CN106423272B - A kind of load type titania/graphene oxide bead and the preparation method and application thereof - Google Patents
A kind of load type titania/graphene oxide bead and the preparation method and application thereof Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 96
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 56
- 239000011324 bead Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims abstract description 31
- 230000001699 photocatalysis Effects 0.000 claims abstract description 21
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 11
- 239000010439 graphite Substances 0.000 claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims abstract description 9
- 238000001179 sorption measurement Methods 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 7
- 238000010531 catalytic reduction reaction Methods 0.000 claims abstract description 7
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 4
- 239000002351 wastewater Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- 239000003643 water by type Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000006722 reduction reaction Methods 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000007900 aqueous suspension Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000001110 calcium chloride Substances 0.000 claims description 6
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229910002567 K2S2O8 Inorganic materials 0.000 claims description 5
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 238000004900 laundering Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 241001474374 Blennius Species 0.000 claims 1
- 229910021642 ultra pure water Inorganic materials 0.000 claims 1
- 239000012498 ultrapure water Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 abstract description 8
- 229940072056 alginate Drugs 0.000 abstract description 8
- 235000010443 alginic acid Nutrition 0.000 abstract description 8
- 229920000615 alginic acid Polymers 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000661 sodium alginate Substances 0.000 abstract description 2
- 229940005550 sodium alginate Drugs 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- 239000011651 chromium Substances 0.000 description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 229910001430 chromium ion Inorganic materials 0.000 description 3
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 3
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Physical Water Treatments (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of load type titania/graphene oxide bead and the preparation method and application thereof, which includes alginate, and uniform load has the graphene oxide of adsorption capacity and has the nano-titanium dioxide of photocatalytic activity on bead.The specific steps of preparation are as follows: graphene oxide will be made after graphite oxidation and ultrasonic Separation first, then graphene oxide, titanium dioxide and sodium alginate are uniformly mixed with water, mixture is added drop-wise in calcium chloride solution again and prepares uniform bead, finally collect bead and washs to obtain final products.The product has many advantages, such as that raw material sources are extensive, preparation process is simple, are easily industrialized production.The product has good photo catalytic reduction ability to hexavalent chromium.
Description
Technical field
The invention belongs to environment-friendly function materials and water process new technical field, and in particular to and a kind of load type titania/
Graphene oxide bead and the preparation method and application thereof.
Background technique
The more serious area of China's heavy metal pollution, has influenced agricultural product and drinking water safety, the area of especially severe,
Basic farmland is changed to town site.How heavy metal containing sewage is handled, it is ensured that agricultural product and drinking water safety, and
Basic farmland area is no longer contaminated, is the key that solve China's heavy metal pollution.Chromium is relatively common heavy metal, sexavalence and
Trivalent is chromium two kinds of forms common in water body.Cr VI generally exists in water with ionic forms, is easy to move in the environment
It moves and enrichment, toxicity is 100 times bigger than trivalent chromium.Trivalent chromium exists in acid condition with cationic form, and in alkaline item
Hydroxide precipitating is easily formed under part.Therefore, the method for hexavalent chromium wastewater processing is usually first to restore hexavalent chromium
For trivalent chromic ion, then trivalent chromic ion is removed by chemical precipitation method.By hexavalent chrome reduction be trivalent chromium be Cr VI
The first step of wastewater treatment, main method have chemical reduction method and photocatalytic method etc..Photocatalytic method is compared with other methods, tool
Have the advantages that easy to operate, short processing time, at low cost, effect is good.Photochemical catalyst in core status is to photocatalysis effect
It is affected, therefore, developing efficient photochemical catalyst becomes the key of photocatalysis treatment hexavalent chromium wastewater.
Titanium dioxide is common catalysis material, is widely used in fields such as environmental protection, chemical industry, the energy.But titanium dioxide
Titanium is generally nanostructure, and hydrophilic radical is contained on surface, is not easy to separate from water body after the completion of photocatalytic process, limit
Its application in practical projects.It, can be before keeping its photocatalytic activity by titanium dichloride load on suitable carrier
It puts and improves its solid-liquid separation capability.Alginate can be used as the carrier of carried titanium dioxide, can be by titanium dioxide
It is dispersed in alginate, uniform easily separated photocatalysis bead is then made.And then solves titanium dioxide not
Segregative problem.
