CN116422296B - Birnessite/fulvic acid composite adsorbent and preparation method and application thereof - Google Patents
Birnessite/fulvic acid composite adsorbent and preparation method and application thereof Download PDFInfo
- Publication number
- CN116422296B CN116422296B CN202310345337.5A CN202310345337A CN116422296B CN 116422296 B CN116422296 B CN 116422296B CN 202310345337 A CN202310345337 A CN 202310345337A CN 116422296 B CN116422296 B CN 116422296B
- Authority
- CN
- China
- Prior art keywords
- birnessite
- fulvic acid
- mixed solution
- composite adsorbent
- heavy metal
- 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.)
- Active
Links
- PUKLDDOGISCFCP-JSQCKWNTSA-N 21-Deoxycortisone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)C)(O)[C@@]1(C)CC2=O PUKLDDOGISCFCP-JSQCKWNTSA-N 0.000 title claims abstract description 106
- FCYKAQOGGFGCMD-UHFFFAOYSA-N Fulvic acid Natural products O1C2=CC(O)=C(O)C(C(O)=O)=C2C(=O)C2=C1CC(C)(O)OC2 FCYKAQOGGFGCMD-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 239000002509 fulvic acid Substances 0.000 title claims abstract description 106
- 229940095100 fulvic acid Drugs 0.000 title claims abstract description 106
- 239000003463 adsorbent Substances 0.000 title claims abstract description 86
- 239000002131 composite material Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000011259 mixed solution Substances 0.000 claims abstract description 49
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 48
- 239000002351 wastewater Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims abstract description 15
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000011565 manganese chloride Substances 0.000 claims abstract description 15
- 229940099607 manganese chloride Drugs 0.000 claims abstract description 15
- 235000002867 manganese chloride Nutrition 0.000 claims abstract description 15
- 150000002500 ions Chemical class 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 39
- 230000008569 process Effects 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 238000010924 continuous production Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 17
- 229910052793 cadmium Inorganic materials 0.000 description 14
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 14
- GFORUURFPDRRRJ-UHFFFAOYSA-N [Na].[Mn] Chemical compound [Na].[Mn] GFORUURFPDRRRJ-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 9
- 230000007547 defect Effects 0.000 description 5
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004108 freeze drying Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- AJAMDKATKXGWKD-UHFFFAOYSA-M sodium manganese(2+) oxygen(2-) hydroxide Chemical compound [OH-].[Na+].[O-2].[Mn+2] AJAMDKATKXGWKD-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- 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
- B01J20/04—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
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
-
- 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
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a birnessite/fulvic acid composite adsorbent, and a preparation method and application thereof, wherein the preparation method comprises the following steps: respectively mixing potassium permanganate, sodium salt and water to prepare a mixed solution, mixing manganese chloride, fulvic acid and water to prepare a mixed solution, mixing the two mixed solutions, and stirring to obtain the birnessite/fulvic acid composite adsorbent. The composite adsorbent prepared by the invention has the advantages of large specific surface area, multiple adsorption sites, large adsorption capacity, good stability, environmental protection and the like, is a novel heavy metal ion adsorbent with low cost and excellent performance, can be widely used for adsorbing heavy metal ions in water, has good adsorption effect and high adsorption efficiency, has very high use value and very good application prospect, and has very important practical significance for realizing the effective treatment of heavy metal polluted wastewater. The preparation method also has the advantages of simple process, controllable process, continuous production and the like, is suitable for large-scale preparation and is convenient for industrialized application.
Description
Technical Field
The invention belongs to the field of heavy metal pollution prevention and control, relates to a heavy metal adsorption material, in particular to a birnessite/fulvic acid composite adsorbent and a preparation method thereof, and further relates to application of the birnessite/fulvic acid composite adsorbent in the aspect of adsorbing heavy metal ions in a solution system.
