CN114870802A - Method for preparing magnetic porous carbon composite adsorption material by multi-element solid waste synergism - Google Patents
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention relates to a method for preparing a magnetic porous carbon composite adsorption material by the cooperation of multiple solid wastes. The method comprises the following steps: adding the dewatered sludge, agricultural and forestry wastes and industrial wastes into a ball milling tank, adding KOH solution, and carrying out wet mixing and grinding for 2-20 hours by using a ball mill to obtain uniformly mixed slurry; drying the slurry, and then putting the dried slurry into a tubular furnace for carbonization at 400-950 ℃ for 1-5 h to obtain a magnetic porous carbon crude product; washing the magnetic porous carbon composite adsorbing material with dilute hydrochloric acid and deionized water in sequence until the material is neutral, and drying the material to obtain the magnetic porous carbon composite adsorbing material; the agricultural and forestry waste is straw or fruit shell; the industrial waste is steel slag, iron tailings, crushed furnace slag or iron-containing dedusting ash. The raw materials of the invention have low price and wide sources, are all solid wastes, and have one-step grinding, activation and magnetization, thereby improving the production efficiency and having excellent product performance.
Description
Technical Field
The invention belongs to the field of solid waste resource utilization and sewage treatment, and particularly relates to a magnetic porous carbon composite adsorption material prepared from municipal sludge, agricultural and forestry wastes, steel slag, tailings and other multi-component solid wastes.
Background
With the rapid development of national urbanization and industrialization, the production and discharge of various solid wastes, such as various agricultural and forestry wastes, sludge, steel slag, tailings and the like, are increased. Most of the solid wastes are incinerated, buried and composted, wherein the incineration still causes secondary pollution to the atmosphere, and the land resources and even the soil are seriously occupied by the buried and composted wastes, so that the solid wastes are recycled to become useful materials such as ceramic grains, ceramic tiles, adsorbents and the like, and the current green disposal trend is achieved.
Agricultural and forestry wastes such as straws, husks and the like have high carbon content and contain a large amount of organic components such as lignin, cellulose and the like, and are one of the most extensive raw materials for preparing the activated carbon adsorbent; the carbon content in the sludge reaches 30 percent, and the organic matter content is sufficient, so the preparation of the adsorbent by carbonizing the sludge as a raw material also receives wide attention. Wengen Wen et al in CN 112194131A using KOH/ZnCl 2 The compound solution is used as an activating agent, paper-making sludge particles are soaked in the compound solution in a ratio of 4:1, and the compound solution is carbonized at 450-700 ℃ for 50min to obtain a paper-making sludge carbonaceous adsorbent; the preparation method comprises the steps of mixing sludge, montmorillonite, clay, activated carbon, a curing agent and the like in a ratio of 3:4:1:1:1 in CN 105536685A, and roasting at 800-1000 ℃ to obtain a sewage adsorbent.
For convenience sakeThe method for recycling the adsorbent from the purified waste liquid and preparing the magnetic adsorbent is a good solution. At present, the method for preparing the magnetic adsorbent is mainly to add a magnetic source directly or to impregnate a magnetic iron salt as a magnetic additive, for example, a method for preparing the magnetic biochar adsorbent by impregnating a mixed solution of ferric chloride and manganese chloride with a Perilla honey shell and then carrying out hydrothermal treatment is disclosed in CN 113663643A; for example, CN103521179A discloses a method for preparing a composite fertilizer by using sludge as a raw material and phenolic resin-silica sol as a binder and Fe 3 O 4 Adhering the powder, and then preparing the magnetic adsorbent by pyrolysis; further, as disclosed in CN106076257A, a method for preparing magnetic activated carbon by binding municipal sludge and steel slag with sodium silicate as a binder and pyrolyzing the bound materials in one step is disclosed.
Although the method proposes the preparation of the magnetic adsorbent by utilizing the solid wastes, a large amount of ferromagnetic solution is used, so that the cost is increased; or the magnetic substance is adhered by using the adhesive, so that the product is easy to block the pore channels by the adhesive. Meanwhile, the magnetic porous carbon adsorbent is prepared by utilizing multi-component solid wastes in a one-step synergistic manner according to the characteristics of the raw materials, and reports are not found.