In the photocatalytic process of hexavalent chromium, hexavalent chromium captures light firstly the need of close photochemical catalyst
It gives birth to electronics and is reduced to trivalent chromic ion.Titanium dioxide and alginate are lower to the adsorption capacity of hexavalent chromium, therefore
Hexavalent chromium is not easy to influence photocatalysis efficiency close to photochemical catalyst.Surface of graphene oxide contains a large amount of active group,
There is stronger adsorption capacity to hexavalent chromium.Graphene oxide and titanium dioxide are added on carrier jointly, can be improved solidifying
The reduction efficiency of hexavalent chromium can be improved to the adsorption capacity of hexavalent chromium in glue bead.In addition, reduzate three
Valence chromium ion can be oxidized graphene and alginate Adsorption.
Summary of the invention
The technical problems to be solved by the present invention are: in view of the problems of the existing technology, developing a kind of efficient and easily dividing
From the load type titania that can be used for photo catalytic reduction hexavalent chromium/graphene oxide bead；And a kind of technique letter
List prepares quick load type titania/graphene oxide bead preparation method；A kind of above-mentioned support type dioxy is also provided
Change the method that titanium/graphene oxide bead is applied to photo catalytic reduction hexavalent chromium.
In order to solve the above technical problems, the invention adopts the following technical scheme: a kind of load type titania/graphite oxide
Alkene bead, which is characterized in that the bead includes alginate, and uniform load has the graphite oxide of adsorption capacity on the bead
Alkene and the nano-titanium dioxide for having photocatalytic activity.
As a general technical idea, the present invention provides a kind of system of load type titania/graphene oxide bead
Preparation Method is that graphene oxide and nano-titanium dioxide are supported in alginate, and the photochemical catalyst of preparation has adsorption energy
Power and photocatalytic activity are easy to be separated by solid-liquid separation and recycle, the specific steps are as follows:
(1) by graphite powder, K2S2O8And P2O5It is small that the reaction 2~8 at 50~100 DEG C is added in 10~50 mL concentrated sulfuric acids
When, the graphite powder, K2S2O8With P2O5Mass ratio be 1:(0.5~2): the mass concentration of (0.5~2), the concentrated sulfuric acid is
90~98%, be subsequently cooled to 20~40 DEG C, 800~1200 mL ultrapure waters be added, place 8~12 hours, by product wash to
Obtain pre-oxidation graphite after neutrality after drying at 40~80 DEG C；
(2) the pre-oxidation graphite that step (1) obtains is added in 200~300 mL concentrated sulfuric acids, adds NaNO3With
KMnO4, the mass concentration of the concentrated sulfuric acid is 90~98%, the pre-oxidation graphite, NaNO3With KMnO4Mass ratio be 1:
(0.5~2): (10~50) are reacted 2~6 hours at 0~5 DEG C, are warming up at 30~40 DEG C and are reacted 1~4 hour, are added
200~800 mL ultrapure waters, react 1~6 hour under the conditions of 80~100 DEG C, be then added 800~1200 mL ultrapure waters and
20~60 mL H2O2, the H2O2Mass concentration is 20~30%, and the reaction was continued 1~6 hour, and obtained product quality is dense
Degree washs for 5~15% HCl solution, is washed with massive laundering to neutrality, and ultrasonic disperse 1~4 hour at 30~60 DEG C obtains
The graphene oxide aqueous suspensions for being 1~10 mg/mL to mass concentration；
(3) the graphene oxide aqueous suspensions that 10~300 mL steps (2) obtain are added to 100~2500 mL ultrapure waters
In, the graphene oxide aqueous suspensions mass concentration is 1~10 mg/mL, 1~25 g titanium dioxide is added, stirs evenly, then
1~30 g sodium alginate is added, heating stirs evenly, obtains mixed liquor within ultrasonic disperse 10~120 minutes；
(4) mixed liquor described in step (3) is added drop-wise to formation in 800~4000 mL calcium chloride solutions with syringe
The uniform bead of grain, the calcium chloride mass concentration are 1~10%, react 2~12 hours at room temperature, bead is collected and washed
Stable load type titania/graphene oxide bead is obtained after washing repeatedly.
The present invention also provides a kind of above-mentioned load type titania/graphene oxide beads to be applied to photo catalytic reduction six
The method of valence chromium ion, comprising the following steps:
Taking a certain amount of hexavalent chromium wastewater and adjusting pH value is 1.0~11.0, and the mass concentration of the hexavalent chromium wastewater is 1
A certain amount of load type titania/graphene oxide bead is added in waste water, in every liter of waste water by~5000 mg/L
Additive amount is calculated as 1 ~ 100 g with load type titania/graphene oxide bead weight in wet base, is gone back under ultraviolet lamp irradiation condition
Original reaction, and controlling reaction temperature is 10~50 DEG C, the reaction time is 0 ~ 24 h, by load type titania/graphene oxide
Bead separation, completes the reduction to hexavalent chromium.
Compared with the prior art, the advantages of the present invention are as follows:
1, the raw material sources that load type titania of the invention/graphene oxide bead uses are extensive and cheap,
It is all common chemical products.
2, load type titania of the invention/graphene oxide bead is easy to separate from solution, can simplify and actually answer
Operating process in, conducive to recycling for bead.
3, load type titania of the invention/graphene oxide bead preparation process is simple, with short production cycle, is easy to
Realize industrialized production.
4, load type titania of the invention/graphene oxide bead is high to the reduction efficiency of Cr VI, is Cr VI
The processing of waste water provides technical support.
Detailed description of the invention
Fig. 1 is load type titania/graphene oxide bead digital photograph of the embodiment of the present invention 1.
Specific embodiment
The present invention is described in further details below with reference to Figure of description and specific embodiment.
Embodiment 1:
A kind of load type titania of the present invention/graphene oxide bead is by graphene oxide and nanometer two
It is titania oxide supported that the photochemical catalyst of preparation has adsorption capacity and photocatalytic activity in alginate, be easy to be separated by solid-liquid separation and
It recycles, the specific steps are as follows:
By 6 g graphite powders, 5 g K2S2O8With 5 g P2O5It is added in the concentrated sulfuric acid that 24 mL mass concentrations are 98%, 80
Reacted 4.5 hours at DEG C, be added 1000 mL ultrapure waters after being cooled to room temperature, after placing 12 hours by obtained product wash to
Pre-oxidation graphene is dried to obtain after neutrality at 60 DEG C；Obtained pre-oxidation graphite, which is added to 240 mL mass concentrations, is
In 98% concentrated sulfuric acid, 5 g NaNO are added3With 30 g KMnO4, reacted 4 hours at 0 DEG C, be warming up at 35 DEG C and react 2
Hour, be added 500 mL ultrapure waters, react 1 hour under the conditions of 98 DEG C, be then added at room temperature 1000 mL ultrapure waters with
The dense H of 40 mL2O2, the reaction was continued 2 hours, and obtained product is washed with the HCl solution that mass concentration is 10%, uses massive laundering
It washs to neutrality and adds water constant volume, obtain within ultrasonic disperse 2 hours at 50 DEG C the graphene oxide water that mass concentration is 5 mg/mL
Suspension.
60 mL graphene oxide aqueous suspensions are added in 300 mL ultrapure waters, the graphene oxide aqueous suspensions quality
Concentration is 5 mg/mL, and 4.5 g titanium dioxide are added, stirs evenly, adds 4.5 g sodium alginates, heats, stirs evenly, and is surpassed
Sound disperses to obtain mixed liquor in 30 minutes；By mixed liquor with syringe be added drop-wise in 1200 mL calcium chloride solutions formed particle it is uniform
Bead, the calcium chloride mass concentration be 4%, at room temperature react 4 hours, bead is collected and wash repeatedly after obtain surely
Fixed bead.
