CN107970886A - A kind of graphene oxide and the composite modified zeolite filler of iron chloride and preparation method thereof - Google Patents
A kind of graphene oxide and the composite modified zeolite filler of iron chloride and preparation method thereof Download PDFInfo
- Publication number
- CN107970886A CN107970886A CN201711100057.9A CN201711100057A CN107970886A CN 107970886 A CN107970886 A CN 107970886A CN 201711100057 A CN201711100057 A CN 201711100057A CN 107970886 A CN107970886 A CN 107970886A
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- China
- Prior art keywords
- graphene oxide
- zeolite
- fecl
- modified zeolite
- modified
- Prior art date
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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 283
- 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 167
- 239000002131 composite material Substances 0.000 title claims abstract description 102
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 title claims abstract description 24
- 239000000945 filler Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000010457 zeolite Substances 0.000 claims abstract description 136
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 135
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 108
- 238000001179 sorption measurement Methods 0.000 claims abstract description 96
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- -1 is not supported gap Chemical compound 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 56
- 238000001354 calcination Methods 0.000 claims description 48
- 238000001035 drying Methods 0.000 claims description 23
- 239000012153 distilled water Substances 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- 229910002804 graphite Inorganic materials 0.000 claims description 11
- 239000010439 graphite Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000003837 high-temperature calcination Methods 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
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 241000446313 Lamella Species 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 18
- 239000000706 filtrate Substances 0.000 abstract description 17
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000004021 humic acid Substances 0.000 description 41
- 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 40
- 238000000034 method Methods 0.000 description 34
- 229940012189 methyl orange Drugs 0.000 description 33
- 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 32
- 238000010521 absorption reaction Methods 0.000 description 29
- 230000009102 absorption Effects 0.000 description 27
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 20
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
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- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
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- 239000001263 FEMA 3042 Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products 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-PPKXGCFTSA-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
- 229910052782 aluminium Inorganic materials 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
- 230000008901 benefit Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
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- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 2
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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 2
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- 229910052714 tellurium Inorganic materials 0.000 description 2
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- 239000003053 toxin Substances 0.000 description 2
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- QAQSNXHKHKONNS-UHFFFAOYSA-N 1-ethyl-2-hydroxy-4-methyl-6-oxopyridine-3-carboxamide Chemical compound CCN1C(O)=C(C(N)=O)C(C)=CC1=O QAQSNXHKHKONNS-UHFFFAOYSA-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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
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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
- B01J20/0225—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
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—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
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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
- B01J20/28—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
Abstract
The present invention relates to a kind of graphene oxide and the composite modified zeolite filler of iron chloride and preparation method thereof, modified zeolite filtrate includes natural zeolite, is not supported gap, iron oxide adsorption layer, graphene oxide layer, the outer surface of natural zeolite is loaded with modified layer, the modified layer be by iron oxide adsorption layer it is interlaced with graphene oxide layer together with, have the gap not being supported between iron oxide adsorption layer and graphene oxide layer.Modified zeolite filtrate of the present invention has extremely strong hydrophilicity and adsorption capacity.The preparation method of the present invention is with graphene oxide and FeCl3As modifying agent, modified zeolite is used to prepare, preparation method load factor of the invention is high, and load effect is good, and is suitable for industrial production, convenient and practical.
Description
Technical field
The present invention relates to a kind of graphene oxide and the composite modified zeolite filler of iron chloride and preparation method thereof, belong to oxidation
The innovative technology of graphene and the composite modified zeolite filler of iron chloride and preparation method thereof.
Background technology
With the quickening of China's process of industrialization, the pollution level in source quality is progressively deepened.At the same time, people couple
Also it is being continuously improved with the requirement of water water quality.The new water standard in China adds 71 indexs altogether, organic matter, heavy metal and
Microbiological indicator item number is all dramatically increased.Wherein organic compound index increase ratio accounts for 70%.And micro- Organic Pollutants
Index, especially low molecular weight dissolved organic matter are one of difficulties of water treatment field.These changes go out water supply plant
The requirement of water water quality is harsher.
Therefore, conventional handling technology of water supply（Coagulation-precipitation-filtering-disinfection）It cannot meet people to water quality mark
Accurate demand, urgently needs to be improved common process.In conventional water treatment process, filtering is water process common process
In together most important treatment process, and remove drinking water micropollutants last one of barrier [2].And in filtering technique
Most important is exactly filtrate.It is relatively low there are specific surface area since the filtrate its own face property used at present is bad, intensity compared with
Weak, adsorption capacity is low, and in natural water the defects of band negative point, it is weaker to result in the adsorption capacity of existing filtrate, for organic matter,
Heavy metal and the adsorption effect of microorganism are bad.Therefore it is net largely to limit filtering technique for filtrate its own face property problem
The lifting of water effect, causes existing water factory's effluent quality to be extremely difficult to require.In order to solve the problems, such as that filtrate exists, correlation is ground
Study carefully scholar and expert has carried out the research and exploration of many, wherein the surface modification to filtrate is the hot spot of research.For current
Surface cutoff performance modification is carried out with filtrate extensive, cheap, that intensity is high, chemical stability is good, improves the ratio of filtrate
Surface area and adsorption capacity, improve the mechanical performance and cutoff performance of filtrate, become the problem of in the urgent need to address.
In numerous traditional filter mediums, zeolite not only has mechanical performance height, and wear-resistant strength is big, and pore structure is more,
Specific surface area is big, stable chemical performance, it is cheap the advantages that；Meanwhile as filtrate, it has ion-exchange performance, acidproof
The characteristics of performance, sieve performance, therefore favored be subject to numerous researchers and water factory purchaser.But natural zeolite is due to this
It is negatively charged in natural water caused by the structure of body aluminium silicate salt, cause the adsorption energy force difference to anion organic matter in water.This
Outside, natural zeolite surface has the connectivity between small non-structural impurity, internal aperture, hole and hole small.These natural zeolites
The limitation of its own face property, limits its application in water treatment field, therefore, zeolite is modified, to strengthen it
Adsorption capacity and interception capacity become the emphasis studied from now on.
