CN113385147B - Application and method of composite adsorption material for simultaneously removing phenol and Cr (VI) in wastewater - Google Patents
Application and method of composite adsorption material for simultaneously removing phenol and Cr (VI) in wastewater Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 77
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 60
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000002351 wastewater Substances 0.000 title claims abstract description 31
- 239000002131 composite material Substances 0.000 title claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 109
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 74
- 239000011651 chromium Substances 0.000 claims description 71
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 23
- 229910052804 chromium Inorganic materials 0.000 claims description 23
- 239000012028 Fenton's reagent Substances 0.000 claims description 14
- 239000003463 adsorbent Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
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- 238000002360 preparation method Methods 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
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- 238000003756 stirring Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
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- POLIXZIAIMAECK-UHFFFAOYSA-N 4-[2-(2,6-dioxomorpholin-4-yl)ethyl]morpholine-2,6-dione Chemical compound C1C(=O)OC(=O)CN1CCN1CC(=O)OC(=O)C1 POLIXZIAIMAECK-UHFFFAOYSA-N 0.000 claims description 3
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- 238000006243 chemical reaction Methods 0.000 abstract description 9
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 57
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
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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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
- C07F7/087—Compounds of unknown structure containing a Si-O-Si sequence
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
- C07F7/0872—Preparation and treatment thereof
- C07F7/0874—Reactions involving a bond of the Si-O-Si linkage
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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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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- 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
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/11—Compounds covalently bound to a solid support
Abstract
The invention discloses an application and a method of a composite adsorption material for simultaneously removing phenol and Cr (VI) in wastewater, belonging to the technical field of wastewater treatment. The method comprises mixing EDTA-Silica and EDTA-Fe 2+ The two composite adsorption materials of the Silica are efficiently used for synchronously removing phenol and Cr (VI) in the waste liquid. Research results show that in a binary simulated waste liquid system, based on Fenton reaction catalysis characteristics and metal chelating characteristics of ligand EDTA in two adsorption materials, the method has excellent removal effect in the treatment process of phenol-Cr (VI) simulated waste liquid by utilizing the forward synergistic effect of phenol and Cr (VI), and the used solid adsorption material is convenient to recycle and has no secondary pollution. In practical application, the use of the two materials can be flexibly selected according to the specific conditions of industrial wastewater and the emission standard; the method has wide application prospect in the field of treatment of industrial wastewater in paint, printing ink, leather, textile industry and the like.
Description
Technical Field
The invention belongs to the technical field of degrading phenol and removing chromium by an adsorption method, and relates to application and a method of a composite adsorption material for simultaneously removing phenol and Cr (VI) in wastewater.
Background
Phenol is an important industrial emission, has high toxicity, can cause the death of aquatic organisms and the yield reduction or dead of crops, and has side effects of cancerogenesis, teratogenesis, mutation and the like on human bodies. As the pollutants which are preferentially controlled, monitored and treated by the environmental protection departments of various countries, the detection rate and the exceeding rate of phenol in polluted water bodies are high. At present, the main treatment idea of phenol is to utilize classical Fenton reaction, namely Fe 2+ /Fe 3+ Cyclic oxidation betweenOriginal promotion of H 2 O 2 Releasing hydroxyl radical HO. And degrading phenol via HO. The hydroxyl radical HO. Is released. By adding the liquid chelating agent EDTA into the classical Fenton reaction system, the Selamawit et al avoids the condition limitation of low pH in the classical Fenton reaction, but has the problem of secondary pollution because the EDTA is in a liquid state. And heavy metal ion chromium exists in the actual phenol industrial wastewater, and hexavalent chromium Cr (VI) has the advantages of easy absorption by organisms, strong toxicity, strong corrosiveness, cancerogenicity and other harm, and seriously threatens the ecological system and even human health. The international anticancer research center and the american toxicology organization have listed it as one of the 8 most serious chemicals that damage the human body.