Background
Heavy metals enter the water body and can bring great harm to the environment and human beings. For example, the emission of large amounts of high-concentration cadmium-containing wastewater generated during mining, mineral separation, smelting and the like in the cadmium industry is a main source of cadmium pollutants, and thus, pollution of drinking water, soil and the like is caused. 70% of rivers/lakes worldwide are polluted by cadmium to different degrees, and trace (0.01-0.001 mg/L) of heavy metal cadmium in natural water can produce toxic effects, so that the heavy metal cadmium can cause great harm to human organs, particularly kidneys. Therefore, how to lead the heavy metal-containing wastewater to reach the standard before being discharged is an unprecedented scientific task.
At present, the treatment technology of wastewater containing heavy metals mainly comprises chemical coagulating sedimentation, electrochemical sedimentation, ion exchange, membrane treatment technology, adsorption method and the like, wherein the adsorption method is one of the most common technologies for treating heavy metal pollution of water, so that searching for an efficient, low-cost and environment-friendly adsorption material also becomes a research hot spot. The birnessite has the advantages of weak crystal form, finer particles, low charge zero point, high cation exchange capacity, strong oxidizing capacity and the like, thereby playing an important role in the adsorption and desorption and oxidation-reduction processes of heavy metals in water and soil. However, the sodium manganese dioxide nano-particles prepared at present have the defects of easy agglomeration, poor stability in aqueous solution and the like, and can reduce the specific surface area and limit the reactivity. In recent years, there have been a great deal of studies on the preparation of adsorbents by compositing metal oxides with birnessite, but these adsorbents are mainly composited by adsorption reaction, and thus the prepared adsorbents have poor stability of metal oxides on the surface and are liable to desorb to cause secondary pollution. Therefore, the birnessite-based composite adsorbent which has the advantages of large specific surface area, multiple adsorption sites, large adsorption capacity, good stability and environmental protection is obtained, and has important practical significance for the effective treatment of heavy metal wastewater.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the birnessite/fulvic acid composite adsorbent which has the advantages of large specific surface area, more adsorption sites, large adsorption capacity, good stability and environmental protection, and the preparation method and the application thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
The preparation method of the birnessite/fulvic acid composite adsorbent comprises the following steps:
S1, mixing potassium permanganate, sodium salt and water to obtain a mixed solution 1, and mixing manganese chloride, fulvic acid and water to obtain a mixed solution 2;
S2, mixing the mixed solution 1 with the mixed solution 2, and stirring to obtain the birnessite/fulvic acid composite adsorbent.
According to the preparation method of the birnessite/fulvic acid composite adsorbent, in the step S1, the concentration of potassium permanganate in the mixed solution 1 is 0.02-0.5 mol/L, the concentration of sodium salt in the mixed solution 1 is 0.03-0.15 mol/L, the sodium salt is sodium hydroxide, the concentration of manganese chloride in the mixed solution 2 is 0.02-0.5 mol/L, and the concentration of fulvic acid in the mixed solution 2 is 3-9.5 g/L.
In the further improved preparation method of the birnessite/fulvic acid composite adsorbent, in the step S2, the mixed solution 2 is added into the mixed solution 1, the adding rate of the mixed solution 2 is 1.5-2 mL/min, the volume ratio of the mixed solution 2 to the mixed solution 1 is 1:1.9-2.1, and the stirring time is 18-24 h.
In the further improved preparation method of the birnessite/fulvic acid composite adsorbent, in the step S2, the adding rate of the mixed solution 2 is 1.67mL/min, the volume ratio of the mixed solution 2 to the mixed solution 1 is 1:2, and the stirring time is 22h.
The preparation method of the birnessite/fulvic acid composite adsorbent is further improved, in the step S2, after stirring is completed, the method further comprises the steps of centrifuging, washing, drying, grinding and sieving the stirred product, wherein deionized water is used as washing liquid for washing the precipitate obtained by centrifugation until the conductivity of the washing liquid is smaller than 10 mu S cm -1, and the size of the sieved sieve mesh is 80 meshes.
