionized water and 10~40mL ethyl alcohol are uniformly mixed, weigh (5) stalk fibre that step obtains
Plain, suitable six nitric hydrates cerium, is added in the ethanol solution, stirring while adding keeps stalk cellulose equal after mixing
It is even to disperse and be completely dissolved six nitric hydrate ceriums；Addition 0.1~0.5g polyvinylpyrrolidone is then proceeded to, and stirring makes it
Dissolution；
(7) mixture of step (6) is transferred in autoclave, is reacted 15~24 hours at 160~180 DEG C；
(8) after moisture removal being centrifuged to the reaction product of step (7), it is unreacted that removal first is cleaned with ethyl alcohol
Polyvinylpyrrolidone, then the unreacted inorganic ions of removal is cleaned with deionized water, until the pH value of solution is not less than 6.8,
Reaction product after cleaning is placed in baking oven and dries that obtain stalk cellulose-cerium oxide within 10~20 hours multiple at 50~70 DEG C
Close object finished product.
Photocatalysis chromate waste water is carried out using stalk cellulose of the invention-cerium oxide compound according to the following steps: (1) being taken
6mg stalk cellulose-cerium oxide compound finished product is added to 30mL and contains in hexavalent chromium wastewater, the sexavalence containing hexavalent chromium wastewater
Chromium initial concentration C0For 7mg/L, pH value 5.11；(2) the resulting stalk cellulose of step (1)-cerium oxide compound is contained
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, it stirs 30 minutes, controlled at 25 DEG C；(4) after stirring, xenon lamp is opened, by the solidliquid mixture of step (3) in xenon
It is irradiated 30~90 minutes under lamp, xenon lamp power is 400W；(5) after photocatalysis, the useless containing Cr VI of 5mL step (4) is extracted
Water, filtering；(6) 2mL clear liquid is taken, treated that hexavalent chromium concentration Ce is 1.792mg/L with determined by ultraviolet spectrophotometry；(7)
Removal rate=1- (Ce/C after calculating photocatalysis0) * 100%=74.4%.
Embodiment 11
A kind of stalk cellulose of the invention-cerium oxide complex catalysts reduction treatment chromate waste water method, is successively wrapped
Include following steps:
(1) 10~20 grams of straw pulps are weighed, are added to TEMPO and 0.5~1.5 gram of sodium bromide containing 0.05~0.2 gram
Aqueous solution in；
(2) liquor natrii hypochloritis of configuration quality score 3~6% is adjusted with the hydrochloric acid solution of 0.05~0.3 mol/L
Its pH is in suitable range；
(3) (2) are slowly added into mixed liquor obtained by step (1), are vigorously stirred；
(4) with the sodium hydroxide solution regulating step of 0.2~1.0 mol/L, (3) pH in suitable range and keeps reacting
A few hours；
(5) it after the reaction product suction filtration of step (4) removes moisture removal, is cleaned with deionized water and is cleaned repeatedly, until solution
Reaction product after cleaning is placed in baking oven the drying at 40~60 DEG C and obtains the straw up to Nano grade by pH value close to 7.0
Stalk fiber element；
(6) 5~10mL deionized water and 10~40mL ethyl alcohol are uniformly mixed, weigh (5) stalk fibre that step obtains
Plain, suitable six nitric hydrates cerium, is added in the ethanol solution, stirring while adding keeps stalk cellulose equal after mixing
It is even to disperse and be completely dissolved six nitric hydrate ceriums；Addition 0.1~0.5g polyvinylpyrrolidone is then proceeded to, and stirring makes it
Dissolution；
(7) mixture of step (6) is transferred in autoclave, is reacted 15~24 hours at 160~180 DEG C；
(8) after moisture removal being centrifuged to the reaction product of step (7), it is unreacted that removal first is cleaned with ethyl alcohol
Polyvinylpyrrolidone, then the unreacted inorganic ions of removal is cleaned with deionized water, until the pH value of solution is not less than 6.8,
Reaction product after cleaning is placed in baking oven and dries that obtain stalk cellulose-cerium oxide within 10~20 hours multiple at 50~70 DEG C
Close object finished product.
Photocatalysis chromate waste water is carried out using stalk cellulose of the invention-cerium oxide compound according to the following steps: (1) being taken
6mg stalk cellulose-cerium oxide compound finished product is added to 30mL and contains in hexavalent chromium wastewater, the sexavalence containing hexavalent chromium wastewater
Chromium initial concentration C0For 10mg/L, pH value 5.11；(2) the resulting stalk cellulose of step (1)-cerium oxide compound is contained
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, it stirs 30 minutes, controlled at 25 DEG C；(4) after stirring, xenon lamp is opened, by the solidliquid mixture of step (3) in xenon
It is irradiated 30~90 minutes under lamp, xenon lamp power is 400W；(5) after photocatalysis, the useless containing Cr VI of 5mL step (4) is extracted
Water, filtering；(6) 2mL clear liquid is taken, treated that hexavalent chromium concentration Ce is 7.130mg/L with determined by ultraviolet spectrophotometry；(7)
Removal rate=1- (Ce/C after calculating photocatalysis0) * 100%=28.7%.
It is drawn to the data summarization such as following table of 1~embodiment of embodiment 11, and according to the data of embodiment 2,5,6,7,8
At Fig. 4, according to the data drafting pattern 5 of Examples 1 to 4.
Can be seen that be 3mg/L for initial concentration and pH value is 4.02~6.93 containing Cr VI from summary sheet and Fig. 5
Waste water is put into the waste water of 30mL according to 6mg stalk cellulose-cerium oxide compound, is removed within Hg lamp irradiation 90 minutes or more
Rate is more than 90%.
