CN107970886B - Graphene oxide and ferric chloride composite modified zeolite filter material and preparation method thereof - Google Patents
Graphene oxide and ferric chloride composite modified zeolite filter material and preparation method thereof Download PDFInfo
- Publication number
- CN107970886B CN107970886B CN201711100057.9A CN201711100057A CN107970886B CN 107970886 B CN107970886 B CN 107970886B CN 201711100057 A CN201711100057 A CN 201711100057A CN 107970886 B CN107970886 B CN 107970886B
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- Prior art keywords
- graphene oxide
- zeolite
- fecl
- modified zeolite
- adsorption
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 298
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 174
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 169
- 239000002131 composite material Substances 0.000 title claims abstract description 106
- 239000000463 material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 229910021578 Iron(III) chloride Inorganic materials 0.000 title claims abstract description 28
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 title claims abstract description 21
- 238000001179 sorption measurement Methods 0.000 claims abstract description 139
- 239000010457 zeolite Substances 0.000 claims description 140
- 229910021536 Zeolite Inorganic materials 0.000 claims description 138
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 64
- 238000001354 calcination Methods 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 32
- 239000003607 modifier Substances 0.000 claims description 29
- 239000012153 distilled water Substances 0.000 claims description 23
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 238000004140 cleaning Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 6
- 238000003837 high-temperature calcination Methods 0.000 claims description 5
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 238000000643 oven drying Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 23
- 238000011068 loading method Methods 0.000 abstract description 16
- 238000009776 industrial production Methods 0.000 abstract description 4
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 45
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- 229940012189 methyl orange Drugs 0.000 description 34
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 33
- 230000004048 modification Effects 0.000 description 29
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- -1 ammonium ions Chemical class 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 10
- 125000000524 functional group Chemical group 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
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- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 4
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
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- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 3
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- 235000015523 tannic acid Nutrition 0.000 description 3
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- 238000002411 thermogravimetry Methods 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
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- 229910052802 copper Inorganic materials 0.000 description 2
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- 238000011835 investigation Methods 0.000 description 2
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- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
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- 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 description 1
- JRLTTZUODKEYDH-UHFFFAOYSA-N 8-methylquinoline Chemical group C1=CN=C2C(C)=CC=CC2=C1 JRLTTZUODKEYDH-UHFFFAOYSA-N 0.000 description 1
- 238000004483 ATR-FTIR spectroscopy Methods 0.000 description 1
- 229910018516 Al—O Inorganic materials 0.000 description 1
- ZETHHMPKDUSZQQ-UHFFFAOYSA-N Betulafolienepentol Natural products C1C=C(C)CCC(C(C)CCC=C(C)C)C2C(OC)OC(OC)C2=C1 ZETHHMPKDUSZQQ-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
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- 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 description 1
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- 229910018557 Si O Inorganic materials 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
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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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0288—Halides of compounds other than those provided for in B01J20/046
-
- 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
- B01J20/28059—Surface area, e.g. B.E.T specific surface area being less than 100 m2/g
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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
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention relates to a graphene oxide and ferric chloride composite modified zeolite filter material and a preparation method thereof. The modified zeolite filter material has extremely strong hydrophilic performance and adsorption capacity. The preparation method of the invention uses graphene oxide and FeCl 3 The preparation method of the invention has high loading rate and good loading effect, is suitable for industrial production, and is convenient and practical.
Description
Technical Field
The invention relates to a graphene oxide and ferric chloride composite modified zeolite filter material and a preparation method thereof, and belongs to an innovative technology of the graphene oxide and ferric chloride composite modified zeolite filter material and the preparation method thereof.
Background
With the acceleration of the industrialization process in China, the pollution degree in the water quality of the water source is gradually increased. Meanwhile, the requirements of people on the quality of water are continuously improved. The new water quality standard of China is increased by 71 indexes in total, and the index item numbers of organic matters, heavy metals and microorganisms are greatly increased. Wherein the index increasing proportion of the organic compound accounts for 70 percent. And the index of micro-polluted organic matters, especially low molecular weight soluble organic matters, is one of the difficult problems in the field of water treatment. These changes are more demanding in terms of the quality of the water produced by the water supply plant.
Therefore, conventional feedwater treatment processes (coagulation-precipitation-filtration-disinfection) have failed to meet the needs of water quality standards, and improvements in conventional processes are urgently needed. In conventional water treatment processes, filtration is one of the most important treatment processes in conventional water treatment processes, and is also the last barrier to remove micro-contaminants in drinking water [2]. And the most important filtering technology is the filtering material. The existing filter material has the defects of poor surface property, low specific surface area, weak strength, low adsorption capacity, negative points in natural water and the like, so that the existing filter material has weak adsorption capacity and poor adsorption effect on organic matters, heavy metals and microorganisms. Therefore, the problem of the surface property of the filter material greatly limits the improvement of the water purifying effect of the filtering process, so that the water quality of the effluent of the existing water plant is difficult to meet the requirement. Many researches and researches are performed by related researchers and specialists in order to solve the problems of the filter materials, wherein the surface modification of the filter materials is a research hotspot. The method is used for modifying the surface interception performance of the filter material with wide application, low price, high strength and good chemical stability, improves the specific surface area and the adsorption capacity of the filter material, and improves the mechanical property and interception performance of the filter material, thus becoming the problem which needs to be solved urgently.
In a plurality of traditional filter media, the zeolite has the advantages of high mechanical property, high wear resistance, multiple pore structures, large specific surface area, stable chemical property, low price and the like; meanwhile, as a filter material, the filter material has the characteristics of ion exchange performance, acid resistance and screening performance, and is favored by a plurality of researchers and water plant buyers. However, natural zeolite is negatively charged in natural water due to its own structure of aluminum silicate, resulting in poor adsorption of anionic organics in water. In addition, the natural zeolite has non-structural impurities on the surface, small internal pore diameter and small connectivity among pores. The limitations of the surface properties of these natural zeolites themselves limit their use in the field of water treatment, and therefore modification of zeolites to enhance their adsorption and retention capacities is a key point of future research.
