CN117101600A - Heavy metal ion adsorbent and preparation method and application thereof - Google Patents
Heavy metal ion adsorbent and preparation method and application thereof Download PDFInfo
- Publication number
- CN117101600A CN117101600A CN202311128230.1A CN202311128230A CN117101600A CN 117101600 A CN117101600 A CN 117101600A CN 202311128230 A CN202311128230 A CN 202311128230A CN 117101600 A CN117101600 A CN 117101600A
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- CN
- China
- Prior art keywords
- slurry
- steel slag
- red mud
- heavy metal
- metal ion
- 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
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 72
- 239000003463 adsorbent Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
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- 239000010959 steel Substances 0.000 claims abstract description 108
- 239000002893 slag Substances 0.000 claims abstract description 107
- 239000002002 slurry Substances 0.000 claims abstract description 79
- 150000002500 ions Chemical class 0.000 claims abstract description 48
- 239000002245 particle Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 28
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- 238000001238 wet grinding Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000010000 carbonizing Methods 0.000 claims abstract description 8
- 230000007935 neutral effect Effects 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 7
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- 239000011734 sodium Substances 0.000 claims description 32
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- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 1
- SXGZJKUKBWWHRA-UHFFFAOYSA-N 2-(N-morpholiniumyl)ethanesulfonate Chemical compound [O-]S(=O)(=O)CC[NH+]1CCOCC1 SXGZJKUKBWWHRA-UHFFFAOYSA-N 0.000 description 1
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 1
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 208000010392 Bone Fractures Diseases 0.000 description 1
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- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 206010010356 Congenital anomaly Diseases 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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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- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
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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
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/043—Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- 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
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- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
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Abstract
The invention discloses a preparation method of a heavy metal ion adsorbent, the heavy metal ion adsorbent and application thereof. The preparation method comprises the following steps: obtaining a mixture of steel slag and red mud; adding water to the mixture of steel slag and red mud obtained in the above step, and wet-milling using a ball mill, thereby obtaining slurry 1; CO is introduced into the slurry 1 under the stirring condition 2 Carbonizing the modified porous skeleton particles in the slurry 1 by gas to obtain slurry 2; and filtering the slurry 2 to obtain a solid, washing the solid to a neutral pH, and drying to obtain the heavy metal ionA sub-adsorbent. According to the invention, two industrial solid wastes, namely steel slag and red mud, are used as reaction raw materials, the cost is low, the porous adsorption material loaded with nano calcium carbonate is prepared under the condition of room temperature, the adsorption efficiency is high, and the high additional value utilization of the steel slag and the red mud and the treatment of wastewater are realized.
Description
Technical Field
The invention belongs to the technical field of solid waste treatment, and particularly relates to a method for preparing a carbonized modified heavy metal adsorbent for removing heavy metal ions in water by utilizing solid waste (such as steel slag, red mud and the like), the carbonized modified heavy metal adsorbent prepared by the method and application of the carbonized modified heavy metal adsorbent.
Background
Steel slag is a solid waste produced in the steel industry. About 1.5 to 2.5t of steel slag can be produced by-product per 1t of crude steel. The steel slag yield in 2020 reaches 1.6 hundred million tons. The steel slag is piled up in the open air and placed for treatment, so that a large amount of land is occupied, and heavy metals in the steel slag can enter a water source and the land to cause groundwater pollution and soil pollution under the scouring of rainwater, thereby affecting the growth of plants and the health of human beings. Steel slag is used in industries such as cement, concrete and the like, but the added value is low, and a steel slag high-value utilization technology needs to be developed.
Red mud is also called red mud, and industrial solid waste discharged after alumina is extracted from bauxite. Red mud is an insoluble residue and can be classified into sintered red mud, bayer process red mud and combined process red mud. A large amount of red mud cannot be fully and effectively utilized, and can be stacked only by virtue of a large-area storage yard, so that a large amount of land is occupied, and serious pollution is caused to the environment. The generation of a large amount of red mud has caused various direct and indirect influences on the production and life of human beings, so the yield and harm of the red mud are reduced to the maximum extent, and the realization of multi-channel and large-amount recycling is also urgent.
In recent years, environmental pollution has become a concern. With the development of industrialization, the problems of heavy metal wastewater in the industries of nonferrous metal production, mining, chemical industry and the like are increasingly serious. These contaminations not only cause serious damage to the ecological environment but also cause considerable damage to the physical health of humans. Lead is liable to cause anemia, injure brain cells of human, cause congenital mental retardation, nerve dysfunction and kidney injury, etc. Cadmium can prevent the absorption of calcium by human body, resulting in osteoporosis, fracture, bone pain, bone injury, and even cancer. Even if the concentration of heavy metals is small when discharged with wastewater, pollution may be caused by enrichment. Therefore, a technology for treating heavy metal sewage needs to be actively explored, and the pollution of water resources is relieved.
