CN112051315A - Preparation method and application of iron-containing carbon-based composite material based on dye chemical wastewater coagulated sludge - Google Patents
Preparation method and application of iron-containing carbon-based composite material based on dye chemical wastewater coagulated sludge Download PDFInfo
- Publication number
- CN112051315A CN112051315A CN202010973531.4A CN202010973531A CN112051315A CN 112051315 A CN112051315 A CN 112051315A CN 202010973531 A CN202010973531 A CN 202010973531A CN 112051315 A CN112051315 A CN 112051315A
- Authority
- CN
- China
- Prior art keywords
- iron
- composite material
- containing carbon
- based composite
- sludge
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
-
- 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
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Environmental & Geological Engineering (AREA)
- Engineering & Computer Science (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method and application of an iron-containing carbon-based composite material based on dye chemical wastewater coagulated sludge. The preparation method comprises the steps of pretreating dye chemical wastewater coagulated sludge by adopting an iron salt coagulation method, drying and grinding to obtain dried sludge, wherein the dye chemical wastewater coagulated sludge contains organic pollutants; carbonizing the dried sludge, wherein nitrogen is adopted as protective atmosphere, the temperature is increased to more than 400 ℃, and the temperature is kept for 120min or more; and then immediately cooling to room temperature to obtain the iron-containing carbon-based composite material. According to the invention, ferric salt coagulated sludge generated in the dye chemical wastewater treatment process is prepared into the iron-containing carbon-based composite material through a pyrolysis method, the iron-containing carbon-based composite material is used for detecting inorganic mercury and adsorbing hexavalent chromium, and the electrochemical detection performance and the adsorption performance of the material obtained through pyrolysis are obviously improved.
Description
Technical Field
The invention relates to a solid waste treatment and resource utilization technology, in particular to a preparation method and application of an iron-containing carbon-based composite material based on dye chemical wastewater coagulated sludge.
Background
The basic raw materials for industrial production of dyes are benzene, naphthalene, anthraquinone, aniline, nitrobenzene and phenols, the water solubility of the compounds is high, the wastewater contains a large amount of pollutants difficult to degrade biologically, and the COD value can even reach tens of thousands to hundreds of thousands. The iron salt coagulation method is usually adopted for pretreatment, and because the industry has long-term 'heavy water and light mud', a large amount of mud is not properly arranged, and the mud treatment situation is more and more severe.
The patent application specification with the publication number of CN104772143A discloses a preparation method of a supported sludge-based catalyst for removing low-concentration carbon disulfide, which takes sludge as a carrier and is subjected to ZnCl treatment2Chemical activation, adding into metal salt solution for supercritical loading, and roasting at a certain temperature; placing the roasted sludge-based activated carbon into alkaline solution, ultrasonically dipping and drying to prepare the supported sludge-based catalyst, wherein the catalyst is used for low-concentration CS2And (4) removing the catalytic hydrolysis.
The patent application specification with the publication number of CN106944053A discloses a preparation method of a sludge carbon-based Fenton catalyst, which takes sludge as a raw material, prepares activated carbon with high specific surface area by pyrolysis, and then prepares the high-activity catalyst by taking the activated carbon as a carrier to load iron; the sludge is firstly driedGrinding and sieving, activating by using a composite activating agent, performing high-temperature anaerobic pyrolysis by using a certain temperature rise procedure after activation to obtain sludge coal, performing acid washing, water washing, drying, grinding and sieving to obtain sludge activated carbon with a high specific surface area, soaking the sludge activated carbon serving as a carrier in ferrous sulfate for 1h, stirring for 24h, drying for 12h, calcining the dried activated carbon to obtain the high-activity sludge carbon-based catalyst, wherein the specific surface area of the prepared catalyst is 350-450 m2The water-soluble rhodamine B complex has a specific molecular weight of 2-5 nm and can remove azo dye rhodamine B in water.
The patent application specification with the publication number of CN111389363A discloses a magnetic biochar adsorbing material based on sulfate-reduced sludge, a preparation method and application thereof. The obtained magnetic biochar adsorbing material is used for adsorbing methyl orange.
Therefore, the conventional sludge treatment techniques include landfill, land use and incineration, but secondary environmental pollution may be caused using the conventional sludge treatment method due to heavy metals, organic pollutants, etc. contained in the sludge. The iron-rich elements in the dye chemical wastewater iron salt coagulated sludge are treated by adopting the traditional sludge treatment technology, so that the treatment cost is high, and the resource waste is caused.
Disclosure of Invention
The invention provides a preparation method and application of an iron-containing carbon-based composite material based on dye chemical wastewater coagulated sludge, and the application mainly refers to the application of the iron-containing carbon-based composite material based on dye chemical wastewater coagulated sludge in the detection of inorganic mercury and the adsorption of hexavalent chromium.
The invention is realized by adopting the following technical scheme: a preparation method of an iron-containing carbon-based composite material based on dye chemical wastewater coagulation sludge comprises the following steps:
pretreating dye chemical wastewater coagulated sludge by adopting an iron salt coagulation method, drying and grinding to obtain dried sludge, wherein the dye chemical wastewater coagulated sludge contains organic pollutants;
carbonizing the dried sludge, wherein nitrogen is adopted as protective atmosphere, the temperature is increased to more than 400 ℃, and the temperature is kept for 120min or more;
and then immediately cooling to room temperature to obtain the iron-containing carbon-based composite material.