Currently, for modification of zeolite, zeolite framework element modification and surface modification are mainly focused. The modification of zeolite framework elements is a method of increasing the void fraction and specific surface area of zeolite by changing the silica-alumina ratio of zeolite or eliminating impurity elements in zeolite. The modification method can better enable the zeolite to exert ion interaction performance and improve the adsorption performance. The main methods include heat treatment, acid treatment, salt treatment, etc. The research on the surface modification of zeolite refers to the effect of improving the adsorption performance and the interception performance of the zeolite by loading the zeolite with a modifier to improve the surface property of the zeolite. The main methods include coating modification, organic modification, chemical vapor deposition modification and the like, which can partially improve the retention property and adsorption property of zeolite, but have the problem of non-negligible. For example, some researchers use trimethylchlorosilane to carry out surface modification on zeolite by chemical vapor deposition, and the modified zeolite not only maintains a porous structure, but also has a good hydrophobic surface, so that Volatile Organic Compounds (VOCs) can be selectively adsorbed and removed, and the modified zeolite has certain utilization value in the aspects of air purification and wastewater treatment containing the Volatile Organic Compounds (VOCs). However, the method needs a vacuum device, has large investment and complex operation, and is difficult to popularize and apply industrially. Researchers find that zeolite modified by ionic surfactant can effectively remove oxyacid anions in water and greatly improve the capability of removing organic matters while maintaining the capability of removing heavy metal ions, ammonium ions and other inorganic matters. However, the silylation treatment has its own disadvantage that the organosilane compound can modify the whole pore canal, so that the inner surface properties of zeolite are greatly changed in addition to the pore diameter, which may affect the adsorption and catalytic properties of zeolite.
In coating modification, ferric chloride modifiers are often used in filter material modification, because ferric chloride modifiers can increase the roughness, porosity and specific surface area of the zeolite surface, and also can increase the electropositivity of the zeolite surface. The iron oxide modified zeolite has excellent performance on adsorption of organic matters and heavy metal ions, but the adsorption capacity is still not improved sufficiently. For example, zhao Yanfeng et al [8] prepared by a low-temperature repeated soaking method, the adsorption rate of the obtained ferric chloride modified zeolite to chromium is obviously improved, but the adsorption rate of the ferric chloride modified zeolite is not greatly improved compared with that of common activated zeolite. Some researchers modify by using HCL and ferric chloride, the adsorption rate of the obtained ferric chloride modified zeolite to chromium is improved to a certain extent, but the highest removal rate of the obtained modified zeolite to chromium is only 83.7%. Therefore, how to better improve the adsorption capacity of the ferric chloride modified zeolite is a problem to be solved.
Graphene oxide is one of the derivatives of graphite, and was reported in the beginning of the fifty-nineteenth century. Graphene oxide has the properties of high specific surface area, nano-structure material, excellent mechanical properties, a large number of active functional groups and the like, and has a high adsorption capacity on micro-pollutants, so that the graphene oxide is interesting to many experts and scholars.
Foreign researchers have adsorbed phenol by liquid phase chemical deposition using trimethylchlorosilane surface modified zeolite Y. The test results show that: the Si/Al ratio on the surface of the zeolite is improved, the adsorption rate of phenol by the modified zeolite is very fast, the adsorption rate is improved by 30% compared with that of the original zeolite, and the improvement amplitude is still lower although the adsorption rate is improved to a certain extent. Some researchers have studied adsorption of tannic acid by cetyl-brominated pyridine surface-modified zeolite, and found that the adsorption rate of tannic acid by the modified zeolite is improved, but the adsorption effect is influenced by coexisting Cu < 2+ > and pH, the concentration of Cu < 2+ > is increased, and the adsorption capacity of tannic acid is reduced. Still other researchers first utilize graphene oxide to adsorb humic acid (humic acid) under aqueous medium conditions. As a result, it was found that graphene oxide has higher adsorption capacity than graphite and activated carbon, and the adsorption capacity is as high as 190mg g < -1 >. However, graphene oxide is too expensive to be suitable for industrial production.
The domestic researchers obtain the iron-carrying modified zeolite by coating iron on the surface of the zeolite. Analysis of test results: the adsorption capacity of the modified zeolite to fluorine is obviously improved after modification compared with that before modification. However, the defluorination capacity of the material is not high compared with that of defluorination filter materials such as activated alumina, bone charcoal and the like, the purpose of replacing the traditional defluorination filter materials cannot be achieved, and the loading capacity and the adsorption capacity of iron are required to be improved by other methods. Still other researchers have utilized graphene oxide modified sand to obtain GO-sad adsorbents. The test result shows that the adsorption capacity and the adsorption quantity of GO-sad to Methylene Blue (MB) and Pb (II) are obviously increased and are more than 10 times of that of the raw sand. Other researchers have prepared RNA-GO that is stable in nature and that can be stably dispersed in water and studied its adsorption of microcystin peptides (microcystin-LR) in drinking water. As a result, it has been found to be suitable for use in adsorbing trace contaminants in the water quality of contaminated drinking water sources. The experimental results show that the graphene oxide has good effect on the treatment of micro-polluted water, but because the graphene oxide is high in cost, the cost of directly loading the filter material with the graphene oxide is too high, and the method is not suitable for mass industrial production.
Although coating modification and hybrid modification techniques are widely used, and result in improved adsorption capacity and retention properties of the zeolite. However, the popularization of the modified zeolite filter materials in the field of water treatment still encounters a plurality of bottleneck problems, which are mainly represented by the following aspects, for example, the loading rate of the modifier is not high, and the adsorption capacity of pollutants cannot be further improved. The adsorption capacity of the modified zeolite to a certain specific pollutant is obviously improved, but the adsorption effect to another pollutant is obviously reduced, and the like.
In addition, the use of the modifier is concerned. The adsorption effect of the independent graphene oxide on the micro-pollutants is good, but the use of the graphene oxide body as the adsorbent is too large, and the high cost of the graphene oxide determines that the modification by the graphene oxide is not suitable for industrial mass production. The independent ferric chloride modification has the problem of low load rate, the adsorption capacity is not obviously improved, and the problem of replacing the existing filter material cannot be achieved.
Disclosure of Invention
The invention aims to provide a graphene oxide and ferric chloride composite modified zeolite filter material in consideration of the problems, and the modified zeolite filter material has extremely strong hydrophilic performance and adsorption capacity.
The invention aims to provide a preparation method of a graphene oxide and ferric chloride composite modified zeolite filter material in consideration of the problems. The preparation method provided by the invention has the advantages of high loading rate, good loading effect, suitability for industrial production, convenience and practicability.