The existing heavy metal sewage treatment methods comprise adsorption, deposition, coagulation, ion exchange, membrane separation, solvent extraction and the like. The adsorption method is widely applied to the treatment of heavy metal sewage due to high efficiency, simple operation and wide applicability. The traditional adsorbents comprise active carbon, zeolite, kaolin, graphene, clay, cellulose and the like, and the adsorbents have the problems of low adsorption efficiency, non-regeneration and the like. Therefore, a novel adsorption material for efficiently treating heavy metal sewage needs to be found.
In this respect, patent application number CN202211627722.0 discloses a magnetic biochar composite adsorbent, a preparation method thereof and an application of adsorbing heavy metal chromium (VI), and the steps are as follows: cleaning, drying, crushing and sieving the waste biomass material to obtain a biochar raw material, mixing the biochar raw material with an alkali solution, stirring to remove impurities, and cleaning and drying to obtain alkaline biochar; fully and uniformly mixing alkaline biochar with a methanol solution of polyethyleneimine, and then carrying out a crosslinking reaction with a glutaraldehyde solution to obtain amino modified biochar; dispersing carboxyl ferroferric oxide magnetic nanospheres into 2-morpholinoethanesulfonic acid buffer solution in an ultrasonic way, adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysuccinimide, continuing to uniformly disperse in the ultrasonic way, then carrying out shaking treatment on the mixture for 10-30 min by a shaking table, and centrifuging the mixture to obtain activated carboxyl ferroferric oxide nano particles; dispersing the prepared amino modified biochar in a buffer solution, adding activated carboxyl ferroferric oxide nano particles, carrying out ultrasonic mixing uniformly, carrying out shaking table shaking treatment overnight, carrying out magnetic separation on the product, washing, and drying to obtain the magnetic biochar composite adsorbent.
Patent application No. CN201810465390.8 discloses an adsorbent based on waste steel slag, a preparation method and application thereof, wherein an oxidation product generated by impurities in pig iron in a steelmaking process is subjected to magnetic separation and screening to obtain steel slag tailings with fineness less than 150 meshes and iron content below 5%, 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 Cr-containing processed steel slag based on waste steel slag can be obtained 6+ Novel adsorbent for wastewater.
Although the adsorbent is low in cost due to the resource utilization of waste biomass materials or steel slag, the adsorption effect is still to be enhanced. Therefore, it is necessary to further improve the preparation method of the steel slag-based heavy metal adsorbent, improve the adsorption effect of the steel slag-based heavy metal adsorbent on various heavy metal ions, and simultaneously recycle other solid wastes such as steel slag and/or red mud.
Disclosure of Invention
In order to solve the problems, the invention aims to provide the carbonized modified steel slag-based heavy metal ion adsorbent for removing heavy metal ions in water, and the preparation method and the application thereof.
According to one embodiment of the present invention, there is provided a method for preparing a heavy metal ion adsorbent comprising the steps of:
s1: grinding and screening the dry steel slag and the dry red mud respectively, and then dispersing and mixing the screened steel slag and the red mud to obtain a mixture of the steel slag and the red mud;
s2: adding water to the mixture of steel slag and red mud obtained in step S1, stirring, and wet-milling using a ball mill, thereby obtaining slurry 1 containing porous particles;
s3: under stirring to step S2CO is introduced into the slurry 1 2 Carbonizing the modified porous skeleton particles in the slurry 1 by gas to obtain slurry 2, wherein the slurry 2 comprises a porous skeleton and nano carbonate particles loaded on the surfaces of the pores; and
s4: the slurry 2 of step S3 is filtered to obtain a solid, and the solid is washed to a neutral pH and dried (e.g., heated to a boiling state of water, and the water is evaporated), thereby obtaining the heavy metal ion adsorbent.
Carbonization in the present invention refers to the mixing of hydroxide or metal ions with CO in slurry 1 2 And (3) a process of generating carbonate by reaction.
Fig. 1 shows a process flow diagram of the preparation of the heavy metal ion adsorbent of the present invention. As shown in fig. 1, the general process for preparing the heavy metal ion adsorbent according to the present invention comprises the steps of respectively drying steel slag and red mud, mixing and ball milling. To the obtained ingredients, water was added and wet milling was performed, thereby obtaining slurry 1. Carbon dioxide was introduced into the slurry 1, and carbonization was performed to obtain a slurry 2. The slurry 2 was filtered and boiled, thereby obtaining an adsorbent.
More particularly, the preparation method of the invention relates to a carbonized modified steel slag-based adsorbent for removing heavy metal ions in water and a preparation method thereof.