As an improvement of the above technical solution, the organic pollutants include at least one of benzenes, naphthalenes, anthraquinones, anilines, nitrobenzenes, and phenols.
As a further improvement of the technical scheme in the previous step, the dried sludge is carbonized at the temperature of 20-500 ℃, wherein nitrogen is adopted as protective atmosphere, the initial temperature is 20 ℃, the temperature is increased for 200-500 ℃, the temperature increase rate is 2.4 ℃/min, and the temperature is maintained for 180min after the temperature is 500 ℃.
Further, the dried sludge is put into a tubular furnace for carbonization at 20-500 ℃, and is cooled to room temperature along with the tubular furnace after carbonization.
The application of the iron-containing carbon-based composite material based on the dye chemical wastewater coagulation sludge in the detection of inorganic mercury adopts the following steps:
completely dissolving the iron-containing carbon-based composite material in deionized water in a mode of 2mg:1.5mL, and uniformly dispersing to obtain a sample solution;
dripping the sample solution on the outer surface of the glassy carbon electrode, standing at room temperature and airing for later use;
and performing electrochemical detection on the inorganic mercury concentration in the solution to be detected by using the glassy carbon electrode and a square wave stripping voltammetry, wherein the specific parameters are as follows: the initial voltage is-0.5V, the end voltage is 0.8V, the amplification voltage is 0.004V, the amplitude is 0.025V, and the frequency is 15 Hz; an electrolyte solution of sodium acetate with pH value of 5 is used, the enrichment voltage is-1.3V, the enrichment time is 180s, the desorption potential is 1.2V, and the desorption time is 120 s.
As an improvement of the above technical solution, before the glassy carbon electrode is dripped with the sample solution, the method further comprises the following processing steps:
polishing the glassy carbon electrode until the surface of the glassy carbon electrode is smooth and is a mirror surface;
cleaning the surface of the glassy carbon electrode;
and drying the cleaned glassy carbon electrode at normal temperature for later use.
Further, the glassy carbon electrodes are respectively polished by using alumina powder with gradually reduced particle size; preferably, the glassy carbon electrode is respectively polished by using alumina powders with the grain sizes of 1.0 μm, 0.3 μm and 0.05 μm in sequence;
and/or, when in cleaning, sequentially using the following components in a volume ratio of 1: 1, respectively carrying out ultrasonic cleaning on the glassy carbon electrode by using absolute ethyl alcohol and deionized water.
And furthermore, the preparation method of the iron-containing carbon-based composite material adopts any one of the preparation methods of the iron-containing carbon-based composite material based on the dye chemical wastewater coagulation sludge.
The application of the iron-containing carbon-based composite material based on the dye chemical wastewater coagulation sludge in the adsorption of hexavalent chromium comprises the following steps:
adding the iron-containing carbon-based composite material into the solution to be adsorbed to adsorb the hexavalent chromium.
As an improvement of the technical scheme, the preparation method of the iron-containing carbon-based composite material adopts any one of the preparation methods of the iron-containing carbon-based composite material based on dye chemical wastewater coagulated sludge.
The invention has the following beneficial effects:
(1) according to the invention, the ferric salt coagulated sludge generated by dye chemical wastewater treatment is used for preparing the iron-containing carbon-based composite material through a pyrolysis method, the process is simple, the cost is low, the resource utilization of solid waste is realized, and the feasibility is realized;
(2) the detection sensitivity of the carbonized iron-containing carbon-based composite material to inorganic mercury is remarkably improved, and the lowest detection limit is reduced to 0.004 mu M from 0.045 mu M before treatment;
(3) under the optimized reaction parameters, the adsorption removal rate of the prepared iron-containing carbon-based composite material to hexavalent chromium is over 99% in a short time.
(4) The sludge before treatment has a loose and irregular structure, forms compact particles after pyrolysis, has a pore structure, and is beneficial to the adsorption of heavy metals; the iron-containing carbon-based composite material has uniform element distribution, and the stability of the effect is improved; therefore, the key point of the invention is that ferric salt coagulated sludge generated in the dye chemical wastewater treatment process is prepared into the iron-containing carbon-based composite material by a pyrolysis method, the iron-containing carbon-based composite material is used for detecting inorganic mercury and adsorbing hexavalent chromium, and the electrochemical detection performance and the adsorption performance of the material obtained by pyrolysis are obviously improved.
Drawings
FIG. 1 is a flow chart of a preparation method of an iron-containing carbon-based composite material based on dye chemical wastewater coagulation sludge.
Fig. 2 is a graph showing anodic stripping voltammetry when inorganic mercury is detected by using a bare Glassy Carbon Electrode (GCE), an electrode loaded with a ferric carbon-based composite material before carbonization (before calcination/GCE), and an electrode loaded with a ferric carbon-based composite material after carbonization (after calcination/GCE), respectively.
FIG. 3 shows Hg in the detection of inorganic mercury by using electrode loaded with carbonized iron-containing carbon-based composite material2+Electrochemical response diagram and current and Hg2+Is shown in linear relationship.
FIG. 4 is a Scanning Electron Micrograph (SEM) of 1 μm prior to pyrolysis of a feedstock according to the present invention.