In addition to landfill leachate, phenol and Cr (vi) are also ubiquitous in paint, ink, leather and textile industry emissions. Thus, the treatment of industrial wastewater in which phenol and Cr (vi) coexist has been a worldwide problem. At present, the treatment methods of the wastewater mainly comprise a Fenton oxidation method, a photocatalytic oxidation method, an improved Fenton oxidation method and a low-temperature plasma technology. The idea of these methods is to convert highly toxic phenol and Cr (VI) into low-toxic or non-toxic substances by chemical oxidation and then remove them by precipitation or the like. Although the treatment methods can achieve better removal effect, the treatment methods have the defects that the influence of pH is large in the treatment process, the content of iron and chromium in the solution after the reaction is insufficient to reach the emission standard, the cost is high and the like.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide an application and a method of a composite adsorbing material for simultaneously removing phenol and Cr (VI) in wastewater.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
the invention discloses an application of a composite adsorption material in simultaneously removing phenol and Cr (VI) in wastewater, wherein the composite adsorption material is EDTA-Silica and/or EDTA-Fe 2+ -a Silica adsorbent material; wherein:
the structural formula of the EDTA-Silica adsorbing material is shown in the following formula I:
the EDTA-Fe 2+ The structural formula of the Silica adsorption material is shown in the following formula II;
preferably, the waste water is a waste liquid from industrial fields related to paints, inks, leather and textiles.
Preferably, the EDTA-Silica adsorption material has a phenol and Cr (VI) removing rate of 95% or more and a total chromium removing rate of 85% or more.
Preferably, the EDTA-Fe 2+ The removal rate of the Silica adsorption material to phenol and Cr (VI) is more than 92 percent, and the removal rate of the Silica adsorption material to total chromium is more than 82 percent.
Preferably, the preparation method of the EDTA-Silica adsorption material comprises the following steps:
adding 3-aminopropyl trimethoxy silane into toluene suspension containing active Silica gel, stirring at 80deg.C under nitrogen to obtain mixture, cleaning, and drying to obtain Silica-NH 2 ；
Silica-NH 2 Dissolving in N-methyl-2-pyrrolidone solution, adding ethylenediamine tetraacetic acid dianhydride, stirring at 60deg.C under nitrogen protection to obtain reactant, cleaning, and drying to obtain EDTA-Silica adsorption material.
Further preferably, the specific preparation is as follows: adding 0.75mL of 3-aminopropyl trimethoxysilane (APTS) into a toluene suspension of 3.0000g of active Silica gel, mechanically stirring at 80deg.C under nitrogen protection for 24h, cooling the mixture, sequentially cleaning with toluene, ethanol and deionized water, and drying at 65deg.C for 24h to obtain Silica-NH 2 The method comprises the steps of carrying out a first treatment on the surface of the 2.0000g of Silica-NH to be prepared 2 Dissolving in 35.00mL of N-methyl-2-pyrrolidone solution, adding 0.3000g of ethylenediamine tetraacetic acid dianhydride, mechanically stirring at 60 ℃ for 12 hours under the protection of nitrogen, cleaning sequentially with 2-methylpyrrolidone, ethanol and deionized water, and drying a solid sample at 65 ℃ for 24 hours to obtain the EDTA-Silica adsorption material.
Preferably, the EDTA-Fe 2+ The preparation method of the Silica adsorption material comprises the following steps:
immersing EDTA-Silica adsorption material into FeSO 4 ·7H 2 In O solution, adsorbing for 2h to obtain EDTA-Fe 2+ -a Silica adsorbent material.
Further preferably, according to m (EDTA-Silica): v (FeSO) 4 ·7H 2 O) =1.00 g: the EDTA-Silica adsorption material is added with 1 mmol/LFASO at the temperature of 20-40 ℃ and the dosage ratio of 200-400r/min 4 ·7H 2 In O solution, adsorbing for 2h to obtain EDTA-Fe 2+ -a Silica adsorbent material.
The invention also discloses a method for cooperatively removing phenol and Cr (VI) in wastewater, which comprises the following steps:
adding EDTA-Silica adsorption material into the wastewater to be treated, and adding FeSO-containing material 4 ·7H 2O and H2 O 2 In Fenton reagent, fully and uniformly mixed, sealed in a constant-temperature water bath shaking table, and subjected to adsorption treatment for 2-4h at 20-40 ℃ at the rotating speed of 200-400 r/min.