The technical scheme of the invention is as follows: the graphene oxide and ferric chloride composite modified zeolite filter material comprises natural zeolite, unsupported gaps, an iron oxide adsorption layer and graphene oxide sheets, wherein the outer surface of the natural zeolite is loaded with a modified layer, the modified layer is formed by mutually interlacing the iron oxide adsorption layer and the graphene oxide sheets, and the unsupported gaps are arranged between the iron oxide adsorption layer and the graphene oxide sheets.
The preparation method of the graphene oxide and ferric chloride composite modified zeolite filter material comprises the following steps:
1) Cleaning with distilled water, calcining in a calciner at 200-400 ℃ for 1-3 h, and cooling to room temperature;
2) Soaking in 1-3 mol/L hydrochloric acid for 12-24 hr, washing with distilled water, stoving in 100-150 deg.c stoving box and cooling at room temperature;
3)FeCl 3 modified natural zeolite stage: by FeCl 3 As a modifier, natural zeolite is modified, feCl is added 3 Mixing the solution with pretreated natural zeolite, stirring uniformly, adding tinfoil, sealing, placing in a calciner, calcining at 250-450deg.C for 1-3 hr, cooling to room temperature, cleaning with distilled water, oven drying at 100-150deg.C to obtain FeCl 3 Modified zeolite;
4) For FeCl 3 The surface of the modified zeolite is modified: graphene oxide is used as a modifier for FeCl 3 Modifying the surface of modified zeolite, dissolving graphene oxide powder in deionized distilled water, performing ultrasonic dispersion for 10-60 min to prepare a graphene oxide solution with the concentration of 10-100 mg/L for standby, and mixing the graphene oxide solution with FeCl in the first stage 3 Mixing the modified zeolite uniformly, adding tin foil, sealing and placing in a calciner, wherein the calcination temperature is controlled to be 100-200 ℃, and the calcination time is controlledCooling to room temperature for 0.5-5 hr, washing with distilled water, stoving at 100-150 deg.c in stoving box to obtain graphene oxide-FeCl 3 Composite modified zeolite.
Aiming at the problems existing in the prior modified zeolite, the invention adopts a coating modification method, and uses graphene oxide and FeCl under the condition of high-temperature calcination 3 And combining to carry out composite modification on the surface of the zeolite. Graphene oxide and FeCl 3 The graphene oxide and ferric chloride composite modified zeolite filter material and the preparation method thereof are used as a modifier for preparing modified zeolite, and have the following advantages and effects compared with the prior art:
1) Graphene oxide-FeCl 3 The loading rate and the loading capacity of the composite modified zeolite surface modifier reach 95.38% and 958.39ug g-1 respectively, the loading rate is high, and the loading effect is good;
2) Graphene oxide-FeCl compared with natural zeolite 3 The composite modified zeolite is rich in a large number of hydrophilic functional groups such as hydroxyl groups and carboxyl groups, and the functional groups enable the modified zeolite to have extremely strong hydrophilic performance and adsorption capacity;
3) Graphene oxide-FeCl 3 The composite modified zeolite has complex surface structure, while the natural zeolite has smooth surface, and the graphene oxide-FeCl 3 The specific surface area of the composite modified zeolite is 11.7852m2.g < -1 >, the specific surface area of the natural zeolite is 4.2321m2.g < -1 >, and the graphene oxide-FeCl 3 The specific surface area of the composite modified zeolite is obviously increased and is 2.785 times that of the natural zeolite before modification;
4)FeCl 3 and the composite modification effect of the graphene oxide on the zeolite is obvious, and when the concentration of raw water humic acid is 2mg/L, the graphene oxide-FeCl is prepared 3 The removal rate of humic acid by the composite modified zeolite and the natural zeolite respectively reaches 95.38 percent and 16.2 percent, and the removal rate of humic acid is improved by 79.18 percent after modification compared with that before modification; graphene oxide-FeCl for adsorption capacity 3 The composite modified zeolite is also 4.9 times that of the natural zeolite;
5) While the modified zeolite obviously promotes micro-pollutants, the adsorption rate of heavy metal ions and organic pollutants is still higher at the temperature of 25 ℃, and raw water Cu is still higher 2+ When the concentration is 2mg/L and the zeolite adding amount is 5g and the pH=7, the graphene oxide-FeCl is oxidized 3 Composite modified zeolite and natural zeolite pair Cu 2+ The removal rate of (2) is 56% and 87%, respectively, which is improved by 55.36% for the adsorption capacity; graphene oxide-FeCl 3 The composite modified zeolite is 1.42 times of the natural zeolite; graphene oxide-FeCl 3 The equilibrium adsorption capacity of the composite modified zeolite and the natural zeolite to methyl orange is 0.0603mg/g and 0.0118mg/g respectively, and the former is 5 times that of the latter.
6) The adsorption of natural zeolite to methyl orange is mainly physical adsorption, the chemical adsorption is weaker, and the graphene oxide-FeCl 3 The adsorption of the composite modified zeolite to MO has physical adsorption and chemical adsorption, and the chemical adsorption is stronger. Graphene oxide-FeCl compared with natural zeolite 3 The adsorption mechanism of the composite modified zeolite is more superior and the adsorption capacity is stronger.
Drawings
FIG. 1 is a schematic diagram of the structure of the present invention;
FIG. 2 is a schematic diagram of graphene oxide-FeCl 3 A preparation process flow chart of the composite modified zeolite;
FIG. 3 is a graph of natural zeolite and graphene oxide-FeCl 3 SEM photograph of composite modified zeolite surface morphology structure, including natural zeolite, 50K X; graphene oxide-FeCl 3 Composite modified zeolite, 5k×; graphene oxide-FeCl 3 Composite modified zeolite, 10k×;
FIG. 4 is a diagram of a natural zeolite, graphene oxide and graphene oxide-FeCl 3 FTIR spectra of the composite modified zeolite;
fig. 5 is a DSC profile of graphene oxide.
Detailed Description
Examples:
the structural schematic diagram of the graphene oxide and ferric chloride composite modified zeolite filter material is shown in fig. 1, and comprises natural zeolite 1, an unsupported gap 2, an ferric oxide adsorption layer 3 and a graphene oxide sheet layer 4, wherein the outer surface of the natural zeolite 1 is loaded with a modified layer, the ferric oxide adsorption layer 3 and the graphene oxide sheet layer 4 are mutually staggered, and the unsupported gap 2 is arranged between the ferric oxide adsorption layer 3 and the graphene oxide sheet layer 4.
The modified layer is supported on the outer surface of the natural zeolite 1 by fractional high temperature calcination.