FIG. 5 is a Scanning Electron Micrograph (SEM) of the feedstock of the present invention at 200nm prior to pyrolysis.
FIG. 6 is a Scanning Electron Micrograph (SEM) of 1 μm after pyrolysis of a feedstock according to the present invention.
FIG. 7 is a Scanning Electron Micrograph (SEM) of 200nm after pyrolysis of a feedstock according to the present invention.
FIGS. 8 to 14 are energy spectrum analysis (EDS) charts of the raw material of the present invention, wherein FIG. 8 is an EDS layered image of 1 μm of the raw material of the present invention; FIG. 9 is an EDS layer image of 1 μm oxygen in the feedstock of the present invention; FIG. 10 is an EDS layer image of 1 μm iron in the feedstock of the present invention; FIG. 11 is an EDS layer image of 1 μm carbon in the feedstock of the present invention; FIG. 12 is an EDS layer image of 1 μm nitrogen in the feedstock of the present invention; FIG. 13 is an EDS electron image of a raw material of 1 μm in the present invention, and FIG. 14 is an EDS spot analysis image of a raw material of the present invention.
Fig. 15 to 22 are energy spectrum analysis (EDS) diagrams of the iron-containing carbon-based composite material prepared in the present invention, wherein fig. 15 is an EDS layered image of a raw material of 1 μm in the present invention; FIG. 16 is an EDS layer diagram of 1 μm oxygen in the feedstock of the present invention; FIG. 17 is an EDS layer image of 1 μm iron in the feedstock of the present invention; FIG. 18 is an EDS layer image of 1 μm carbon in the feedstock of the present invention; FIG. 19 is an EDS layer image of 1 μm sulfur in the feedstock of the present invention; FIG. 20 is an EDS layer diagram of 1 μm nitrogen in the feedstock of the present invention; FIG. 21 is an EDS electron image of a raw material of 1 μm in the present invention, and FIG. 22 is an EDS spot analysis image of a raw material in the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The application of the iron-containing carbon-based composite material based on dye chemical wastewater coagulation sludge in the detection of inorganic mercury is introduced in the embodiment, the problems of high treatment cost and resource waste of the traditional sludge treatment technology are solved, and the iron-containing carbon-based composite material based on dye chemical wastewater coagulation sludge is applied to the field of electrochemical detection of environmental pollutants such as inorganic mercury.
Referring to fig. 1, a method for preparing an iron-containing carbon-based composite material based on dye chemical wastewater coagulation sludge includes the following steps:
(1) pretreating dye chemical wastewater coagulated sludge by adopting an iron salt coagulation method, drying and grinding to obtain dried sludge, wherein the dye chemical wastewater coagulated sludge contains organic pollutants; wherein the organic contaminants include at least one of benzenes, naphthalenes, anthraquinones, anilines, nitrobenzenes, phenols.
(2) Carbonizing the dried sludge, wherein nitrogen is adopted as protective atmosphere, the temperature is increased to more than 400 ℃, and the temperature is kept for 120min or more; in the embodiment, the dried sludge is carbonized at 20-500 ℃, wherein nitrogen is used as protective atmosphere, the initial temperature is 20 ℃, the temperature is increased to 200-500 ℃, the temperature increase rate is 2.4 ℃/min, and the temperature is maintained for 180min after the temperature is 500 ℃.
(3) And then immediately cooling to room temperature to obtain the iron-containing carbon-based composite material.
The application of the iron-containing carbon-based composite material based on dye chemical wastewater coagulation sludge in the detection of inorganic mercury is characterized in that the application comprises the following steps:
(1) the iron-containing carbon-based composite material is completely dissolved in deionized water in a mode of 2mg:1.5mL, and a sample solution is obtained after uniform dispersion. In this example, 2mg of each sample before and after calcination was weighed in 1.5mL of deionized water and dispersed uniformly by ultrasonic oscillation for 5 minutes.
(2) And dripping the sample solution on the outer surface of the glassy carbon electrode, and standing and airing at room temperature for later use. In this example, 6. mu.L of the uniformly dispersed sample solution was dropped on the surface of the glassy carbon electrode treated as described above, and allowed to stand at room temperature for air-drying. Wherein, a pretreatment is carried out before the glassy carbon electrode is dripped with a sample solution, and the treatment steps are as follows:
a. the glassy carbon electrodes are respectively polished by using alumina powder with gradually reduced particle size in sequence, in the embodiment, the glassy carbon electrodes are preferably polished by using alumina powder with particle size of 1.0 μm, 0.3 μm and 0.05 μm in sequence until the surface of the glassy carbon electrode is smooth and is a mirror surface;
b. sequentially using absolute ethyl alcohol (volume ratio is 1: 1) and deionized water to carry out ultrasonic cleaning on the glassy carbon electrode for 2min so as to clean the surface of the glassy carbon electrode; wherein, the ultrasonic cleaning time and times can be set according to the experience of the technicians in the field;
c. and drying the cleaned glassy carbon electrode at normal temperature for later use. Blow-drying with nitrogen may also be used in other embodiments.
(3) And performing electrochemical detection on the inorganic mercury concentration in the solution to be detected by using the glassy carbon electrode and a square wave stripping voltammetry, wherein the specific parameters are as follows: the initial voltage is-0.5V, the end voltage is 0.8V, the amplification voltage is 0.004V, the amplitude is 0.025V, and the frequency is 15 Hz; an electrolyte solution of sodium acetate with pH value of 5 is used, the enrichment voltage is-1.3V, the enrichment time is 180s, the desorption potential is 1.2V, and the desorption time is 120 s.
In the present embodiment, normal temperature refers to the temperature conventional in the chemical field, such as 20 ℃; room temperature also refers to temperatures conventional in the chemical arts, such as 25 ℃.
Example 2
The embodiment introduces the application of the iron-containing carbon-based composite material based on the dye chemical wastewater coagulation sludge in the absorption of hexavalent chromium, so that the iron-containing carbon-based composite material based on the dye chemical wastewater coagulation sludge is applied to the treatment field of absorption of environmental pollutants such as hexavalent chromium.
When the iron-containing carbon-based composite material based on the dye chemical wastewater coagulated sludge is applied to adsorption of hexavalent chromium, the following steps are adopted:
pretreating dye chemical wastewater coagulated sludge by adopting an iron salt coagulation method, drying and grinding to obtain dried sludge, wherein the dye chemical wastewater coagulated sludge contains organic pollutants;
carbonizing the dried sludge at 20-500 ℃, wherein nitrogen is adopted as a protective atmosphere, the initial temperature is 20 ℃, the temperature is increased for 200-500 ℃, the temperature increase rate is 2.4 ℃/min, and the temperature is maintained for 180min after the temperature is 500 ℃;
then cooling to room temperature instantly to obtain the iron-containing carbon-based composite material;
and adding the iron-containing carbon-based composite material into a solution to be adsorbed to adsorb hexavalent chromium.
The preparation method of the iron-containing carbon-based composite material is similar to that described in example 1, and is not described in detail herein.
When the iron-containing carbon-based composite material is used for adsorbing hexavalent chromium, the iron-containing carbon-based composite material is added into the hexavalent chromium-containing liquid to be adsorbed, and is vibrated and mixed for a certain time. In this embodiment, the pH during adsorption can be adjusted to be acidic or neutral, and the shaking and mixing time is more than 40 minutes.
The embodiment provides a method for detecting the influence of potassium dichromate solutions with different initial concentrations on the adsorption rate of an iron-containing carbon-based composite material, which comprises the following steps:
respectively and accurately weighing 80mg of the iron-containing carbon-based composite material, adding the iron-containing carbon-based composite material into 50mL of potassium dichromate solutions with different initial concentrations, controlling the pH value of the reaction to be 3, tightly covering a cover, keeping the speed of 150r/min, shaking for 40 minutes, and measuring the influence of the initial concentration of the potassium dichromate on the adsorption rate of the potassium dichromate, wherein the results are shown in Table 1.
TABLE 1 influence of initial concentration of potassium dichromate solution on Cr6+ adsorption removal rate
| Serial number | Initial concentration (mg/L) of potassium dichromate solution | Adsorption rate |
| 1 | 20 | 99.4％ |
| 2 | 40 | 96.7％ |
| 3 | 60 | 64.1％ |
| 4 | 80 | 58.0％ |
| 5 | 100 | 54.4％ |
From Table 1It is known that when the initial concentration of the potassium dichromate solution is 20mg/L, the prepared iron-containing carbon-based composite material is opposite to Cr6+The adsorption rate of the iron-containing carbon-based composite material is best, and the adsorption rate of the iron-containing carbon-based composite material is obviously reduced along with the continuous increase of the initial concentration of the solution.
The embodiment also provides the iron-containing carbon-based composite material pair Cr under different pH values6+The detection method for the influence of the adsorption rate comprises the following detection steps:
80mg of the iron-containing carbon-based composite material was accurately weighed by using a balance, and added to 50mL of potassium dichromate solution having an initial concentration of 20mg/L, respectively, the cover was closed, shaking was performed at a rate of 150r/min for 40 minutes at different pH values, and the adsorption rate was measured, and the results are shown in Table 2.
TABLE 2 pH vs. Cr6+Influence of adsorption removal Rate
| Serial number | pH | Adsorption rate |
| 1 | 3 | 99.4％ |
| 2 | 5 | 98.9％ |
| 3 | 7 | 98.5％ |
| 4 | 9 | 17.5％ |
As can be seen from Table 2, the iron-containing carbon-based composite material is expected to be specific to Cr when the pH is acidic and neutral6+The adsorption rate of the iron-containing carbon-based composite material is excellent, and when the pH value is alkaline, the adsorption performance of the iron-containing carbon-based composite material is greatly reduced.
The embodiment also provides Cr pairs with different reaction times6+The detection method for the influence of the adsorption removal rate comprises the following detection steps:
80mg of the iron-containing carbon-based composite material was accurately weighed using a balance, added to 50mL of a potassium dichromate solution having an initial concentration of 20mg/L, the reaction pH was controlled to 3, the lid was closed, shaking was performed at a rate of 150r/min, samples were taken every 10 minutes, and the adsorption rates at different times were measured, and the results are shown in Table 3.
TABLE 3 reaction time vs. Cr6+Influence of adsorption removal Rate
| Serial number | Time (min) | Adsorption rate |
| 1 | 10 | 95.3％ |
| 2 | 20 | 96.4％ |
| 3 | 30 | 97.1％ |
| 4 | 40 | 99.4％ |
| 5 | 50 | 99.4％ |
| 6 | 60 | 99.4％ |
As can be seen from Table 3, the iron-containing carbon-based composite material is aligned with Cr in 0 to 40 minutes with increasing reaction time6+The adsorption rate of (A) is also continuously increased, and when the adsorption rate exceeds 40 minutes, Cr is added6+Almost completely adsorbed and removed by the iron-containing carbon-based composite material, and the adsorption rate of the iron-containing carbon-based composite material is not changed any more.
Under the optimized reaction parameters of the embodiment, the adsorption removal rate of the prepared iron-containing carbon-based composite material on hexavalent chromium in a short time exceeds 99%.
Example 3
The invention also provides a method for detecting inorganic mercury by using a bare Glassy Carbon Electrode (GCE), an electrode loaded with a material before pyrolysis (before calcination/GCE) and an electrode loaded with an iron-containing carbon-based composite material (after calcination/GCE), which comprises the following steps:
(1) and respectively taking the bare glassy carbon electrode, the electrode loaded with the iron-containing carbon-based composite material before carbonization and the electrode loaded with the iron-containing carbon-based composite material after carbonization as working electrodes in a three-electrode system of an electrochemical workstation, and detecting the concentration of inorganic mercury in the liquid to be detected under the power-on state of the three-electrode system.
The method comprises the following steps of: polishing the electrode until the surface of the electrode is smooth and is a mirror surface; then, sequentially using absolute ethyl alcohol and deionized water with the same volume to ultrasonically clean the polished electrode to remove impurities adsorbed on the surface of the electrode; and then, drying the cleaned electrode at normal temperature for later use to obtain the bare glassy carbon electrode.
The preparation of the electrode loaded with the iron-containing carbon-based composite material before carbonization comprises the following steps: drying and grinding the ferric salt coagulated sludge to obtain the dried sludge. Weighing 2mg of dried sludge into 1.5mL of deionized water, and ultrasonically oscillating for 5 minutes to uniformly disperse to obtain a sample solution. And (3) dripping 6 mu L of uniformly dispersed sample solution on the surface of the treated glassy carbon electrode, standing and airing at room temperature to obtain the electrode loaded with the iron-carbon-based composite material before carbonization.
The preparation method of the electrode loaded with the carbonized iron-containing carbon-based composite material comprises the following steps: drying and grinding the ferric salt coagulated sludge to obtain dried sludge; putting the dried sludge into a tubular furnace for carbonization at 20-500 ℃; during carbonization, nitrogen is adopted as protective atmosphere, and the reaction conditions are as follows: the initial temperature is 20 ℃, the temperature is increased to 200-500 ℃, the heating rate is 2.4 ℃/min, the temperature is maintained at 500 ℃ for 180min, then the temperature is cooled to room temperature along with the furnace, the iron-containing carbon-based composite material is prepared, 2mg of the iron-containing carbon-based composite material is weighed into 1.5mL of deionized water, and the mixture is subjected to ultrasonic oscillation for 5 min to be uniformly dispersed, so that a sample solution is obtained. And (3) dripping 6 mu L of uniformly dispersed sample solution on the surface of the treated glassy carbon electrode, standing and airing at room temperature to obtain the electrode loaded with the carbonized iron-carbon-based composite material.
(2) When the electrochemical workstation detects inorganic mercury, the electrochemical detection is carried out on the inorganic mercury by using a square wave stripping voltammetry, and the specific parameters are as follows: the initial voltage is-0.5V, the end voltage is 0.8V, the amplification voltage is 0.004V, the amplitude is 0.025V, and the frequency is 15 Hz. The electrolyte solution used was sodium acetate (pH 5), the enrichment voltage: -1.3V, the enrichment time was 180s, the desorption potential was 1.2V, and the desorption time was 120 s. The steps of detecting inorganic mercury by an electrochemical workstation are as follows:
firstly, the concentration of inorganic mercury in the liquid to be detected is C0Then the electrochemical workstation obtains0Corresponding current value I0(ii) a Secondly, adding a known amount of inorganic mercury into the liquid to be detected, so that the inorganic mercury in the liquid to be detected is concentratedDegree C0+C1Then the electrochemical workstation obtains0+C1Corresponding current value I1(ii) a Then, adding inorganic mercury with known amount into the solution to be detected at least once, wherein the concentration of the inorganic mercury in the solution to be detected is C0+nC1And n is the currently increased number of times of the inorganic mercury, then the electrochemical workstation obtains the result of the comparison with C0+nC1Corresponding current value In(ii) a Since the electrochemical response and the measured inorganic mercury concentration are in a linear relationship, I0、C1、I1、InAre all known values, and therefore C is calculated0。
In this example, the anodic stripping voltammogram of the inorganic mercury detected by using the bare Glassy Carbon Electrode (GCE), the electrode loaded with the iron-containing carbon-based composite material before carbonization (before calcination/GCE), and the electrode loaded with the iron-containing carbon-based composite material after carbonization (after calcination/GCE) shown in fig. 2 was obtained. When the electrode shown in FIG. 3, which uses the iron-containing carbon-based composite material after the loaded carbonization, was used to detect inorganic mercury, the electrode was used to detect Hg2+Electrochemical response diagram and current and Hg2+Is shown in linear relationship.
Referring to fig. 2, it can be seen that the detection sensitivity of the carbonized iron-containing carbon-based composite material for inorganic mercury is significantly improved compared to that before carbonization, and the minimum detection limit for inorganic mercury is reduced from 0.045 μ M to 0.004 μ M before carbonization.
Example 4
The embodiment also provides a scanning electron microscope image of 1 μm before the pyrolysis of the dye chemical wastewater coagulated sludge as shown in fig. 4, a scanning electron microscope image of 200nm before the pyrolysis of the dye chemical wastewater coagulated sludge as shown in fig. 5, a scanning electron microscope image of 1 μm after the pyrolysis of the dye chemical wastewater coagulated sludge as shown in fig. 6, and a scanning electron microscope image of 200nm after the pyrolysis of the dye chemical wastewater coagulated sludge as shown in fig. 7. Referring to fig. 8 to 14, fig. 8 to 14 are graphs of energy spectrum analysis (EDS) of the raw material of the present invention. Referring to fig. 15 to 22, fig. 15 to 22 are energy spectrum analysis (EDS) diagrams of the iron-containing carbon-based composite material prepared according to the present invention.
As can be seen from the figures 4 to 7, the sludge structure before pyrolysis is loose and irregular, compact particles are formed after pyrolysis, and the sludge has a pore structure, so that the adsorption of heavy metals is facilitated. And elements in the iron-containing carbon-based composite material are uniformly distributed, so that the stability of the experimental effect is improved.
As can be seen from the energy spectrum analysis (EDS) charts of the raw materials in fig. 8 to 14, the raw materials contain elements such as Fe, C, O, Br, N, and S, and the content of Fe is the highest.
As can be seen from the energy spectrum analysis (EDS) diagrams of the iron-containing carbon-based composite materials in fig. 15 to 22, the iron-containing carbon-based composite material prepared by the present invention contains elements such as Fe, C, O, Br, N, and S, wherein the content of Fe is the highest, the contents of three elements, i.e., Fe, C, and O, are increased as compared to the raw material, and the contents of three elements, i.e., Br, N, and S, are lower than the contents of three elements, i.e., Br, N, and S, in the raw material.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the iron-containing carbon-based composite material based on the dye chemical wastewater coagulation sludge is characterized by comprising the following steps of:
pretreating dye chemical wastewater coagulated sludge by adopting an iron salt coagulation method, drying and grinding to obtain dried sludge, wherein the dye chemical wastewater coagulated sludge contains organic pollutants;
carbonizing the dried sludge, wherein nitrogen is adopted as protective atmosphere, the temperature is increased to more than 400 ℃, and the temperature is kept for 120min or more;
and then immediately cooling to room temperature to obtain the iron-containing carbon-based composite material.
2. The method for preparing the iron-containing carbon-based composite material based on the dye chemical wastewater coagulation sludge according to claim 1, wherein the organic pollutants comprise at least one of benzene, naphthalene, anthraquinone, aniline, nitrobenzene and phenol.
3. The method for preparing the iron-containing carbon-based composite material based on the dye chemical wastewater coagulation sludge as claimed in claim 1, wherein the dried sludge is carbonized at 20 ℃ to 500 ℃, nitrogen is used as a protective atmosphere, the initial temperature is 20 ℃, the temperature is increased for 200min to 500 ℃, the temperature increase rate is 2.4 ℃/min, and the temperature is maintained for 180min after the temperature is 500 ℃.
4. The method for preparing the iron-containing carbon-based composite material based on the dye chemical wastewater coagulation sludge as claimed in claim 3, wherein the dried sludge is carbonized in a tubular furnace at 20-500 ℃, and cooled to room temperature along with the tubular furnace after carbonization.
5. The application of the iron-containing carbon-based composite material based on dye chemical wastewater coagulation sludge in the detection of inorganic mercury is characterized in that the application comprises the following steps:
completely dissolving the iron-containing carbon-based composite material in deionized water in a mode of 2mg:1.5mL, and uniformly dispersing to obtain a sample solution;
dripping the sample solution on the outer surface of the glassy carbon electrode, standing at room temperature and airing for later use;
and performing electrochemical detection on the inorganic mercury concentration in the solution to be detected by using the glassy carbon electrode and a square wave stripping voltammetry, wherein the specific parameters are as follows: the initial voltage is-0.5V, the end voltage is 0.8V, the amplification voltage is 0.004V, the amplitude is 0.025V, and the frequency is 15 Hz; an electrolyte solution of sodium acetate with pH value of 5 is used, the enrichment voltage is-1.3V, the enrichment time is 180s, the desorption potential is 1.2V, and the desorption time is 120 s.
6. The application of the iron-containing carbon-based composite material based on dye chemical wastewater coagulation sludge in detecting inorganic mercury according to claim 5, wherein the glassy carbon electrode further comprises the following processing steps before the sample solution is dripped:
polishing the glassy carbon electrode until the surface of the glassy carbon electrode is smooth and is a mirror surface;
cleaning the surface of the glassy carbon electrode;
and drying the cleaned glassy carbon electrode at normal temperature for later use.
7. The application of the iron-containing carbon-based composite material based on dye chemical wastewater coagulating sludge in detecting inorganic mercury according to claim 6, wherein the glassy carbon electrodes are respectively polished by sequentially using alumina powder with gradually reduced particle size; preferably, the glassy carbon electrode is respectively polished by using alumina powders with the grain sizes of 1.0 μm, 0.3 μm and 0.05 μm in sequence;
and/or, when in cleaning, sequentially using the following components in a volume ratio of 1: 1, respectively carrying out ultrasonic cleaning on the glassy carbon electrode by using absolute ethyl alcohol and deionized water.
8. The application of the iron-containing carbon-based composite material based on dye chemical wastewater coagulating sludge in detecting inorganic mercury according to claim 5, wherein the preparation method of the iron-containing carbon-based composite material adopts the preparation method of the iron-containing carbon-based composite material based on dye chemical wastewater coagulating sludge according to any one of claims 1 to 4.
9. The application of the iron-containing carbon-based composite material based on dye chemical wastewater coagulation sludge in the adsorption of hexavalent chromium is characterized in that the application comprises the following steps:
adding the iron-containing carbon-based composite material into the solution to be adsorbed to adsorb the hexavalent chromium.
10. The use of the iron-containing carbon-based composite material based on dye chemical wastewater coagulating sludge in adsorbing hexavalent chromium according to claim 9, wherein the preparation method of the iron-containing carbon-based composite material is the preparation method of the iron-containing carbon-based composite material based on dye chemical wastewater coagulating sludge according to any one of claims 1 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010973531.4A CN112051315A (en) | 2020-09-16 | 2020-09-16 | Preparation method and application of iron-containing carbon-based composite material based on dye chemical wastewater coagulated sludge |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010973531.4A CN112051315A (en) | 2020-09-16 | 2020-09-16 | Preparation method and application of iron-containing carbon-based composite material based on dye chemical wastewater coagulated sludge |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112051315A true CN112051315A (en) | 2020-12-08 |
Family
ID=73603220
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010973531.4A Pending CN112051315A (en) | 2020-09-16 | 2020-09-16 | Preparation method and application of iron-containing carbon-based composite material based on dye chemical wastewater coagulated sludge |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112051315A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111389363A (en) * | 2020-04-02 | 2020-07-10 | 四川省地质矿产勘查开发局四0五地质队 | Magnetic biochar adsorbing material based on sulfate-reduced sludge and preparation method and application thereof |
| CN114146683A (en) * | 2021-11-16 | 2022-03-08 | 哈尔滨工业大学 | Method for preparing carbon-based adsorption material by utilizing sewage deep treatment coagulated sludge and application thereof |
| CN114602436A (en) * | 2022-04-02 | 2022-06-10 | 中州水务控股有限公司 | Preparation method of magnetized ferric salt sludge |
| CN114146683B (en) * | 2021-11-16 | 2024-05-10 | 哈尔滨工业大学 | Method for preparing carbon-based adsorption material by deeply treating coagulated sludge with sewage and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105859105A (en) * | 2016-06-20 | 2016-08-17 | 深圳市圆周率环境科技有限公司 | Sludge treatment and recycling method |
| CN106076241A (en) * | 2016-06-06 | 2016-11-09 | 东南大学 | A kind of waterworks sludge is utilized to remove the method for dyestuff in water |
| CN106944053A (en) * | 2017-02-14 | 2017-07-14 | 浙江省农业科学院 | A kind of sludge carbon base type Fenton catalyst and its preparation method and application |
| CN107200385A (en) * | 2017-07-18 | 2017-09-26 | 甘琦 | A kind of method that iron carbon or Fenton sludge prepare porous light electrolysis particle in utilization waste water treatment process |
| CN108854959A (en) * | 2018-07-04 | 2018-11-23 | 湖南农业大学 | A kind of preparation method and applications of nano zero valence iron sludge based biomass charcoal |
| CN110115974A (en) * | 2019-06-05 | 2019-08-13 | 中国科学院城市环境研究所 | A kind of decoloring material and its preparation method and application and wastewater decoloring method |
| CN111389363A (en) * | 2020-04-02 | 2020-07-10 | 四川省地质矿产勘查开发局四0五地质队 | Magnetic biochar adsorbing material based on sulfate-reduced sludge and preparation method and application thereof |
-
2020
- 2020-09-16 CN CN202010973531.4A patent/CN112051315A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106076241A (en) * | 2016-06-06 | 2016-11-09 | 东南大学 | A kind of waterworks sludge is utilized to remove the method for dyestuff in water |
| CN105859105A (en) * | 2016-06-20 | 2016-08-17 | 深圳市圆周率环境科技有限公司 | Sludge treatment and recycling method |
| CN106944053A (en) * | 2017-02-14 | 2017-07-14 | 浙江省农业科学院 | A kind of sludge carbon base type Fenton catalyst and its preparation method and application |
| CN107200385A (en) * | 2017-07-18 | 2017-09-26 | 甘琦 | A kind of method that iron carbon or Fenton sludge prepare porous light electrolysis particle in utilization waste water treatment process |
| CN108854959A (en) * | 2018-07-04 | 2018-11-23 | 湖南农业大学 | A kind of preparation method and applications of nano zero valence iron sludge based biomass charcoal |
| CN110115974A (en) * | 2019-06-05 | 2019-08-13 | 中国科学院城市环境研究所 | A kind of decoloring material and its preparation method and application and wastewater decoloring method |
| CN111389363A (en) * | 2020-04-02 | 2020-07-10 | 四川省地质矿产勘查开发局四0五地质队 | Magnetic biochar adsorbing material based on sulfate-reduced sludge and preparation method and application thereof |
Non-Patent Citations (6)
| Title |
|---|
| GANG LIU等: "Recycling Iron Containing Sludges from Electroflocculation of Printing and Dyeing Wastewater to Anode Materials for Li-ion Battery", 《CHEMSUSCHEM》 * |
| YU FENG 等: "Distribution and speciation of iron in Fe-modifid biochars and its application in removal of As(V), As(III), Cr(VI), and Hg(II): An X-ray absorption study", 《JOURNAL OF HAZARDOUS MATERIALS》 * |
| 中国环境保护产业协会编: "《注册环保工程师专业考试复习教材 水污染防治工程技术与实践 上 第4版》", 31 March 2017, 中国环境出版社 * |
| 周秀英 等: "水环境重金属检测技术研究进展", 《广东化工》 * |
| 张仁泽 等: "TpPa-1/Nafion 修饰电极的差分脉冲阳极溶出伏安法同时测定铜离子和汞离子", 《分析试验室》 * |
| 骆欣等: "《微滤膜组合技术处理废水的研究》", 31 January 2019, 中国矿业大学出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111389363A (en) * | 2020-04-02 | 2020-07-10 | 四川省地质矿产勘查开发局四0五地质队 | Magnetic biochar adsorbing material based on sulfate-reduced sludge and preparation method and application thereof |
| CN114146683A (en) * | 2021-11-16 | 2022-03-08 | 哈尔滨工业大学 | Method for preparing carbon-based adsorption material by utilizing sewage deep treatment coagulated sludge and application thereof |
| CN114146683B (en) * | 2021-11-16 | 2024-05-10 | 哈尔滨工业大学 | Method for preparing carbon-based adsorption material by deeply treating coagulated sludge with sewage and application thereof |
| CN114602436A (en) * | 2022-04-02 | 2022-06-10 | 中州水务控股有限公司 | Preparation method of magnetized ferric salt sludge |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111268880A (en) | Preparation method and application of metal ion modified sludge-based biochar | |
| CN111620431A (en) | Application of adsorbed-desorbed waste biochar in degradation of persistent organic pollutants by activated persulfate | |
| CN112051315A (en) | Preparation method and application of iron-containing carbon-based composite material based on dye chemical wastewater coagulated sludge | |
| CN113061441B (en) | Biochar loaded iron material for oxidizing and repairing organic pollution of soil water body and preparation method and application thereof | |
| CN110898802B (en) | Sludge-based biochar and preparation method and application thereof, acetic acid modified sludge-based biochar and preparation method and application thereof | |
| CN104229949B (en) | Preparation and the application thereof of load iron ion and manganese ion NACF composite cathode | |
| Qi et al. | Simultaneous removal of methylene blue and copper (II) ions by photoelectron catalytic oxidation using stannic oxide modified iron (III) oxide composite electrodes | |
| CN107321350A (en) | Sludge base Co/Fe bimetallics are combined type Fenton catalyst and its preparation method and application | |
| CN110833817A (en) | Dry synthesis method of rice hull biochar loaded nano-iron material | |
| CN107262096A (en) | A kind of preparation method of support type charcoal catalysis material | |
| Seredych et al. | Effect of the graphene phase presence in nanoporous S-doped carbon on photoactivity in UV and visible light | |
| CN110152702A (en) | Derivative nitrogen carbon nanomaterial of a kind of organic backbone and its preparation method and application | |
| CN108128838A (en) | Modified clean water sludge load zero-valent iron material and preparation method and application | |
| CN111715186A (en) | Method for removing p-nitrophenol in water by biochar composite material containing free radicals | |
| Wu et al. | Redox properties of nano-sized biochar derived from wheat straw biochar | |
| CN109092245A (en) | A kind of tripolite loading carbon nanotube adsorption agent and preparation method thereof | |
| CN113003648B (en) | Method for treating heavy metal/organic matter composite polluted wastewater by solid waste biomass carbonized material | |
| CN108311105B (en) | Preparation method of molybdenum phosphide nanoparticle-doped biomass carbon material with mesh structure | |
| CN112156751B (en) | Preparation method of magnetic biochar for purifying cadmium-containing wastewater | |
| CN109796058B (en) | Method for treating hexavalent chromium and organic pollutant combined pollution by adopting biochar | |
| CN115069216B (en) | Preparation method and application of magnetic activated biochar | |
| CN111426734B (en) | Nano Cu/graphene composite material modified electrode, preparation method thereof and application of nano Cu/graphene composite material modified electrode in detection of hydroquinone | |
| CN112221470B (en) | Sewage treatment material with composite porous structure and preparation method and application thereof | |
| CN114247427A (en) | Sludge-based magnetic biochar adsorbing material and preparation method and application thereof | |
| CN113877522A (en) | Preparation method and application of diatomite-based adsorbent loaded with iron-manganese oxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |