CN106423272A - Supported titanium dioxide/graphene oxide pellets and preparation method and application thereof - Google Patents
Supported titanium dioxide/graphene oxide pellets and preparation method and application thereof Download PDFInfo
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- CN106423272A CN106423272A CN201610855388.2A CN201610855388A CN106423272A CN 106423272 A CN106423272 A CN 106423272A CN 201610855388 A CN201610855388 A CN 201610855388A CN 106423272 A CN106423272 A CN 106423272A
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- graphene oxide
- bead
- load type
- type titania
- mass concentration
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 106
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 59
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000008188 pellet Substances 0.000 title abstract 7
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims abstract description 32
- 230000001699 photocatalysis Effects 0.000 claims abstract description 22
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 12
- 239000010439 graphite Substances 0.000 claims abstract description 12
- 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 claims abstract description 9
- 229940072056 alginate Drugs 0.000 claims abstract description 9
- 235000010443 alginic acid Nutrition 0.000 claims abstract description 9
- 229920000615 alginic acid Polymers 0.000 claims abstract description 9
- 230000009467 reduction Effects 0.000 claims abstract description 9
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910001430 chromium ion Inorganic materials 0.000 claims abstract description 4
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 4
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- 239000011324 bead Substances 0.000 claims description 51
- 239000002351 wastewater Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000006722 reduction reaction Methods 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 230000002829 reductive effect Effects 0.000 claims description 10
- 235000011149 sulphuric acid Nutrition 0.000 claims description 10
- 239000003643 water by type Substances 0.000 claims description 10
- 239000007900 aqueous suspension Substances 0.000 claims description 8
- 239000011941 photocatalyst 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
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000001117 sulphuric acid Substances 0.000 claims description 6
- 229910002567 K2S2O8 Inorganic materials 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 5
- 230000004044 response Effects 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000004900 laundering Methods 0.000 claims description 3
- -1 place 8~12 hours Substances 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 2
- 239000012498 ultrapure water Substances 0.000 claims description 2
- 241000195474 Sargassum Species 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 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 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 239000000661 sodium alginate Substances 0.000 abstract 1
- 229940005550 sodium alginate Drugs 0.000 abstract 1
- 239000011651 chromium Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 5
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 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
- 150000001336 alkenes Chemical class 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
- 238000004519 manufacturing process 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
- 230000009286 beneficial effect Effects 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
- 230000008859 change Effects 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
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 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
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000010865 sewage 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
-
- 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
Landscapes
- 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 invention relates to supported titanium dioxide/graphene oxide pellets and a preparation method and application of the supported titanium dioxide/graphene oxide pellets. The pellets comprise alginate, and graphene oxide with adsorption capacity and nanometer titanium dioxide with photocatalytic activity are uniformly supported on the pellets. The preparation method particularly comprises the following steps: firstly, oxidizing and ultrasonically separating graphite to prepare the graphene oxide, and then uniformly mixing the graphene oxide, titanium dioxide and sodium alginate with water, adding a mixture drop by drop to a calcium chloride solution to prepare uniform pellets, finally collecting the pellets and washing to obtain the final products. The products have the advantages of wide sources of raw materials, simple preparation process, easy industrial production and the like, and further have good photocatalytic reduction abilities for hexavalent chromium ions.
Description
Technical field
The invention belongs to environment-friendly function material and water process new technical field and in particular to a kind of load type titania/
Graphene oxide bead and preparation method and application.
Background technology
The more serious area of China's heavy metal pollution, has had influence on agricultural product and drinking water safety, the area of especially severe,
Basic farmland is changed to town site.How to process heavy metal containing sewage it is ensured that agricultural product and drinking water safety, and
Basic farmland area is no longer contaminated, is the key solving China's heavy metal pollution.Chromium is relatively common heavy metal, sexavalence and
Trivalent is two kinds of common in water body forms of chromium.Cr VI is general in water to be existed it is easy to move in the environment with ionic formses
Move and be enriched with, big 100 times than trivalent chromium of its toxicity.Trivalent chromium is existed with cationic form in acid condition, and in alkaline bar
It is easily formed hydroxide precipitation under part.Therefore, hexavalent chromium is usually reduced by hexavalent chromium wastewater is processed method first
For trivalent chromic ion, then by chemical precipitation method, trivalent chromic ion is removed.Hexavalent chrome reduction is Cr VI for trivalent chromium
The first step of wastewater treatment, main method has chemical reduction method and photocatalytic method etc..Photocatalytic method, compared with other methods, has
Have the advantages that easy and simple to handle, process time is short, low cost, effect are good.The photocatalyst being in core status is to photocatalysis effect
Impact is larger, and therefore, developing efficient photocatalyst becomes the key of photocatalysis treatment hexavalent chromium wastewater.
Titanium dioxide is conventional catalysis material, and it is widely used in fields such as environmental protection, chemical industry, the energy.But titanium dioxide
Titanium is generally nanostructured, and hydrophilic group is contained on surface, is difficult to separate from water body, limits after the completion of photocatalytic process
Its application in Practical Project.By titanium dichloride load on suitable carrier, can be before keeping its photocatalytic activity
Put its solid-liquid separation capability of raising.Alginate can be used to the carrier as carried titanium dioxide, can be by titanium dioxide
It is dispersed in alginate, then make uniformly easily separated photocatalysis bead.And then solve titanium dioxide not
Segregative problem.
In the photocatalytic process of hexavalent chromium, hexavalent chromium is firstly the need of close photocatalyst, and then captures light
Give birth to electronics and be reduced to trivalent chromic ion.Titanium dioxide and alginate are relatively low to the absorbability of hexavalent chromium, therefore
Hexavalent chromium is not easy to, near photocatalyst, affect photocatalysis efficiency.Surface of graphene oxide contains substantial amounts of active group,
There is stronger absorbability to hexavalent chromium.Graphene oxide and titanium dioxide are added on carrier jointly, can improve solidifying
The absorbability to hexavalent chromium for the glue bead, and then the reduction efficiency of hexavalent chromium can be improved.Additionally, reduzate three
Valency chromium ion can be with oxidized Graphene and alginate Adsorption.
Content of the invention
The technical problem to be solved is：The problem existing for prior art, a kind of efficient and easy point of exploitation
From the load type titania/graphene oxide bead that can be used for photo catalytic reduction hexavalent chromium；And a kind of letter of technique
Preparation method that is single, preparing quick load type titania/graphene oxide bead；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.
For solving above-mentioned technical problem, the present invention employs the following technical solutions：A kind of load type titania/graphite oxide
It is characterised in that described bead includes alginate, on described bead, uniform load has the graphite oxide of absorbability to alkene bead
Alkene and the nano titanium oxide having photocatalytic activity.
As a total technology design, the present invention provides a kind of system of load type titania/graphene oxide bead
Preparation Method, is that graphene oxide and nano titanium oxide are supported in alginate, the photocatalyst of preparation has energy of adsorption
Power and photocatalytic activity, it is easy to solid-liquid separation and recycling, comprise the following steps that：
（1）By graphite powder, K2S2O8And P2O5It is added in 10～50 mL concentrated sulphuric acids and react 2～8 hours at 50～100 DEG C,
Described graphite powder, K2S2O8With P2O5Mass ratio be 1：（0.5～2）：（0.5～2）, the mass concentration of described concentrated sulphuric acid is 90～
98%, it is subsequently cooled to 20～40 DEG C, adds 800～1200 mL ultra-pure waters, place 8～12 hours, product is washed to neutrality
Obtain after being dried at 40～80 DEG C afterwards pre-oxidizing graphite；
（2）By step（1）The pre-oxidation graphite obtaining is added in 200～300 mL concentrated sulphuric acids, adds NaNO3And KMnO4,
The mass concentration of described concentrated sulphuric acid is 90～98%, described pre-oxidation graphite, NaNO3With KMnO4Mass ratio be 1：（0.5～2）：
（10～50）, react 2～6 hours at 0～5 DEG C, be warmed up to and react 1～4 hour at 30～40 DEG C, add 200～800
ML ultra-pure water, reacts 1～6 hour under the conditions of 80～100 DEG C, is subsequently adding 800～1200 mL ultra-pure waters and 20～60 mL
H2O2, described H2O2Mass concentration is 20～30%, continues reaction 1～6 hour, and the product obtaining mass concentration is 5～15%
HCl solution washing, washed to neutrality with massive laundering, and ultrasonic disperse obtain mass concentration in 1～4 hour at 30～60 DEG C
Graphene oxide aqueous suspensions for 1～10 mg/mL；
（3）By 10～300 mL steps（2）The graphene oxide aqueous suspensions obtaining are added in 100～2500 mL ultra-pure waters, institute
Stating graphene oxide aqueous suspensions mass concentration is 1～10 mg/mL, adds 1～25 g titanium dioxide, stirs, add 1
～30 g sodium alginates, heating, stir, ultrasonic disperse obtains mixed liquor in 10～120 minutes；
（4）By step（3）It is equal that described mixed liquor syringe is added drop-wise to formation granule in 800～4000 mL calcium chloride solutions
Even bead, described calcium chloride mass concentration is 1～10%, reacts 2～12 hours at room temperature, bead is collected and washs many
Stable load type titania/graphene oxide bead is obtained after secondary.
The present invention also provides a kind of above-mentioned load type titania/graphene oxide bead to be applied to photo catalytic reduction six
The method of valency chromium ion, comprises the following steps：
Taking a certain amount of hexavalent chromium wastewater and to adjust pH value be 1.0～11.0, the mass concentration of described hexavalent chromium wastewater is 1～
5000 mg/L, a certain amount of load type titania/graphene oxide bead are added in waste water, adding in every liter of waste water
Dosage is calculated as 1 ~ 100 g with load type titania/graphene oxide bead weight in wet base, is reduced under the conditions of ultra violet lamp
Reaction, and controlling reaction temperature is 10～50 DEG C, the response time is 0 ~ 24 h, will be little for load type titania/graphene oxide
Ball separates, and completes the reduction to hexavalent chromium.
Compared with prior art, it is an advantage of the current invention that：
1st, the raw material sources that the load type titania of the present invention/graphene oxide bead uses are extensive and cheap, are all
Conventional chemical products.
2nd, the load type titania of the present invention/graphene oxide bead is easy to separate from solution, can simplify actual answering
With in operating process, recycling beneficial to bead.
3rd, the preparation process is simple of the load type titania of the present invention/graphene oxide bead, with short production cycle it is easy to
Realize industrialized production.
4th, the load type titania of the present invention/graphene oxide bead is high to chromic reduction efficiency, is Cr VI
The process of waste water provides technical support.
Brief description
Fig. 1 is the digital photograph of the load type titania/graphene oxide bead of the embodiment of the present invention 1.
Specific embodiment
Below with reference to Figure of description and specific embodiment, the present invention is described in further details.
Embodiment 1：
A kind of load type titania of the present invention/graphene oxide bead, is by graphene oxide and nanometer titanium dioxide
Titanium is supported in alginate, the photocatalyst of preparation there is absorbability and photocatalytic activity it is easy to solid-liquid separation and again profit
With comprising the following steps that：
By 6 g graphite powders, 5 g K2S2O8With 5 g P2O5Being added to 24 mL mass concentrations is in 98% concentrated sulphuric acid, at 80 DEG C
Lower reaction 4.5 hours, adds 1000 mL ultra-pure waters after being cooled to room temperature, after placing 12 hours by the product obtaining wash in
It is dried to obtain pre-oxidation Graphene at 60 DEG C after property；It is 98% that the pre-oxidation obtaining graphite is added to 240 mL mass concentrations
Concentrated sulphuric acid in, add 5 g NaNO3With 30 g KMnO4, react 4 hours at 0 DEG C, be warmed up to reaction 2 at 35 DEG C little
When, add 500 mL ultra-pure waters, react 1 hour under the conditions of 98 DEG C, then add 1000 mL ultra-pure waters and 40 at room temperature
The dense H of mL2O2, continue reaction 2 hours, the product obtaining washed with the HCl solution that mass concentration is 10%, is washed with massive laundering
To the neutral and constant volume that adds water, at 50 DEG C, ultrasonic disperse obtains the graphene oxide water that mass concentration is 5 mg/mL for 2 hours and hangs
Liquid.
60 mL graphene oxide aqueous suspensions are added in 300 mL ultra-pure waters, described graphene oxide aqueous suspensions quality
Concentration is 5 mg/mL, adds 4.5 g titanium dioxide, stirs, add 4.5 g sodium alginates, and heating stirs, and surpasses
Sound dispersion obtains mixed liquor in 30 minutes；Mixed liquor syringe is added drop-wise to formation granule in 1200 mL calcium chloride solutions uniform
Bead, described calcium chloride mass concentration is 4%, reacts 4 hours at room temperature, bead is collected and washs obtain after repeatedly steady
Fixed bead.
The digital photograph of above-mentioned prepared load type titania/graphene oxide bead is as shown in figure 1, its outward appearance is in ash
Color, the uniform particle sizes of bead.
Embodiment 2：
The load type titania of the present invention/graphene oxide bead is used for the hexavalent chromium in photo catalytic reduction waste water, bag
Include following steps：
It is 1 L that load type titania/graphene oxide bead that embodiment 1 is obtained is added to volume, and initial concentration is 20
In the hexavalent chromium wastewater of mg/L, the addition in every liter of waste water is with load type titania/graphene oxide bead weight in wet base gauge
For 10 g, it is configured to six pending wastewater samples that pH value excursion is 2 ~ 7 respectively, carries out under the conditions of ultra violet lamp
Reduction reaction, and controlling reaction temperature is 25 DEG C, the response time is 12 h, with the mode that filters by load type titania/oxygen
Graphite alkene bead separates, and completes the reduction to hexavalent chromium.Be not reduced in determined by ultraviolet spectrophotometry waste water
The amount of hexavalent chromium, the clearance result of calculating is as shown in table 1：
Table 1：The impact to hexavalent chromium in load type titania/graphene oxide bead reductive water for the pH value
| PH value | 2 | 3 | 4 | 5 | 6 | 7 |
| Hexavalent chromium removal rate（%） | 99 | 79 | 43 | 26 | 21 | 16 |
As shown in Table 1, raise with pH value, load type titania/graphene oxide bead is imitated to the reduction of hexavalent chromium
Rate reduces, and pH value is that when 2, degradation rate reaches 99%.
Embodiment 3：
The load type titania of the present invention/graphene oxide bead is used for the hexavalent chromium in photo catalytic reduction waste water, bag
Include following steps：
It is 1 L that load type titania/graphene oxide bead that embodiment 1 is obtained is added to volume, and initial concentration is 20
In the hexavalent chromium wastewater of mg/L, original ph is 2, and the addition in every liter of waste water is with load type titania/graphene oxide
Bead wet weight is calculated as 5,10,20 g, carries out reduction reaction under the conditions of ultra violet lamp, and controlling reaction temperature is 25 DEG C,
Response time is 12 h, is separated load type titania/graphene oxide bead with the mode filtering, complete to Cr VI from
The reduction of son.The amount of the hexavalent chromium with not being reduced in determined by ultraviolet spectrophotometry waste water, the clearance result of calculating
As shown in table 2：
Table 2：The impact to hexavalent chromium in load type titania/graphene oxide bead reductive water for the dosage
| Dosage（g） | 5 | 10 | 20 |
| Hexavalent chromium removal rate（%） | 78 | 99 | 100 |
As shown in Table 2, ultra violet lamp is after 12 hours, load type titania/graphene oxide bead dosage be 10 g and
During 20 g, hexavalent chromium can be reduced completely substantially, and the Cr VI that dosage is during 5 g only 78% is 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,
With the various process programs of present inventive concept no substantial differences all in protection scope of the present invention.
Claims (2)
1. a kind of load type titania/graphene oxide bead is it is characterised in that described bead includes alginate, described
On bead, uniform load has the graphene oxide of absorbability and has the nano titanium oxide of photocatalytic activity,
Described load type titania/graphene oxide bead is that graphene oxide and nano titanium oxide are supported on Sargassum
In hydrochlorate, the photocatalyst of preparation has absorbability and photocatalytic activity it is easy to solid-liquid separation and recycling, and concrete steps are such as
Under：
（1）By graphite powder, K2S2O8And P2O5It is added in 10～50 mL concentrated sulphuric acids and react 2～8 hours at 50～100 DEG C,
Described graphite powder, K2S2O8With P2O5Mass ratio be 1：（0.5～2）：（0.5～2）, the mass concentration of described concentrated sulphuric acid is 90～
98%, it is subsequently cooled to 20～40 DEG C, adds 800～1200 mL ultra-pure waters, place 8～12 hours, product is washed to neutrality
Obtain after being dried at 40～80 DEG C afterwards pre-oxidizing graphite；
（2）By step（1）The pre-oxidation graphite obtaining is added in 200～300 mL concentrated sulphuric acids, adds NaNO3And KMnO4,
The mass concentration of described concentrated sulphuric acid is 90～98%, described pre-oxidation graphite, NaNO3With KMnO4Mass ratio be 1：（0.5～2）：
（10～50）, react 2～6 hours at 0～5 DEG C, be warmed up to and react 1～4 hour at 30～40 DEG C, add 200～800
ML ultra-pure water, reacts 1～6 hour under the conditions of 80～100 DEG C, is subsequently adding 800～1200 mL ultra-pure waters and 20～60 mL
H2O2, described H2O2Mass concentration is 20～30%, continues reaction 1～6 hour, and the product obtaining mass concentration is 5～15%
HCl solution washing, washed to neutrality with massive laundering, and ultrasonic disperse obtain mass concentration in 1～4 hour at 30～60 DEG C
Graphene oxide aqueous suspensions for 1～10 mg/mL；
（3）By 10～300 mL steps（2）The graphene oxide aqueous suspensions obtaining are added in 100～2500 mL ultra-pure waters, institute
Stating graphene oxide aqueous suspensions mass concentration is 1～10 mg/mL, adds 1～25 g titanium dioxide, stirs, add 1
～30 g sodium alginates, heating, stir, ultrasonic disperse obtains mixed liquor in 10～120 minutes；
（4）By step（3）It is equal that described mixed liquor syringe is added drop-wise to formation granule in 800～4000 mL calcium chloride solutions
Even bead, described calcium chloride mass concentration is 1～10%, reacts 2～12 hours at room temperature, bead is collected and washs many
Stable load type titania/graphene oxide bead is obtained after secondary.
2. a kind of load type titania as claimed in claim 1/graphene oxide bead is applied to photo catalytic reduction sexavalence
The method of chromium ion, comprises the following steps：
Taking a certain amount of hexavalent chromium wastewater and to adjust pH value be 1.0～11.0, the mass concentration of described hexavalent chromium wastewater is 1～
5000 mg/L, a certain amount of load type titania/graphene oxide bead are added in waste water, adding in every liter of waste water
Dosage is calculated as 1 ~ 100 g with load type titania/graphene oxide bead weight in wet base, is reduced under the conditions of ultra violet lamp
Reaction, and controlling reaction temperature is 10～50 DEG C, the response time is 0 ~ 24 h, will be little for load type titania/graphene oxide
Ball separates, and completes the reduction to hexavalent chromium.
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