At present, it is main to concentrate zeolitic frameworks element modified and surface modification for the modification of zeolite.For zeolitic frameworks member
The modification of element, is the impurity element in the silica alumina ratio or cancellation zeolite by varying zeolite, so as to increase the voidage of zeolite
With the method for specific surface area.This method of modifying can preferably allow zeolite to play ion interactive performance and improve its adsorptivity
Energy.Main method has heat treatment, acid treatment, salt treatment etc..Research for zeolite surface modifications, that is, refer to by being born to zeolite
Modifying agent is carried to improve the surface nature of zeolite, has the function that to strengthen zeolite adsorption performance and cutoff performance.Main method has
It is coating modified, it is organically-modified, chemical vapour deposition be modified the methods of, these methods can partly improve zeolite cutoff performance and
Absorption property, but there is also it is very important the problem of.Such as some researchers use trim,ethylchlorosilane chemical evapn
Deposition carries out surface modification to zeolite, and modified zeolite both keeps loose structure, and has good hydrophobic surface, so energy
Enough selective absorptions remove volatile organic compounds (VOCs), in air purification and containing volatile organic matter（VOCs）Waste water
There is certain utility value in terms of processing.But this method needs vacuum plant, investment is larger, and operation is more complicated, it is difficult to
Commercial introduction application.Researcher has found, the zeolite being modified with ionic surface active agent, keep it is original went removing heavy metals from
While son, ammonium ion and other inorganic matter abilities, the Oxoanions in water removal can be also effectively removed, and substantially increase
The ability of its organics removal.But the shortcomings that silanization treatment also has itself, organic silane compound can to whole duct into
Row modification, therefore in addition to aperture is changed, the inner surface property of zeolite also varies widely, it is possible to influence the absorption of zeolite with
Catalytic performance.
In coating modified, iron chloride modifying agent is typically used in modification of filtration medium, because iron chloride modifying agent can increase
Add roughness, porosity and the specific surface area of zeolite surface, moreover it is possible to increase the electropositive of zeolite surface.Iron oxide modified zeolite pair
The absorption of organic matter and heavy metal ion all has excellent performance, but adsorption capacity improves still deficiency.For example, Zhao Yanfeng etc.
[8] with low temperature, repeatedly prepared by infusion method, and gained iron chloride modified zeolite significantly improves the adsorption rate of chromium, but itself and common activation
The adsorption rate of zeolite is little compared to lifting.Some researchers are then modified using HCL and iron chloride, and gained iron chloride is modified boiling
Stone also improves the adsorption rate of chromium, but gained modified zeolite is only 83.7% to the highest removal rate of chromium.Therefore, how
The adsorption capacity of iron chloride modified zeolite is preferably improved, being one has the problem of to be solved.
Graphene oxide is one of derivative of graphite, and earlier 1850s are just related to the report of graphene oxide
Road.Because graphene oxide possesses high-specific surface area, nano structural material, excellent mechanical property and substantial amounts of active function groups
Etc. property, and its micropollutants are shown with the concern that higher adsorption capacity causes many experts and scholar.
External researcher is inhaled by the method for liquid phase chemical deposition with trim,ethylchlorosilane surface modified Y zeolite
Attached phenol.Result of the test shows：The Si/Al ratio example of zeolite surface improves, and the speed of modified zeolite adsorbing phenol is very fast,
Adsorption rate improves 30% than former zeolite, although there is certain lifting, lifting amplitude is still relatively low.Some researchers pass through 16
The acid research of cetylpyridinium bromide surface modification zeolite absorbing tannin, it is found that modified zeolite increases the adsorption rate of tannic acid,
But its adsorption effect is received and influenced be subject to Cu2+ and pH coexists, the concentration increase of Cu2+, the adsorption capacity drop of tannic acid
It is low.Also some researchers adsorb humic acid using graphene oxide first under the conditions of aqueous medium（Humic acid）.As a result send out
Existing, graphene oxide has the adsorption capacity of higher than graphite and activated carbon, and adsorption capacity is up to 190mgg-1.But aoxidize
Graphene cost is too high, is not suitable for industrial production.
Domestic researcher obtains carrying iron modified zeolite by applying iron in zeolite surface.Test result analysis obtain：Change
Property zeolite is after modification than being before modified significantly improved the adsorption capacity of fluorine.But its fluorine removal capacity and activated alumina, bone
The defluoridation filter materials such as charcoal are unable to reach the purpose for substituting traditional defluoridation filter material, it is also necessary to improve by other methods compared to not high
The load capacity and adsorption capacity of iron.Also some researchers are modified sand using graphene oxide, obtain GO-sand adsorbents.
Result of the test shows that GO-sand is to methylene blue（MB）And Pb（II）Adsorption capacity and adsorbance substantially increase, be roughing sand
More than 10 times.Other researcher be prepared for property it is stable and can the RNA-GO of stable dispersion in water, have studied it
To micro toxin peptide in drinking water（Microcapsule algae toxin）Absorption.It turns out that it is suitably applied, absorption is contaminated to drink
Trace contaminant in source quality.These Experiment Results illustrate that processing of the graphene oxide for micro-polluted water has good effect
Fruit, but because graphene oxide involves great expense, it is directly too high with the cost of graphene oxide-loaded filtrate, be not suitable for high-volume work
Industry produces.Although coating modified be widely used with mixed and modified technology, and obtains the adsorption capacity of zeolite and retention property
Improve.But popularization of the modified zeolite filtrate in Water purification field still runs into many bottleneck problems, is mainly manifested in following several
A aspect:Such as modifying agent load factor is not high, cannot be further enhanced to the adsorption capacity of pollutant.Modified zeolite pair
A certain specific pollutant adsorption capacity significantly improves, but obvious reduction of adsorption effect to another pollutant etc. is asked
Topic.
In addition, the use aspect for modifying agent.Independent graphene oxide is good to the adsorption effect of micropollutants, still
Excessive using graphene oxide body as adsorbent amount, the high cost of graphene oxide determines only to be changed with graphene oxide
Sexual incompatibility industrial mass production.Single iron chloride be modified there are load factor it is not high the problem of, it lifts adsorption capacity
Unobvious, are unable to reach the problem of substituting existing filtrate.
The content of the invention
A kind of graphene oxide and the composite modified zeolite of iron chloride are provided it is an object of the invention to consider the above problem
Filtrate, modified zeolite filtrate of the present invention have extremely strong hydrophilicity and adsorption capacity.
Another object of the present invention is to consider the above problem and to provide a kind of graphene oxide composite modified with iron chloride
The preparation method of zeolite filler.The preparation method load factor of the present invention is high, and load effect is good, and is suitable for industrial production, side
Just it is practical.
The technical scheme is that：The graphene oxide of the present invention and the composite modified zeolite filler of iron chloride, include
Natural zeolite, the gap not being supported, iron oxide adsorption layer, graphene oxide layer, the outer surface of natural zeolite are loaded with changing
Property layer, the modified layer be by iron oxide adsorption layer it is interlaced with graphene oxide layer together with, iron oxide adsorption layer and oxygen
There is the gap not being supported between graphite alkene lamella.
The preparation method of graphene oxide of the present invention and the composite modified zeolite filler of iron chloride, includes the following steps：
1）Cleaned up with distilled water, be put in calcining furnace after 200~400 DEG C of 1~3h of calcining, be cooled to room temperature；
2）With salt 12~24h of acid soak of 1~3mol/L, cleaned up with distilled water, be put in 100~150 DEG C of drying baker drying,
It is stand-by after room temperature cooling；
3）FeCl3The modified natural zeolite stage：Use FeCl3For modifying agent, natural zeolite is modified, by FeCl3Solution and pretreatment
Natural zeolite afterwards is mixed evenly, and adds tinfoil sealing to be positioned in calcining furnace, calcining heat is controlled at 250~450 DEG C, is forged
Time control is burnt in 1~3h, after being cooled to room temperature, is cleaned up with distilled water, is placed on 100~150 DEG C of drying bakers drying, is obtained
FeCl3Modified zeolite；
4）To FeCl3The surface of modified zeolite is modified：Using graphene oxide as modifying agent, to FeCl3Modified zeolite surface
It is modified, graphene oxide powder is dissolved in deionized-distilled water, 10~60min of ultrasonic disperse, it is configured to 10~
The graphene oxide solution of 100mg/L is stand-by, by graphene oxide solution and the FeCl of first stage3Modified zeolite mixing is equal
It is even, add tinfoil sealing to be positioned in calcining furnace, at 100~200 DEG C, calcination time control is cold in 0.5~5h for calcining heat control
But to after room temperature, cleaned up with distilled water, be placed under the conditions of 100~150 DEG C of drying baker and dry, be prepared into graphene oxide-
FeCl3Composite modified zeolite.
The present invention for current modified zeolite there are the problem of, employ coating modified method, be subject to high-temperature calcination condition
Under with graphene oxide and FeCl3It is combined, to zeolite surface modification for composite.With graphene oxide and FeCl3As modification
Agent, is used to prepare modified zeolite, graphene oxide of the invention and the composite modified zeolite filler of iron chloride and preparation method thereof, phase
Had the following advantages for the prior art and effect：
1）Graphene oxide-FeCl3Composite modified zeolite surface modifications agent load factor and load capacity respectively reach 95.38% He
958.39ug g-1, load factor is high, and load effect is good；
2）Compared with natural zeolite, graphene oxide-FeCl3Composite modified zeolite is rich in a large amount of hydrophilic functional groups, as hydroxyl,
Carboxyl, these functional groups make modified zeolite have extremely strong hydrophilicity and adsorption capacity；
3）Graphene oxide-FeCl3Composite modified zeolite surface is complicated, and natural zeolite surface is smooth, and graphene oxide-
FeCl3The specific surface area of composite modified zeolite is 11.7852m2g-1, and the specific surface area of natural zeolite is 4.2321m2g-
1, graphene oxide-FeCl3The specific surface area of composite modified zeolite significantly increases, and is 2.785 times of natural zeolite before modified；
4）FeCl3Composite modified significant effect with graphene oxide to zeolite, when raw water humic acid concentration is 2mg/L, oxidation
Graphene-FeCl3Composite modified zeolite and natural zeolite respectively reach 95.38% and 16.2% to humic acid removal rate, modified
Than improving 79.18% before modified；For adsorption capacity, graphene oxide-FeCl3Composite modified zeolite is also than natural zeolite
4.9 again；
5）While modified zeolite is obvious to micropollutants lifting, still there is higher suction to heavy metal ion and organic pollution
Attached rate is 25 DEG C, raw water Cu in temperature2+Concentration is 2mg/L and zeolite dosage is 5g, during pH=7, graphene oxide-FeCl3It is multiple
Modified zeolite and natural zeolite are closed to Cu2+Removal rate be respectively 56% and 87%, 55.36% is improved, for adsorption capacity；Oxygen
Graphite alkene-FeCl3Composite modified zeolite is 1.42 times of natural zeolite；Graphene oxide-FeCl3Composite modified zeolite and day
Right zeolite is respectively 0.0603mg/g and 0.0118 mg/g to the equilibrium adsorption capacities of methyl orange, the former is 5 times of the latter；
6）Based on physical absorption, chemisorbed is weaker for the absorption of Methyl Orange by Natrual Zeolite, and graphene oxide-FeCl3It is multiple
Absorption of the modified zeolite to MO is closed at the same time there are physical absorption and chemisorbed, and chemisorbed is stronger.Compared with natural zeolite,
Graphene oxide-FeCl3The adsorption mechanism of composite modified zeolite is more superior, and adsorption capacity is also stronger.
Brief description of the drawings
Fig. 1 is the structure diagram of the present invention；
Fig. 2 is graphene oxide-FeCl3The preparation technology flow chart of composite modified zeolite；
Fig. 3 is natural zeolite and graphene oxide-FeCl3The SEM photograph of composite modified zeolite surface morphosis, including
There is a natural zeolite, 50k ×；Graphene oxide~FeCl3Composite modified zeolite, 5k ×；Graphene oxide~FeCl3It is composite modified
Zeolite, 10k ×；
Fig. 4 is natural zeolite, graphene oxide and graphene oxide~FeCl3The FTIR spectrum figure of composite modified zeolite；
Fig. 5 is the DSC curve figure of graphene oxide.
Embodiment
Embodiment：
The structure diagram of the present invention is as shown in Figure 1, the graphene oxide and the composite modified zeolite filler of iron chloride of the present invention, bag
Include natural zeolite 1, the gap not being supported 2, iron oxide adsorption layer 3, graphene oxide layer 4, the outer surface of natural zeolite 1
Be loaded with modified layer, the modified layer be by iron oxide adsorption layer 3 it is interlaced with graphene oxide layer 4 together with, iron oxide
There is the gap 2 not being supported between adsorption layer 3 and graphene oxide layer 4.