The ferric oxide adsorption layer 3 is nano Fe 2 O 3 And (3) particles.
The nano Fe 2 O 3 The radius size of the particles is 1 to 5nm.
The graphene oxide sheet layer 4 has a thickness of 0.8 to 1.6nm and an extended length of 20. Mu.m.
The invention adds high-temperature calcination condition based on the surface coating method, and refers to FeCl 3 And Graphene Oxide (GO) with high specific surface area is used as a modifier, and the surface of the natural zeolite is modified by a modification method of fractional high-temperature calcination to obtain graphene oxide-FeCl 3 The optimal preparation condition of the composite modified zeolite (called GOFMZ for short) obviously improves the filtration performance and the adsorption performance of the modified zeolite. And the effect of the catalyst on removing humic acid, copper ions and methyl orange is studied.
In order to further improve the adsorption performance of the modified zeolite, the invention overcomes the defects existing in the prior study of using a single modifier and adopts FeCl 3 And graphene oxide with high specific surface area is used as a modifier to carry out surface modification on the natural zeolite. The whole preparation operation flow is as follows:
cleaning with distilled water, calcining in a calciner at 200-400 ℃ for 1-3 h, and cooling to room temperature; soaking in 1-3 mol/L hydrochloric acid for 12-24 hr, washing with distilled water, stoving in 100-150 deg.c stoving box to obtain pretreated zeolite, and cooling at room temperature; first stage, feCl 3 As a modifier, a natural zeolite (hereinafter, the first stage means FeCl) 3 Modified natural zeolite stage): feCl is added 3 (1-3 mol/L) solution according to a certain adding ratio (FeCl) 3 Natural zeolite) (0.1-0.5 ml/g) (FeCl) 3 The ratio of the volume of the solution to the mass of the natural zeolite) and the pretreated natural zeolite are mixed and stirred uniformly, the mixture is sealed by tin paper and placed in a calciner, the calcination temperature is controlled between 250 and 450 ℃, and the calcination time is controlled to be 1Cooling to room temperature for 3h, cleaning with distilled water, and drying in a drying box at 100-150 ℃ to obtain FeCl in the first stage 3 Modified zeolite; in the second stage, graphene oxide is used as a modifier, and FeCl in the first stage is treated 3 The modified zeolite surface is modified (hereinafter, the second stage refers to this stage): dissolving graphene oxide powder in deionized distilled water, performing ultrasonic dispersion for 10-60 min to prepare a graphene oxide solution of 10-100 mg/L for standby, and mixing the graphene oxide solution according to a certain adding ratio (graphene oxide/FeCl) 3 Modified zeolite) (5-50 ug/g) (mass of graphene oxide and FeCl) 3 Mass ratio of modified zeolite) to FeCl of the first stage 3 Uniformly mixing modified zeolite, adding tin foil, sealing, placing in a calciner, controlling the calcination temperature to be 100-200 ℃, controlling the calcination time to be 0.5-5 h, cooling to room temperature, cleaning with distilled water, and drying in a drying box at 100-150 ℃ to obtain graphene oxide-FeCl 3 Composite modified zeolite (GOFMZ for short, GO-FeCl) 3 Composite modified zeolite).
Secondly, in the preparation process, in order to clarify the influence of each influence factor on zeolite modification, graphene oxide-FeCl is obtained 3 The optimal preparation process conditions of the composite modified zeolite adopt orthogonal tests and continuity tests in the preparation experiments; in order to detect the optimization effect of the surface characteristics, graphene oxide-FeCl 3 The composite modified zeolite is used for static adsorption experiments of micro pollutants such as humic acid (humic acid); to scientifically analyze and characterize graphene oxide-FeCl 3 The surface structure and surface characteristics of the composite modified zeolite are that the experiment adopts various advanced high-resolution instruments to perform the reaction on the natural zeolite and the graphene oxide-FeCl 3 The surface properties of the composite modified zeolite were tested: for example, analysis of graphene oxide-FeCl using Scanning Electron Microscopy (SEM) 3 Morphological characteristics of oxide on the surface of the composite modified zeolite sample; thermogravimetric analysis (DSC) further analyzes the effect of calcination temperature on modified zeolite surface functionality; characterization of graphene oxide-FeCl by Fourier Infrared Spectroscopy (ATR FTIR) 3 Information of the composite modified zeolite surface and graphene oxide chemical functional groups; specific surface area measurement analysis (BET) measurementGraphene oxide-FeCl 3 Specific surface area of the composite modified zeolite sample, and the like.
Finally, in order to explore the adsorption capacity of zeolite, the adsorption characteristics of modified zeolite on micro-pollutants such as humic acid, heavy metal ion copper and organic pollutant methyl orange are studied, and the specific operation method is that raw water solution with gradient concentration of each pollutant is prepared at room temperature and pH=7, and 10g of graphene oxide-FeCl is weighed 3 Putting the composite modified zeolite and 10g of natural zeolite into an existing conical bottle with 150ml of pollutant raw water solution, putting the conical bottle on a shaker, shaking for 2 hours at the rotating speed of 100r/min, and analyzing the influence of raw water containing pollutants with different concentrations on the adsorption effect. Then the method is adopted to respectively carry out the preparation of graphene oxide-FeCl 3 The addition amount and pH value of the composite modified zeolite and the natural zeolite are experimentally researched. The obtained data are fitted by using Freundich and Langmuir isothermal adsorption characteristic equations and primary and secondary dynamics equations to obtain the adsorption characteristic mode and the time-dependent change relation of the adsorption rate of the modified zeolite.
The test material and the test equipment provided by the invention are as follows:
natural zeolite (abbreviated as ROZ): sieving natural zeolite with diameter of 0.4-1.5 mm, cleaning with distilled water, calcining in a calciner at 200-450 deg.c for 1-3 hr, and cooling to room temperature; soaking in 1-3 mol/L hydrochloric acid for 12-24 hr, washing with distilled water, stoving in 100-150 deg.c stoving box and cooling at room temperature. And (3) a modifier: feCl with mass concentration of 2mol/L 3 ·6H 2 O solution (analytically pure). The preparation (0.5% o-phenanthroline solution, 10% hydroxylamine hydrochloride, 25% hydrochloric acid, saturated sodium acetate, buffer solution, etc.) for measuring iron by using the o-phenanthroline spectrophotometry; preparing the medicament required by raw water: humic acid HA: fulvic acid ≡ 90%, copper powder (Cu, 63.55), methyl orange (C) 14 H 14 N 3 SO 3 Na, 327.33), and the like; other auxiliary agents: nitric acid (HNO) 3 63), sodium hydroxide (NaOH, 40.01), alcohol (C) 2 H 6 O, 46.07), and the like. The reagent for measuring copper by diacetal oxalyl dihydrazone spectrophotometry is as follows: ammonia (NH) 3 ·H 2 O, 35.05), acetaldehyde (CH 3 CHO, 44.05), lemonTriammonium citrate (C) 6 H 5 O 7 (NH 4 ) 3 243.22), bicyclohexanoyl dihydrazone (C) 14 H 22 N 4 O 2 278.35), ammonium chloride (NH) 4 Cl, 53.49), copper powder (Cu, 63.55), and the like.