The invention also provides a birnessite/fulvic acid composite adsorbent which comprises birnessite and fulvic acid, wherein the fulvic acid is loaded on the surface, pores and sheets of the birnessite, and the mass content of the fulvic acid in the birnessite/fulvic acid composite adsorbent is 2% -20%.
The birnessite/fulvic acid composite adsorbent is further improved and prepared by the preparation method.
As a general technical concept, the invention also provides application of the birnessite/fulvic acid composite adsorbent in treating heavy metal wastewater.
The application is further improved, and the application comprises the steps of mixing and stirring the birnessite/fulvic acid composite adsorbent with heavy metal wastewater to finish the treatment of heavy metal in the wastewater, wherein the mass volume ratio of the birnessite/fulvic acid composite adsorbent to the heavy metal wastewater is 0.1 g/300 mL.
According to the application, the method is further improved, the heavy metal ions in the heavy metal wastewater are Cd 2+, the initial concentration of the heavy metal ions in the heavy metal wastewater is less than or equal to 200mg/L, the pH value of the heavy metal wastewater is 6, and the stirring time is 24 hours.
Compared with the prior art, the invention has the advantages that:
(1) Aiming at the defects of easy agglomeration, stability and the like of the existing birnessite, the defects of poor stability, easy secondary pollution and the like of the birnessite-based composite adsorbent, the invention creatively provides a preparation method of the birnessite/birnessite composite adsorbent, wherein the birnessite is synchronously added in the formation process of the birnessite, so that the birnessite can be uniformly dispersed and loaded on the surface of the birnessite by utilizing a coprecipitation reaction, and loaded in pores and sheets of the birnessite, wherein the birnessite is uniformly dispersed on the surface of the birnessite, so that the specific surface area and the adsorption capacity of the adsorbent are improved, and the surface of the birnessite is provided with a large amount of negative charges and metal ion complexing sites due to the fact that the birnessite is a natural organic complex, and the birnessite is uniformly loaded on the surface of the birnessite, so that the birnessite is loaded in the pores and the birnessite, the birnessite is better in the water environment, and the service life of the adsorbent is prolonged, and the service life of the birnessite is prolonged. In addition, compared with metal oxide, the fulvic acid adopted in the invention is a biomass material, has better safety and lower price, and is beneficial to obtaining the adsorption material with low cost and environmental protection. The birnessite/fulvic acid composite adsorbent prepared by the invention has the advantages of large specific surface area, more adsorption sites, large adsorption capacity, good stability, environmental protection and the like, is a novel heavy metal ion adsorbent with low cost and excellent performance, can be widely used for adsorbing heavy metal ions in water, has good adsorption effect and high adsorption efficiency, has high use value and good application prospect, and has very important practical significance for realizing the effective treatment of heavy metal polluted wastewater. Meanwhile, the preparation method provided by the invention has the advantages of simple process, controllable process, continuous production and the like, is suitable for large-scale preparation, and is convenient for industrial application.
(2) According to the preparation method, the mixed solution 2 containing the fulvic acid is added into the mixed solution 1 containing the potassium permanganate, and the mixed solution 2 containing the fulvic acid is optimized to have the addition rate of 1.5-2 mL/min, particularly, the addition rate of 1.67mL/min, so that more dispersed complex particles are formed, the specific surface area of the material is larger, the adsorption performance is better, meanwhile, the stirring time of the mixed solution containing the potassium permanganate, the sodium salt, the manganese chloride and the fulvic acid is optimized to be 18-24 h, and the stirring time is optimized to be 18-24 h, particularly, the stirring time is 22h, so that the coprecipitation reaction is balanced, the fulvic acid is uniformly dispersed and loaded on the surface of the birnessite, and is loaded in pores and sheets of the birnessite.