Preferably, according to m (EDTA-Silica): m (FeSO) 4 ·7H 2 O)：V(H 2 O 2 ) =1.00 g: (0.003-0.005) g: (0.2-0.4) mL, EDTA-Silica adsorbing material is added into the mixture containing FeSO 4 ·7H 2O and H2 O 2 Adsorption treatment is carried out in Fenton reagent.
The invention also discloses a method for cooperatively removing phenol and Cr (VI) in wastewater, which comprises the following steps:
EDTA-Fe is taken 2+ -Silica adsorbent material added to the wastewater to be treated, then added to a reactor containing H alone 2 O 2 In Fenton reagent, fully and uniformly mixed, sealed in a constant-temperature water bath shaking table, and subjected to adsorption treatment for 2-4h at 20-40 ℃ at the rotating speed of 200-400 r/min.
Preferably EDTA-Fe 2+ Silica and H-containing 2 O 2 The dosage ratio of Fenton reagent is as follows: m (EDTA-Fe) 2+ -Silica)：V(H 2 O 2 )＝1.00g：(0.2～0.4)mL。
Compared with the prior art, the invention has the following beneficial effects:
1. EDTA ligands on the adsorbent material have metal chelating properties with which different effects can be achieved: (i) EDTA-Silica can be used as a catalyst for heterogeneous Fenton reaction by chelating iron ions in a Fenton reagent, and is used for improving the degradation efficiency of phenol organic pollutants. (ii) The catalyst is used as a chromium adsorbing material, and can effectively reduce the content of total chromium in waste liquid. (iii) The pH application range of the Fenton reaction can be effectively widened by using the catalyst as an adsorption material for ferric iron.
2. EDTA-Silica and EDTA-Fe on the basis of forward synergy of phenol and Cr (VI) 2+ The Silica solid adsorption material is suitable for the synergistic removal of Cr (VI) and phenol binary solution. And the total chromium removal rate can reach eighty percent, thereby solving the defect that Cr (VI) is only degraded and not removed in the prior literature.
3. In the binary waste liquid containing phenol and Cr (VI), the added Fenton reagent contains excessive Fe 2+ After the adsorption material is treated, the total iron content can completely reach the emission standard.
4. Compared with the liquid chelating agent adopted in the previous research, the solid chelating agent adopted in the research is convenient for subsequent treatment and is not easy to cause secondary pollution.
Drawings
FIG. 1 is a graph showing the results of an EDTA-Silica adsorption material for use in the removal of phenol-Cr (VI) binary simulation waste liquid; wherein, (a) is the removal rate of phenol, total chromium and Cr (VI); (b) is the residual total iron content;
FIG. 2 shows EDTA-Fe 2+ The experimental result diagram of the removal of the silicon metal chelating adsorption material for the phenol-Cr (VI) binary simulation waste liquid; wherein, (a) is the removal rate of phenol, total chromium and Cr (VI); (b) is the residual total iron content;
FIG. 3 is a mechanical drawing of the co-removal of phenol-Cr (VI) by the adsorbent material.
Detailed Description
In order to enable those skilled in the art to better understand the present invention, the following description will make clear and complete descriptions of the technical solutions according to the embodiments of the present invention with reference to the accompanying drawings. It will be apparent that the described embodiments are merely some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and the claims of the present invention and the above figures are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate such that the embodiments of the invention described herein may be implemented in sequences other than those illustrated or otherwise described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the attached drawing figures:
the main raw materials used in the invention are as follows: EDTA-Silica adsorbent and EDTA-Fe 2+ The Silica adsorption materials are all prepared by laboratories; the phenol-Cr (VI) binary wastewater simulation liquid is self-matched in a laboratory, and the wastewater simulation liquid prepared by the invention is a common composition in different industrial wastewater, and has representativeness and universality; the chemical reagents used were all commercial analytical grade commercial products.