GrapHene Oxide (GO for short) (analytically pure, nanjing first-come nanomaterial technologies limited) with material parameters shown in table 1;
test equipment: SRJX-8-13 high-temperature box type resistance furnace, KQ-300 VDE type three-frequency digital control ultrasonic cleaner, SHZ-B type constant temperature oscillator, AL204 electronic balance, DHG-9145A type electrothermal constant temperature blast drying oven, S3400N scanning electron microscope, TENSOR 27 Fourier transform infrared spectrometer, pHS-3B type precision pH meter, ASAP2020 specific surface area determinator, SDT2960 differential-thermogravimetric analyzer, X Pert PRO type X-ray diffractometer, T6 type ultraviolet spectrophotometer, SHA-N type electrothermal constant temperature water bath.
Graphene oxide-FeCl 3 Preparation of composite modified zeolite (graphene oxide-ferric chloride composite modified zeolite):
graphene oxide-FeCl 3 The preparation flow of the composite modified zeolite is shown in figure 2. The preparation process is as follows: cleaning with distilled water, calcining in a calciner at 200-400 ℃ for 1-3 h, and cooling to room temperature; soaking in 1-3 methyl orange L/L hydrochloric acid for 12-24 h, cleaning with distilled water, drying in a 100-150 ℃ drying box, and cooling at room temperature for later use; first stage, feCl 3 As modifier, the natural zeolite is modified (hereinafter the first stage is referred to as this stage): feCl is added 3 The solution (1-3 methyl orange L/L) is added according to a certain adding ratio (FeCl) 3 Natural zeolite) (0.1-0.5 ml/g) (FeCl) 3 The ratio of the volume of the solution to the mass of the natural zeolite) and the pretreated natural zeolite are mixed and stirred uniformly, the mixture is filled with tinfoil and placed in a calciner in a sealing way, the calcination temperature is controlled between 250 and 450 ℃, the calcination time is controlled between 1 and 3 hours, the mixture is cooled to room temperature and then cleaned by distilled water, and the mixture is placed in a drying box at 100 to 150 ℃ for drying, thus obtaining FeCl in the first stage 3 Modified zeolite; in the second stage, graphene oxide is used as a modifier, and FeCl in the first stage is treated 3 Modified zeolite surface modificationColumn modification (hereinafter, the second stage refers to this stage): dissolving graphene oxide powder in deionized distilled water, performing ultrasonic dispersion for 30min to prepare a graphene oxide solution of 10-100 mg/L for standby, and adding the graphene oxide solution (graphene oxide/FeCl) according to a certain adding ratio 3 Modified zeolite) (5-50 ug/g) (mass of graphene oxide and FeCl) 3 Mass ratio of modified zeolite) to FeCl of the first stage 3 Mixing the modified zeolite uniformly, adding tin foil, sealing and placing in a calciner, controlling the calcination temperature to be 100-200 ℃, controlling the calcination time to be 0.5-5, cooling to room temperature, cleaning with distilled water, drying in a drying box at 100-150 ℃, and placing in a polyethylene bag for standby.
Graphene oxide-FeCl 3 Test of static adsorption amount of humic acid (humic acid) by composite modified zeolite (graphene oxide-ferric chloride composite modified zeolite):
a. weighing 1g of humic acid powder, putting into a clean 250ml beaker, adding distilled water for complete dissolution, draining into a 1L volumetric flask by using a glass rod, and fixing the volume to 1L to obtain 1g/L humic acid stock solution;
b. 2ml of humic acid stock solution was pipetted with a 2ml pipette to prepare 2mg/L raw water, and UV254 was measured;
c. using humic acid stock solutions to prepare 0 methyl orange L/L, 0.3 methyl orange L/L, 0.6 methyl orange L/L, 0.9 methyl orange L/L, 1.2 methyl orange L/L, 1.5 methyl orange L/L, 1.8 methyl orange L/L, 2.1 methyl orange L/L and 0 methyl orange L/L, 5 methyl orange L/L, 10 methyl orange L/L, 20 methyl orange L/L, 30 methyl orange L/L, 40 methyl orange L/L and 50 methyl orange L/L respectively, and measuring UV254 thereof;
d. weighing 5g of graphene oxide-Fecl by using an electronic balance 3 Pouring the composite modified zeolite sample into a 250ml clean conical flask, and adding 150ml of raw water (2 mg/L);
characterization of modified zeolite surface properties:
the prepared and dried and stored modified zeolite surface was subjected to the following performance characterization: scanning Electron Microscopy (SEM) tests the surface morphology of the modified zeolite, fourier transform infrared spectroscopy (FTIR) and X-ray diffractometer (XRD) tests analyze the surface functional groups and determine if the modifier is successfully attached, thermogravimetric analysis (DSC) obtains the optimal calcination temperature, and specific surface area measurement (BET) analyzes the surface adsorption characteristics of the modified zeolite.
Natural zeolite and graphene oxide-FeCl 3 Adsorption characteristics of composite modified zeolite for each contaminant:
the pollutant content and the graphene oxide-FeCl are researched by a continuous experiment mode 3 Graphene oxide-FeCl by adding amount, pH value and other factors of composite modified zeolite and natural zeolite 3 The effect of the composite modified zeolite and the natural zeolite on the adsorption effect of various pollutants. The specific method is that an aqueous solution with the gradient concentration of each pollutant is prepared under the conditions of room temperature and pH=7, and 10g of graphene oxide-FeCl is weighed 3 Putting the composite modified zeolite and 10g of natural zeolite into an existing conical bottle with 150ml of pollutant raw water solution, putting the conical bottle on a shaker, shaking for 2 hours at the rotating speed of 100r/min, and analyzing the influence of raw water containing pollutants with different concentrations on the adsorption effect. Then the method is adopted to respectively carry out the preparation of graphene oxide-FeCl 3 The addition amount and pH value of the composite modified zeolite and the natural zeolite are experimentally researched. The obtained data are fitted by using Freundich and Langmuir isothermal adsorption characteristic equations and primary and secondary dynamics equations to obtain the adsorption characteristic mode and the time-dependent change relation of the adsorption rate of the modified zeolite. The formula is as follows; freundich adsorption isothermal equation (7-1); langmuir adsorption isothermal equation (7-2); first order kinetic equation (7-3); quasi-second order kinetic equation (7-4).