(3) The birnessite/fulvic acid composite adsorbent comprises birnessite and fulvic acid, wherein the fulvic acid is loaded on the surface, pores and sheets of the birnessite, and the mass content of the fulvic acid in the birnessite/fulvic acid composite adsorbent is 2% -20%. In the invention, the adsorption performance of the adsorbent can be further improved on the premise of ensuring that the birnessite nano-particles have better dispersibility by optimizing the content of the birnessite, because when the content of the birnessite in the adsorbent is lower (such as lower than 2%), less birnessite is unfavorable for effectively improving the dispersibility of the birnessite nano-particles, so that the adsorbent still has the defects of easy agglomeration, small specific surface area and the like, and when the content of the birnessite in the adsorbent is higher (such as higher than 20%), too much birnessite can block pores of the birnessite, thereby being unfavorable for improving the adsorption amount of the adsorbent, bringing about cost increase and bringing about secondary pollution risk due to bivalent manganese generated by reduction.
(4) The invention also provides application of the birnessite/fulvic acid composite adsorbent in treating heavy metal wastewater, taking heavy metal cadmium wastewater as an example, and the birnessite/fulvic acid composite adsorbent and the heavy metal cadmium wastewater are mixed and stirred, so that heavy metal cadmium in the wastewater can be rapidly and thoroughly removed, and the birnessite/fulvic acid composite adsorbent has the advantages of convenience in operation, high treatment efficiency, good removal effect and the like, and has important significance in effectively removing heavy metal in water.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
FIG. 1 is a TEM image of a birnessite/fulvic acid composite adsorbent prepared in example 1 of the present invention.
Fig. 2 is an XRD pattern of the birnessite/fulvic acid composite adsorbent prepared in examples 1 and 3 of the present invention.
FIG. 3 is an isothermal diagram showing adsorption CdCIIC of birnessite/birnessite and 15wt% of birnessite in example 4 of the present invention.
Detailed Description
The invention is further described below in connection with the drawings and the specific preferred embodiments, but the scope of protection of the invention is not limited thereby.
In the following examples, materials and instruments used are commercially available unless otherwise specified. The process adopted is a conventional process, the equipment adopted is a conventional equipment, and the obtained data are all average values of more than three repeated experiments.
Example 1
The preparation method of the birnessite/fulvic acid composite adsorbent comprises the following steps:
(1) 6.292g of manganese chloride is added into 300mL of deionized water, uniformly mixed, then 0.922g of fulvic acid is added, and uniformly mixed, so as to obtain a mixed solution of manganese chloride and fulvic acid.
(2) 1.58G of potassium permanganate is added into 200mL of deionized water to obtain 50mmol/L potassium permanganate solution, 0.8g of sodium hydroxide is added into 400mL of deionized water to obtain 50mmol/L sodium hydroxide solution, and the obtained potassium permanganate solution and the sodium hydroxide solution are uniformly mixed to obtain a mixed solution of potassium permanganate and sodium hydroxide.
(3) Adding the mixed solution of manganese chloride and fulvic acid prepared in the step (1) into the mixed solution of potassium permanganate and sodium hydroxide prepared in the step (2) by using a constant flow pump, wherein the flow rate of the constant flow pump is 1.67mL/min, the reaction time is 3 hours, continuing to magnetically stir for 18 hours, centrifuging to obtain precipitate, washing with deionized water until the conductivity of the supernatant is less than 10 mu S cm -1, freeze-drying, grinding into powder, and sieving (the sieve holes are 80 meshes) to obtain the birnessite/fulvic acid composite adsorbent which is marked as 5wt% of the birnessite/birnessite.
The sodium manganese ore/fulvic acid composite adsorbent prepared in the embodiment comprises sodium manganese ore and fulvic acid, wherein the fulvic acid is loaded on the surface, pores and sheets of the sodium manganese ore, and the mass content of the fulvic acid in the sodium manganese ore/fulvic acid composite adsorbent is 5%.
FIG. 1 is a TEM image of a birnessite/fulvic acid composite adsorbent prepared in example 1 of the present invention. As shown in fig. 1, the birnessite/fulvic acid composite adsorbent has petal shape, and the dispersibility of the adsorbent is remarkably improved after the fulvic acid is loaded.
In addition, through tests, the specific surface area of the birnessite/fulvic acid composite adsorbent is increased from 161.32m 2/g to 254.77m 2/g through loading the fulvic acid.
Example 2
The preparation method of the birnessite/fulvic acid composite adsorbent comprises the following steps:
(1) 6.292g of manganese chloride is added into 300mL of deionized water, uniformly mixed, then 1.84g of fulvic acid is added, and uniformly mixed, so as to obtain a mixed solution of manganese chloride and fulvic acid.
(2) 1.58G of potassium permanganate is added into 200mL of deionized water to obtain 50mmol/L potassium permanganate solution, 0.8g of sodium hydroxide is added into 400mL of deionized water to obtain 50mmol/L sodium hydroxide solution, and the obtained potassium permanganate solution and the sodium hydroxide solution are uniformly mixed to obtain a mixed solution of potassium permanganate and sodium hydroxide.
(3) Adding the mixed solution of manganese chloride and fulvic acid prepared in the step (1) into the mixed solution of potassium permanganate and sodium hydroxide prepared in the step (2) by using a constant flow pump, wherein the flow rate of the constant flow pump is 1.67mL/min, the reaction time is 3 hours, continuing to magnetically stir for 18 hours, centrifuging to obtain precipitate, washing the precipitate with deionized water until the conductivity of the supernatant is less than 10 mu S cm -1, freeze-drying, grinding into powder, and sieving (the sieve holes are all 80 meshes) to obtain the birnessite/fulvic acid composite adsorbent.
The sodium manganese ore/fulvic acid composite adsorbent prepared in the embodiment comprises sodium manganese ore and fulvic acid, wherein the fulvic acid is loaded on the surface, pores and sheets of the sodium manganese ore, and the mass content of the fulvic acid in the sodium manganese ore/fulvic acid composite adsorbent is 10%.
In addition, through tests, the specific surface area of the birnessite/fulvic acid composite adsorbent is increased from 161.32m 2/g to 236.37m 2/g through loading the fulvic acid.
Example 3
A preparation method of a birnessite/fulvic acid composite adsorbent for efficiently treating cadmium-containing wastewater comprises the following steps:
(1) 6.292g of manganese chloride is added into 300mL of deionized water, evenly mixed, then 2.75g of fulvic acid is added, evenly mixed, and a mixed solution of manganese chloride and fulvic acid is obtained.
(2) 1.58G of potassium permanganate is added into 200mL of deionized water to obtain 50mmol/L potassium permanganate solution, 0.8g of sodium hydroxide is added into 400mL of deionized water to obtain 50mmol/L sodium hydroxide solution, and the obtained potassium permanganate solution and the sodium hydroxide solution are uniformly mixed to obtain a mixed solution of potassium permanganate and sodium hydroxide.
(3) Adding the mixed solution of manganese chloride and fulvic acid prepared in the step (1) into the mixed solution of potassium permanganate and sodium hydroxide prepared in the step (2) by using a constant flow pump, wherein the flow rate of the constant flow pump is 1.67mL/min, the reaction time is 3 hours, continuing to magnetically stir for 18 hours, centrifuging to obtain precipitate, washing the precipitate with deionized water until the conductivity of the supernatant is less than 10 mu S cm -1, freeze-drying, grinding into powder, and sieving (the sieve holes are 80 meshes) to obtain the birnessite/fulvic acid composite adsorbent which is recorded as 15wt% of the birnessite/birnessite.
The sodium manganese ore/fulvic acid composite adsorbent prepared in the embodiment comprises sodium manganese ore and fulvic acid, wherein the fulvic acid is loaded on the surface, pores and sheets of the sodium manganese ore, and the mass content of the fulvic acid in the sodium manganese ore/fulvic acid composite adsorbent is 15%.
Fig. 2 is an XRD pattern of the birnessite/fulvic acid composite adsorbent prepared in examples 1 and 3 of the present invention. As shown in figure 2, the XRD spectrum of the birnessite/fulvic acid composite adsorbent prepared by the invention is basically consistent with that of birnessite without the fulvic acid.