Above-mentioned modified layer is supported on the outer surface of natural zeolite 1 by branch's high-temperature calcination.
Above-mentioned iron oxide adsorption layer 3 is nanometer Fe2O3Particle.
Above-mentioned nanometer Fe2O3The radius size of particle is 1 to 5nm.
The thickness of above-mentioned graphene oxide layer 4 is 0.8~1.6nm, 20 μm of length of run.
The present invention is subject to high-temperature calcination condition on the basis of face coat method, quotes FeCl3With the oxygen of high-specific surface area
Graphite alkene（GO）As modifying agent, using the method for modifying of substep high-temperature calcination, surface modification is carried out to natural zeolite, is obtained
Graphene oxide-FeCl3Composite modified zeolite（Abbreviation GOFMZ）Optimum preparating condition, significantly improve the mistake of modified zeolite
Filter performance and absorption property.And have studied its to humic acid, copper ion, methyl orange removal effect.
In order to further improve the absorption property of modified zeolite, the present invention is changed to have studied and deposited using single modifying agent
Deficiency, using FeCl3Surface modification is carried out to natural zeolite as modifying agent with the graphene oxide of high-specific surface area.It is whole
A preparation manipulation flow is：
Cleaned up with distilled water, be put in calcining furnace after 200~400 DEG C of 1~3h of calcining, be cooled to room temperature；With 1~3mol/L
Salt 12~24h of acid soak, cleaned up with distilled water, be put in the drying of 100~150 DEG C of drying bakers, obtain pretreatment zeolite, room
It is stand-by after temperature cooling；First stage, FeCl3For modifying agent, to natural zeolite（Abbreviation natural zeolite）It is modified（First stage hereinafter
All refer to FeCl3The modified natural zeolite stage）：By FeCl3（1~3mol/L）Solution adds ratio by certain（FeCl3/ naturally boiling
Stone）（0.1~0.5ml/g）（FeCl3The volume of solution and the mass ratio of natural zeolite）Mixed with pretreated natural zeolite
Conjunction stirs evenly, and adds tinfoil sealing to be positioned in calcining furnace, and at 250~450 DEG C, calcination time is controlled 1 for calcining heat control
~3h, after being cooled to room temperature, is cleaned up with distilled water, is placed on 100~150 DEG C of drying baker drying, is obtained the first stage
FeCl3Modified zeolite；Second stage, graphene oxide are modifying agent, to the FeCl of first stage3Modified zeolite surface is changed
Property（Second stage all refers to this stage hereinafter）：Graphene oxide powder is dissolved in deionized-distilled water, ultrasonic disperse 10~
60min, is configured to that the graphene oxide solution of 10~100mg/L is stand-by, and graphene oxide solution is added ratio by certain（Oxygen
Graphite alkene/FeCl3Modified zeolite）（5~50ug/g）（The quality and FeCl of graphene oxide3The mass ratio of modified zeolite）
With the FeCl of first stage3Modified zeolite is uniformly mixed, and adds tinfoil sealing to be positioned in calcining furnace, calcining heat is controlled 100
~200 DEG C, calcination time control after being cooled to room temperature, is cleaned up with distilled water in 0.5~5h, be placed on drying baker 100~
Dried under the conditions of 150 DEG C, be prepared into graphene oxide-FeCl3Composite modified zeolite（Abbreviation GOFMZ, GO-FeCl3It is composite modified
Zeolite）.
Secondly in preparation process, for influence of the apparent each influence factor to Zeolite modifying, obtain graphene oxide-
FeCl3The best conditions of preparation pr ocess of composite modified zeolite, prepares experiment and employs orthogonal test and continuity test；In order to examine
The effect of optimization of its surface characteristic is surveyed, by graphene oxide-FeCl3Composite modified zeolite is used for micropollutants such as humic acid（It is rotten
Phytic acid）Staticadsorption experiment；In order to scientifically analyze and characterization graphene oxide-FeCl3The surface knot of composite modified zeolite
Structure and surface characteristic, this experiment using a variety of advanced high-resolution instruments to natural zeolite natural zeolite and graphene oxide-
FeCl3The surface property of composite modified zeolite is detected：Such as use scanning electron microscope（SEM）Analysis graphene oxide-
FeCl3The morphological feature of composite modified zeolite sample oxide on surface；Thermogravimetric analysis（DSC）Further analyze calcining heat pair
The influence of modified zeolite surface functional group；Fourier infrared spectrum（ATR FTIR）Characterize graphene oxide-FeCl3It is composite modified
Zeolite surface and the information of graphene oxide chemical functional group；Specific area measuring is analyzed（BET）Measuring and calculating graphene oxide-
FeCl3Specific surface area of composite modified zeolite sample etc..
Finally in order to probe into zeolite adsorption ability, the present invention have studied modified zeolite to micropollutants humic acid, heavy metal
The characterization of adsorption of ion copper and organic pollution methyl orange, concrete operation method are that each dirt is configured under conditions of room temperature and pH=7
The raw water solution of thing gradient concentration is contaminated, weighs 10g graphene oxides-FeCl3Composite modified zeolite and 10g natural zeolite is to
In the conical flask for having 150ml pollutant raw water solution, it is placed in concussion instrument, under conditions of rotating speed 100r/min, shakes 2h, point
Analyse influence of the raw water containing various concentrations pollutant to adsorption effect.Then using the above method again respectively to graphite oxide
Alkene-FeCl3The dosage of composite modified zeolite and natural zeolite, pH value carry out Experimental Research.The data of acquisition are used
Freundich and Langmuir isothermal adsorption characteristics equation and first order kinetics and pseudo-second order kinetic equation model, to obtain
The adsorpting characteristic pattern and the rate of adsorption of modified zeolite change with time relation.
Test material of the present invention and equipment：
Natural zeolite（Abbreviation ROZ）：Sieve takes a diameter of 0.4~1.5mm of natural zeolite, is cleaned up with distilled water, is put in and forges
In burning stove after 200~450 DEG C of 1~3h of calcining, it is cooled to room temperature；With salt 12~24h of acid soak of 1~3mol/L, distilled water is used
Clean up, be put in 100~150 DEG C of drying baker drying, it is stand-by after room temperature cooling.Modifying agent：Mass concentration is 2mol/L's
FeCl3·6H2O solution（Analyze pure）.Medicament needed for Phen Spectrophotometric Determination of Iron（0.5% phenanthroline solution, 10% salt
Sour azanol, 25% hydrochloric acid, saturation sodium acetate and buffer solution etc.）；Configure medicament needed for raw water：Humic acid HA：Huang Fu Suan≤
90%, copper powder（Cu, 63.55）, methyl orange（C14H14N3SO3Na, 327.33）Deng；Other assistant medicaments：Nitric acid（HNO3, 63）、
Sodium hydroxide（NaOH, 40.01）, alcohol（C2H6O, 46.07）Deng.Double acetaldehyde oxalyl dihydrazone spectrophotometry survey medicament needed for copper：
Ammonium hydroxide（NH3·H2O, 35.05）, acetaldehyde（CH3CHO, 44.05）, Triammonium citrate（C6H5O7(NH4)3, 243.22）, bicyclohexanone
Oxalyl dihydrazone（C14H22N4O2, 278.35）, ammonium chloride（NH4Cl, 53.49）, copper powder（Cu, 63.55）Deng.
Graphene oxide（GrapHene Oxide, abbreviation GO）（Analyze pure, the limited public affairs of Nanjing Xian Feng nano materials science and technology
Department）, material parameter is as shown in table 1；
Testing equipment：SRJX-8-13 high temperature box type resistance furnaces, three frequency numerical control ultrasonic cleaner of KQ~300VDE types, SHZ~B
Type constant temperature oscillator, AL204 electronic balances, DHG -9145A type electric heating constant-temperature blowing drying boxes, S3400N scanning electron microscopies
Mirror, 27 Fourier transformation infrared spectrometers of TENSOR, pHS~3B type precision pH meters, ASAP2020 specific surface area measuring instruments,
SDT2960 differentials --- thermogravimetric analyzer, X Pert PRO type X-ray diffractometers, T6 type ultraviolet specrophotometers, SHA~N-type
Electric-heated thermostatic water bath.
Graphene oxide-FeCl3Composite modified zeolite（The composite modified zeolite of graphene oxide-iron chloride）Prepare：
Graphene oxide-FeCl3Composite modified zeolite manufacture procedure is as shown in Figure 2.Preparation process is as follows：Cleaned with distilled water dry
Only, it is put in calcining furnace after 200~400 DEG C of 1~3h of calcining, is cooled to room temperature；With the salt acid soak 12 of 1-3 methyl oranges l/L~
24h, is cleaned up with distilled water, is put in 100~150 DEG C of drying baker drying, stand-by after room temperature cooling；First stage, FeCl3For
Modifying agent, is modified natural zeolite（The first stage all refers to this stage hereinafter）：By FeCl3（1-3 methyl oranges l/L）Solution is by certain
Add ratio（FeCl3/ natural zeolite）（0.1~0.5ml/g）（FeCl3The volume of solution and the mass ratio of natural zeolite）With
Pretreated natural zeolite is mixed evenly, and adds tinfoil sealing to be positioned in calcining furnace, calcining heat control 250~
450 DEG C, calcination time is controlled in 1~3h, after being cooled to room temperature, is cleaned up with distilled water, is placed on 100~150 DEG C of drying bakers
Drying, obtains the FeCl of first stage3Modified zeolite；Second stage, graphene oxide are modifying agent, to the FeCl of first stage3
Modified zeolite surface is modified（Second stage all refers to this stage hereinafter）：Graphene oxide powder is dissolved in deionization distillation
In water, ultrasonic disperse 30min, it is stand-by to be configured to the graphene oxide solution of 10~100mg/L, and graphene oxide solution is pressed one
Fixed adds ratio（Graphene oxide/FeCl3Modified zeolite）（5~50ug/g）（The quality and FeCl of graphene oxide3Modified boiling
The mass ratio of stone）With the FeCl of first stage3Modified zeolite is uniformly mixed, and is added tinfoil sealing to be positioned in calcining furnace, is calcined
At 100~200 DEG C, calcination time control after being cooled to room temperature, is cleaned up, is placed on 0.5~5 temperature control with distilled water
Dried under the conditions of 100~150 DEG C of drying baker, graphene oxide FMZ will be obtained, it is spare inside Polythene Bag.
Graphene oxide-FeCl3Composite modified zeolite（The composite modified zeolite of graphene oxide-iron chloride）To humic acid
(referred to as:Humic acid) static adsorbance test：
A, weigh 1g humic acid powder to be put into clean 250ml beakers, add distilled water and be completely dissolved, drained with glass bar
Into 1L volumetric flasks, constant volume to 1L, obtains the humic acid stock solution of 1g/L；
B, 2ml humic acid stock solutions are pipetted with 2ml pipettes, is configured to the raw water of 2mg/L, measures its UV254；
C, 0 methyl orange l/L, 0.3 methyl orange l/L, 0.6 methyl orange l/L, 0.9 methyl orange is respectively configured with humic acid stock solution
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, the humic acid of 40 methyl orange l/L, 50 methyl orange l/L use it is molten
Liquid, measures its UV254 respectively；
D, 5g graphene oxides-Fecl is weighed with electronic balance3Composite modified zeolite sample, is poured into the clean tapers of 250ml
In bottle, 150ml raw waters are added（2mg/L）；
Modified zeolite surface property characterizes：
It will prepare and the modified zeolite surface of kept dry carry out following performance characterization：Scanning electron microscope（SEM）The modified boiling of test
Stone surface appearance feature, Fourier Transform Infrared Spectroscopy（FTIR）With X-ray diffractometer (XRD) test analysis surface functional group simultaneously
Judge whether modifying agent successfully adheres to, thermogravimetric analysis（DSC）Optimum calcinating temperature is obtained, specific area measuring (BET) analysis changes
The adsorption characteristic of property zeolite.
Natural zeolite and graphene oxide-FeCl3Characterization of adsorption of the composite modified zeolite to each pollutant：
Pollutant load, graphene oxide-FeCl are have studied by way of continuity experiment3Composite modified zeolite and natural boiling
Factor pair graphene oxide-the FeCl such as the dosage of stone, pH value3Composite modified zeolite and natural zeolite are adsorbed in each pollutant imitates
The influence of fruit.Specific method is the raw water solution that each pollutant gradient concentration is configured under conditions of room temperature and pH=7, is weighed
10g graphene oxides-FeCl3Taper of composite modified zeolite and the 10g natural zeolite to existing 150ml pollutant raw water solution
In bottle, it is placed in concussion instrument, under conditions of rotating speed 100r/min, shakes 2h, analyze the raw water containing various concentrations pollutant
Influence to adsorption effect.Then using the above method again respectively to graphene oxide-FeCl3Composite modified zeolite and natural boiling
The dosage of stone, pH value carry out Experimental Research.By the data of acquisition Freundich and Langmuir isothermal adsorption characteristics equations
And first order kinetics and pseudo-second order kinetic equation model, to obtain the adsorpting characteristic pattern of modified zeolite and the rate of adsorption at any time
Between variation relation.Formula is as follows；Freundich Tellurium determinations（7-1）；Langmuir Tellurium determination formulas（7-2）；
First _ order kinetics equation（7-3）；Pseudo-second order kinetic equation（7-4）.
Result of the test：
1st, orthogonal experiment
Using multi objective orthogonal experimental method, with the load factor α of modifying agent（%）And to humic acid（HA）Static Adsorption remove
Rate β（%）For evaluation index, graphene oxide~FeCl is determined3The optimum preparating condition of composite modified zeolite.By orthogonal test
Very poor size R values in table, comprehensive analysis determine the influence degree of different factors in composite modified zeolite preparing process（Table 2）.R
Value is bigger, and influence of the corresponding factor of influence to modified zeolite surface property is bigger.
Test result indicates that（It is shown in Table 1）：IOCS prepares optimum process condition：First stage, FeCl3For modifying agent,
FeCl3（2 methyl orange lL-1）/ zeolite is added than the mlg-1 of C1=0.125, calcining heat T1=290 DEG C, calcination time t1
=2.5h；Second stage, graphene oxide is modifying agent, to FeCl3Modified zeolite further carries out surface modification, graphite oxide
Alkene and FeCl3Modified zeolite is added than the ugg-1 of C2=10, calcining heat T2=190 DEG C, calcination time t2=1.5h.
2nd, continuity is tested
In t1=2.5h, T1=290 DEG C, C2=10ug g-1, t2=1.5h, under conditions of T2=190 DEG C, change first stage FeCl3
Ratio is added with natural zeolite：0.075,0.1,0.125,0.15,0.175,0.2,0.225ml g-1.Test result indicates that：Work as C1
During≤0.125ml g~1, humic acid removal rate rises always, increases to 97.01% from 43.28%, then tends towards stability, surface
Load factor is on a declining curve always, drops to 85% from 96.67%, after fall off rate is first slow soon.This is primarily due to, with C1 values
Increase, more modifying agent are gradually supported on zeolite surface, and the addition of modifying agent changes the absorption property of zeolite, so humic acid
Removal rate rises.But in certain reaction temperature and under the conditions of the reaction time, speed under load is certain, when C1 is increased to
During 0.125ml g-1, the FeCl of zeolite surface3Modifying agent saturation, humic acid removal rate kept stable at this time, under load factor
Drop is faster.Therefore, the first stage makes an offer to buy than that should be 0.125.
Using the above method again respectively to first stage calcining heat, first stage calcination time, second stage oxidation stone
Black alkene and FeCl3Modified zeolite adds ratio, second stage calcining heat, and second stage calcination time carries out Experimental Research, as a result
Show, the optimum temperature of first stage calcining is 290 DEG C, and the optimal calcination time of first stage is 2.5h, and second stage aoxidizes
Graphene and FeCl3The optimal of modified zeolite is added than being 190 DEG C for the optimum calcinating temperature of 10ug g~1, second stage, the
The optimal calcination time of two-stage is 1.5h.
3rd, SEM scanning electron microscopic observations
Graphene oxide-FeCl3Composite modified zeolite dramatically increases the removal ability of humic acid than natural zeolite.This is mainly
Specific surface area and characterization of adsorption is caused to have notable difference and cause due to the difference of the surface morphological structure of both（See figure
4）.
From the figure 3, it may be seen that natural zeolite surfacing is smooth, adsorption capacity is small, and specific surface area is small (4.2321m2g-1).
Its EDAX results shows that the ratio that C, O, Al, Si, Fe element account for its gross mass is respectively：2.307%th, 51.067%,
0.639%th, 45.247% and 0.74%；Graphene oxide-FeCl3Composite modified zeolite surface is complicated, and concrete dynamic modulus is presented
Structure, specific surface area reach 11.7852m2g-1, and the specific surface area than natural zeolite adds 2.78 times；In graphite oxide
Alkene~FeCl3Composite modified zeolite surface, the ratio that C, O, Al, Si, Fe element account for its gross mass are respectively：17.604%,
44.881%, 5.485%, 27.392%, 4.637%.According to energy spectrum analysis, graphene oxide-FeCl3Composite modified zeolite
The ratio between surface mass element is：C:O:Al:Si:Fe=1.467:2.805:0.203:0.975:0.083；With natural zeolite ratio,
Graphene oxide~FeCl3Composite modified zeolite surface C element and Fe element showed increaseds, Fe elements are mainly derived from FeCl3
Intermediate modified dose, add the electropositive of zeolite surface；C element is mainly derived from graphene oxide modifying agent, adds zeolite
The functional groups such as the hydroxyl on surface, carboxyl, add the adsorption capacity of zeolite.
4th, Fourier Transform Infrared Spectroscopy（FTIR）Analysis
As shown in figure 4, graphene oxide-FeCl3Composite modified zeolite occurs and aoxidizes at 1619cm-1 and 1724cm-1
The same peak value of graphene.C=C stretching vibration peaks are belonged at 1619cm-1, edge hydroxyl or C=O are belonged at 1724cm-1
Stretching vibration ν C=O；Natural zeolite, graphene oxide and graphene oxide-FeCl3Composite modified zeolite at 3450cm-1 by
There is wide and strong absorption band in the stretching vibration coupling of-OH, this band belongs to hydrone stretching vibration band；Natural zeolite and oxygen
Graphite alkene-FeCl3There is the skeletal vibration band of Si-O-Si, the suction at 793cm-1 at 1043cm-1 in composite modified zeolite
It is the vibration absorption peak in oxygen-octahedron to receive peak, and the absworption peak at 471cm-1 is drawn by the flexural vibrations of Si-O or Al-O
Rise.This explanation after being modified using graphene oxide solution to natural zeolite, successfully born by graphene oxide
It is downloaded to FeCl3Modified zeolite surface.
5th, the thermogravimetric analysis of modified zeolite（DSC）
As shown in figure 5, when graphene oxide heats up in atmosphere, heat flow curve occurs two at 230 DEG C or so and 517 DEG C or so
Wide and strong peak value, while weight declines quickly at the two peak values, illustrate graphene oxide in 230 DEG C or so generation functions
Completely burned reaction occurs at 517 DEG C or so for the complete fracture of group, graphene oxide.
According to Fig. 3 and Fig. 5, graphene oxide-FeCl3Composite modified zeolite prepares the calcining heat T2 of second stage
At=190 DEG C, load factor and humic acid removal rate are respectively 95.38% and 97.01%；During T2=210 DEG C, load factor and humic acid are gone
Except rate is respectively 93.61% and 53.73%, calcining heat T2 is increased to 210 DEG C from 190 DEG C, and load factor and removal rate humic acid divide
1.77% and 43.28% are not have dropped.During calcining heat T2=210 DEG C of this explanation second stage, the functional group of graphene oxide is
Through starting to be broken.But in calcining heat T2=190 DEG C, graphene oxide-FeCl3Composite modified zeolite surface graphene oxide
Functional group still preserves completely.The functional group on these modified zeolite surfaces is the activated adoption site for removing pollutant, to modification
Zeolite adsorption pollutant plays critical effect.
6th, natural zeolite and graphene oxide-FeCl3Characterization of adsorption of the composite modified zeolite to humic acid
（1）Raw water humic acid content, graphene oxide-FeCl are have studied by way of continuity experiment3Composite modified zeolite
The factor pair graphene oxide such as dosage, pH value with natural zeolite-FeCl3Composite modified zeolite and natural zeolite are in humic acid
The influence of adsorption effect.As a result measure compared with natural zeolite, graphene oxide-FeCl3Composite modified zeolite is to humic acid
Removal rate significantly improves.When raw water humic acid concentration is 2mg/L, the composite modified zeolite of graphene oxide-iron chloride, natural boiling
Stone is maximum to the removal rate of humic acid, is respectively 97.5%, 22%.With the increase of raw water humic acid concentration, graphene oxide-
FeCl3Composite modified zeolite goes straight down to less than 60% to the removal rate of humic acid.Interpretation of result：Zeolite passes through FeCl3And oxygen
After graphite alkene is modified, absorption property significantly improves, with the raising of raw water humic acid concentration, graphene oxide-FeCl3It is multiple
The adsorption site for closing modified zeolite surface is gradually occupied until saturation, so as to cause graphene oxide-FeCl3Composite modified boiling
Stone declines the eliminating rate of absorption of humic acid.Again to graphene oxide-FeCl3Composite modified zeolite and natural zeolite add
Amount, pH value carry out Experimental Research, the results showed that, graphene oxide-FeCl3Composite modified zeolite and natural zeolite it is most effective
Dosage be respectively 30g and 15g, Optimal pH=7.
（2）Using Freundich and Langmuir isothermal adsorption characteristics equation and first order kinetics and pseudo-second order kinetic
Equation model, probes into graphene oxide-FeCl3Adsorption mechanism of the composite modified zeolite with natural zeolite to humic acid.As a result such as
Shown in Fig. 5, natural zeolite and graphene oxide-FeCl3Absorption of the composite modified zeolite to humic acid all more meets Freundich
Isothermal adsorption characteristics model, natural zeolite meet the adsorption process of humic acid first _ order kinetics equation form, and graphene oxide-
FeCl3Composite modified zeolite is than affinity bigger that natural zeolite adsorbs humic acid；Graphene oxide-FeCl3Composite modified boiling
Stone is to the rate of adsorption of humic acid compared with natural zeolite bigger；For adsorption capacity, the former is 4.9 times of the latter.
7th, natural zeolite and graphene oxide-FeCl3Composite modified zeolite is to Cu2+Characterization of adsorption
（1）Cu in raw water is have studied by way of continuity experiment2+Concentration, graphene oxide-FeCl3Composite modified zeolite with
Factor pair graphene oxide-the FeCl such as the dosage of natural zeolite, pH value3Composite modified zeolite and natural zeolite are in Cu2+Absorption
The influence of effect the result shows that, natural zeolite and graphene oxide-FeCl3Composite modified zeolite is to Cu2+Removal rate with original
Water Cu2+The increase of concentration and decline.As raw water Cu2+Concentration from 2mg/L increase to 50mg/L when, natural zeolite is to Cu2+Removal rate
Drop to 8.62% from 56%, graphene oxide-FeCl3Composite modified zeolite is to Cu2+Removal rate drops to 31.98 from 88.50.
Graphene oxide and FeCl3Modifying agent significantly improves zeolite to Cu2+Absorption property, with raw water Cu2+The increase of concentration is inhaled
Attached to reach saturation, removal rate declines.Again to graphene oxide-FeCl3The dosage of composite modified zeolite and natural zeolite, pH value
Carry out Experimental Research, the results showed that graphene oxide-FeCl3The most effective dosage of composite modified zeolite and natural zeolite
Respectively 30g and 15g, Optimal pH=7.
(2) Freundich and Langmuir isothermal adsorption characteristics equation and first order kinetics and pseudo-second order kinetic are used
Equation model, probes into graphene oxide-FeCl3Composite modified zeolite is with natural zeolite to Cu2+Adsorption mechanism.Natural zeolite
To Cu2+Absorption meets Freundlich isothermal adsorption characteristics models, to Cu2+Carry out physical absorption；Graphene oxide-FeCl3It is multiple
Modified zeolite is closed to Cu2+Absorption more meets Langmuir isothermal adsorption characteristics models, to Cu2+Adsorption process while existence
Reason absorption and chemisorbed, and based on chemisorbed.Natural zeolite is to Cu2+Adsorption process meet pseudo-second order kinetic equation
Form, graphene oxide-FeCl3Composite modified zeolite is than affinity bigger that natural zeolite adsorbs humic acid；Natural zeolite
Than graphene oxide-FeCl3Composite modified zeolite is to Cu2+The rate of adsorption it is fast；For adsorption capacity, the former is the latter
1.42 again.
8th, natural zeolite and graphene oxide-FeCl3Characterization of adsorption of the composite modified zeolite to methyl orange methyl orange
(1) with Freundlich and Langmuir isothermal adsorption characteristics curve linear to methyl orange methyl orange Isothermal Adsorption Characteristics
Curve.Fitting.The absorption of Methyl Orange by Natrual Zeolite meets Freundich isothermal adsorption characteristics patterns, using physical absorption as
Main, chemisorptive properties are weak.Graphene oxide-FeCl3Absorption of the composite modified zeolite to methyl orange meets at the same time
Freundich and Langmuir isothermal adsorption characteristics patterns, there are physical absorption and chemisorption, but chemisorption energy
Power is stronger.
（2）Adsorption time and Adsorption of Methyl Orange amount curve are drawn by way of continuity experiment, then is moved with first order reaction
Mechanical equation and pseudo-second order kinetic equation linear fit are to the curve.Test result indicates that natural zeolite and graphene oxide-
FeCl3Composite modified zeolite all more meets Adsorption of Methyl Orange process pseudo-second order kinetic fit correlation, to first after Zeolite modifying
The absorption of base orange accelerates.Natural zeolite and graphene oxide-FeCl3Composite modified zeolite inhales the balance of Adsorption of Methyl Orange process
Attached capacity is respectively Qe natural zeolite=0.0118 (mg/g), Qe graphene oxides~FeCl3Composite modified zeolite=0.0603
(mg/g), the latter is the former 5 times, and the time for reaching adsorption equilibrium is respectively 90min, 60min.
1 single-layer graphene oxide of table and dispersion liquid characterization parameter
Table 2-1 Characterization parameters of methyl orange nolayer graphene oxide and
dispersion
2 graphene oxides of table~FeCl3Composite modified zeolite prepares orthogonal test
Note：Ki（α、β）Represent acquired result of the test when the factor takes horizontal i on any one row（α、β）The sum of；R（α、β）For K1~K5
Very poor value.
The fit parameter values of the Freundich and Langmuir isothermal adsorption characteristics equations of 3 humic acid of table compare
7 humic acids of Table ' s Parameter of Freundich and Langmuir methyl oranges dels
4 Cu of table2+Freundich and Langmuir isothermal adsorption characteristics equation model parameters
The relevant parameter of the Freundlich and Langmuir isothermal adsorption characteristics linear fits of 5 methyl orange methyl orange of table
Claims (8)
1. a kind of graphene oxide and the composite modified zeolite filler of iron chloride, it is characterised in that include natural zeolite, do not born
The gap of load, iron oxide adsorption layer, graphene oxide layer, the outer surface of natural zeolite are loaded with modified layer, which is
By iron oxide adsorption layer it is interlaced with graphene oxide layer together with, between iron oxide adsorption layer and graphene oxide layer
There is the gap not being supported.
2. graphene oxide according to claim 1 and the composite modified zeolite filler of iron chloride, it is characterised in that above-mentioned to change
Property layer is supported on the outer surface of natural zeolite by branch's high-temperature calcination.
3. graphene oxide according to claim 1 and the composite modified zeolite filler of iron chloride, it is characterised in that above-mentioned oxygen
It is nanometer Fe to change iron adsorption layer2O3Particle.
4. graphene oxide according to claim 1 and the composite modified zeolite filler of iron chloride, it is characterised in that above-mentioned to receive
Rice Fe2O3The radius size of particle is 1 to 5nm.
5. graphene oxide according to claim 1 and the composite modified zeolite filler of iron chloride, it is characterised in that above-mentioned oxygen
The thickness of graphite alkene lamella 4 is 0.8~1.6nm, 20 μm of length of run.
6. the preparation method of graphene oxide according to claim 1 and the composite modified zeolite filler of iron chloride, its feature
It is to include the following steps：
1）Cleaned up with distilled water, be put in calcining furnace after 200~400 DEG C of 1~3h of calcining, be cooled to room temperature；
2）With salt 12~24h of acid soak of 1~3mol/L, cleaned up with distilled water, be put in 100~150 DEG C of drying baker drying,
It is stand-by after room temperature cooling；
3）FeCl3The modified natural zeolite stage：Use FeCl3For modifying agent, natural zeolite is modified, by FeCl3Solution and pretreatment
Natural zeolite afterwards is mixed evenly, and adds tinfoil sealing to be positioned in calcining furnace, calcining heat is controlled at 250~450 DEG C, is forged
Time control is burnt in 1~3h, after being cooled to room temperature, is cleaned up with distilled water, is placed on 100~150 DEG C of drying bakers drying, is obtained
FeCl3Modified zeolite；
4）To FeCl3The surface of modified zeolite is modified：Using graphene oxide as modifying agent, to FeCl3Modified zeolite surface into
Row is modified, and graphene oxide powder is dissolved in deionized-distilled water, 10~60min of ultrasonic disperse, it is configured to 10~
The graphene oxide solution of 100mg/L is stand-by, by graphene oxide solution and the FeCl of first stage3Modified zeolite mixing is equal
It is even, add tinfoil sealing to be positioned in calcining furnace, at 100~200 DEG C, calcination time control is cold in 0.5~5h for calcining heat control
But to after room temperature, cleaned up with distilled water, be placed under the conditions of 100~150 DEG C of drying baker and dry, be prepared into graphene oxide-
FeCl3Composite modified zeolite.
7. graphene oxide according to claim 6 and the composite modified zeolite filler of iron chloride, it is characterised in that above-mentioned step
It is rapid 3) by the FeCl of 1~3mol/L3Solution presses FeCl3/ natural zeolite add than for 0.1~0.5ml/g with it is pretreated
Natural zeolite is mixed evenly, this is added than being FeCl3The volume of solution and the mass ratio of natural zeolite.
8. graphene oxide according to claim 6 and the composite modified zeolite filler of iron chloride, it is characterised in that above-mentioned step
It is rapid that graphene oxide solution 4) is pressed into graphene oxide/FeCl3Modified zeolite is added than for 5~50ug/g and first stage
FeCl3Modified zeolite is uniformly mixed, this adds the quality and FeCl than being graphene oxide3The mass ratio of modified zeolite.
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