Qe＝KfCe1/n (7-1)
:Qe＝bq0Ce/(1+bCe) (7-2)
Test results:
1. orthogonal experiments
The method adopts a multi-index orthogonal experiment method, takes the load rate alpha (%) of the modifier and the static adsorption removal rate beta (%) of Humic Acid (HA) as evaluation indexes, and determines graphene oxide-FeCl 3 Optimal preparation conditions of the composite modified zeolite. The degree of influence of different factors in the preparation process of the composite modified zeolite is determined by comprehensively analyzing the R value of the range size in the orthogonal test table (table 2). The larger the R value, the greater the effect of the corresponding impact factor on the surface properties of the modified zeolite.
The experimental results showed (see table 1): the optimal technological conditions for IOCS preparation are as follows: first stage, feCl 3 As modifier, feCl 3 (2 methyl orange l.L-1)/zeolite addition ratio C1=0.125 ml.g-1, calcination temperature T1=290 ℃, calcination time t1=2.5 h; in the second stage, graphene oxide is used as a modifier for FeCl 3 The modified zeolite is further subjected to surface modification, and graphene oxide and FeCl 3 The addition ratio of the modified zeolite C2=10ug.g < -1 >, the calcination temperature T2=190 ℃ and the calcination time T2=1.5 h.
2. Continuity experiments
The first stage FeCl was changed under t1=2.5 h, t1=290 ℃, c2=10 ug·g-1, t2=1.5 h, t2=190 ℃ 3 The addition ratio of the zeolite to the natural zeolite is as follows: 0.075,0.1,0.125,0.15,0.175,0.2,0.225ml g-1. The experimental results show that: when C1 is less than or equal to 0.125 ml.g-1, the humic acid removal rate is always increased from 43.28% to 97.01%, then the humic acid removal rate is stabilized, the surface load rate is always reduced from 96.67% to 85%, and the reduction rate is slow and fast. This is mainly because as the C1 value increases, more modifier is gradually loaded on the zeolite surface, and the addition of the modifier changes the adsorption performance of the zeolite, so the humic acid removal rate increases. However, under the conditions of a certain reaction temperature and a certain reaction time, the loading rate is constant, and when the C1 is increased to 0.125ml g < -1 >, the FeCl on the zeolite surface is increased 3 The modifier is saturated, the humic acid removal rate is basically kept stable, and the load rate is reduced more rapidly. Therefore, the cost ratio of the first stage should be 0.125.
The method is adopted to respectively perform the first stageCalcination temperature, first-stage calcination time, second-stage graphene oxide and FeCl 3 The experimental study of the addition ratio of the modified zeolite, the calcination temperature of the second stage and the calcination time of the second stage shows that the optimal temperature for the calcination of the first stage is 290 ℃, the optimal calcination time of the first stage is 2.5h, and the graphene oxide and FeCl of the second stage 3 The optimal adding ratio of the modified zeolite is 10ug g-1, the optimal calcining temperature in the second stage is 190 ℃, and the optimal calcining time in the second stage is 1.5h.
3. SEM scanning electron microscope observation
Graphene oxide-FeCl 3 The composite modified zeolite has obviously raised humic acid eliminating capacity compared with natural zeolite. This is mainly caused by the difference in specific surface area and adsorption characteristics due to the difference in surface morphology between them (see fig. 4).
As can be seen from FIG. 3, the natural zeolite has a smooth and flat surface, a small adsorption capacity and a small specific surface area (4.2321m2.g-1). The energy spectrum analysis result shows that the proportion of C, O, al, si, fe elements in the total mass is respectively as follows: 2.307%, 51.067%, 0.639%, 45.247% and 0.74%; graphene oxide-FeCl 3 The surface structure of the composite modified zeolite is complex, the composite modified zeolite presents a porous structure, the specific surface area reaches 11.7852m2.g < -1 >, and the specific surface area is increased by 2.78 times compared with that of the natural zeolite; in the process of oxidizing graphene to FeCl 3 The proportion of C, O, al, si, fe elements on the surface of the composite modified zeolite to the total mass of the composite modified zeolite is as follows: 17.604%,44.881%,5.485%,27.392% and 4.637%. From the energy spectrum analysis, graphene oxide-FeCl 3 The ratio of the surface material elements of the composite modified zeolite is as follows: o: al: si: fe=1.467:2.805:0.203:0.975:0.083; compared with natural zeolite, graphene oxide-FeCl 3 The C element and the Fe element on the surface of the composite modified zeolite are obviously increased, and the Fe element mainly comes from FeCl 3 An intermediate modifier which increases the electropositivity of the zeolite surface; the C element is mainly derived from the graphene oxide modifier, so that functional groups such as hydroxyl, carboxyl and the like on the surface of the zeolite are increased, and the adsorption capacity of the zeolite is increased.
4. Fourier transform Infrared Spectroscopy (FTIR) analysis
As shown in fig. 4, graphene oxide-FeCl 3 The composite modified zeolite showed peaks at 1619cm-1 and 1724cm-1 similar to those of graphene oxide. A C=C stretching vibration peak at 1619cm-1, an edge hydroxyl group at 1724cm-1 or a C=O stretching vibration vc=O; natural zeolite, graphene oxide and graphene oxide-FeCl 3 The composite modified zeolite has a wide and strong absorption band at 3450cm < -1 > due to the telescopic vibration coupling of-OH, and the band belongs to a water molecule telescopic vibration band; natural zeolite and graphene oxide-FeCl 3 The composite modified zeolite has skeleton vibration band of Si-O-Si at 1043cm < -1 >, absorption peak at 793cm < -1 > is vibration absorption peak in silicon oxygen tetrahedron, and absorption peak at 471cm < -1 > is caused by bending vibration of Si-O or Al-O. This shows that graphene oxide has been successfully loaded to FeCl after modification of natural zeolite with graphene oxide solution 3 Modifying the zeolite surface.
