CN109761427A - A kind of method of resource for the sewage producing the generation of graphene factory - Google Patents
A kind of method of resource for the sewage producing the generation of graphene factory Download PDFInfo
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- CN109761427A CN109761427A CN201910160439.3A CN201910160439A CN109761427A CN 109761427 A CN109761427 A CN 109761427A CN 201910160439 A CN201910160439 A CN 201910160439A CN 109761427 A CN109761427 A CN 109761427A
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Abstract
The invention discloses a kind of method of resource of sewage for producing the generation of graphene factory, comprising the following steps: Step 1: the pH for adjusting sewage adds ZnO/La to acidity2O3Composite catalyst；It is irradiated Step 2: sewage is placed under ultraviolet light, is filtered after irradiation, is dry, obtaining crude product；Step 3: washing the ZnO/La in removal crude product using strong acid2O3Composite catalyst, then it is washed to neutrality, it filters, obtain photo-reduction product after drying；Step 4: the second intermediate product of calcining, obtains product type graphene.The present invention have many advantages, such as easy to operate, easily controllable, mild condition, it is highly-safe, low for equipment requirements, be easy to large-scale recovery.
Description
Technical field
The invention belongs to reutilization of the sewage fields, are related to the method for resource more particularly to a kind of production stone of a kind of sewage
The method of resource for the sewage that Mo Xi factory generates.
Background technique
With the extensive use of graphene, produces the sewage that graphene generates and increasingly increase, for graphene wastewater treatment
Technique it is few, and wastewater treatment be not easy it is up to standard.A kind of current graphene production wastewater treatment system includes that pretreatment is single
Member, filter element and evaporative crystallization unit reach the zero-emission for guaranteeing graphene production waste water and guarantee graphene production waste water
The purpose that high efficiente callback utilizes, but this process is various, takes up a large area, complex process.
Summary of the invention
The present invention provides a kind of method of resource of sewage for producing the generation of graphene factory, to overcome lacking for the prior art
It falls into.
To achieve the above object, the present invention provides a kind of method of resource of sewage for producing the generation of graphene factory, packet
Include following steps: Step 1: the pH for adjusting sewage adds ZnO/La to acidity2O3Composite catalyst；Step 2: sewage is set
It is irradiated under ultraviolet light, is filtered after irradiation, is dry, obtaining crude product；Step 3: being washed in removal crude product using strong acid
ZnO/La2O3Composite catalyst, then it is washed to neutrality, it filters, obtain photo-reduction product after drying；Step 4: in calcining second
Between product, obtain product type graphene.
Further, the present invention provides a kind of method of resource of sewage for producing the generation of graphene factory, can also have
Such feature: where solid particle and ZnO/La in step 1, in sewage2O3The mass ratio of composite catalyst is 20:1-
4:1。
Wherein, the quality of the solid particle in sewage is 0.2-0.6g, ZnO/La2O3The quality of composite catalyst is 10-
150mg。
Further, the present invention provides a kind of method of resource of sewage for producing the generation of graphene factory, can also have
Such feature: where ZnO/La2O3Composite catalyst is prepared by sol-gel method, La2O3Quality doping ratio
For 0.01-3%.
Further, the present invention provides a kind of method of resource of sewage for producing the generation of graphene factory, can also have
Such feature: where in step 1, the pH value of sewage is adjusted to 3-6 using acid solution.
Further, the present invention provides a kind of method of resource of sewage for producing the generation of graphene factory, can also have
Such feature: where in step 2, the wavelength of ultraviolet light is 185-400nm.
Further, the present invention provides a kind of method of resource of sewage for producing the generation of graphene factory, can also have
Such feature: where in step 2, the irradiation time of ultraviolet light is 10-28 days.
Further, the present invention provides a kind of method of resource of sewage for producing the generation of graphene factory, can also have
Such feature: where in step 2, filtered filter cake is dried in a vacuum drying oven, and drying temperature is 60-100 DEG C, is done
The dry time is 6-24h；Filtered to dry in a vacuum drying oven in step 3, drying temperature is 60-100 DEG C, drying time
For 6-24h.
Further, the present invention provides a kind of method of resource of sewage for producing the generation of graphene factory, can also have
Such feature: where in step 4, photo-reduction product is placed in tube furnace, is calcined under nitrogen protection, calcining temperature
Degree is 200-500 DEG C, calcination time 2-6h.
The beneficial effects of the present invention are: the present invention provides a kind of recycling side of sewage for producing the generation of graphene factory
Method has used environment amenable ZnO/La2O3Composite catalyst is as photochemical catalyst, ZnO/La2O3Composite catalyst is insoluble in
Water will not generate pollution to environment, avoid and additional manpower and material resources be spent to carry out subsequent processing.Simultaneously using ultraviolet radioactive
Method reduction makes the sewage for producing the generation of graphene factory obtain recycling, and the solid particle in sewage is converted into hydroxyl and C
The photo-reduction product of=C, can be used as optical material, be also used as saturable absorber, realize the quilt of high pulse energy output
Dynamic Q-switched laser, is a kind of potential pulsed laser material；Calcined product contains only the class of C=C, C-C, O-H and C-H
Graphene, can be used as battery electrode material, and the recycling of resource can be achieved in two kinds of products.Entire resource reclaim process, operation
Simply, easily controllable, mild condition is highly-safe, low for equipment requirements, is easy to large-scale recovery.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of the solid particle of sewage, crude product, photo-reduction product and product in embodiment 1；
Fig. 2 a is the scanning electron microscope (SEM) photograph of the solid particle of sewage in embodiment 1；
Fig. 2 b is the scanning electron microscope (SEM) photograph of crude product in embodiment 1；
Fig. 2 c is the scanning electron microscope (SEM) photograph of photo-reduction product in embodiment 1；
Fig. 2 d is the scanning electron microscope (SEM) photograph of product in embodiment 1.
Specific embodiment
The present invention is further explained in the light of specific embodiments.
Embodiment 1
The present embodiment provides a kind of method of resource of sewage for producing the generation of graphene factory, comprising the following steps:
Step 1: taking trade effluent 200mL, the quality of solid particle is 0.2g in sewage.Wherein, the solid particle is main
For graphene oxide.
Adjust the pH=3 of sewage.Wherein it is possible to adjust the pH value of sewage using hydrochloric acid solution.
Then, 10mg ZnO/La is added2O3Composite catalyst stirs evenly.ZnO/La2O3Composite catalyst passes through molten
Glue-gel method is prepared, La2O3Quality doping ratio be 1.5%.
Step 2: sewage is placed under wavelength X=185nm ultraviolet light, irradiate 10 days.After the completion of irradiation, filtering will be filtered
Cake is placed in a vacuum drying oven drying and goes to remove water, and drying temperature is 80 DEG C, and drying time 12h obtains crude product.
Wherein, the power of ultraviolet source is 5W.
Step 3: washing the ZnO/La in removal crude product using excessive strong acid2O3Composite catalyst.Wherein, strong acid can
Using hydrochloric acid, sulfuric acid or nitric acid etc..Excessive strong acid refers to, more than the ZnO/La that can wash away addition2O3The strong acid of composite catalyst
Amount, with guarantee wash away ZnO/La completely2O3Composite catalyst.
Then, neutrality is washed to using distilled water, then filtered, filter cake is placed in a vacuum drying oven drying and goes to remove water, is done
Dry temperature is 80 DEG C, and drying time 12h obtains photo-reduction product.
Step 4: photo-reduction product is placed in tube furnace, is calcined under nitrogen protection, calcination temperature is 200 DEG C,
Calcination time is 2h, obtains product black powder class graphene, and the quality of product type graphene is 0.16g.
The photo-reduction product and step that the crude product that obtains respectively to the solid particle in sewage, step 2, step 3 obtain
Rapid four obtained products carry out infrared, scanning electron microscope and elemental analysis detection.
Fig. 1 is the infrared spectrogram of the solid particle of sewage, crude product, photo-reduction product and product, wherein spectrum a, b,
C, d is respectively the infrared spectroscopy of the solid particle of sewage, crude product, photo-reduction product and product.Fig. 2 a, 2b, 2c and 2d difference
For the solid particle of sewage, crude product, photo-reduction product and product scanning electron microscope (SEM) photograph.Following table is the solid particle, thick of sewage
The Elemental analysis data of product, photo-reduction product and product, wherein RmFor the molar ratio of O and H.
The solid particle of sewage, crude product, photo-reduction product and product Elemental analysis data
| Sample | C (mass percent wt%) | H (mass percent wt%) | Rm |
| The solid particle of sewage | 49.57 | 2.76 | 1.08 |
| Crude product | 26.30 | 2.33 | / |
| Photo-reduction product | 61.30 | 2.35 | 0.97 |
| Product | 61.05 | 1.40 | 1.68 |
As shown in figure 1 shown in spectrum c, photo-reduction product is in 3425,1617 and 1203cm-1The absorption peak at place is respectively belonging to O-
H, the stretching vibration of C=C and C-O, with document [Zhang et al.Preparation of large-size graphene
oxide-like with hydroxyl groups and its optoelectronic
Properties.Opt.Mater.75 (2018) 561-566.] in the class graphene oxide GOLH containing hydroxyl surface official
It can roll into a ball identical.As shown in Figure 2 c, photo-reduction product has the class graphite oxide containing hydroxyl in lamellar structure, with above-mentioned document
The layer structure of alkene GOLH is similar.Therefore, the photo-reduction product that step 3 obtains can be used as optical material.
Shown in spectrum d, Fig. 2 d and table 1 as shown in figure 1, product is the class graphene with two-dimensional system.
Embodiment 2-70
Embodiment 2-70 provides a kind of method of resource of sewage for producing the generation of graphene factory, specific steps and implementation
Example 1 is essentially identical, and difference is only that the operating condition of each step, the specific data of embodiment 2-70 are as shown in the table, wherein step
Rapid two is identical with the drying condition in step 3, as the drying temperature in following table and drying time.
The specific data of embodiment 2-70
In embodiment 2-70, solid particle, crude product, photo-reduction product and the infrared spectroscopy of product of sewage, scanning are electric
Mirror and Elemental analysis data are approximate with embodiment 1, therefore omit.
Claims (8)
1. a kind of method of resource for the sewage for producing the generation of graphene factory, it is characterised in that: the following steps are included:
Step 1: the pH for adjusting sewage adds ZnO/La to acidity2O3Composite catalyst；
It is irradiated Step 2: sewage is placed under ultraviolet light, is filtered after irradiation, is dry, obtaining crude product；
Step 3: washing the ZnO/La in removal crude product using strong acid2O3Composite catalyst, then it is washed to neutrality, it filters, is dry
Photo-reduction product is obtained after dry；
Step 4: calcining second intermediate product, obtains product type graphene.
2. the method for resource for the sewage that production graphene factory according to claim 1 generates, it is characterised in that:
Wherein, solid particle and ZnO/La in step 1, in the sewage2O3The mass ratio of composite catalyst is 20:1-4:1.
3. the method for resource for the sewage that production graphene factory according to claim 1 generates, it is characterised in that:
Wherein, ZnO/La2O3Composite catalyst is prepared by sol-gel method, La2O3Quality doping ratio be 0.01-
3%.
4. the method for resource for the sewage that production graphene factory according to claim 1 generates, it is characterised in that:
Wherein, in step 1, the pH value of sewage is adjusted to 3-6 using acid solution.
5. the method for resource for the sewage that production graphene factory according to claim 1 generates, it is characterised in that:
Wherein, in step 2, the wavelength of ultraviolet light is 185-400nm.
6. the method for resource for the sewage that production graphene factory according to claim 1 generates, it is characterised in that:
Wherein, in step 2, the irradiation time of ultraviolet light is 10-28 days.
7. the method for resource for the sewage that production graphene factory according to claim 1 generates, it is characterised in that:
Wherein, in step 2, filtered filter cake is dried in a vacuum drying oven, and drying temperature is 60-100 DEG C, drying time
For 6-24h；
Filtered to dry in a vacuum drying oven in step 3, drying temperature is 60-100 DEG C, drying time 6-24h.
8. the method for resource for the sewage that production graphene factory according to claim 1 generates, it is characterised in that:
Wherein, in step 4, the photo-reduction product is placed in tube furnace, is calcined under nitrogen protection, calcination temperature
It is 200-500 DEG C, calcination time 2-6h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113387515A (en) * | 2021-06-24 | 2021-09-14 | 广西科学院 | Graphene material production wastewater treatment process |
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