It can be seen that under same pH from summary sheet and Fig. 4, stalk cellulose-cerium oxide is compound in a certain range
The increase of object throwing amount, removal rate are gradually increased；It can be seen that from summary sheet and Fig. 5 and thrown in stalk cellulose-cerium oxide compound
It measures in identical situation, when pH value is between 4.02~5.11, removal rate highest.
It is concentration expressed in percentage by weight that percentage concentration is not specified in text.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 merely the preferable possible embodiments of the present invention, non-therefore limitation patent protection model of the invention
It encloses.In addition to the implementation, the present invention can also have other embodiments, such as can be by ratios such as the quality of each ingredient and volumes
Example amplification several times.It is all using equivalent substitution or equivalent transformation formed technical solution, all fall within the present invention claims protection model
In enclosing.Technical characteristic of the present invention without description can realize that details are not described herein by or using the prior art.
Claims (5)
1. a kind of stalk cellulose-cerium oxide compound photo catalytic reduction processing waste water containing chrome method, which is characterized in that including
Following steps:
(1) weigh 10 ~ 20 grams of straw pulps, be added to the tetramethyl piperidine nitrogen oxides TEMPO and 0.5 containing 0.05 ~ 0.2 gram ~
In the aqueous solution of 1.5 grams of sodium bromides, the first mixed liquor is obtained；
(2) liquor natrii hypochloritis of configuration quality score 3 ~ 6% adjusts its pH, pH with the hydrochloric acid solution of 0.05 ~ 0.3 mol/L
Range is 9 ~ 11；
(3) liquor natrii hypochloritis that step (2) obtains is slowly added into the first mixed liquor obtained by step (1), is vigorously stirred,
Obtain the second mixed liquor；
(4) pH of the second mixed liquor obtained with the sodium hydroxide solution regulating step (3) of 0.2 ~ 1.0 mol/L, pH range
It is 9 ~ 11, reaction obtains third mixed liquor；
(5) it after the third mixed liquor suction filtration that step (4) obtains being removed moisture removal, is cleaned with deionized water and is cleaned repeatedly, until the
The pH value of three mixed liquors is 7.0, and the third mixed liquor after cleaning is placed in baking oven the drying at 40 ~ 60 DEG C and obtains Nano grade
Stalk cellulose；
(6) 5 ~ 10 ml deionized waters and 10 ~ 40 milliliters of ethyl alcohol are uniformly mixed and obtain ethanol solution, by six nitric hydrates
The stalk cellulose that cerium, step (5) obtain is added in ethanol solution after mixing, and stirring while adding keeps stalk cellulose equal
It is even to disperse and be completely dissolved six nitric hydrate ceriums, 0.1 ~ 0.5 gram of polyvinylpyrrolidone of addition is then proceeded to, and stirring makes it
Dissolution, obtains the 4th mixed liquor；
(7) the 4th mixed liquor that step (6) obtains is transferred in autoclave, it is small that 15 ~ 24 is reacted at 160 ~ 180 DEG C
When, the 5th mixed liquor after being reacted；
(8) after moisture removal is centrifuged in the 5th mixed liquor obtained to step (7), removal unreacted first is cleaned with ethyl alcohol
Polyvinylpyrrolidone, then the unreacted inorganic ions of removal is cleaned with deionized water, until the pH value of the 5th mixed liquor is not
Lower than 6.8, the 5th mixed liquor after cleaning is placed in baking oven to dry 10 ~ 20 hours at 50 ~ 70 DEG C obtains stalk cellulose-
Cerium oxide compound finished product；
(9) it takes 5 ~ 10 milligrams of stalk celluloses-cerium oxide compound finished product to be added to 30 milliliters to contain in hexavalent chromium wastewater, it is described to contain
The Cr VI initial concentration C of hexavalent chromium wastewater0For 3 ~ 7 mg/litres, pH value is 4.01 ~ 6.93；
(10) glass is added to containing hexavalent chromium wastewater containing stalk cellulose-cerium oxide compound finished product by step (9) is resulting
In container, sealing；
(11) glass container of step (10) is put into the camera bellows of photo catalysis reactor and is stirred, controlled at 25 DEG C,
Obtain solidliquid mixture；
(12) after through step (11) stirring, xenon lamp is opened, the solidliquid mixture that step (11) obtains is irradiated under xenon lamp
35 ~ 120 minutes, carry out photocatalysis；
(13) after through step (12) photocatalysis, the solidliquid mixture of 5 milliliters of processed steps (12) is extracted, filtering obtains
To clear liquid；
(14) clear liquid for taking 2 milliliters of steps (13) to obtain, it is compound through stalk cellulose-cerium oxide with determined by ultraviolet spectrophotometry
Object light is catalyzed the hexavalent chromium concentration C after reduction treatmente；It calculates through stalk cellulose-cerium oxide compound photo catalytic reduction processing
Hexavalent chromium removal rate=(C/ C after chromate waste water0) * 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, which is characterized in that in step (3), stirring frequency is not less than 200 revs/min.
3. a kind of stalk cellulose according to claim 1-cerium oxide compound photo catalytic reduction processing waste water containing chrome
Method, which is characterized in that in step (6), the quality of the stalk cellulose is 0.05 ~ 0.25 gram, six nitric hydrate ceriums
Quality is 20 ~ 50 milligrams.
4. a kind of stalk cellulose according to claim 1-cerium oxide compound photo catalytic reduction processing waste water containing chrome
Method, which is characterized in that in step (11), mixing time is 30 ~ 60 minutes.
5. a kind of stalk cellulose according to claim 1-cerium oxide compound photo catalytic reduction processing waste water containing chrome
Method, which is characterized in that the power of xenon lamp described in step (12) is 400W.
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