According to the preparation method, sodium silicate and sodium metaaluminate are generated by eroding steel slag and aluminosilicate in the red mud by alkali in the red mud, so that pores are generated in the steel slag and red mud particles, and insoluble nano carbonate formed by carbonization is attached to the surface of a framework, so that the specific surface area of the adsorbent is improved. In addition, the red mud and the steel slag can synergistically improve the reactivity of the aluminosilicate, increase the number of active sites on the surface of the adsorbent, and improve the adsorption rate of heavy metal ions in water.
The above steps S1 to S4 of the production method of the present invention are described below, respectively.
Step S1 is a pretreatment step of metallurgical solid waste raw materials such as steel slag, red mud and the like. Specifically, in step S1, the steel slag and the red mud may be dried and then respectively put into a ball mill for ball milling. And (3) sieving the ball-milled steel slag and red mud through 100-200 mesh sieves respectively. And then, the sieved steel slag and the red mud are dispersed and mixed, and the mixture of the steel slag and the red mud is obtained after homogenization.
Preferably, the grinding time of the dried steel slag and the dried red mud in the step S1 is respectively 20-60min. The contact area of the steel slag and the red mud can be increased by the step.
The mixing mass ratio of the dry steel slag to the dry red mud in the step S1 is 1:0.2-4.0.
Step S2 can obtain porous steel slag and red mud particles as well as alkali metal hydroxide. In one example, step S2 includes adding distilled water to the steel slag and red mud mixture mixed in step S1, stirring uniformly, and sufficiently wet-milling to obtain slurry 1 using a small ball mill. The ball mill in the step S2 is fully wet-milled for 0.2-3.5h at a rotating speed of 50-100rpm. In the step S2, the mass ratio of the steel slag and red mud mixture to water is 1:2.0-6.0, preferably, the water is distilled water.
By the above-described sufficiently wet grinding, a slurry 1 containing porous steel slag and red mud particles and alkali metal hydroxide can be formed. In slurry 1, the solids content may be 40-60 wt%. The step utilizes the alkali in the red mud to excite the activity of the steel slag, increases the number of active sites on the surface of the adsorbent, and erodes the steel slag and red mud particles to form porous particles with loose porosity and large specific surface area.
Specifically, wet milling of steel slag and red mud at room temperature can form porous particles, with calcareous and aluminosilicates being the major components thereof. The steel slag comprises the following chemical components: caO content is 36.92%, siO 2 The content is 17.34 percent, fe 2 O 3 20.28% of MgO, 6.82% of Al 2 O 3 The content is 4.54%, the MnO content is 7.74%, and P 2 O 5 Content 2.78%, K 2 O content was 0.06%. The chemical components of the red mud are as follows: al (Al) 2 O 3 The content is 25.6%, siO 2 The content is 18.54%, the CaO content is 20.10%, fe 2 O 3 Content 4.39%, na 2 O was 8.29%.
In the wet grinding process, free calcium oxide and magnesium oxide in the steel slag are dissolved in the slurry,alkali metal hydroxides (preferably calcium hydroxide and magnesium hydroxide) are formed. Meanwhile, na in red mud 2 O is dissolved into the slurry to form an alkaline environment, aluminosilicate in the steel slag and the red mud is eroded to generate sodium silicate and sodium metaaluminate, so that pores are generated in the steel slag and the red mud particles, a porous framework comprising the porous steel slag framework and the porous red mud particle framework is formed, and meanwhile, the specific surface area of the reaction is increased.
Step S3 involves the loading of the nanocarbon salt (preferably at least one of calcium carbonate and magnesium carbonate). In one example, step S3 includes introducing CO into the slurry 1 obtained in step S2 2 And fully carbonizing the metal hydroxide in the slurry 1 and the steel slag and red mud ore phase bodies by adopting magnetic stirring to obtain the slurry 2. The slurry 2 comprises a porous skeleton and nano carbonate particles supported on the pore surfaces.
Particularly, after carbon dioxide is introduced, the carbon dioxide and calcium hydroxide and magnesium hydroxide generated in the step S2 and mineral phases (tricalcium silicate, dicalcium silicate and the like) of the steel slag and the red mud are subjected to carbonization reaction to generate nano calcium carbonate and magnesium carbonate, and the nano calcium carbonate and the magnesium carbonate are loaded on a framework. Further increase the reaction area of the adsorbent and heavy metal ions.
Preferably, in step S3, a base such as sodium hydroxide or calcium hydroxide is added to promote the formation of the skeleton.
In step S3, the CO 2 The purity of the gas can be 95 to 99 percent, the flow rate is 0.2 to 1.2L/min, the carbonization temperature is 50 to 75 ℃, the reaction time is 1.1 to 2.5 hours, and the stirring speed is 300 to 1800rpm.
In one example, the preparation method of the present invention may further comprise S2-1 after step S2: adding the sodium fulvate solution into the slurry 1, and uniformly mixing to obtain a slurry 3 containing sodium fulvate activated alkali metal ions, wherein the addition amount of the sodium fulvate is 0.03-0.10 wt% relative to the total weight of the dry steel slag and the dry red mud;
wherein the step S3 comprises introducing CO into the slurry 2-1 obtained in the step S2-1 at room temperature 2 And (3) carbonizing the activated alkali metal in the slurry 2-1 to obtain a slurry 3, and simultaneously releasing fulvic acid in water.
By adding a sodium fulvate solution to the slurry 1 prior to step S3 to obtain a solution comprising sodium fulvate activated alkali metal ions, the carbonization efficiency in step S3 can be further improved. Sodium fulvate is a humic acid macromolecule which can be dissolved in water or acid, and is slightly alkaline. The basic structure of the sodium fulvate is an aromatic ring and an alicyclic ring, and the ring is connected with carboxyl, hydroxyl, carbonyl, quinolyl, methoxy and other functional groups, so that the sodium fulvate can exchange with heavy metal ions and has a heavy metal adsorption function. The complexation of the sodium fulvate can promote the leaching of metal ions such as calcium and magnesium of steel slag in the slurry 1, so as to accelerate the carbonization reaction of the calcium and magnesium ions and dissolved carbon dioxide and promote the formation of nano carbonate particles. At the same time, the carbonization reaction can also release fulvic acid in water and wash it out in a subsequent step.
Therefore, by adding the sodium fulvate solution, the carbonization reaction of step S3 can be made to proceed under very mild conditions such as room temperature and normal pressure, and a low carbon dioxide flow rate. Preferably, at this time, the flow rate of carbon dioxide introduced into the slurry 2 in the step S3 is 0.2-1.2L/min, the carbonization temperature is 20-30 ℃, the reaction time is 0.5-1h, and the stirring speed is 300-600rpm.
In another aspect, the present invention also provides a heavy metal ion adsorbent prepared by any of the methods described above. The heavy metal ion adsorbent of the present invention comprises a porous skeleton and a nano carbonate covered on the surface of the skeleton.
More preferably, the present invention also provides a preparation method comprising:
s1: grinding and screening the dry steel slag and the dry red mud respectively, and then dispersing and mixing the screened steel slag and the red mud to obtain a mixture of the steel slag and the red mud;
s2: adding water to the mixture of steel slag and red mud obtained in step S1, stirring, and wet-milling using a ball mill, thereby obtaining slurry 1 containing porous particles;
s2-1: after the step S2, adding the sodium fulvate solution into the slurry 1, and uniformly mixing to obtain slurry 2-1, wherein the addition amount of the sodium fulvate is 0.03-0.10 wt% relative to the total weight of the dry steel slag and the dry red mud;
s3: introducing CO into the slurry 2-1 obtained in the step S2-1 under stirring 2 Carbonizing the modified porous silica-alumina skeleton particles in the slurry 2-1 by gas to obtain a slurry 2, wherein the slurry 2 comprises porous silica-alumina gel skeleton and nano carbonate particles loaded on the surfaces of pores; and
s4: filtering the slurry 2 of the step S3 to obtain a solid, washing the solid to a neutral pH, and drying to obtain the heavy metal ion adsorbent.
As calcium hydroxide and magnesium hydroxide are formed, they can clog the pores in the steel slag and red mud, thereby rendering a portion of the calcium oxide and magnesium oxide insoluble. For this purpose, the applicant preferably introduces a step S2-1 between step S2 and step S3, adding a sodium fulvate solution to the slurry 1, mixing uniformly, preferably continuing wet milling, to obtain a slurry 2-1. Sodium fulvate has chelation with free calcium ions and magnesium ions in the aqueous solution, so that the dissolution of calcium oxide and magnesium oxide can be greatly promoted. The chelate of calcium and magnesium ions is not stabilized by hydroxides and carbonates, and therefore, the chelate is converted into magnesium hydroxide and calcium hydroxide after formation, and then further converted into calcium carbonate and magnesium carbonate in step S3. And the soluble salts of fulvic acid are removed by washing in step S4.
In a further aspect, the invention also provides application of the heavy metal ion adsorbent in removing heavy metal ions in sewage.