Example 1: removal of phenol, chromium and iron in binary simulation waste liquid by EDTA-Silica adsorption material
1. Preparation of phenol-Cr (VI) binary waste water simulation liquid
(i) Preparation of binary simulated wastewater stock solution
Accurately weigh 0.5733g K 2 Cr 2 O 7 And 0.1250g of phenol, respectively dissolved and fixed to 250.0mL to obtain 200mg/L concentrationCr (VI) stock solution and 500mg/L phenol stock solution.
(ii) Preparation of binary wastewater simulation liquid
10mL of phenol and Cr (VI) stock solution are respectively taken, mixed and fixed to 100.0mL to obtain a binary wastewater simulation solution containing 20mg/LCr (VI) and 50mg/L phenol. The pH is adjusted with hydrochloric acid or sodium hydroxide solution.
2. EDTA-Silica adsorbing material is prepared by referring to the existing synthesis method. Specific methods of preparation can be made with reference to the methods disclosed in the prior art documents, such as [1]T.J.Wenzel,R.Evertsen,B.E.Perrins,T.B.Light Jr.A.C.Bean,Anal.Chem.70 (1998) 2085 ] [2]Franklin P.Aguiar,Israel F.Costa,Jos e Geraldo P. EspI nola, wagner M. Faustino. Luminecent hybrid materials functionalized with lanthanideethylenodiaminotetraacetate complexes containing. Beta. -diketonate as antenna ligands. Journal of Lumineancence 170 (2016) 538-546.
Accurately weighing two parts of 0.3000g EDTA-Silica adsorption material, respectively transferring 20.00mL binary wastewater simulation solutions with pH of 3.0 and 6.0, and adding FeSO 0.0013mg 4 ·7H 2 O and 0.07mL H 2 O 2 Fenton reagent of (C). Sealing, placing in a constant-temperature water bath table, adsorbing at 30deg.C for 4 hr at 200r/min, filtering, and collecting supernatant.
3. Using inductively coupled plasma emission spectrometry (ICP-AES) and deionized water as a blank solution to measure the total chromium concentration in the solution before and after adsorption and the total iron concentration remained after adsorption;
4. adopting a visible spectrophotometry, taking deionized water as a blank solution, and respectively obtaining linear standard curves between phenol absorbance and concentration: y=0.141 x-0.004476, and a linear standard curve between Cr (vi) absorbance and concentration: y=0.225 x+0.0025. According to the standard curve, the initial concentration and the equilibrium concentration of phenol and Cr (VI) in the waste liquid are measured respectively, and the removal rates of phenol, cr (VI) and total chromium are calculated respectively according to the following formula.
wherein ：C0 -initial concentration, mg/L; c (C) e Concentration at equilibrium, mg/L.
FIG. 1 shows the use of EDTA-Silica adsorbent material for the removal of phenol-Cr (VI) binary analog waste liquid. Wherein, the graphs (a) and (b) are respectively the removal rate of phenol, cr (VI) and total chromium by the adsorption material and the total iron content remained after treatment. As is clear from FIG. 1 (a), the EDTA-Silica adsorbent has a removal rate of phenol and Cr (VI) of 95% or more and a removal rate of total chromium of 85% or more, and exhibits a good removal effect due to the excellent metal chelating property of hexadentate ligand EDTA. Meanwhile, the pH has little influence on the removal rate of phenol and Cr (VI), and has little influence on the removal rate of total chromium, so that the use of the adsorption material can effectively expand the pH range of waste liquid research. In addition, as is clear from FIG. 1 (b), the total iron content remaining in the treated waste liquid was 1.688 and 2.811mg/L, respectively, which all meet the national emission standards (10 mg/L for the emission standard of water pollution in the iron and steel industry, 7mg/L for the emission standard of pollutants in the coal industry, 5mg/L for the emission standard of pollutants in the electroplating, and 5mg/L for the water quality standard of sewage discharged into city).
Studies have shown that: the EDTA-Silica adsorption material can be effectively applied to the treatment of phenol-Cr (VI) binary waste liquid.