Load type titania obtained above/graphene oxide bead digital photograph is as shown in Figure 1, its appearance is in ash
Color, the uniform particle sizes of bead.
Embodiment 2:
Load type titania of the invention/graphene oxide bead for the Cr VI in photo catalytic reduction waste water from
Son, comprising the following steps:
It is 1 L, initial concentration that load type titania made from embodiment 1/graphene oxide bead, which is added to volume,
In hexavalent chromium wastewater for 20 mg/L, the additive amount in every liter of waste water is with load type titania/graphene oxide bead weight in wet base
Amount is calculated as 10 g, six wastewater samples to be processed that pH value variation range is 2 ~ 7 is configured to respectively, under ultraviolet lamp irradiation condition
Reduction reaction is carried out, and controlling reaction temperature is 25 DEG C, the reaction time is 12 h, with the mode of filtering by support type titanium dioxide
Titanium/graphene oxide bead separation, completes the reduction to hexavalent chromium.It is not gone back in determined by ultraviolet spectrophotometry waste water
The amount of former hexavalent chromium, the results are shown in Table 1 for the removal rate of calculating:
Influence of the table 1:pH value to hexavalent chromium in load type titania/graphene oxide bead reductive water
| PH value | 2 | 3 | 4 | 5 | 6 | 7 |
| Hexavalent chromium removal rate (%) | 99 | 79 | 43 | 26 | 21 | 16 |
As shown in Table 1, as pH value increases, load type titania/graphene oxide bead goes back hexavalent chromium
Former efficiency reduces, and degradation rate reaches 99% when pH value is 2.
Embodiment 3:
Load type titania of the invention/graphene oxide bead for the Cr VI in photo catalytic reduction waste water from
Son, comprising the following steps:
It is 1 L, initial concentration that load type titania made from embodiment 1/graphene oxide bead, which is added to volume,
In hexavalent chromium wastewater for 20 mg/L, initial pH value 2, the additive amount in every liter of waste water is with load type titania/oxidation stone
Black alkene bead wet weight is calculated as 5,10,20 g, and reduction reaction is carried out under ultraviolet lamp irradiation condition, and controlling reaction temperature is 25
DEG C, the reaction time is 12 h, separates load type titania/graphene oxide bead with the mode of filtering, completes to sexavalence
The reduction of chromium ion.With the amount for the hexavalent chromium not being reduced in determined by ultraviolet spectrophotometry waste water, the removal rate of calculating
The results are shown in Table 2:
Table 2: influence of the dosage to hexavalent chromium in load type titania/graphene oxide bead reductive water
| Dosage (g) | 5 | 10 | 20 |
| Hexavalent chromium removal rate (%) | 78 | 99 | 100 |
As shown in Table 2, for ultraviolet light irradiation after 12 hours, load type titania/graphene oxide bead dosage is 10
Hexavalent chromium can be reduced completely substantially when g and 20 g, and dosage be 5 g when only have 78% Cr VI to be reduced.
The above is only the preferred embodiment of the present invention, protection scope of the present invention is not limited merely to above-described embodiment,
Various process programs with present inventive concept without substantial differences are in protection scope of the present invention.
Claims (1)
1. a kind of load type titania/graphene oxide bead is applied to the method for photo catalytic reduction hexavalent chromium, including
Following steps:
Taking a certain amount of hexavalent chromium wastewater and adjusting pH value is 1.0~11.0, the mass concentration of the hexavalent chromium wastewater is 1~
A certain amount of load type titania/graphene oxide bead is added in waste water, adding in every liter of waste water by 5000 mg/L
Dosage is calculated as 1 ~ 100 g with load type titania/graphene oxide bead weight in wet base, is restored under ultraviolet lamp irradiation condition
Reaction, and controlling reaction temperature is 10~50 DEG C, the reaction time is 12 ~ 24 h, and load type titania/graphene oxide is small
Ball separation, completes the reduction to hexavalent chromium；
The load type titania/graphene oxide bead is that graphene oxide and nano-titanium dioxide are supported on seaweed
In hydrochlorate, the photochemical catalyst of preparation has adsorption capacity and photocatalytic activity, is easy to be separated by solid-liquid separation and recycle, specific steps are such as
Under:
(1) by graphite powder, K2S2O8And P2O5It is added in 10~50 mL concentrated sulfuric acids and is reacted 2~8 hours at 50~100 DEG C,
The graphite powder, K2S2O8With P2O5Mass ratio be 1:(0.5~2): (0.5~2), the mass concentration of the concentrated sulfuric acid is 90~
98%, 20~40 DEG C are subsequently cooled to, 800~1200 mL ultrapure waters are added, places 8~12 hours, product is washed to neutrality
Obtain pre-oxidation graphite after drying at 40~80 DEG C afterwards；
(2) the pre-oxidation graphite that step (1) obtains is added in 200~300 mL concentrated sulfuric acids, adds NaNO3And KMnO4,
The mass concentration of the concentrated sulfuric acid is 90~98%, the pre-oxidation graphite, NaNO3With KMnO4Mass ratio be 1:(0.5~2):
(10~50) are reacted 2~6 hours at 0~5 DEG C, are warming up at 30~40 DEG C and are reacted 1~4 hour, are added 200~800
ML ultrapure water reacts 1~6 hour under the conditions of 80~100 DEG C, 800~1200 mL ultrapure waters and 20~60 mL is then added
H2O2, the H2O2Mass concentration is 20~30%, and the reaction was continued 1~6 hour, is 5~15% by obtained product mass concentration
HCl solution washing, washed with massive laundering to neutrality, and ultrasonic disperse 1~4 hour at 30~60 DEG C obtains mass concentration
For the graphene oxide aqueous suspensions of 1~10 mg/mL；
(3) the graphene oxide aqueous suspensions that 10~300 mL steps (2) obtain are added in 100~2500 mL ultrapure waters, institute
Stating graphene oxide aqueous suspensions mass concentration is 1~10 mg/mL, and 1~25 g titanium dioxide is added, stirs evenly, adds 1
~30 g sodium alginates, heating, stir evenly, obtain mixed liquor within ultrasonic disperse 10~120 minutes；
(4) by mixed liquor described in step (3) with syringe be added drop-wise in 800~4000 mL calcium chloride solutions formed particle it is equal
Even bead, the calcium chloride mass concentration are 1~10%, react 2~12 hours at room temperature, bead is collected and is washed more
Stable load type titania/graphene oxide bead is obtained after secondary.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610855388.2A CN106423272B (en) | 2016-09-28 | 2016-09-28 | A kind of load type titania/graphene oxide bead and the preparation method and application thereof |
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| CN108295827A (en) * | 2017-12-23 | 2018-07-20 | 佛山科学技术学院 | A kind of method of graphene-supported visible light-responsible titanium dioxide |
| CN108246337B (en) * | 2018-02-05 | 2021-04-09 | 中南林业科技大学 | Photocatalytic pellet for mining area wastewater remediation and preparation method thereof |
| CN108579628A (en) * | 2018-04-25 | 2018-09-28 | 北京师范大学 | A kind of kappa-carrageenan/graphene oxide gel bead and its preparation method and application |
| CN108837851B (en) * | 2018-07-12 | 2021-08-13 | 湖北科技学院 | Nano TiO for efficiently adsorbing-reducing highly toxic hexavalent chromium ions2Pre-radiation grafting synthesis method of base photocatalyst |
| CN111054395B (en) * | 2019-12-10 | 2021-06-25 | 中国环境科学研究院 | Visible-light-driven photocatalyst, and preparation method and application thereof |
| CN114950498B (en) * | 2022-05-16 | 2023-12-22 | 江苏农林职业技术学院 | Recyclable efficient photocatalytic material and preparation method and application thereof |
| CN115212868B (en) * | 2022-08-31 | 2023-08-18 | 四川大学 | Nano metal particle loaded reduced graphene oxide aerogel and preparation method thereof |
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