CN113877522A - Preparation method and application of diatomite-based adsorbent loaded with iron-manganese oxide - Google Patents
Preparation method and application of diatomite-based adsorbent loaded with iron-manganese oxide Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 239000003463 adsorbent Substances 0.000 title claims abstract description 43
- WQHONKDTTOGZPR-UHFFFAOYSA-N [O-2].[O-2].[Mn+2].[Fe+2] Chemical compound [O-2].[O-2].[Mn+2].[Fe+2] WQHONKDTTOGZPR-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 51
- 239000000243 solution Substances 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002270 dispersing agent Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims abstract description 16
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000011565 manganese chloride Substances 0.000 claims abstract description 16
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 16
- 239000002244 precipitate Substances 0.000 claims abstract description 15
- 239000002699 waste material Substances 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 229910052603 melanterite Inorganic materials 0.000 claims abstract description 6
- 230000001105 regulatory effect Effects 0.000 claims abstract description 6
- 239000000725 suspension Substances 0.000 claims abstract description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 6
- 230000032683 aging Effects 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000011363 dried mixture Substances 0.000 claims abstract description 3
- 239000011651 chromium Substances 0.000 claims description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 238000002791 soaking Methods 0.000 claims description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- 238000003760 magnetic stirring Methods 0.000 claims description 8
- 238000011282 treatment Methods 0.000 claims description 8
- 239000002351 wastewater Substances 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- 239000005909 Kieselgur Substances 0.000 claims 4
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims 4
- 238000001179 sorption measurement Methods 0.000 description 33
- 239000011550 stock solution Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 239000010842 industrial wastewater Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 229910001430 chromium ion Inorganic materials 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 230000002431 foraging effect Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000010840 domestic wastewater Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011221 initial treatment Methods 0.000 description 1
- 231100001240 inorganic pollutant Toxicity 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/14—Diatomaceous earth
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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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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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/42—Materials comprising a mixture of inorganic materials
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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Abstract
The invention discloses a preparation method and application of a diatomite-based adsorbent loaded with iron-manganese oxide. The method comprises the following steps: step one, pretreating waste diatomite; step two, according to the diatomite, the dispersant and the FeSO4·7H2O、KMnO4、MnCl2·4H2The mass ratio of O is 10-15: 0.5-0.75: 7-10: 2.5-3.5: 2-3, preparing raw materials; dissolving the diatomite and a dispersing agent into deionized water, and performing ultrasonic treatment for 1.5-2. h to fully disperse the diatomite and the dispersing agent to obtain a uniform suspension; step four, respectively adding the dissolved FeSO into the solution4·7H2O、KMnO4、MnCl2·4H2O, regulating the pH of the mixed solution to 7-8 by using a 5M NaOH solution while violently stirring; fifthly, placing the mixture on a magnetic stirrer to stir so as to enable the mixture to react fully; sixthly, standing and aging at room temperature for 12h, filtering and separating precipitates after obvious layering occurs, and washing with deionized water; and seventhly, drying the mixture in an oven at 100-110 ℃ for about 4 hours, taking out and grinding the dried mixture to obtain the diatomite-based modified adsorbent loaded with the iron-manganese oxide.
Description
Technical Field
The invention belongs to the technical field of water environment adsorption materials, and particularly relates to a preparation method and application of a diatomite-based adsorbent loaded with iron-manganese oxide.
Background
In recent years, along with the continuous acceleration of industrialization and urban modernization processes in China, various requirements of the current society are met, and meanwhile, more and more serious environmental pollution problems correspondingly appear. Meanwhile, various organic pollutants, inorganic pollutants, viruses and the like are continuously introduced into the water environment in large quantities, and have serious life health threats to all organisms including human beings, so that the water environment pollution becomes a problem to be solved, and necessary advanced treatment on various polluted water bodies is not slow.
The pollution sources of the water environment mainly come from various industrial wastewater and urban domestic wastewater which are discharged into rivers and lakes without treatment or only through primary treatment, wherein the industrial wastewater has huge harm and high treatment difficulty and needs to draw sufficient attention. The industrial wastewater mainly takes the forms of heavy metal industrial wastewater, organic pollution wastewater and the like. Among heavy metal pollution, chromium is a very common pollutant and has high toxicity and difficult treatment. Therefore, researchers at home and abroad attach great importance to the treatment of the chromium-containing wastewater. Considering that the iron oxide and the manganese oxide have good adsorption and oxidation properties on heavy metals in a water body, and the mixture of the two oxides can effectively prevent the agglomeration among particles; the diatomite surface has a large amount of free hydroxyl and associated hydroxyl, plays an important role in catalytic reaction and interface adsorption reaction, can form hydrogen bonds with hydroxyl, amino, ketone, carboxyl and the like of some organic molecules to enable the diatomite to be adsorbed on the surface, and simultaneously realizes secondary recycling of the waste diatomite. Therefore, the novel adsorbent is prepared on the surface of the diatomite matrix by loading the iron-manganese oxide, and is applied to the treatment process of the chromium-containing wastewater.
Disclosure of Invention
The technical problem to be solved is as follows: the invention mainly provides a preparation method and application of a diatomite-based adsorbent loaded with iron-manganese oxide, and solves the technical problems of high cost, poor effect and the like in the prior art.
In order to achieve the purpose, the preparation method of the diatomite-based adsorbent loaded with the iron-manganese oxide comprises the following steps:
step one, pretreating waste diatomite;
step two, according to the diatomite, the dispersant and the FeSO4·7H2O、KMnO4、MnCl2·4H2The mass ratio of O is 10-15: 0.5-0.75: 7-10: 2.5-3.5: 2-3, preparing raw materials;
dissolving the diatomite and a dispersing agent into deionized water, and performing ultrasonic treatment for 1.5-2. h to fully disperse the diatomite and the dispersing agent to obtain a uniform suspension;
step four, respectively adding the dissolved FeSO into the solution4·7H2O、KMnO4、MnCl2·4H2O, regulating the pH of the mixed solution to 7-8 by using a 5M NaOH solution while violently stirring;
fifthly, placing the mixture on a magnetic stirrer to stir so as to enable the mixture to react fully;
sixthly, standing and aging at room temperature for 12h, filtering and separating precipitates after obvious layering occurs, and washing with deionized water;
and seventhly, drying the mixture in an oven at 100-110 ℃ for about 4 hours, taking out and grinding the dried mixture to obtain the diatomite-based modified adsorbent loaded with the iron-manganese oxide.
Further, the step of preprocessing comprises:
soaking waste diatomite with a preset fixed mass in a NaOH solution and carrying out magnetic stirring for 25-40 min;
then filtering and taking out the diatomite, and centrifuging for 10-15 min in a centrifuge to dry the diatomite;
soaking the dried diatomite in concentrated hydrochloric acid, magnetically stirring for 5-10 minutes, and repeating the process for 2-3 times;
taking out a diatomite sample, and washing the diatomite sample for 2-3 times by using distilled water;
and (4) putting the diatomite into an oven for drying and grinding into powder to obtain a pretreated diatomite sample for later use.
Furthermore, in the first step, the concentration of the NaOH solution is 3mol/L, the concentration of the concentrated hydrochloric acid is 10mol/L, and the volume is 250 mL. Further, the mass ratio of the diatomite, the dispersing agent, FeSO4 & 7H2O, KMnO4 and MnCl2 & 4H2O in the second step is that the mass ratio of the diatomite, the dispersing agent, FeSO4 & 7H2O, KMnO4 and MnCl2 & 4H2O is 10: 0.5:
7:2.5:2。
further, the temperature of the magnetic stirrer is 55-65 ℃, the stirring speed is 220r/min, and the stirring is continued for 1.5-2.5 h.
In order to achieve the purpose, the ferrimanganic oxide-loaded diatomite-based adsorbent prepared by the preparation method of the ferrimanganic oxide-loaded diatomite-based adsorbent is applied to treatment of chromium-containing wastewater.
Compared with the prior art, the preparation method and the application of the diatomite-based adsorbent loaded with the iron-manganese oxide have the following technical effects:
1. the raw materials are rich, the acquisition way is simple, the price is low, and no danger exists; meanwhile, the waste diatomite can be recycled, and waste is changed into valuable.
2. The preparation method has simple process and good removal effect on the chromium-containing wastewater; the synthetic load of the iron-manganese oxide and the diatomite can effectively avoid the defect of easy agglomeration, enhance the adsorption efficiency of the diatomite and have a certain oxidation effect on heavy metal ions.
3. The relationship between the equilibrium adsorption quantity of the diatomite-based adsorbent loaded by the iron-manganese oxide and the concentration of the residual chromium ions in the solution after adsorption equilibrium is respectively fitted by adopting four isothermal adsorption models of Langmuir, Frondlich, Dubinin-Radushkevich (D-R) and Tekin. The fitting result shows that the correlation coefficient R of the Langmuir isothermal adsorption model2The maximum value is best fit for the adsorption process of Cr (VI), the maximum adsorption quantity is 54.872mg/g, and the maximum adsorption quantity increases along with the increase of the temperature.
4. AThe results of the fit of the dynamic models of pseudo-one and pseudo-second for adsorbing Cr (VI) by using the diatomite-based adsorbent loaded with the iron-manganese oxide show that the dynamic models of pseudo-second can better fit the adsorption process, and the correlation coefficient R20.9996 is achieved, and the removal rate of Cr (VI) reaches 90.2 percent.
Description of the drawings:
fig. 1 is a schematic diagram of a process flow for preparing a ferrimanganic oxide supported diatomite-based adsorbent according to the present invention.
The specific implementation mode is as follows:
the following description will explain embodiments of the present invention in further detail with reference to the accompanying drawings.
Example 1
As shown in fig. 1, a preparation method of a ferrimanganic oxide-supported diatomite-based adsorbent comprises the following steps:
firstly, pretreating used waste diatomite from Nanjing breweries: firstly, soaking a certain mass of waste diatomite in NaOH solution and carrying out magnetic stirring for 25-40 min, then filtering and taking out the diatomite, centrifuging for 10-15 min in a centrifuge to dry the diatomite, soaking the dried diatomite in concentrated hydrochloric acid and carrying out magnetic stirring for 5-10 min, repeating the process for 2-3 times, taking out a diatomite sample, washing the diatomite sample with distilled water for three times, putting the diatomite sample into an oven at a set temperature of 110-130 ℃ for 12h, drying, taking out the diatomite sample, and grinding the diatomite sample into powder to obtain a pretreated diatomite sample for later use.
Step two, according to the diatomite, the dispersant and the FeSO4·7H2O、KMnO4、MnCl2·4H2The mass ratio of O is 10-15: 0.5-0.75: 7-10: 2.5-3.5: 2 to 3. Firstly, dissolving diatomite and a dispersing agent in deionized water, performing ultrasonic treatment for 1.5-2. h to fully disperse the diatomite and the dispersing agent to obtain uniform suspension, and then respectively adding dissolved FeSO into the solution4·7H2O、KMnO4、MnCl2·4H2And O, regulating the pH of the mixed solution to 7-8 by using a 5M NaOH solution while violently stirring, then placing the mixed solution on a magnetic stirrer, setting the temperature to be 55-65 ℃, and stirringThe rotating speed is 120 plus materials/min, stirring is continuously carried out for 1.5-2.5 h, aging is carried out for 12h at room temperature after reaction is fully carried out, filtering and separating precipitates after obvious layering occurs, deionized water is used for cleaning, drying is carried out for about 4h at the temperature of 100-110 ℃ in an oven, then the precipitates are taken out and ground, and the diatomite-based modified adsorbent loaded by the ferrimanganic oxide is obtained.
Taking the prepared ferrimanganic oxide-loaded diatomite-based adsorbent as an adsorbing material, diluting a chromium standard stock solution step by step to respectively obtain Cr (VI) solutions with the concentrations of 5, 10, 20, 30, 40 and 50mg/L, taking 6 250mL conical flasks, respectively pouring 50mL of Cr (VI) solutions with different concentrations into the conical flasks, adding 30mg of ferrimanganic oxide-loaded diatomite-based adsorbent into each conical flask, simultaneously adjusting the pH value of the Cr (VI) solution to 2.0 by using 0.1M of NaOH solution and 0.1M of HCl solution, respectively putting the conical flasks containing the adsorbent and the solutions into a constant-temperature water bath oscillator, respectively reacting at the rotation speed of 150rpm at the temperature of 25 ℃, 30 ℃ and 35 ℃ for 24 hours, after adsorption equilibrium is reached, respectively taking out a sample, filtering the sample by using a 0.45 mu M pinhole filter, and measuring the concentration of residual metal ions. The relationship between the equilibrium adsorption quantity of the diatomite-based adsorbent loaded by the iron-manganese oxide and the concentration of the residual chromium ions in the solution after adsorption equilibrium is respectively fitted by adopting four isothermal adsorption models of Langmuir, Frondlich, Dubinin-Radushkevich (D-R) and Tekin. The fitting result shows that the correlation coefficient R of the Langmuir isothermal adsorption model2The maximum value is best fit for the adsorption process of Cr (VI), the maximum adsorption quantity is 54.872mg/g, and the maximum adsorption quantity increases along with the increase of the temperature.
Example 2
As shown in fig. 1, a preparation method of a ferrimanganic oxide-supported diatomite-based adsorbent comprises the following steps:
firstly, pretreating used waste diatomite from Nanjing breweries: firstly, soaking a certain mass of waste diatomite in NaOH solution and carrying out magnetic stirring for 25-40 min, then filtering and taking out the diatomite, centrifuging for 10-15 min in a centrifuge to dry the diatomite, soaking the dried diatomite in concentrated hydrochloric acid and carrying out magnetic stirring for 5-10 min, repeating the process for 2-3 times, taking out a diatomite sample, washing the diatomite sample with distilled water for three times, putting the diatomite sample into an oven at a set temperature of 110-130 ℃ for 12h, drying, taking out the diatomite sample, and grinding the diatomite sample into powder to obtain a pretreated diatomite sample for later use.
Step two, according to the diatomite, the dispersant and the FeSO4·7H2O、KMnO4、MnCl2·4H2The mass ratio of O is 10-15: 0.5-0.75: 7-10: 2.5-3.5: 2 to 3. Firstly, dissolving diatomite and a dispersing agent in deionized water, performing ultrasonic treatment for 1.5-2. h to fully disperse the diatomite and the dispersing agent to obtain uniform suspension, and then respectively adding dissolved FeSO into the solution4·7H2O、KMnO4、MnCl2·4H2And O, regulating the pH value of the mixed solution to 7-8 by using a 5M NaOH solution while violently stirring, then placing the mixed solution on a magnetic stirrer, setting the temperature to be 55-65 ℃, the stirring speed to be 120-one and 220r/min, continuously stirring for 1.5-2.5 h, placing the mixed solution at room temperature for aging for 12h after full reaction, filtering and separating precipitates after obvious layering, washing the precipitates by using deionized water, drying the precipitates in an oven at 100-110 ℃ for about 4h, taking out the precipitates, and grinding the precipitates to obtain the diatomite-based modified adsorbent loaded with the ferrimanganic oxide.
In order to fit the adsorption kinetics of the ferrimanganite-loaded diatomite-based adsorbent, the prepared Cr (VI) stock solution is diluted to obtain 10mg/L Cr (VI) solution, 50mL of the Cr (VI) stock solution is added into a group of 250mL conical flasks, 30mg of the ferrimanganite-loaded diatomite-based adsorbent is added, meanwhile, the pH value of the Cr (VI) solution is adjusted to 2.0 by using 0.1M NaOH solution or 0.1M HCl solution, the conical flasks containing the adsorbent and the solution are placed into a constant-temperature water bath oscillator to react at the rotating speed of 150rpm at the temperature of 25 ℃, samples are taken out at the time of 10min, 30min, 60min, 120min, 180min, 240min and 300min and are filtered by using a 0.45 mu M pinhole filter, and the concentration of the residual metal ions is measured. The results of the dynamic model fitting using the pseudo-one and the pseudo-second show that the dynamic model of the pseudo-second can better fit the adsorption process, and the correlation coefficient R20.9996 is achieved, and the removal rate of Cr (VI) reaches 90.2 percent.
Example 3
As shown in fig. 1, a preparation method of a ferrimanganic oxide-supported diatomite-based adsorbent comprises the following steps:
firstly, pretreating used waste diatomite from Nanjing breweries: firstly, soaking a certain mass of waste diatomite in NaOH solution and carrying out magnetic stirring for 25-40 min, then filtering and taking out the diatomite, centrifuging for 10-15 min in a centrifuge to dry the diatomite, soaking the dried diatomite in concentrated hydrochloric acid and carrying out magnetic stirring for 5-10 min, repeating the process for 2-3 times, taking out a diatomite sample, washing the diatomite sample with distilled water for three times, putting the diatomite sample into an oven at a set temperature of 110-130 ℃ for 12h, drying, taking out the diatomite sample, and grinding the diatomite sample into powder to obtain a pretreated diatomite sample for later use.
Step two, according to the diatomite, the dispersant and the FeSO4·7H2O、KMnO4、MnCl2·4H2The mass ratio of O is 10-15: 0.5-0.75: 7-10: 2.5-3.5: 2 to 3. Firstly, dissolving diatomite and a dispersing agent in deionized water, performing ultrasonic treatment for 1.5-2. h to fully disperse the diatomite and the dispersing agent to obtain uniform suspension, and then respectively adding dissolved FeSO into the solution4·7H2O、KMnO4、MnCl2·4H2And O, regulating the pH value of the mixed solution to 7-8 by using a 5M NaOH solution while violently stirring, then placing the mixed solution on a magnetic stirrer, setting the temperature to be 55-65 ℃, the stirring speed to be 120-one and 220r/min, continuously stirring for 1.5-2.5 h, placing the mixed solution at room temperature for aging for 12h after full reaction, filtering and separating precipitates after obvious layering, washing the precipitates by using deionized water, drying the precipitates in an oven at 100-110 ℃ for about 4h, taking out the precipitates, and grinding the precipitates to obtain the diatomite-based modified adsorbent loaded with the ferrimanganic oxide.
Using the prepared ferrimanganic oxide-loaded diatomite-based adsorbent as an adsorption material, diluting a chromium standard stock solution step by step to respectively obtain Cr (VI) solutions with the concentrations of 5, 10, 20, 30, 40 and 50mg/L, taking 6 250mL conical flasks, respectively pouring 50mL of Cr (VI) solutions with different concentrations into the conical flasks, adding 30mg of ferrimanganic oxide-loaded diatomite-based adsorbent into each conical flask, and simultaneously adding 0.1M NaOH solution or 0.1M HCl solution into each conical flaskAdjusting the pH value of the Cr (VI) solution to 2.0, putting the conical flask containing the adsorbent and the solution into a constant-temperature water bath oscillator, reacting at 25 ℃, 30 ℃ and 35 ℃ for 24h at the rotating speed of 150rpm, respectively, taking out samples after adsorption equilibrium is reached, filtering the samples by using a 0.45-micrometer pinhole filter, and measuring the concentration of the residual metal ions. The relationship between the equilibrium adsorption quantity of the diatomite-based adsorbent loaded by the iron-manganese oxide and the concentration of the residual chromium ions in the solution after adsorption equilibrium is respectively fitted by adopting four isothermal adsorption models of Langmuir, Frondlich, Dubinin-Radushkevich (D-R) and Tekin. The fitting result shows that the correlation coefficient R of the Langmuir isothermal adsorption model2The maximum value is best fit for the adsorption process of Cr (VI), the maximum adsorption quantity is 54.872mg/g, and the maximum adsorption quantity increases along with the rise of the temperature.
In order to fit the adsorption kinetics of the ferrimanganite-loaded diatomite-based adsorbent, the prepared Cr (VI) stock solution is diluted to obtain 10mg/L Cr (VI) solution, 50mL of the Cr (VI) stock solution is added into a group of 250mL conical flasks, 30mg of the ferrimanganite-loaded diatomite-based adsorbent is added, meanwhile, the pH value of the Cr (VI) solution is adjusted to 2.0 by using 0.1M NaOH solution or 0.1M HCl solution, the conical flasks containing the adsorbent and the solution are placed into a constant-temperature water bath oscillator to react at the rotating speed of 150rpm at the temperature of 25 ℃, samples are taken out at the time of 10min, 30min, 60min, 120min, 180min, 240min and 300min and are filtered by using a 0.45 mu M pinhole filter, and the concentration of the residual metal ions is measured. The results of the dynamic model fitting using the pseudo-one and the pseudo-second show that the dynamic model of the pseudo-second can better fit the adsorption process, and the correlation coefficient R20.9996 is achieved, and the removal rate of Cr (VI) reaches 90.2 percent.
Claims (6)
1. The preparation method of the diatomite-based adsorbent loaded with the iron-manganese oxide is characterized by comprising the following steps of:
step one, pretreating waste diatomite;
step two, according to the diatomite, the dispersant and the FeSO4·7H2O、KMnO4、MnCl2·4H2Mass of OThe ratio is 10-15: 0.5-0.75: 7-10: 2.5-3.5: 2-3, preparing raw materials;
dissolving the diatomite and a dispersing agent into deionized water, and performing ultrasonic treatment for 1.5-2. h to fully disperse the diatomite and the dispersing agent to obtain a uniform suspension;
step four, respectively adding the dissolved FeSO into the solution4·7H2O、KMnO4、MnCl2·4H2O, regulating the pH of the mixed solution to 7-8 by using a 5M NaOH solution while violently stirring;
fifthly, placing the mixture on a magnetic stirrer to stir so as to enable the mixture to react fully;
sixthly, standing and aging at room temperature for 12h, filtering and separating precipitates after obvious layering occurs, and washing with deionized water;
and seventhly, drying the mixture in an oven at 100-110 ℃ for about 4 hours, taking out and grinding the dried mixture to obtain the diatomite-based modified adsorbent loaded with the iron-manganese oxide.
2. The method of preparing an iron-manganese oxide-supported diatomaceous earth-based adsorbent according to claim 1, wherein: the pretreatment step comprises the following steps:
soaking waste diatomite with a preset fixed mass in a NaOH solution and carrying out magnetic stirring for 25-40 min;
then filtering and taking out the diatomite, and centrifuging for 10-15 min in a centrifuge to dry the diatomite;
soaking the dried diatomite in concentrated hydrochloric acid, magnetically stirring for 5-10 minutes, and repeating the process for 2-3 times;
taking out a diatomite sample, and washing the diatomite sample for 2-3 times by using distilled water;
and (4) putting the diatomite into an oven for drying and grinding into powder to obtain a pretreated diatomite sample for later use.
3. The method of preparing an iron-manganese oxide-supported diatomaceous earth-based adsorbent according to claim 1, wherein: in the first step, the concentration of NaOH solution is 3mol/L, the concentration of concentrated hydrochloric acid is 10mol/L, and the volume is 250 mL.
4. The method of preparing an iron-manganese oxide-supported diatomaceous earth-based adsorbent according to claim 1, wherein: the mass ratio of the diatomite to the dispersant, FeSO4 & 7H2O, KMnO4 and MnCl2 & 4H2O in the second step is that the mass ratio of the diatomite to the dispersant, FeSO4 & 7H2O, KMnO4 and MnCl2 & 4H2O is 10: 0.5: 7: 2.5: 2.
5. the method of preparing an iron-manganese oxide-supported diatomaceous earth-based adsorbent according to claim 1, wherein: in the second step, the temperature of the magnetic stirrer is 55-65 ℃, the stirring speed is 220r/min, and the stirring is continued for 1.5-2.5 h.
6. The use of the ferrimanganic oxide-supported diatomite-based adsorbent prepared by the method for preparing the ferrimanganic oxide-supported diatomite-based adsorbent according to claim 1 in treatment of chromium-containing wastewater.
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