In addition, through tests, the specific surface area of the birnessite/fulvic acid composite adsorbent is increased from 161.32m 2/g to 219.10m 2/g through loading the fulvic acid.
Example 4
The application of the birnessite/fulvic acid composite adsorbent in treating heavy metal wastewater is specifically that the birnessite/fulvic acid composite adsorbent in example 1 and example 3 is used for treating heavy metal cadmium wastewater
0.1G of the birnessite/fulvic acid composite adsorbent prepared in example 1 and example 3 was added to 300mL of heavy metal cadmium wastewater (the initial pH value of the wastewater is 6.0) with a CdCIIC concentration of 200mg/L, and stirred for 24 hours, thereby completing the treatment of heavy metal cadmium in the wastewater.
After the treatment, the supernatant was filtered, and the residual content of CdCIIC was measured by Inductively Coupled Plasma (ICP) and converted to calculate the amount of adsorbent adsorbed CdCIIC.
The results show that:
The adsorption capacity of the birnessite/fulvic acid composite adsorbent (5 wt% birnessite/birnessite) to CdCIIC is 112.09mg/g.
The adsorption capacity of the birnessite/fulvic acid composite adsorbent (15 wt% of the birnessite/birnessite) to CdCIIC is 136.83mg/g.
In addition, in this example, the adsorption effect of birnessite/birnessite composite adsorbent (5 wt% birnessite/birnessite, 15wt% birnessite/birnessite) on heavy metal cadmium wastewater of different concentrations was examined, and the result is shown in fig. 3.
FIG. 3 is an isothermal diagram showing adsorption CdCIIC of birnessite/birnessite and 15wt% of birnessite in example 4 of the present invention. As can be seen from fig. 3, the equilibrium adsorption quantity q e of the adsorbent pair CdCIIC increases with the increase of the equilibrium concentration C e, but q e is basically stable to reach equilibrium after the increase of C e to a certain extent, which is because the specific surface area of the adsorbent and the functional groups are more and sufficient at the low CdCIIC concentration, and the adsorption of the material pair CdCIIC is increased. As the initial concentration of CdCIIC increases, the adsorption sites of the adsorbent gradually saturate, and the amount of adsorbed CdCIIC eventually equilibrates. The saturated adsorption capacity of 5wt% of fulvic acid/birnessite and 15wt% of fulvic acid/birnessite to CdCIIC is 112.09mg/g and 136.83mg/g respectively, and compared with the prior report, the adsorption capacity of the manganese oxide composite adsorption material is higher than that of other types of manganese oxide composite adsorption materials.
According to the results, the method for preparing the birnessite/birnessite composite adsorbent has the advantages of large specific surface area, more adsorption sites, large adsorption capacity, good stability, environment friendliness and the like, is a novel heavy metal ion adsorbent with low cost and excellent performance, can be widely used for adsorbing heavy metal ions in water, has good adsorption effect and high adsorption efficiency, has very high use value and very good application prospect, and has very important practical significance for realizing effective treatment of heavy metal polluted wastewater. Meanwhile, the preparation method provided by the invention has the advantages of simple process, controllable process, continuous production and the like, is suitable for large-scale preparation, and is convenient for industrial application.
The present invention is disclosed in the preferred embodiments, but is not limited thereto. Many variations and modifications of the present invention will be apparent to those skilled in the art, using the methods and techniques disclosed above. Therefore, any simple modification of the above embodiments according to the technical substance of the present invention is still within the scope of the technical solution of the present invention, without departing from the technical solution of the present invention.
Claims (9)
1. The preparation method of the birnessite/fulvic acid composite adsorbent is characterized by comprising the following steps of:
s1, mixing potassium permanganate, sodium salt and water to obtain a mixed solution 1, mixing manganese chloride, fulvic acid and water to obtain a mixed solution 2, wherein the concentration of the fulvic acid in the mixed solution 2 is 3 g/L-9.5 g/L;
s2, adding the mixed solution 2 into the mixed solution 1 according to the adding rate of the mixed solution 2 being 1.5 mL/min-2 mL/min, and stirring for 18-24 h to obtain the birnessite/fulvic acid composite adsorbent.