5. Thermogravimetric analysis of modified zeolite (DSC)
As shown in fig. 5, when the temperature of the graphene oxide is raised in the air, two wide and strong peaks appear in the heat flow curve at about 230 ℃ and about 517 ℃, and simultaneously the weight of the graphene oxide at the two peaks is quickly reduced, which indicates that the graphene oxide has a complete fracture of a functional group at about 230 ℃ and a complete combustion reaction of the graphene oxide at about 517 ℃.
As can be seen from a combination of fig. 3 and 5, graphene oxide-FeCl 3 The loading rate and the humic acid removal rate are respectively 95.38 percent and 97.01 percent when the calcining temperature T2=190 ℃ in the second stage of preparing the composite modified zeolite; when t2=210 ℃, the loading rate and the humic acid removal rate are 93.61% and 53.73%, respectively, and when the calcination temperature T2 is increased from 190 ℃ to 210 ℃, the loading rate and the humic acid removal rate are reduced by 1.77% and 43.28%, respectively. This indicates that at the calcination temperature t2=210℃, the functional groups of graphene oxide have already begun to break. But at the calcination temperature t2=190 ℃, graphene oxide-FeCl 3 The functional group of the graphene oxide on the surface of the composite modified zeolite is still kept intact. The functional groups on the surface of the modified zeolite are active adsorption sites for removing pollutants, and play a key role in adsorbing pollutants by the modified zeolite.
6. Natural zeolite and graphene oxide-FeCl 3 Adsorption characteristics of composite modified zeolite on humic acid
(1) The raw water humic acid content and the graphene oxide-FeCl are researched by a continuous experiment mode 3 Graphene oxide-FeCl by adding amount, pH value and other factors of composite modified zeolite and natural zeolite 3 The effect of the composite modified zeolite and the natural zeolite on the adsorption effect of humic acid. Results it was determined that graphene oxide-FeCl compared to the natural zeolite 3 The removal rate of humic acid by the composite modified zeolite is obviously improved. When the concentration of raw water humic acid is 2mg/L, the removal rates of the graphene oxide-ferric chloride composite modified zeolite and the natural zeolite on humic acid are 97.5% and 22% respectively. Graphene oxide-FeCl with increasing concentration of raw water humic acid 3 The removal rate of humic acid by the composite modified zeolite is always reduced to below 60 percent. Analysis of results: zeolite passing through FeCl 3 And after the graphene oxide is modified, the adsorption performance is obviously improved, and the graphene oxide-FeCl is oxidized along with the improvement of the concentration of raw water humic acid 3 Adsorption sites on the surface of the composite modified zeolite are gradually occupied until saturated, thereby leading to graphene oxide-FeCl 3 The adsorption removal rate of the composite modified zeolite to humic acid is reduced. And then to oxidized graphene-FeCl 3 Experimental investigation on the addition amount and pH value of the composite modified zeolite and the natural zeolite shows that the graphene oxide-FeCl 3 The highest beneficial addition amounts of the composite modified zeolite and the natural zeolite are 30g and 15g respectively, and the optimal pH=7.
(2) Fitting by adopting Freundich and Langmuir isothermal adsorption characteristic equation and primary dynamics and quasi-secondary dynamics equation, and exploring graphene oxide-FeCl 3 Adsorption mechanism of composite modified zeolite and natural zeolite to humic acid. Natural zeolite and graphene oxide-FeCl 3 The adsorption of the composite modified zeolite to the humic acid is more in accordance with a Freundich isothermal adsorption characteristic model, the adsorption process of the natural zeolite to the humic acid is in accordance with a first-order kinetic equation form, and the graphene oxide-FeCl is prepared 3 The affinity of the composite modified zeolite to humic acid is larger than that of the natural zeolite; graphene oxide-FeCl 3 Composite modificationThe adsorption rate of the nature zeolite to humic acid is larger than that of the natural zeolite; the former was 4.9 times as large as the latter in terms of adsorption capacity.
7. Natural zeolite and graphene oxide-FeCl 3 Composite modified zeolite to Cu 2+ Adsorption characteristics of (a)
(1) The Cu in the raw water is researched by a continuous experiment mode 2+ Concentration, graphene oxide-FeCl 3 Graphene oxide-FeCl by adding amount, pH value and other factors of composite modified zeolite and natural zeolite 3 Composite modified zeolite and natural zeolite in Cu 2+ The results show that the natural zeolite and graphene oxide-FeCl 3 Composite modified zeolite to Cu 2+ Is along with the removal rate of raw water Cu 2+ The concentration increases and decreases. As raw water Cu 2+ When the concentration is increased from 2mg/L to 50mg/L, the natural zeolite is used for Cu 2+ The removal rate is reduced from 56% to 8.62%, and the graphene oxide-FeCl 3 Composite modified zeolite to Cu 2+ The removal rate was reduced from 88.50 to 31.98. Graphene oxide and FeCl 3 The modifier obviously improves the Cu content of zeolite 2+ With the adsorption performance of raw water Cu 2+ The increase in concentration saturated adsorption and the removal rate decreased. And then to oxidized graphene-FeCl 3 Experimental investigation on the addition amount and pH value of the composite modified zeolite and the natural zeolite shows that the result shows that the graphene oxide-FeCl 3 The highest beneficial addition amounts of the composite modified zeolite and the natural zeolite are 30g and 15g respectively, and the optimal pH=7.
(2) Fitting by adopting Freundich and Langmuir isothermal adsorption characteristic equation and primary dynamics and quasi-secondary dynamics equation, and exploring graphene oxide-FeCl 3 Composite modified zeolite and natural zeolite pair Cu 2+ Is an adsorption mechanism of (a). Natural zeolite to Cu 2+ Adsorption accords with a Freundlich isothermal adsorption characteristic model, and is specific to Cu 2+ Performing physical adsorption; graphene oxide-FeCl 3 Composite modified zeolite to Cu 2+ Adsorption is more in accordance with Langmuir isothermal adsorption characteristic model, and Cu is adsorbed by 2+ The adsorption process has physical adsorption and chemical adsorption, and the chemical adsorption is the main process. Natural zeolite to Cu 2+ Is in accordance with the form of a quasi-second-level kinetic equationGraphene oxide-FeCl 3 The affinity of the composite modified zeolite to humic acid is larger than that of the natural zeolite; natural zeolite specific graphene oxide-FeCl 3 Composite modified zeolite to Cu 2+ The adsorption rate of (2) is high; the former was 1.42 times as large as the latter with respect to adsorption capacity.
8. Natural zeolite and graphene oxide-FeCl 3 Adsorption characteristics of composite modified zeolite on methyl orange
(1) The linear versus methyl orange isothermal adsorption profile was used with Freundlich and Langmuir isothermal adsorption profiles. Fitting. The adsorption of natural zeolite to methyl orange accords with the characteristic mode of Freundich isothermal adsorption, and the natural zeolite is mainly subjected to physical adsorption and has weak chemical adsorption characteristics. Graphene oxide-FeCl 3 The adsorption of the composite modified zeolite to methyl orange accords with the isothermal adsorption characteristic modes of Freundich and Langmuir, and has physical adsorption and chemical adsorption effects, but has stronger chemical adsorption capability.
(2) And drawing an adsorption time and methyl orange adsorption amount curve by a continuous experiment mode, and linearly fitting the curve by using a first-stage reaction kinetic equation and a quasi-second-stage kinetic equation. Experimental results show that the natural zeolite and the graphene oxide-FeCl 3 The adsorption process of the composite modified zeolite on methyl orange is more in accordance with the quasi-second-level dynamics fitting relation, and the adsorption of the zeolite on methyl orange is faster after the zeolite is modified. Natural zeolite and graphene oxide-FeCl 3 The equilibrium adsorption capacity of the composite modified zeolite to the methyl orange adsorption process is Qe natural zeolite=0.0118 (mg/g), and Qe graphene oxide-FeCl respectively 3 Composite modified zeolite= 0.0603 (mg/g), the latter being 5 times the former, the time to reach adsorption equilibrium being 90min and 60min, respectively.
Table 1 parameters for single layer graphene oxide and dispersion characterization
Table 2-1 Characterization parameters of methyl orange nolayer graphene oxide and dispersion
TABLE 2 graphene oxide to FeCl 3 Composite modified zeolite preparation orthogonal test
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Note that: k (K) i (alpha, beta) represents the sum of test results (alpha, beta) obtained when the factor on any column takes level i; r (alpha, beta) is K 1 ～K 5 Is a very small difference value.
TABLE 3 comparison of fitting parameter values of Freundich and Langmuir isothermal adsorption characteristic equations for humic acid
Table 7 humic acid's Parameter of Freundich and Langmuir methyl orange dels
Table 4 Cu 2+ Fitting parameters to Freundich and Langmuir isothermal adsorption characteristic equations
TABLE 5 relevant parameters for Freundlich and Langmuir isothermal adsorption characteristics Linear fitting of methyl orange
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Claims (5)
1. The preparation method of the graphene oxide and ferric chloride composite modified zeolite filter material is characterized by comprising the following steps of:
1) Cleaning natural zeolite with distilled water, calcining in a calciner at 200-400 ℃ for 1-3 h, and cooling to room temperature;
2) Soaking the natural zeolite treated in the step 1) in 1-3 mol/L hydrochloric acid for 12-24 h, cleaning with distilled water, drying in a drying box at 100-150 ℃ to obtain pretreated zeolite, and cooling at room temperature for later use;
3)FeCl 3 modified natural zeolite stage: by FeCl 3 As a modifier, natural zeolite is modified, feCl is added 3 Mixing the solution with pretreated natural zeolite, stirring uniformly, adding tinfoil, sealing, placing in a calciner, calcining at 250-450deg.C for 1-3 hr, cooling to room temperature, cleaning with distilled water, oven drying at 100-150deg.C to obtain FeCl 3 Modified zeolite;
4) For FeCl 3 The surface of the modified zeolite is modified: graphene oxide is used as a modifier for FeCl 3 Modifying the surface of modified zeolite, dissolving graphene oxide powder in deionized distilled water, performing ultrasonic dispersion for 10-60 min to prepare a graphene oxide solution with the concentration of 10-100 mg/L for standby, and mixing the graphene oxide solution with FeCl in the first stage 3 Uniformly mixing modified zeolite, adding tin foil, sealing, placing in a calciner, controlling the calcination temperature to be 100-200 ℃, controlling the calcination time to be 0.5-5 h, cooling to room temperature, cleaning with distilled water, and drying in a drying box at 100-150 ℃ to obtain graphene oxide-FeCl 3 Composite modified zeolite;
the step 3) is to make 1 to 3mol/L FeCl 3 The solution is prepared according to FeCl 3 The adding ratio of the natural zeolite is 0.1-0.5 ml/g, and the natural zeolite after pretreatment is evenly mixed and stirred, and the adding ratio is FeCl 3 The ratio of the volume of the solution to the mass of the natural zeolite;
the step 4) is to mix the graphene oxide solution according to the ratio of graphene oxide/FeCl 3 The adding ratio of the modified zeolite is 5-50 ug/g and FeCl in the first stage 3 The modified zeolite is uniformly mixed, and the addition ratio is the mass of graphene oxide and FeCl 3 The mass ratio of the modified zeolite;
the graphene oxide and ferric chloride composite modified zeolite filter material comprises natural zeolite, an unsupported gap, an iron oxide adsorption layer and a graphene oxide sheet layer, wherein the outer surface of the natural zeolite is loaded with a modified layer, the modified layer is formed by mutually interlacing the iron oxide adsorption layer and the graphene oxide sheet layer, and the unsupported gap is arranged between the iron oxide adsorption layer and the graphene oxide sheet layer.
2. The method for preparing the graphene oxide and ferric chloride composite modified zeolite filter material according to claim 1, wherein the modified layer is loaded on the outer surface of the natural zeolite through fractional high-temperature calcination.
3. The method for preparing the graphene oxide and ferric chloride composite modified zeolite filter material according to claim 1, wherein the ferric oxide adsorption layer is nano Fe 2 O 3 And (3) particles.
4. The method for preparing the graphene oxide and ferric chloride composite modified zeolite filter material according to claim 3, wherein the nano Fe is characterized in that 2 O 3 The radius size of the particles is 1 to 5nm.
5. The preparation method of the graphene oxide and ferric chloride composite modified zeolite filter material according to claim 1, wherein the thickness of the graphene oxide sheet layer is 0.8-1.6 nm, and the unfolding length is 20 μm.
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