CN108554379B - Adsorbent based on waste steel slag and preparation method and application thereof - Google Patents
Adsorbent based on waste steel slag and preparation method and application thereof Download PDFInfo
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- CN108554379B CN108554379B CN201810465390.8A CN201810465390A CN108554379B CN 108554379 B CN108554379 B CN 108554379B CN 201810465390 A CN201810465390 A CN 201810465390A CN 108554379 B CN108554379 B CN 108554379B
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- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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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
- 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
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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
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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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
- 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
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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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
- 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
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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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
- 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
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4837—Lignin
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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
- 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
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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
- 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
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- Chemical Kinetics & Catalysis (AREA)
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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
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- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to an adsorbent based on waste steel slag, a preparation method and application thereof, and belongs to the field of resource utilization of solid waste. In the invention, in the steelmaking process, an oxidation product generated by impurities in pig iron is subjected to magnetic separation and screening to obtain steel slag tailings with fineness less than 150 meshes and iron content below 5%, then 20% of grinding aid and 30% of surfactant are added for grinding together, and then 15% of HCl is used for cleaning, so that the steel slag containing Cr treated based on waste steel slag is obtained6+A novel adsorbent for waste water. The invention applies the waste steel slag to the heavy metal Cr6+In the treatment of the wastewater, the preparation is simple and convenient, the cost is low, and the removal efficiency can reach about 92 percent.
Description
Technical Field
The invention relates to an adsorbent based on waste steel slag, a preparation method and application thereof, and the adsorbent can efficiently remove Cr in industrial wastewater6+Belonging to the field of solid waste resource utilization and sewage treatment.
Background
Heavy metal ion wastewater is wastewater which has the most serious harm to the environment and human beings, and if the heavy metal is not treated properly, the heavy metal can be enriched in the environment and then cause harm to the human health through a food chain. Up to now, the treatment methods of heavy metal wastewater mainly include neutralization precipitation, sulfide precipitation, bioadsorption, diaphragm electrolysis, reverse osmosis, electrodialysis, evaporative concentration, ion exchange, electrocoagulation and the like. The steel slag contains SiO2、Fe2O3、Al2O3、P2O5And free CaO, MgO and other components, can be processed into particles with the aperture equivalent to that of the activated carbon, has large density, high settling speed in water, short solid-liquid separation treatment period and certain alkalinity and adsorption capacity, has chemical precipitation effect and adsorption effect on heavy metal ions in the wastewater, so that the research on applying the steel slag to the treatment of the heavy metal ion wastewater is more and more in recent years. Researches prove that the method has certain practicability, and opens up a new way of treating waste with waste for the treatment of the heavy metal ion wastewater. The crushed steel slag has small grain size and pore size, large specific surface area, certain adsorption effect on metal ions and great contribution to the removal of the metal ions. This process was confirmed by adsorption experimental studies. Namely, the adsorption curve of metal ions is made under the condition of fixing the consumption of the steel slag.
Disclosure of Invention
One of the purposes of the invention is to provide a novel adsorbent prepared by fully utilizing waste steel slag, aiming at the problem of low removal rate of heavy metal ions in the traditional sewage treatment, the steel slag is loose and porous, has large specific surface area and certain adsorption capacity, andthe steel slag has high density, high settling speed in water and easy solid-liquid separation, so that the steel slag can be used as an adsorbing material for treating industrial wastewater Cr6+And has better industrial application prospect.
The invention also aims to provide a preparation method of the adsorbent based on the waste steel slag.
The invention also aims to provide the adsorbent based on the waste steel slag for adsorbing Cr in industrial wastewater6+The use of (1).
The technical scheme adopted by the invention is as follows: an adsorbent based on waste steel slag is prepared from steel slag tailings, a surfactant and a grinding aid.
Preferably, the adsorbent based on the waste steel slag comprises the following components in percentage by mass: glycerol =5:3: 2.
In the adsorbent based on the waste steel slag, the steel slag tailings contain 35-45 wt% of CaO, 7-15 wt% of MgO and 10-20 wt% of SiO2、1~8%Al2O3And 20-35% Fe2O3。
A preparation method of an adsorbent based on waste steel slag comprises the following steps:
1) carrying out magnetic separation on the steel slag by using a magnetic separator, wherein the iron content of the steel slag after the magnetic separation is less than 7%, grinding the steel slag after the magnetic separation by using a jaw crusher, sieving the steel slag by using a 150-mesh net, and taking undersize materials as steel slag tailings;
2) taking steel slag tailings, calcium lignosulfonate and glycerol, placing the mixture into a stirrer, stirring and mixing uniformly, adding 20-30% of water, stirring uniformly, and preparing steel slag particles with the particle size of 4-5 mm;
3) naturally curing the prepared steel slag particles for 48 hours, placing the steel slag particles into a muffle furnace, roasting the steel slag particles at 500 ℃ for 4 hours to obtain an adsorbent, namely novel steel slag particles, and pickling the steel slag particles with 10% HCl to remove metal ions such as Fe and Mg in the steel slag;
preferably, in the above preparation method of the adsorbent based on waste steel slag, step 3), the prepared steel slag particles are naturally aged for 48 hours, and the steel slag particles are placed into a muffle furnace to be roasted at 500 ℃ for 4 hours to obtain the adsorbent, i.e. the novel steel slag particles.
The adsorbent based on the waste steel slag is used for removing Cr in industrial wastewater6+The method comprises the following steps: and (3) adjusting the pH = 7-11 of the industrial wastewater, uniformly adding the adsorbent into the industrial wastewater according to the proportion of 4-5 kg per cubic meter, and stirring for reacting for 45 min.
The invention has the beneficial effects that:
1) the raw materials are wide in source and low in cost;
2) the raw materials used in the invention are solid wastes in the steel mining industry, belong to resource recycling and are harmless to the environment.
3) The steel slag adsorbent is simple and convenient to prepare, has obvious effect and can be used for treating Cr in industrial wastewater6+The removal rate of the catalyst is as high as about 92 percent, and the catalyst has good industrial prospect.
Drawings
FIG. 1 addition of adsorbent and Cr6+Adsorption rate relationship diagram
FIG. 2 pH and Cr of wastewater6+Adsorption rate relationship diagram
FIG. 3 stirring reaction time and Cr6+And (5) a relational graph.
Detailed Description
The invention is further illustrated by the following specific examples, but is not limited thereto. Because the quality of the sewage and the adopted treatment process are different in various places, the pretreatment parameters can be correspondingly changed, and therefore, the key parameters in the invention can be properly adjusted on the premise of not departing from the essence of the invention and the scope of the appended claims.
Example 1
The chemical compositions of the steel slag taken from the steel slag dump of the Benxi Steel group are shown in Table 1. And (3) carrying out magnetic separation to remove iron by adopting a magnetic separator, wherein the iron content of the steel slag after the magnetic separation is less than 7%, grinding the steel slag after the magnetic separation by using a jaw crusher, sieving the steel slag with a 150-mesh net, and taking undersize products as steel slag tailings.
Taking steel slag tailings, calcium lignosulfonate and glycerol, placing the mixture into a stirrer, stirring and mixing uniformly, adding 25% of water, stirring uniformly, and preparing steel slag particles with the particle size of 4-5 mm.
Naturally curing the prepared steel slag particles for 48 hours, placing the steel slag particles into a muffle furnace, roasting the steel slag particles at 500 ℃ for 4 hours to obtain an adsorbent, namely novel steel slag particles, and pickling the steel slag particles with 10% HCl to remove metal ions such as Fe and Mg in the steel slag.
Weighing 5g of steel slag particles in a 400mL beaker, and then weighing 100mL of Cr with the concentration of 100mg/L6+In the solution, the reaction temperature is (25 +/-1) DEG C. Stirring with electric stirrer at constant speed for 45min, filtering, sampling, and measuring Cr in solution with atomic absorption spectrophotometer6+And (4) concentration. At this time, the steel slag particles are Cr-removed6+The adsorption removal rate of (2) was 92.9%. The steel slag particles are recycled for 2 times after being pickled by 10 percent HCl, and the recycled steel slag particles are used for treating Cr6+The adsorption removal rate of (3) was 89.5%.
TABLE 1 Steel slag chemical composition
Composition (I) | SiO2 | Al2O3 | CaO | MgO | Fe2O3 | Loss |
Ratio (%) | 13.32 | 1.57 | 38.91 | 7.61 | 23.11 | 4.38 |
Example 2
(I) source of wastewater
The sewage comes from industrial production wastewater containing heavy metal ions in the Taizi river chromium factory, the pH is 6.3, and the Cr is6+The concentration of (3) was 142.17 mg/L.
The addition amount of the adsorbent is used for removing metal ion Cr6+Influence of (2)
The method comprises the following steps: 100ml of the waste water was added with the adsorbents prepared in example 1, 0.30g, 0.35g, 0.40 g, 0.45g, 0.50g, 0.55g, and 0.60g, respectively, and reacted for 1 hour, and then Cr in the solution was measured6+The content of (a). The results are shown in FIG. 1.
As can be seen from the test results in FIG. 1, as the amount of the added adsorbent increases, it is added to Cr6+The adsorption rate of (A) is increased. The adsorbent based on the waste steel slag has Cr pairs when the addition amount is 5.0g6+Better adsorption effect.
(III) removing metal ion Cr from wastewater by pH pair6+Influence of (2)
The method comprises the following steps: taking 100ml of sewage, respectively using dilute HCl and NaOH to adjust the pH value to 1, 2, 3, 5, 7, 8, 9, 11 and 12, adding 0.50g of the waste steel slag-based adsorbent prepared in example 1, reacting for 1h, and then measuring Cr in the solution6+The content of (a). The results are shown in FIG. 2.
As can be seen from the results in FIG. 2, the adsorbent based on the waste steel slag has a Cr pair with an increase in the pH of the wastewater6+The adsorption rate of (A) is increased. Has better adsorption effect in the range of pH = 7-11, and can adsorb Cr6+The adsorption rate can reach 91.2-92.7%.
(IV) adsorption time for removing metal ion Cr6+Influence of (2)
The method comprises the following steps: 100ml of waste water was taken, the pH was adjusted to 8, and the solution prepared in example 1 and based on5.0g of adsorbent of the waste steel slag, reacting for 5min, 15min, 25min, 35min, 45min and 55min, and then measuring Cr in the solution6+The content of (a). The results are shown in FIG. 3.
As can be seen from the test results in FIG. 3, the adsorbent based on the waste steel slag has a higher Cr content as the adsorption time is longer6+The adsorption rate of (A) is increased. When the adsorption is carried out for 0.75-1.0 h, the adsorption is carried out on Cr6+The adsorption rate of (b) was 92.9% of the maximum adsorption rate.
Through the screening of conditions, the optimal process conditions are as follows: adjusting the pH of the industrial wastewater to be 7-8, uniformly adding an adsorbent into the industrial wastewater according to the proportion of 5-5.5 kg per cubic meter, stirring and reacting for 0.75-1.0 h, and adding the steel slag adsorbent to Cr6+The adsorption rate of (2) reached 92.7% of the maximum adsorption rate.
Claims (4)
1. A preparation method of an adsorbent based on waste steel slag is characterized by comprising the following steps:
1) carrying out magnetic separation on the steel slag by using a magnetic separator, wherein the iron content of the steel slag after the magnetic separation is less than 7%, grinding the steel slag after the magnetic separation by using a jaw crusher, sieving the steel slag by using a 150-mesh net, and taking undersize materials as steel slag tailings;
2) taking steel slag tailings, calcium lignosulfonate and glycerol, wherein the steel slag tailings comprise the following components in percentage by weight: glycerol =5:3:2, the mixture is put into a stirrer to be stirred and mixed evenly, water is added to be mixed, and after even mixing, steel slag particles are prepared;
3) naturally curing the prepared steel slag particles, placing the steel slag particles into a muffle furnace to be roasted to obtain an adsorbent, namely the steel slag particles, and pickling after the steel slag particles are prepared to remove Fe and Mg metal ions in the steel slag.
2. The method for preparing the waste steel slag-based adsorbent according to claim 1, wherein the method comprises the following steps: the steel slag tailings contain 35-45% of CaO, 7-15% of MgO and 10-20% of SiO by weight percentage2、1~8%Al2O3And 20-35% Fe2O3。
3. The method for preparing the waste steel slag-based adsorbent according to claim 1, wherein the amount of water added in the step 2) is 20-30% of the mixture, and the particle size of the prepared steel slag particles is 4-5 mm.
4. The method of claim 1, wherein the steel slag particles obtained in step 3) are naturally aged for 48 hours, placed in a muffle furnace at 500 ℃ for 4 hours, and acid-washed with 10% HCl.
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CN110950400B (en) * | 2018-09-27 | 2022-02-22 | 宝山钢铁股份有限公司 | Method for removing total nickel and dissolved organic matters in cold rolling nickel-containing wastewater |
CN110627175B (en) * | 2019-09-02 | 2021-11-16 | 济南大学 | Steel slag-based flocculant and preparation method and application thereof |
CN113000011B (en) * | 2021-03-10 | 2022-05-24 | 清华大学 | Heavy metal adsorption material and preparation method and application thereof |
CN116002919A (en) * | 2023-01-10 | 2023-04-25 | 天津大学 | Method for treating acidic mine wastewater by using fly ash |
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