2. The method for preparing the birnessite/fulvic acid composite adsorbent according to claim 1, wherein in the step S1, the concentration of potassium permanganate in the mixed solution 1 is 0.02 mol/L-0.5 mol/L, the concentration of sodium salt in the mixed solution 1 is 0.03 mol/L-0.15 mol/L, the sodium salt is sodium hydroxide, and the concentration of manganese chloride in the mixed solution 2 is 0.02 mol/L-0.5 mol/L.
3. The method for preparing a birnessite/fulvic acid composite adsorbent according to claim 1 or 2, wherein in step S2, the volume ratio of the mixed solution 2 to the mixed solution 1 is 1:1.9-2.1.
4. The method for preparing the birnessite/fulvic acid composite adsorbent according to claim 3, wherein in the step S2, the adding rate of the mixed solution 2 is 1.67 mL/min, the volume ratio of the mixed solution 2 to the mixed solution 1 is 1:2, and the stirring time is 22h.
5. The method for preparing the birnessite/fulvic acid composite adsorbent according to claim 4, wherein in the step S2, after the stirring is completed, the method further comprises the steps of centrifuging, washing, drying, grinding and sieving the product obtained after the stirring, wherein the washing is to wash the precipitate obtained after the centrifugation by using deionized water as a washing liquid until the conductivity of the washing liquid is less than 10 mu S cm -1, and the size of the sieve hole of the sieve is 80 meshes.
6. The birnessite/fulvic acid composite adsorbent prepared by the preparation method of any one of claims 1-5 is characterized by comprising birnessite and fulvic acid, wherein the fulvic acid is loaded on the surface, pores and sheets of the birnessite, and the mass content of the fulvic acid in the birnessite/fulvic acid composite adsorbent is 2% -20%.
7. Use of the birnessite/fulvic acid composite adsorbent according to claim 6 for treating heavy metal wastewater.
8. The method according to claim 7, wherein the method comprises the steps of mixing and stirring the birnessite/fulvic acid composite adsorbent with the heavy metal wastewater to treat the heavy metal in the wastewater, and the mass volume ratio of the birnessite/fulvic acid composite adsorbent to the heavy metal wastewater is 0.1 g/300 mL.
9. The use according to claim 8, wherein the heavy metal ions in the heavy metal wastewater are Cd 2+, the initial concentration of the heavy metal ions in the heavy metal wastewater is less than or equal to 200mg/L, the pH value of the heavy metal wastewater is 6, and the stirring time is 24 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310345337.5A CN116422296B (en) | 2023-03-31 | 2023-03-31 | Birnessite/fulvic acid composite adsorbent and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310345337.5A CN116422296B (en) | 2023-03-31 | 2023-03-31 | Birnessite/fulvic acid composite adsorbent and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116422296A CN116422296A (en) | 2023-07-14 |
| CN116422296B true CN116422296B (en) | 2025-03-18 |
Family
ID=87084847
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310345337.5A Active CN116422296B (en) | 2023-03-31 | 2023-03-31 | Birnessite/fulvic acid composite adsorbent and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116422296B (en) |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011147835A (en) * | 2010-01-19 | 2011-08-04 | Mitsubishi Paper Mills Ltd | Waste liquid treatment method |
| WO2016061265A1 (en) * | 2014-10-14 | 2016-04-21 | Halosource, Inc. | Polymeric hybrid particle containing nano particles and uses |
| CN106140103A (en) * | 2016-06-30 | 2016-11-23 | 安徽建筑大学 | The charing stalk of a kind of mixing modification humic acid/diatomite molecular sieve demanganization adsorbent |
| CN108452766A (en) * | 2018-04-04 | 2018-08-28 | 沈阳化工大学 | A kind of preparation method of tripolite loading birnessite manganese dioxide |
| CN109999909B (en) * | 2019-05-07 | 2021-05-07 | 湖南大学 | Chitosan/diatomite/graphene oxide composite material and its preparation method and application |