Particularly, the adsorbent prepared by the invention can be used for adsorption treatment of heavy metal sewage, wherein the heavy metal ions are lead ions, cadmium ions, copper ions, chromium ions and the like, and the adsorption rate of the heavy metal is more than or equal to 60%, preferably more than or equal to 62%, more than or equal to 65%, more than or equal to 70%, more than or equal to 75%, more than or equal to 80%, more than or equal to 85%, more than or equal to 90%, more than or equal to 95% or more than or equal to 97%.
Compared with the prior art, the invention has the beneficial technical effects that:
according to the invention, steel slag and red mud are subjected to corrosion modification by alkali in the red mud, and a loose and porous steel slag and red mud particle skeleton is prepared by means of the synergistic effect of the steel slag and the red mud, and meanwhile, the subsequent carbonization modification enables the surface of the skeleton to be covered with some nano carbonate particles, so that the specific surface area of the adsorbent is increased, the number of active sites on the surface of the adsorbent is increased, and the adsorption capacity of the adsorbent on heavy metal sewage is improved.
While not being bound by theory, it is believed that the mechanism by which the formed nano-carbonate particles promote heavy metal adsorption is that the nano-carbonate particles act in part to increase specific surface area and in addition have some chemisorption capacity themselves. Carbonates are calcium carbonate and magnesium carbonate. The nano carbonate is calcium carbonate and magnesium carbonate, and is insoluble in water.
In particular, since different crystal planes of the nano carbonate crystal are charged differently and 110 crystal planes are charged negatively, it is presumed that the nano carbonate crystal is more likely to adsorb positively charged metal ions, and the positively charged metal ions are adsorbed on the negatively charged 110 crystal planes, resulting in a strong adsorption capacity of the nano carbonate crystal to metal cations. Therefore, the adsorption of metal cations by the nano carbonate crystals is mostly chemisorbed with a small portion of physical adsorption.
In addition, sodium fulvate can be added as a chelating agent in the method of the invention to promote the leaching of metal ions such as calcium and magnesium in the steel slag, thereby accelerating the carbonization reaction of the calcium and magnesium ions and dissolved carbon dioxide and promoting the formation of nano carbonate on the surface of the porous framework.
The invention uses the steel slag and the red mud as the raw materials of the adsorbent, has low cost, simple preparation method, does not need strict equipment and process conditions, and is convenient for popularization and application.
In addition, the sodium fulvate is an environment-friendly and low-cost organic macromolecular material, so that the sodium fulvate is very suitable for modification of heavy metal ion adsorbents.
Drawings
FIG. 1 is a flow chart of a process for preparing a heavy metal ion adsorbent according to the present invention;
FIG. 2 is an SEM image of a heavy metal adsorbent prepared in example 1;
fig. 3 is an SEM image of the heavy metal adsorbent prepared in example 10.
Detailed Description
FIG. 1 is a flow chart of the process for preparing the heavy metal ion adsorbent according to the present invention. As shown in fig. 1, one example of a process for preparing a heavy metal ion adsorbent includes drying and ball-milling steel slag and red mud to obtain a batch mixture, then adding water to the batch mixture, and wet-milling using a ball mill to obtain slurry 1. Slurry 1 may comprise modified porous silica alumina framework particles. CO is introduced into the slurry 1 2 And carbonizing the slurry 1 by using gas to obtain slurry 2. The slurry 2 may comprise porous silica-alumina framework particles and nano carbonate particles supported on the pore surfaces. Finally, the slurry is filtered and boiled, so that the adsorbent is obtained.
The steel slag raw materials in the following examples are taken from Shanxi steel works, and the chemical components are as follows: caO content is 37.38%, siO 2 The content is 15.58 percent, fe 2 O 3 21.65% of the content, 6.84% of MgO, al 2 O 3 The content is 2.63%, the MnO content is 8.71%, and the P content is 2 O 5 Content 2.40%, K 2 O content was 1.43%.
The red mud raw material is from a Bayer process alumina plant in Shanxi, and the chemical components are mainly as follows: al (Al) 2 O 3 The content is 25.6%, siO 2 The content is 18.54%, the CaO content is 20.10%, fe 2 O 3 Content 4.39%, na 2 O was 8.29%.
Sodium fulvate was from Guangxi agricultural insurance bioengineering company.
Example 1
S1: respectively drying 100 parts of steel slag and 30 parts of red mud, putting into a ball mill, grinding for 30min, and sieving through a 100-200 mesh sieve to obtain steel slag and red mud; mixing the sieved steel slag and red mud in the weight ratio of 1:0.3, and homogenizing to obtain a mixture;
s2: adding 200 parts of distilled water into the steel slag and red mud mixture mixed in the step S1, uniformly stirring, and fully wet-milling for 1h by using a small ball mill to obtain slurry 1;
s3: introducing into the slurry 1 obtained in the step S2CO 2 ，CO 2 The gas flow rate is 1.6L/min, and magnetic stirring is adopted to fully carbonize the mixture to obtain slurry 2, the stirring rate is 500rpm, the reaction time is 1.1h, and the carbonization temperature is 55 ℃;
s4: filtering the slurry 2 in the step S3 to obtain a solid, washing the solid for 3 times until the pH value is neutral, removing soluble alkali and other soluble components in the solid, and drying to obtain the heavy metal ion adsorbent.
Fig. 2 shows an SEM image of the heavy metal ion adsorbent prepared in example 1. As can be seen from the SEM image, the heavy metal ion adsorbent of example 1 forms a porous silica-alumina framework in which carbonate particles are attached to the surface of the framework.
Example 2
The rest is the same as in preparation example 1, except that the grinding time of the steel slag and the red mud in the step S1 is 20min.
Example 3
The rest is the same as in preparation example 1, except that the grinding time of the steel slag and the red mud in the step S1 is 60min.
Example 4
The rest is the same as in preparation example 1, except that the mass ratio of steel slag to red mud in the step S1 is 1:1.
Example 5
The rest is the same as in preparation example 1, except that the mass ratio of steel slag to red mud in the step S1 is 1:1.5.
Example 6
The rest is the same as in preparation example 1, except that in step S2, the mass ratio of distilled water to the steel slag red mud mixture is 1:3.
Example 7
The rest is the same as in preparation example 1, except that the ball milling time of the ball mill in step S2 is 2 hours.
Example 8
The remainder is the same as in preparation example 1, except that CO in step S3 2 The gas flow rate was 1.2L/min.
Example 9
The remainder was the same as in preparation example 1 except that the reaction temperature in step S3 was 75 ℃.
Example 10
S1: respectively drying 100 parts of steel slag and 30 parts of red mud, putting into a ball mill, grinding for 30min, and sieving through a 100-200 mesh sieve to obtain steel slag and red mud; mixing the sieved steel slag and red mud in the weight ratio of 1:0.3, and homogenizing to obtain a mixture;
s2: adding 200 parts of distilled water into the steel slag and red mud mixture mixed in the step S1, uniformly stirring, and fully wet-milling for 1h by using a small ball mill to obtain slurry 1;
s2-1, adding a sodium fulvate solution into the slurry 1, wherein the addition amount of the sodium fulvate is 0.03 weight percent relative to the total weight of the dried steel slag and the dried red mud, and uniformly mixing to obtain slurry 2-1;
s3: introducing CO into the slurry 2-1 obtained in the step S2-1 2 ，CO 2 The gas flow rate is 0.6L/min, and magnetic stirring is adopted to fully carbonize the mixture to obtain slurry 2, the stirring rate is 500rpm, the reaction time is 0.5h, and the carbonization temperature is 22 ℃;
s4: filtering the slurry 2 in the step S3 to obtain a solid, washing the solid for 3 times until the pH value is neutral, removing soluble alkali and other soluble components in the solid, and drying to obtain the heavy metal ion adsorbent.
Fig. 3 is an SEM image of the heavy metal adsorbent prepared in example 10. From the SEM image, it can be seen that the heavy metal adsorbent forms a loose alumino-silicate framework with carbonate particles attached to the framework surface.
Example 11
A heavy metal ion adsorbent was prepared in the same manner as in example 10 except that a sodium fulvate solution was added to the slurry 1 in an amount of 0.09 wt% relative to the total weight of the dried steel slag and the dried red mud.
Example 12
S1: respectively drying 100 parts of steel slag and 30 parts of red mud, putting into a ball mill, grinding for 30min, and sieving through a 100-200 mesh sieve to obtain steel slag and red mud; mixing the sieved steel slag and red mud in the weight ratio of 1:0.3, and homogenizing to obtain a mixture;
s2: adding 200 parts of distilled water into the steel slag and red mud mixture mixed in the step S1, simultaneously adding sodium fulvate accounting for 0.03 weight percent of the total weight of the dried steel slag and the dried red mud, uniformly stirring, and fully wet-grinding for 1h by using a small ball mill to obtain slurry 1;
s3: introducing CO into the slurry 1 obtained in the step S2 2 ，CO 2 The gas flow rate is 0.6L/min, and magnetic stirring is adopted to fully carbonize the mixture to obtain slurry 2, the stirring rate is 500rpm, the reaction time is 0.5h, and the carbonization temperature is 22 ℃;
s4: filtering the slurry 2 in the step S3 to obtain a solid, washing the solid for 3 times until the pH value is neutral, removing soluble alkali and other soluble components in the solid, and drying to obtain the heavy metal ion adsorbent.
Comparative example 1
A heavy metal ion adsorbent was produced in the same manner as in example 1 except that blast furnace slag was used instead of red mud.
Comparative example 2
A heavy metal ion adsorbent was prepared in the same manner as in example 1, except that silica fume was used in place of red mud.
Test examples 1 to 12
1. Carbonization reaction efficiency
Carbonization efficiency is expressed in terms of the amount of carbon dioxide fixed during carbonization of every 100g of dry feedstock over a period of time. Specifically, with 100g of raw materials (raw materials include dried steel slag and red mud, and for the example of adding sodium fulvate, the raw materials also include sodium fulvate) as a standard, CO can be fixed 2 The calculation method of the amount of the catalyst is as follows:
wherein: n is n CO2 CO fixation for 100g feedstock 2 Percentage efficiency (i.e., carbonization efficiency),. DELTA.M 1 To be CO-free 2 Weight loss (mg), Δm, of pre-reaction samples 2 To be CO-free 2 Weight loss (mg) of the sample after the reaction.
The results of the carbonization reaction efficiencies of examples 1 to 12 and comparative examples 1 to 3 are shown in the following table 1:
TABLE 1
| Project | CO 2 Gas flow rate | Reaction time | Carbonization temperature | Carbonization efficiency% |
| Example 1 | 1.6L/min | 1.1h | 55℃ | 10.26 |
| Example 2 | 1.6L/min | 1.1h | 55℃ | 9.53 |
| Example 3 | 1.6L/min | 1.1h | 55℃ | 10.76 |
| Example 4 | 1.6L/min | 1.1h | 55℃ | 10.99 |
| Example 5 | 1.6L/min | 1.1h | 55℃ | 11.69 |
| Example 6 | 1.6L/min | 1.1h | 55℃ | 10.55 |
| Example 7 | 1.6L/min | 1.1h | 55℃ | 11.54 |
| Example 8 | 1.2L/min | 1.1h | 55℃ | 9.64 |
| Example 9 | 1.6L/min | 1.1h | 75℃ | 11.57 |
| Example 10 | 0.6L/min | 0.5h | 22℃ | 16.12 |
| Example 11 | 0.6L/min | 0.5h | 20℃ | 15.58 |
| Example 12 | 1.6L/min | 1.1h | 22℃ | 12.86 |
| Comparative example 1 | 1.6L/min | 1.1h | 55℃ | 9.98 |
| Comparative example 2 | 1.6L/min | 1.1h | 55℃ | 8.12 |
2. Adsorption rate of heavy metal ions in water
100ml of sewage with a lead concentration of 1g/L is taken, 1g of the adsorbent prepared in the above example 1 is added, stirred for 300min on a magnetic stirrer with an oscillation speed of 100r/min, filtered, and Pb in the solution is measured by ICP-AES (Shimadzu inductively coupled plasma mass spectrometer ICPMS-2030) 2+ Concentration, and calculate recovery, the formula is as follows:
R＝(C 0 -C e )/C 0 ×100％
wherein C is 0 Pb 2+ Initial mass concentration of solution, g/L; c (C) e Pb at adsorption equilibrium 2+ The mass concentration of the solution, g/L; r is Pb as heavy metal ion adsorbent 2+ Is not limited, and the adsorption rate of the catalyst is not limited.
The adsorbents prepared in examples 2 to 12 were sequentially subjected to the above-described test, corresponding to examples 2 to 12, respectively.
Replacement of Pb-containing substances 2+ The sewage is Cd-containing with the same concentration 2+ Sewage, cu 2+ Sewage, cr 6+ The experimental tests in the above examples were repeated on the sewage, and the experimental results are shown in table 2 below.
TABLE 2
From the test data in table 2 above, it can be seen that: the heavy metal ion adsorbents prepared in examples 1 to 12 were able to achieve more excellent carbonization efficiency than the methods of comparative examples 1 to 2. In particular, examples 10 to 11 demonstrate that by adding sodium fulvate as a modifier after step S2, the conditions of the carbonization reaction, including carbon dioxide flow rate, reaction temperature and reaction time, can be reduced while improving the carbonization efficiency.
By comparing comparative examples 1 to 2 with example 1, it can be seen that the adsorbent prepared by adding red mud and steel slag as raw materials in a specific ratio significantly improves the adsorption of various heavy metal ions (including Pb 2+ 、Cd 2+ 、Cu 2+ 、Cr 6+ One or more of the above).
By comparing example 1 with examples 10-11, it can be seen that the addition of sodium fulvate further increases the adsorption capacity of the adsorbent for heavy metal sewage.
Example 12 shows that the addition of sodium fulvate in step S2 can promote the adsorption rate of heavy metal ions but is less effective than example 10.
In a word, the method of the invention erodes the steel slag and the red mud through alkali in the red mud, so that the steel slag and the red mud form loose and porous particles, and then the nano calcium carbonate formed by carbonization is attached to the surface of the framework, thereby improving the specific surface area. In addition, the red mud and the steel slag can synergistically improve the reactivity of the aluminosilicate, increase the number of active sites on the surface of the adsorbent, and improve the adsorption rate of heavy metal ions in water. The adsorption rate of heavy metal ions in water can be further improved by adding the sodium fulvate. According to the invention, two industrial solid wastes, namely steel slag and red mud, are used as reaction raw materials, the cost is low, the porous adsorption material loaded with the nano carbonate is prepared under the condition of room temperature, the adsorption efficiency is high, and the high additional value utilization of the steel slag and the red mud and the treatment of wastewater are realized.
The foregoing describes in detail preferred embodiments of the present invention. It should be understood that numerous modifications and variations can be made in accordance with the concepts of the invention without requiring creative effort by one of ordinary skill in the art. Therefore, all technical solutions which can be obtained by logic analysis, reasoning or limited experiments based on the prior art by the person skilled in the art according to the inventive concept shall be within the scope of protection defined by the claims.
Claims (10)
1. The preparation method of the heavy metal ion adsorbent comprises the following steps:
s1: grinding and screening the dry steel slag and the dry red mud respectively, and then dispersing and mixing the screened steel slag and the red mud to obtain a mixture of the steel slag and the red mud;
s2: adding water to the mixture of steel slag and red mud obtained in step S1, stirring, and wet-milling using a ball mill, thereby obtaining slurry 1 containing porous particles;
s3: introducing CO into the slurry 1 obtained in the step S2 under stirring 2 Carbonizing the modified porous skeleton particles in the slurry 1 by gas to obtain slurry 2, wherein the slurry 2 comprises a porous skeleton and nano carbonate particles loaded on the surfaces of the pores; and
s4: filtering the slurry 2 of the step S3 to obtain a solid, washing the solid to a neutral pH, and drying to obtain the heavy metal ion adsorbent.
2. The preparation method according to claim 1, characterized in that the preparation method comprises:
s1: grinding and screening the dry steel slag and the dry red mud respectively, and then dispersing and mixing the screened steel slag and the red mud to obtain a mixture of the steel slag and the red mud;
s2: adding water to the mixture of steel slag and red mud obtained in step S1, stirring, and wet-milling using a ball mill, thereby obtaining slurry 1 containing porous particles;
s2-1: after the step S2, adding the sodium fulvate solution into the slurry 1, and uniformly mixing to obtain slurry 2-1, wherein the addition amount of the sodium fulvate is 0.03-0.10 wt% relative to the total weight of the dry steel slag and the dry red mud;
s3: introducing CO into the slurry 2-1 obtained in the step S2-1 under stirring 2 Carbonizing the modified porous skeleton particles in the slurry 2-1 by gas to obtain slurry 2, wherein the slurry 2 comprises a porous skeleton and nano carbonate particles loaded on the surfaces of the pores; and
s4: filtering the slurry 2 of the step S3 to obtain a solid, washing the solid to a neutral pH, and drying to obtain the heavy metal ion adsorbent.
3. The method according to claim 1 or 2, wherein the grinding time of the dried steel slag and the dried red mud in step S1 is 20 to 60min, respectively.
4. The preparation method according to claim 1 or 2, wherein the mass ratio of the dry steel slag to the dry red mud in the step S1 is 1:0.2-4.0.
5. The preparation method according to claim 1 or 2, wherein the mass ratio of the steel slag and red mud mixture to water in step S2 is 1:2.0-6.0, preferably, the water is deionized water.
6. The process according to claim 1 or 2, wherein the wet milling is carried out in the ball mill in step S2 for a period of 0.2 to 3.5 hours,
optionally, the number of washes in step S4 is 1-3.
7. The method of claim 1, wherein in step S3, the CO 2 The purity of the gas is 95 to 99 percent, the flow rate is 1.2 to 2L/min, the carbonization temperature is 50 to 75 ℃, the reaction time is 1.1 to 2.5 hours, and the stirring speed is 300 to 1800rpm.
8. The method of claim 2, wherein in step S3, the CO 2 The purity of the gas is 95 to 99 percent, the flow rate is 0.2 to 1.2L/min, the carbonization temperature is 20 to 30 ℃, the reaction time is 0.5 to 1h, and the stirring speed is 300 to 600rpm.
9. A heavy metal ion adsorbent, characterized in that the heavy metal ion adsorbent is prepared by the method of any one of claims 1 to 8.
10. The use of the heavy metal ion adsorbent as claimed in claim 8 for removing heavy metal ions from sewage.
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