Disclosure of Invention
The invention aims to provide a method for preparing a magnetic porous carbon composite adsorption material by the cooperation of multiple solid wastes aiming at the defects in the prior art. The method (1) utilizes multi-component solid wastes including sludge, forestry and agricultural residues, steel slag, tailings and the like as main raw materials, (2) under the action of activating agents such as KOH and the like, a ball mill is used for simultaneously completing grinding, mixing and activating processes, an iron source is gathered at the center through high-speed ball milling, generated kinetic energy accelerates etching of KOH to the surface of the raw materials, activation time is greatly shortened, more active sites are provided, and finally, the core-shell structure magnetic porous carbon composite adsorbing material which takes the iron source as a core and is coated by porous carbon is prepared through pyrolysis. The invention can effectively adsorb the waste water, is convenient to recycle, realizes the resource utilization of solid waste, and achieves the environmental treatment aim of treating waste by waste.
The technical scheme adopted by the invention is as follows:
a method for preparing a magnetic porous carbon composite adsorption material by the cooperation of multiple solid wastes comprises the following steps:
(1) dewatering the sludge through a high-speed centrifuge, adding the preliminarily crushed sludge, agricultural and forestry wastes and industrial wastes into a ball milling tank, adding a KOH solution, and carrying out wet mixing and grinding for 2-20 hours by using a ball mill to obtain uniformly mixed slurry;
wherein, the mass ratio is, the sludge after dehydration: agricultural and forestry wastes: industrial waste (1-10): (1-10): (1-10); the concentration of the KOH solution is 1-5 mol/L; the rotation speed of the ball mill is 500-2000 rpm, and the material ball ratio is 1: 4; the solid-liquid ratio of the raw material to the KOH solution is 1: (2-10); the raw materials refer to dewatered sludge, agricultural and forestry wastes and industrial wastes.
The agricultural and forestry waste is straw or fruit shell; the industrial waste is steel slag, iron tailings, crushed furnace slag or iron-containing dedusting ash;
(2) drying the slurry obtained by ball milling in the step (1), and then putting the dried slurry into a tube furnace for carbonization for 1-5 h at 400-950 ℃ in a nitrogen atmosphere to obtain a magnetic porous carbon crude product;
(3) washing the crude product obtained in the step (2) with dilute hydrochloric acid and deionized water in sequence until the crude product is neutral, and drying to obtain a magnetic porous carbon composite adsorption material;
the concentration of the dilute hydrochloric acid used in the step (3) is 0.1-1 mol/L.
The revolution number of the high-speed centrifuge in the step (1) is 2000-10000 rpm;
the total carbon content of the sludge is 20 to 50 percent, and the steel slag or tailings TFe 2 O 3 The content is 20-70%;
the concentration range of the KOH solution is 1-5 mol/L.
The ball mill is a planetary ball mill, and the inner lining of the ball milling tank is made of polytetrafluoroethylene.
The application of the multi-element solid waste synergistic preparation magnetic porous carbon composite adsorption material is used for adsorbing wastewater or sewage.
The invention has the beneficial effects that:
the method is characterized in that multielement solid waste is used as raw materials to be cooperatively prepared (the sludge and the agricultural and forestry waste provide carbon sources, the steel slag and tailings provide iron sources), the raw materials and an activating agent are simultaneously ground in a ball mill by a wet method, the raw materials and the activating agent are fully contacted and mixed, the impregnation process in the traditional method is omitted, the etching of KOH on the surface of the raw materials is accelerated, active sites are increased, the original structure of each raw material is destroyed by high-speed grinding, the steel slag or tailings are gathered at the center of the structure to form a core-shell structure taking the steel slag or the tailings as the center, the activated sludge and the agricultural and forestry waste are carbonized in the subsequent high-temperature process, and pore-forming substances such as iron oxide and ferrous oxide in the original steel slag or tailings are reduced into iron, so that porous carbon is better coated on the steel slag or the tailings, and the strength of the adsorbent is improved while the product is endowed with magnetism.
The traditional magnetic adsorbent mainly adopts coconut shells or coal as a raw material, and the preparation processes mainly comprise two processes, namely, directly taking an iron salt solution as an activating agent, and magnetizing the solution while activating the iron salt solution; the other method is that activation and magnetization are carried out separately, namely, an adsorbent is prepared by activating and calcining a chemical reagent, and then the adsorbent and an iron salt solution are coprecipitated to generate magnetic particles to complete magnetization, the product prepared by the former method has strong magnetism but poor adsorption performance, the latter method has complex steps, the two methods both need the iron salt solution, the cost is slightly high, and the magnetic particles directly attached to the surface of the adsorbent can block pores, so that the adsorption performance is also influenced to a certain extent.
Compared with the traditional method, the method has the advantages that the used raw materials are low in price and wide in source, are all solid wastes, and are ground, activated and magnetized in one step, so that the production efficiency is improved, and the product performance is excellent. As in example 1, the ratio of sludge, straw and steel slag is 5: 5: the magnetic porous carbon adsorbent prepared according to the proportion of 1 has the advantages that the removal rate of 0.1g of sample to 50ml of methylene blue solution with the concentration of 250mg/L reaches 100 percent, under the condition of no change of other conditions, the adsorption quantity to 450mg/L of methylene blue solution can reach 202mg/g, the removal rate is up to 89 percent, and the specific surface area of the sample reaches 448.636m 2 The magnetic separation effect is quite remarkable, and the adsorption capacity and the magnetism are far better than those of most adsorbents prepared by using single solid wastes (sludge and the like) as raw materials and adopting a traditional method.
In the aspect of production cost, because the coconut shells or coal is used as a raw material of the traditional magnetic activated carbon, the price is about 1500-2000 yuan/ton, a large amount of analytically or chemically pure ferric salt solution and activator solution are used, and the production cost of a finished product is about 4000 yuan/ton in addition to equipment, while the cost of each solid waste such as sludge, straws, steel slag, tailings and the like is 400-1000 yuan/ton and the like if the solid waste is treated by a treatment plant.
Drawings
Fig. 1 is a bar graph of the adsorption amounts of the magnetic porous carbon adsorbents obtained in all the examples at different initial concentrations;
fig. 2 is a photograph showing the magnetic separation effect of the magnetic porous carbon adsorbent obtained in example 1;
fig. 3 is a graph of a nitrogen adsorption isotherm and a pore size distribution of the magnetic porous carbon adsorbent obtained in example 1;
fig. 4 is a scanning electron micrograph of the magnetic porous carbon adsorbent obtained in example 1.
Detailed Description
All the raw materials are ground and blended with KOH solution with certain concentration in a planet ball mill, the obtained slurry is dried and then put into a porcelain boat to be heated and carbonized in a tube furnace, and inert gas is continuously introduced for protection in the period. And then, pickling the carbonized product, and finally washing the product to be neutral by using deionized water to obtain the magnetic porous carbon composite adsorbent.
Methylene blue solutions with different concentrations are used for simulating printing and dyeing wastewater to carry out adsorption performance test. Preparing methylene blue solution with the concentration of C0, adding an adsorbent with the mass of m, and oscillating and adsorbing for 12 hours in a constant-temperature gas bath oscillation box at room temperature in a dark place until the adsorption is balanced. Filtering the liquid after adsorption balance, measuring the absorbance of the filtrate at 662nm of an ultraviolet-visible spectrophotometer by using a 10mm cuvette, and obtaining the equilibrium concentration Ce of the filtrate by using a standard curve
The amount of adsorption was determined.
The total carbon content of the sludge is 20 to 50 percent, and the steel slag or tailing TFe 2 O 3 The content is 20-70%.
Example 1
Sludge produced by a certain sewage treatment plant in a new coastal area of Tianjin city, wheat straws around the Tianjin city and steel slag produced by a certain Tianjin steel mill are selected as raw materials, and the main components are shown in Table 1.
And (2) after the sludge is dewatered and dried by a high-speed centrifuge at the rotating speed of 10000rpm, the sludge is mixed with straw and steel slag according to the mass ratio of 5: 5: 1, preparing 3mol/L KOH solution, adding the KOH solution into a polytetrafluoroethylene ball-milling tank, wherein the solid-liquid ratio is 1: and 4, mixing and grinding for 2 hours by using a planetary ball mill at the rotating speed of 2000rpm/min, wherein the material-ball ratio is 1: 4. and drying the slurry obtained after grinding, then putting the dried slurry into a porcelain boat, heating the porcelain boat in a tube furnace to 700 ℃, and keeping the porcelain boat for 2 hours, wherein nitrogen is continuously introduced for protection. And finally, soaking the carbonized product in 1mol/L diluted hydrochloric acid for 2 hours, washing the carbonized product to be neutral by using deionized water, and drying the washed product to obtain the magnetic porous carbon adsorption material. The adsorption amount and removal rate of methylene blue are shown in table 2 and fig. 1.
According to the table 2 and the figure 1, the adsorption capacity of the product on methylene blue can reach 202.31mg/g, the product can reach good removal rate under higher concentration, and the removal rate of 0.1g sample on 50ml methylene blue with the concentration of 450mg/L reaches 89%. As can be seen from figure 2, the product can well complete solid-liquid separation under the action of the external magnetic field of the magnet, and the magnetic separation effect is obvious. The specific surface area of the prepared sample is 448.636m measured by a nitrogen adsorption instrument 2 The nitrogen desorption curve of the sample in FIG. 3 substantially follows the type II adsorption isotherm, i.e., there is an inflection point at the low P/P0 indicating that the monolayer is saturated and corresponds to the completion of monolayer adsorption when P/P0>After 0.1, the adsorption capacity is still increased along with the increase of the relative pressure, the characteristic of multilayer adsorption is embodied, meanwhile, according to the pore size distribution on the graph, the pore size is mostly distributed between 2nm and 50nm, the sample is a mesoporous material, the total pore volume is about 3.98cc/g, and the average pore size is 4.571nm(ii) a According to the scanning electron microscope picture of the sample shown in fig. 4, the rough porous structure coated on the surface can be obviously seen, the pores are developed, a higher specific surface area is provided for the adsorbent, the pore-forming effect of preparation processes such as activation and high-temperature pyrolysis on the raw material is reflected, and the whole particle has certain strength and the pores are not easy to collapse due to the iron source serving as the structure center.
Example 2
Sludge produced by a certain sewage treatment plant in a new coastal area of Tianjin city (same as example 1), peanut shells around Tianjin city and iron tailings produced by a certain mine in Hebei province are selected as raw materials, and the main components are shown in Table 1.
The sludge is dewatered and dried by a high speed centrifuge for 10min at the rotating speed of 10000rpm after being centrifuged by the high speed centrifuge, and then the dewatered and dried sludge is mixed with the peanut shells and the iron tailings according to the mass ratio of 2: 1:2, preparing 2mol/L KOH solution, adding the KOH solution into a polytetrafluoroethylene ball-milling tank, wherein the solid-liquid ratio is 1: 3, mixing and grinding for 4 hours by using a planetary ball mill, wherein the rotating speed is 1500rpm/min, and the material-ball ratio is 1: 4. and drying the slurry obtained after grinding, then putting the slurry into a porcelain boat, heating the porcelain boat in a tube furnace to 600 ℃, and keeping the porcelain boat for 2 hours, wherein nitrogen is continuously introduced for protection. And finally, soaking the carbonized product in 1mol/L diluted hydrochloric acid for 2 hours, washing the carbonized product to be neutral by using deionized water, and drying the washed product to obtain the magnetic porous carbon adsorption material. The adsorption amount and removal rate of methylene blue are shown in table 2 and fig. 1.
Example 3
Sludge produced by a certain sewage treatment plant in a new coastal area of Tianjin (same as example 1), bagasse produced in Tianjin and crushed slag produced in a certain steel mill in Tianjin are selected as raw materials, and the main components are shown in Table 1.
The sludge is dewatered and dried by a high speed centrifuge at the rotating speed of 10000rpm for 10min after being subjected to high speed centrifuge, and then the dewatered and dried sludge is mixed with bagasse and crushed slag according to the mass ratio of 1: 2: 1, preparing a KOH solution with the concentration of 4mol/L, adding the KOH solution into a polytetrafluoroethylene ball-milling tank according to the solid-liquid ratio of 1: and 5, mixing and grinding for 5 hours by using a planetary ball mill, wherein the rotating speed is 1000rpm/min, and the material-ball ratio is 1: 4. and drying the slurry obtained after grinding, then putting the slurry into a porcelain boat, heating the porcelain boat in a tube furnace to 550 ℃, and keeping the porcelain boat for 2 hours, wherein nitrogen is continuously introduced for protection. And finally, soaking the carbonized product in 1mol/L diluted hydrochloric acid for 2 hours, washing the carbonized product to be neutral by using deionized water, and drying the washed product to obtain the magnetic porous carbon adsorption material. The adsorption amount and removal rate of methylene blue are shown in Table 2 and FIG. 1
Example 4
Sludge produced by a certain sewage treatment plant in a new coastal area of Tianjin city (same as example 1), hickory shells around Tianjin city and iron-containing fly ash produced by iron ore in Hebei province are selected as raw materials, and the main components are shown in Table 1.
And (2) centrifuging the sludge for 10min at the rotating speed of 10000rpm by a high-speed centrifuge, dehydrating and drying the sludge, and mixing the dewatered sludge with hickory shells and dedusting ash in a mass ratio of 3: 2: 4, preparing 1mol/L KOH solution, adding the KOH solution into a polytetrafluoroethylene ball-milling tank according to the solid-liquid ratio of 1: 3, mixing and grinding for 6 hours by using a planetary ball mill, wherein the rotating speed is 500rpm/min, and the material-ball ratio is 1: 4. and drying the slurry obtained after grinding, then putting the slurry into a porcelain boat, heating the porcelain boat in a tube furnace to 500 ℃, and keeping the porcelain boat for 2 hours, wherein nitrogen is continuously introduced for protection. And finally, soaking the carbonized product in 1mol/L diluted hydrochloric acid for 2 hours, washing the carbonized product to be neutral by using deionized water, and drying the washed product to obtain the magnetic porous carbon adsorption material. The adsorption amount and removal rate of methylene blue are shown in Table 2 and FIG. 1
Examples of the adsorption applications
50ml of methylene blue solutions with initial concentrations of C0 of 250mg/L, 300mg/L, 350mg/L, 400mg/L and 450mg/L are respectively prepared into a 100ml conical flask, 0.1g of the adsorbents of the 4 cases are added, the temperature is adjusted to room temperature in a constant temperature gas bath oscillation box, and the mixture is oscillated and adsorbed for 12 hours in a dark place until the adsorption balance is reached. Filtering the adsorbed solution, measuring the absorbance of the filtrate at the 662nm absorption wavelength of an ultraviolet-visible spectrophotometer by using a 10mm cuvette, and measuring the equilibrium concentration Ce by using a standard curve thereof, wherein the formula is shown in the specification
The adsorption capacity is shown in Table 2.
Table 1 main components of raw materials used in examples
TABLE 2 adsorption and removal rates for methylene blue solutions of different initial concentrations
According to the adsorption application embodiment, the magnetic adsorbent prepared by using the methods of grinding, activating modification, finally high-temperature carbonization and the like according to respective characteristics of multi-element solid wastes makes up for deficiencies, has excellent performance, greatly improves the utilization rate of the solid wastes, changes wastes into valuables, and realizes the aim of environmental treatment of treating wastes with processes of wastes against one another.
The invention is not the best known technology.
Claims (7)
1. A method for preparing a magnetic porous carbon composite adsorption material by the cooperation of multiple solid wastes is characterized by comprising the following steps:
(1) dewatering the sludge through a high-speed centrifuge, adding the preliminarily crushed sludge, agricultural and forestry wastes and industrial wastes into a ball milling tank, adding a KOH solution, and carrying out wet mixing and grinding for 2-20 hours by using a ball mill to obtain uniformly mixed slurry;
wherein, the mass ratio is, the sludge after dehydration: agricultural and forestry wastes: industrial waste (1-10): (1-10): (1-10); the concentration of the KOH solution is 1-5 mol/L; the rotation speed of the ball mill is 500-2000 rpm, and the material ball ratio is 1: 4; the solid-liquid ratio of the raw material to the KOH solution is 1: (2-10);
the agricultural and forestry waste is straw or fruit shell; the industrial waste is steel slag, iron tailings, crushed furnace slag or iron-containing dedusting ash;
(2) drying the slurry obtained by ball milling in the step (1), and then putting the dried slurry into a tube furnace for carbonization for 1-5 h at 400-950 ℃ in a nitrogen atmosphere to obtain a magnetic porous carbon crude product;
(3) and (3) washing the crude product obtained in the step (2) by using dilute hydrochloric acid and deionized water in sequence until the crude product is neutral, and drying to obtain the magnetic porous carbon composite adsorbing material.
2. The method for preparing the magnetic porous carbon composite adsorbing material by the multi-element solid waste synergistic manner according to claim 1, wherein the concentration of the dilute hydrochloric acid used in the step (3) is 0.1-1 mol/L.
3. The method for preparing the magnetic porous carbon composite adsorbing material by the synergy of the multi-component solid waste and the waste as claimed in claim 1, wherein the revolution number of the high-speed centrifuge in the step (1) is 2000-10000 rpm.
4. The method for preparing the magnetic porous carbon composite adsorption material by the synergism of the multi-element solid waste as claimed in claim 1, wherein the total carbon content of the sludge is 20% -50%, and the steel slag or tailings TFe 2 O 3 The content is 20-70%.
5. The method for preparing the magnetic porous carbon composite adsorbing material by the synergistic effect of the multiple solid wastes according to claim 1, wherein the concentration range of the KOH solution is 1-5 mol/L.
6. The method for preparing the magnetic porous carbon composite adsorption material by the synergistic effect of the multiple solid wastes according to claim 1, characterized in that a ball mill is a planetary ball mill, and the lining of a ball mill tank is polytetrafluoroethylene.
7. The application of the multielement solid waste obtained in claim 1 to synergistically prepare the magnetic porous carbon composite adsorption material is characterized by being used for adsorbing wastewater or sewage.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115784227A (en) * | 2022-11-07 | 2023-03-14 | 河南农业大学 | Method for preparing porous carbon from agriculture and forestry biomass |
| CN115970650A (en) * | 2023-03-20 | 2023-04-18 | 四川省冶勘设计集团生态环境工程有限公司 | Composite biochar and preparation method and application thereof |
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| CN102530941A (en) * | 2011-12-16 | 2012-07-04 | 北京工业大学 | Sludge-based activated carbon and preparation method thereof |
| CN112354516A (en) * | 2020-10-26 | 2021-02-12 | 哈尔滨工业大学 | Method for preparing magnetic sludge-based biochar material from sludge and application of magnetic sludge-based biochar material |
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2022
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102530941A (en) * | 2011-12-16 | 2012-07-04 | 北京工业大学 | Sludge-based activated carbon and preparation method thereof |
| CN112354516A (en) * | 2020-10-26 | 2021-02-12 | 哈尔滨工业大学 | Method for preparing magnetic sludge-based biochar material from sludge and application of magnetic sludge-based biochar material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115784227A (en) * | 2022-11-07 | 2023-03-14 | 河南农业大学 | Method for preparing porous carbon from agriculture and forestry biomass |
| CN115970650A (en) * | 2023-03-20 | 2023-04-18 | 四川省冶勘设计集团生态环境工程有限公司 | Composite biochar and preparation method and application thereof |
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