| CN110052248A (en) * | 2019-05-08 | 2019-07-26 | 中国科学院城市环境研究所 | A kind of humic acid modified charcoal of ferrimanganic and the preparation method and application thereof |
| CN110314639B (en) * | 2019-07-11 | 2022-03-11 | 沈阳理工大学 | A kind of modified birnessite and its preparation method and application |
| CN115090275A (en) * | 2022-06-10 | 2022-09-23 | 南京工业大学 | A kind of nanocomposite material for sewage treatment and its application |
-
2023
- 2023-03-31 CN CN202310345337.5A patent/CN116422296B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| Cd(II) retention and remobilization on δ-MnO2 and Mn(III)-rich δ-MnO2 affected by Mn(II);Qian Sun et al.;《Environment International》;20190622;第130卷;文献号：104932（1-9） * |
| Removal and recovery of strontium (Sr(II)) from seawater by Fe3O4/MnO2/fulvic acid nanocomposite;Nayereh Ghaeni et al.;《Marine Chemistry》;20190521;第213卷;33-39 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116422296A (en) | 2023-07-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103506065B (en) | A kind of Magnetic heavy metal adsorbent with casing-core structure and preparation method thereof | |
| CN109622598B (en) | A method for remediation of heavy metal contaminated soil based on the principle of primary battery | |
| CN112221461A (en) | Phosphorus adsorption material and preparation method thereof | |
| CN111203177A (en) | A kind of efficient treatment method of EDTA-Pb wastewater | |
| CN109833849A (en) | Modification biological charcoal and the preparation method and application thereof for As polluted soil reparation | |
| CN109126717B (en) | Iron-based adsorbent and preparation method thereof | |
| CN113578263A (en) | Preparation method of adsorption material and wastewater dephosphorization process | |
| CN116422296B (en) | Birnessite/fulvic acid composite adsorbent and preparation method and application thereof | |
| CN113083246B (en) | TEMPO oxidation modified straw fiber material, and preparation method and application thereof | |
| CN106732345A (en) | A kind of composite adsorbing material for heavy metal containing wastewater treatment and preparation method thereof | |
| CN105251470A (en) | Adsorbing agent for removing phosphorus and heavy metal ions and preparation method thereof | |
| CN110152614B (en) | A kind of preparation method of surface-modified iron-based mercury adsorbent | |
| CN106861598B (en) | CuS nanocrystalline adsorbent and its preparation method and its application in the treatment of electroplating copper wastewater | |
| CN114713184B (en) | Heavy metal adsorbent for removing cadmium ions in water body and preparation method and application thereof | |
| CN100562590C (en) | A quick and non-toxic gold extraction method | |
| CN111250052A (en) | Multi-group chelating magnetic hypha water purifying agent and preparation method and application thereof | |
| CN106365244B (en) | A suspension liquid iron-containing composite reagent and preparation method thereof, and method for efficiently removing selenate in water | |
| CN114797812A (en) | Magnetic magnesium hydroxide @ iron oxide composite nanomaterial and preparation method and application thereof | |
| CN115007120A (en) | Mesoporous composite material for selectively adsorbing manganese and preparation method and application thereof | |
| CN109811130B (en) | A method for recovering thallium and mercury from smelting acid wastewater | |
| CN115376717A (en) | A method for adsorbing and reducing hexavalent uranyl ions and its application | |
| CN113173619A (en) | Application of disordered mesoporous carbon modified nano zero-valent iron in removal of V (V) in water | |
| Chi et al. | Selective recycle of Cd (0) based on pH/T switchable controlled Cd (II) adsorption on ion-imprinted polymer | |
| CN112892492B (en) | A magnetic titanium-containing mineral/humic acid composite adsorption material and its preparation method and application | |
| CN114291863B (en) | Method for efficiently removing complex lead in high-salt wastewater by using phosphorus modified nano zero-valent iron |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |