CN110395718A - A kind of biomass graphene and preparation method thereof and the application in processing waste water from dyestuff - Google Patents
A kind of biomass graphene and preparation method thereof and the application in processing waste water from dyestuff Download PDFInfo
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- CN110395718A CN110395718A CN201910697913.6A CN201910697913A CN110395718A CN 110395718 A CN110395718 A CN 110395718A CN 201910697913 A CN201910697913 A CN 201910697913A CN 110395718 A CN110395718 A CN 110395718A
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- biomass graphene
- cellulose
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- waste water
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
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- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
Abstract
The invention belongs to dye wastewater treatment technology fields, and in particular to a kind of biomass graphene and preparation method thereof and the application in processing waste water from dyestuff.Preparation method is as follows, by NiCl2It is configured to aqueous solution, NiCl is added into cellulose2Aqueous solution is heated to cellulose leather hard；It is taped against in corundum Noah's ark, carries out heat scission reaction, obtain solid powder；It is placed in hydrochloric acid, three times, each return time is 4h to hot reflow treatment, is dried in vacuo after being washed with deionized to neutrality to get biomass graphene.Biomass graphene prepared by the present invention, which handles the waste water containing methylene blue and rhodamine B, has preferable effect.The present invention turns waste into wealth, and provides a kind of environmentally protective, high-valued approach, and the method for being used to handle dyestuff waste liquid for abandoned biomass, has achieved the purpose that the treatment of wastes with processes of wastes against one another.
Description
Technical field
The invention belongs to dye wastewater treatment technology fields, and in particular to prepare biomass using cellulose and nickel chloride
Graphene, and dyestuff in waste liquid is adsorbed using it as adsorbent.
Background technique
Corn stover is a kind of common cellulose-containing biological material of richness, is considered as most worthy all the time
Also it is easiest to the renewable resource being wasted, China is as large agricultural country, and after reform and opening-up, agricultural development is even more swift and violent,
Correspondingly, the yield of corn stover is also more and more.It is some of since corn stover is rich in a large number of nutrients and minerals
By Fertilizer Transformed, fodder, but because its added value is lower, so crop land mostly uses greatly combustion (of oil) insitu at present, this will generate a large amount of
Smog, discharge a large amount of greenhouse gases, burn it is improper also will cause soil hardening, this is not only caused serious environmental pollution,
A kind of even more waste of renewable resource.In the trend for greatly developing agricultural modernization, should Kingsoft Yin Shan clear water again
Under the advocating in green hill, how high-efficiency environment friendly processing and become more and more important using abandoned biomass resource.
With the fast development of printing and dyeing industry, more and more dyeing waste waters have been discharged into water environment, these dyestuffs
Have the characteristics that strong toxicity, type are more, quantity is more, coloration is high, the difficult health for being decomposed by the microorganisms, seriously endangering the mankind.
Wherein, if methylene blue and rhodamine B will cause the various clinical symptoms such as nausea, diarrhea, expiratory dyspnea, therefore into human body
Waste water must be driven off the dyestuff wherein contained before discharging.
Summary of the invention
We, through processes such as catalytic pyrolysis, have synthesized biomass graphene using cellulose as raw material, and as adsorbent
Adsorption treatment has been carried out to waste water from dyestuff, achieved the purpose that the treatment of wastes with processes of wastes against one another, turned waste into wealth.Device therefor of the invention is simple,
Easy to operate, required abundant raw material is easy to get and inexpensively, products therefrom is big to Dye Adsorption amount, it is widely applicable, there is practical application.
To solve the above-mentioned problems, the present invention is achieved through the following technical solutions: a kind of biomass graphene, preparation
Method includes the following steps:
1) by NiCl2It is configured to aqueous solution, NiCl is added into cellulose2Aqueous solution is heated to cellulose leather hard；
2) by the resulting cellulose tiling to corundum Noah's ark of step 1), heat scission reaction is carried out, solid powder is obtained；
3) the resulting solid powder of step 2) is placed in hydrochloric acid, hot reflow treatment three times, is washed with deionized into
It is dried in vacuo after property to get biomass graphene.
Preferably, above-mentioned a kind of biomass graphene, in step 1), in mass ratio, nickel chloride: cellulose=1:1-3.
Preferably, above-mentioned a kind of biomass graphene, in step 1), NiCl2The concentration of aqueous solution is 20-50g/L.
Preferably, above-mentioned a kind of biomass graphene, in step 1), the cellulose is from corn stover.
Preferably, above-mentioned a kind of biomass graphene, in step 2), the temperature of the heat scission reaction is 700-
1200 DEG C, time 1-5h.
Preferably, above-mentioned a kind of biomass graphene, in step 3), the concentration of the hydrochloric acid is 1-5molL-1。
Preferably, above-mentioned a kind of biomass graphene, in step 3), the temperature of the hot reflow treatment is 60-90
DEG C, time 2-6h.
Application of the above-mentioned any biomass graphene in waste water of the processing containing methylene blue or rhodamine B
Preferably, above-mentioned application, method is as follows, adds in the waste water of Xiang Hanyou methylene blue or rhodamine B above-mentioned
Any biomass graphene, by solid-to-liquid ratio, the ratio that adds is 1g:1-5L, at 30 DEG C, oscillation rate 180rmin-1Item
Under part, oscillation absorption 4-24h.
Preferably, above-mentioned application, the concentration of the waste water containing methylene blue or rhodamine B are 15-35mg
L-1.The beneficial effects of the present invention are:
1, the biomass graphene adsorption treatment of dye waste liquid that the present invention prepares is high-efficient.
2, the present invention preparation raw materials used amount of biomass graphene is easy to get more, low in cost.
3, implementation of the invention can avoid raw material (such as corn stover) from being drawn by undeservedly processing (such as combustion (of oil) insitu) significantly
The environmental pollution risen, meets Green Sustainable theory.
4, the made biomass graphene of the present invention all has extraordinary place to MB and Rh B waste liquid in wider Acidity Range
Effect is managed, there is practical application.
5, the present invention integrates the treatment of wastes with processes of wastes against one another, turns waste into wealth, and synthesized biomass graphene, which is slightly handled, will have more
It is widely applied.
In conclusion MB, Rh B dyestuff waste liquid can be effectively treated in biomass graphene prepared by the present invention, and raw material is easy
, preparation flow is simple, has practical application.
Detailed description of the invention
Fig. 1 is the FT-IR map of biomass graphene prepared by cellulose and embodiment 1.
Fig. 2 is the XRD spectrum of biomass graphene prepared by cellulose and embodiment 1.
Fig. 3 is the Raman map of biomass graphene prepared by embodiment 1.
Fig. 4 be the biomass graphene for preparing under different acidity to the absorption property analysis chart of methylene blue (MB).
Fig. 5 is the adsorption isotherm of the biomass graphene for preparing to methylene blue.
Fig. 6 be the biomass graphene for preparing under different acidity to the absorption property analysis chart of rhodamine B (Rh B).
Fig. 7 is the adsorption isotherm of the biomass graphene for preparing to methylene blue.
Specific embodiment
The preparation of 1 biomass graphene of embodiment
1. the preparation of biomass graphene
1) by 4.0g NiCl2It is placed in 100mL volumetric flask, distilled water and constant volume is added, it is molten to obtain required nickel chloride
Liquid；5.0g cellulose (CS) is placed in 150mL beaker, 80mL nickel chloride solution is added, and be placed on heater plate extremely
Cellulose leather hard, the leather hard are that the moisture content of cellulose is 45%-55%.
The cellulose is from corn stover.
2) above-mentioned cellulose is tiled into corundum Noah's ark, is put it into tube furnace, lead to N2, and 900 DEG C of set temperature,
So that cellulose is carried out heat scission reaction 2h, obtains solid powder.
3) obtained solid powder 3molL-1Three times, each return time is 4h to hot reflow treatment to hydrochloric acid at 85 DEG C,
Finally powder is washed till after neutrality with deionized water and is dried in vacuo to get biomass graphene BGM.
2. the characterization of biomass graphene
IR detection is carried out to the BGM of the cellulose in embodiment 1 and preparation, it will be seen from figure 1 that raw cellulose exists
3345cm-1、2898cm-1、1635cm-1、1374cm-1The infrared peak that place occurs is respectively belonging to-OH ,-CH, C=C ,-CH2、-CH
Flexible and flexural vibrations peak；Compare the infrared signature peak of products therefrom BGM, it is known that the characteristic peak of hydroxyl and other groups disappears
It loses, shows the peeling of corresponding group, and there is no infrared actives by the C=C in graphene, i.e., are not in appoint in infared spectrum
What peak, it is consistent with diagramatic curve, illustrate successfully to be prepared for biomass graphene.
XRD analysis is carried out to the BGM of the cellulose in embodiment 1 and preparation, is occurred in the XRD spectrum of CS in Fig. 2
The appearance of 14.8 °, 16.6 °, 22.7 ° three characteristic peaks illustrates that cellulose has certain crystal form, and for BGM, these three peaks
While disappearance, occur apparent 26 ° (002), 42.5 ° (100), 53.7 ° of (004) three diffraction maximum, illustrates gained biomass
Carbon material has the characteristic peak of graphene.
Fig. 3 is the Raman figure of BGM, it can be clearly seen that 1330cm-1And 1600cm-1There is the peak D and the peak G, table respectively in place
Show that the C atom in resulting materials contains sp2And sp3Two kinds of hydridization forms, it was demonstrated that the synthesis of biomass graphene, in 2650cm-1There is the peak characteristic peak 2D of graphene sheet layer in place, illustrates that gained biomass graphene has multilayered structure.
Processing of the 2 biomass graphene of embodiment to Asia containing methyl blue waste water
Methylene blue (MB) simulated waste that secure ph is 2,4,6,8,12 respectively, MB concentration is 20mgL-1, use
BGM prepared by embodiment 1 carries out adsorption treatment to it respectively, wherein BGM:MB=1g:1L, adsorption time 4h, adsorption temp
It is 30 DEG C.
Absorption result is as shown in figure 4, it can easily be seen that MB waste liquid for different acidity, BGM have very it from figure
Good adsorption treatment effect, adsorption rate have practical application up to 96% or more.
In conjunction with Fig. 5, it is apparent from, with the increase of dyestuff MB initial concentration, adsorbent B GM also increases with it its adsorbance,
Steady state value is finally reached, i.e. maximal absorptive capacity is 281.9mg g-1, obtained experimental data is fitted, is as a result met
Langmuir Adsorption Model illustrates that adsorbent B GM is adsorbed as mono layer adsorption for dyestuff MB.
3 biomass graphene of embodiment is to the processing containing rhodamine B
Rhodamine B (Rh B) simulated waste that secure ph is 2,4,6,8,12 respectively, Rh B concentration is 20mgL-1,
Adsorption treatment is carried out to it respectively with BGM prepared by embodiment 1, wherein Rh B:MB=1g:1L, adsorption time 4h, absorption temperature
Degree is 30 DEG C.
Absorption result is as shown in fig. 6, it can easily be seen that BGM is suitable for handling the Rh B waste liquid of different acidity, adsorption rate from figure
Up to 95% or more, there is practical application.
By Fig. 7, it is apparent from, with the increase of dyestuff RhB initial concentration, adsorbent B GM also increases with it its adsorbance,
Steady state value is finally reached, i.e. maximal absorptive capacity is 244.8mg g-1, obtained experimental data is fitted, is as a result met
Langmuir Adsorption Model illustrates that adsorbent B GM is adsorbed as mono layer adsorption for dyestuff RhB.Because BGM contaminates two kinds
The maximal absorptive capacity of material MB and RhB is not much different, thus it is speculated that its adsorption mechanism should be total with the π-π between BGM and dye molecule
Based on yoke effect.
Claims (10)
1. a kind of biomass graphene, which is characterized in that preparation method includes the following steps:
1) by NiCl2It is configured to aqueous solution, NiCl is added into cellulose2Aqueous solution is heated to cellulose leather hard；
2) by the resulting cellulose tiling to corundum Noah's ark of step 1), heat scission reaction is carried out, solid powder is obtained；
3) the resulting solid powder of step 2) is placed in hydrochloric acid, hot reflow treatment three times, is washed with deionized to neutrality
It is dried in vacuo to get biomass graphene.
2. a kind of biomass graphene according to claim 1, which is characterized in that in step 1), in mass ratio, chlorination
Nickel: cellulose=1:1-3.
3. a kind of biomass graphene according to claim 1, which is characterized in that in step 1), NiCl2Aqueous solution it is dense
Degree is 20-50g/L.
4. a kind of biomass graphene according to claim 1, which is characterized in that in step 1), the cellulose comes
From in corn stover.
5. a kind of biomass graphene according to claim 1, which is characterized in that in step 2), the Pyrolysis
The temperature answered is 700-1200 DEG C, time 1-5h.
6. a kind of biomass graphene according to claim 1, which is characterized in that in step 3), the hydrochloric acid it is dense
Degree is 1-5molL-1。
7. a kind of biomass graphene according to claim 1, which is characterized in that in step 3), at the hot reflux
The temperature of reason is 60-90 DEG C, time 2-6h.
8. any biomass graphene described in claim 1-7 is in waste water of the processing containing methylene blue or rhodamine B
Application.
9. application according to claim 8, which is characterized in that method is as follows, Xiang Hanyou methylene blue or rhodamine B it is useless
Any biomass graphene described in claim 1-7 is added in water, by solid-to-liquid ratio, adding ratio is 1g:1-5L, 30
DEG C, oscillation rate 180rmin-1Under conditions of, oscillation absorption 4-24h.
10. application according to claim 9, which is characterized in that the waste water containing methylene blue or rhodamine B
Concentration is 15-35mgL-1。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111690186A (en) * | 2020-06-23 | 2020-09-22 | 扬州华通橡塑有限公司 | High-wear-resistance and impact-resistant composite rubber and preparation method thereof |
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| CN111690186A (en) * | 2020-06-23 | 2020-09-22 | 扬州华通橡塑有限公司 | High-wear-resistance and impact-resistant composite rubber and preparation method thereof |
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Application publication date: 20191101 |