2+ Example 2: removal of phenol, chromium and iron in binary simulation waste liquid by EDTA-Fe-Silica adsorption material
1.0000g of EDTA-Silica mentioned in example 1 was weighed and adsorbed at 30℃and 200r/min to 20.00mL of 1mmol/L FeSO 4 ·7H 2 O solution (pH 4.64) for 2h to obtain EDTA-Fe 2+ Silica (Metal Fe 2+ The bonding amount was 0.86mg/g Silica ). Two portions of 0.3000g EDTA-Fe are weighed 2+ The Silica adsorption material was removed with 20.00mL of simulated waste liquid having pH 3.0 and 6.0, and 0.07mL of H was added, respectively 2 O 2 . Sealing, placing in a constant-temperature water bath table, adsorbing at 30deg.C for 4 hr at 200r/min, filtering, and collecting supernatant. The adsorption material p-phenol, cr were obtained by the method mentioned in example 1(VI) and total chromium removal rate, and residual total iron content in the waste liquid.
As can be seen from FIG. 2 (a), EDTA-Fe 2+ The removal rate of the Silica adsorption material on phenol and Cr (VI) can reach more than 92 percent, the removal rate of the Silica adsorption material on total chromium can reach more than 82 percent, and the Silica adsorption material also has positive effects in treating the simulated waste liquid containing phenol-Cr (VI), and is equivalent to the removal effect of EDTA-Silica materials. As can be seen from FIG. 2 (b), EDTA-Fe 2+ The content of residual total iron in the waste liquid after the treatment of the Silica adsorption material is 1.166 mg/L and 3.833mg/L respectively, and the national emission standard is also satisfied. Studies have shown that: EDTA-Fe 2+ Silica is equally suitable for treating phenol-containing Cr (VI) binary waste liquid systems.
EDTA-Silica and EDTA-Fe 2+ The mechanism of removal of phenol-Cr (VI) in binary waste liquid systems by Silica adsorption materials is shown in FIG. 3, and when EDTA-Silica is used to treat the simulated waste liquid (scheme I in FIG. 3), it is necessary to add Fenton reagent (Fe 2+ ，H 2 O 2 ) EDTA-Silica can be used for chelating Fe in Fenton reagent 2+ EDTA-Fe formation 2+ Silica as heterogeneous catalyst for phenol degradation (FIG. 3 (1)); when EDTA-Fe is used 2+ When the Silica treatment simulates wastewater (scheme II in FIG. 3), the metal Fe is sequestered in the material 2+ Only H needs to be added into the simulated waste liquid 2 O 2 . When two materials adsorb phenol and Cr (VI) in a binary system, the characteristic is that:
(1) The adsorption material is used as a catalytic carrier to effectively promote H 2 O 2 Producing HO with strong oxidizing property, ensuring Fe 2+ And Fe (Fe) 3+ Efficient circulation of the redox reaction between (fig. 3 (2)) to promote degradation of phenol for removal (fig. 3 (4)).
(2) Cr (VI) with strong oxidizing property can also participate in a Fenton reaction system (3 in fig. 3), and further promotes the degradation of phenol, thereby being beneficial to improving the degradation rate of phenol. It can be seen that there is a positive synergy between phenol and Cr (VI).
(3) By utilizing the metal chelating property of EDTA, on one hand, the hydrolysis of ferric ions can be avoided, and the pH application range of the method is further widened; on the other hand, the residual iron ions in the Fenton reagent and various forms of chromium (5 in fig. 3) existing in the solution can be effectively removed, so that the content of the residual iron ions and the chromium (5) in fig. 3 can meet the environmental emission requirements.
In summary, the method provided by the invention is to mix EDTA-Silica and EDTA-Fe 2+ Two composite adsorption materials of Silica are used for efficient synergistic removal of phenol and Cr (VI) in waste liquid. Research results show that in a binary simulated waste liquid system, based on Fenton reaction catalysis characteristics and metal chelating characteristics of ligand EDTA in two adsorption materials, the method has excellent removal effect in the treatment process of phenol-Cr (VI) simulated waste liquid by utilizing the forward synergistic effect of phenol and Cr (VI), and the used solid adsorption material is convenient to recycle and has no secondary pollution. In practical application, the use of the two materials can be flexibly selected according to the specific conditions of industrial wastewater and the emission standard; the method has wide application prospect in the field of treatment of industrial wastewater in paint, printing ink, leather, textile industry and the like.
The above is only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited by this, and any modification made on the basis of the technical scheme according to the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. The application of the composite adsorption material in the simultaneous removal of phenol and Cr (VI) in wastewater is characterized in that the composite adsorption material is EDTA-Silica and/or EDTA-Fe 2+ -a Silica adsorbent material; wherein:
the structural formula of the EDTA-Silica adsorbing material is shown in the following formula I:
the EDTA-Fe 2+ The structural formula of the Silica adsorption material is shown in the following formula II;
I
II
wherein,
represents a Silica;
when EDTA-Silica is used to treat wastewater, fenton reagent including Fe is added to the wastewater 2+ 、H 2 O 2 ；
When EDTA-Fe is used 2+ When the Silica is used for treating wastewater, H is added into the wastewater 2 O 2 。
2. The use according to claim 1, wherein the EDTA-Silica adsorbent has a removal rate of more than 95% for phenol and Cr (vi) and more than 85% for total chromium.
3. The use according to claim 1, wherein the EDTA-Fe 2+ The removal rate of the Silica adsorption material to phenol and Cr (VI) is more than 92 percent, and the removal rate of the Silica adsorption material to total chromium is more than 82 percent.
4. The use according to claim 1, wherein the EDTA-Silica adsorbing material is prepared by the following method:
adding 3-aminopropyl trimethoxy silane into toluene suspension containing active Silica gel, stirring at 80deg.C under nitrogen to obtain mixture, cleaning, and drying to obtain Silica-NH 2 ；
Silica-NH 2 Dissolving in N-methyl-2-pyrrolidone solution, adding ethylenediamine tetraacetic acid dianhydride, stirring at 60deg.C under nitrogen protection to obtain reactant, cleaning, and drying to obtain EDTA-Silica adsorption material.
5. Such as weightThe use according to claim 1 or 4, wherein the EDTA-Fe 2+ The preparation method of the Silica adsorption material comprises the following steps:
immersing EDTA-Silica adsorption material into FeSO 4 ·7H 2 Adsorbing 2h in O solution to obtain EDTA-Fe 2+ -a Silica adsorbent material.
6. The method according to claim 5, wherein the adsorption treatment is carried out at 30℃and 200 r/min.
7. A method for cooperatively removing phenol and Cr (vi) from wastewater, comprising:
the EDTA-Silica adsorbing material as defined in claim 1, which is added to the waste water to be treated, and then FeSO-containing material is added 4 ·7H 2 O and H-containing 2 O 2 In Fenton reagent, fully and uniformly mixed, sealed in a constant-temperature water bath shaking table, and subjected to adsorption treatment for 2-4h at 20-40 ℃ at the rotating speed of 200-400 r/min.
8. The method for cooperatively removing phenol and Cr (VI) from wastewater according to claim 7, characterized in that EDTA-Silica adsorbent, feSO 4 ·7H 2 O and H 2 O 2 The dosage ratio of (2) is 1.00g: (0.003-0.005) g: (0.2 to 0.4) mL.
9. A method for cooperatively removing phenol and Cr (vi) from wastewater, comprising:
taking EDTA-Fe as defined in claim 1 2+ -Silica adsorbent material added to the wastewater to be treated, then added to a reactor containing H alone 2 O 2 In Fenton reagent, fully and uniformly mixed, sealed in a constant-temperature water bath shaking table, and subjected to adsorption treatment for 2-4h at 20-40 ℃ at the rotating speed of 200-400 r/min.
10. The method for cooperatively removing phenol and Cr (VI) from wastewater according to claim 9, characterized in that EDTA-Fe 2 + Silica and H-containing 2 O 2 The dosage ratio of Fenton reagent is 1.00g: (0.2 to 0.4) mL.
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